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as used herein , the term &# 34 ; compound &# 34 ; is intended to mean any reaction product formed by adsorption and desorption of a gaseous reactant on a solid reactant within the scope of the invention . in practicing the discrete staging of a constant pressure engine cycle according to the invention , a plurality of two or more different solid reactants are selected , and a different solid reactant is introduced into a different reactor or reaction site in the heat pump apparatus . the different compounds of a set , series or group of compounds used in the process are selected such that the temperature of adsorption of the low vapor pressure compound at low pressure , is higher than the desorption temperature of the next higher vapor pressure compound at high pressure . each of the compounds of such sets or groups each also exhibit different vapor pressure curves , i . e ., each has a different vapor pressure - temperature relationship , and which is independent of the concentration of the gaseous reactant . by selecting appropriate compounds and arranging them in the aforesaid sequence , the process cycle will be carried out so that the heat of adsorption is always at an adequate temperature to drive the next or subsequent desorption reaction in the cycle . preferably the compounds of the series are selected so that none of the compounds in the same reactor have an additional coordination step at lower equilibrium temperature which may adsorb more reactant gas from the other compounds during temperature equilibrium or shut - down condition which would reduce cycle performance during intermittent operation . moreover , masses of each compound are adjusted so that an approximately equal amount of heat is required to desorb each compound . specific reactants used to form compounds useful in the invention include metal oxides , hydrides , halides , carbonates , nitrites , nitrates , oxalates , sulfides and sulfates . preferred metals for the inorganic salts are selected from alkali and alkaline earth metals , transition metals , aluminum , zinc , cadmium and tin . preferred transition metals are manganese , iron , nickel , and cobalt . hereinafter these reactants will be sometimes referred to as solids , salts or solid reactants . gaseous reactants which are adsorbed on the solids to form compounds which are especially useful in the processes of the invention are ammonia , water , methyl amine and methanol , ammonia being especially suitable because it is stable , and forms high energy complexes . however , hydrogen , carbon dioxide , sulfur dioxide , other lower alkanols , lower alkanes , particularly methane and ethane , pyridine , alkylamines , polyamines and phosphine may also be used . these gaseous reactants may also be referred to as refrigerants herein . in a specific example of a set or series of compounds , to illustrate a system according to the invention , salts mgbr 2 , mgcl 2 , srbr 2 and srcl 2 are used in a heat pump consisting of four separate reaction vessels or separate heat - transfer regions in one or more reactors . the compounds comprise the ammonia ligand complex compound of the aforesaid salts with the mgbr 2 and mgcl 2 salts forming complexes containing 2 to 6 nh 3 , srbr 2 containing 2 to 8 nh 3 and srcl 2 containing 1 to 8 nh 3 . fig1 illustrates schematically an example of an apparatus embodiment for carrying out the discrete constant pressure staged heat pump . the salts are charged to reactors 12 , 14 , 16 and 18 , respectively , in successive ascending order of the complex compound ligand vapor pressure . thus , first reactor 12 is charged with mgbr 2 , reactor 14 with mgcl 2 , reactor 16 with srbr 2 , and reactor 18 with srcl 2 . the apparatus includes a burner 20 , heat exchanger 22 , evaporator 24 and condenser 26 together with appropriate valves and conduits for directing ammonia gas from and to the reactors and the condenser and evaporator , and valves 52 , 54 and 56 for directing heat transfer fluid between the reactors as well as pumps and heat exchange conduits for pumping heat transfer fluid within the system . in the first half - cycle , reactor 12 containing the high temperature salt mgbr 2 is at high pressure corresponding to ( 1 ) in fig2 and reactor 16 containing srbr 2 is also at high pressure corresponding to ( 3 ). reactors 14 and 18 are at low pressure , reactor 18 containing srcl 2 and reactor 14 containing mgcl 2 , corresponding to ( 7 ) and ( 9 ), respectively . during the first - half cycle , valves 52 and 56 are positioned so that pump 19 circulates heat transfer fluid through reactors 14 and 16 , thereby transferring energy released during gas adsorption from reactor 14 to the solid reactant in reactor 16 to drive the desorption reaction occurring there . with the valve settings and proper positioning of valve 15 , energy released during the adsorption in reactor 18 is rejected or recovered via heat exchanger 22 . in this first half of the heat exchange cycle , valve 25 is also positioned for directing ammonia vapor from reactors 12 and 16 to condenser 26 and from evaporator 24 to reactors 14 and 18 . pump 17 circulates heat transfer fluid from burner 20 to reactor 12 to drive the desorption of the compound in that reactor . before start of the second half - cycle of the process , a short phase of heat recuperation and temperature shifting is required . the valve positions are charged so that reactors 12 and 14 are coupled , and reactors 16 and 18 are coupled , respectively , for heat transfer communication . heat transfer fluid is pumped through each pair of coupled reactors to transfer heat from the hotter to the colder reactor . thus , reactor 12 is cooled while reactor 14 is heated ; reactor 16 is cooled while reactor 18 is heated . this terminates the recuperative and temperature adjustment phase in preparation for the second half - cycle . in the second half - cycle burner 20 is not used . solid reactant in reactor 14 desorbs its gaseous reactant , driven by heat from the adsorption reaction in reactor 12 . the compound in reactor 18 desorbs , driven by heat released from adsorption of the compound in reactor 16 . ammonia from the desorption reactions is directed to the condenser 26 , and ammonia for the adsorption reactions is obtained from evaporator 24 . at the conclusion of the second half - cycle , another phase of recuperation and temperature adjustment as previously described readies the system for repeating the first half - cycle . in this example , using the aforesaid adsorption and desorption pressures and temperatures , the condensation temperature in condenser 26 is 315 ° k and in the evaporator , 275 ° k . the apparatus of fig1 could also be modified with reactors 12 and 16 combined and reactors 14 and 18 combined in single vessels , respectively , since both reactors in either pair are always at the same pressure . all four compounds may be located in a single reactor , with the heat pump consisting of two such reactors , each operating at alternately high and low pressure . points 1 - 10 on the phase diagram of fig2 illustrate the discrete staging that occurs in the reactors at the various temperatures and pressures as the ammonia ligand is alternately adsorbed and desorbed on the metal salts . at ( 1 ), prime heat from a source , for example burner 20 in fig1 is used to partially or fully desorb mgbr 2 6nh 3 to mgbr 2 2nh 3 . at ( 2 ), mgcl 2 6nh 3 is desorbed , at ( 3 ) srbr 2 8nh 3 is desorbed , and at ( 4 ) srcl 2 8nh 3 is desorbed . gaseous reactant from the desorptions is condensed at ( 5 ) releasing heat , which may be recovered by any heat exchange means . the desorption reactions are carried out at a single pressure , 16 . 28 bar . the adsorption phase of the reaction is carried out at a lower pressure , 4 . 6 bar with the aforesaid complexes , ammonia being directed to a lower pressure and evaporated at ( 6 ), absorbing heat . the ammonia vapor is then adsorbed into the four complex compounds at points ( 7 ), ( 8 ), ( 9 ) and ( 10 ). heat released from the adsorption at ( 7 ) is rejected externally by heat exchanger 22 ( fig1 ), and heat from the other three adsorption reactions is used to drive the desorption reactions illustrated by the arrows between points ( 8 ) and ( 4 ), ( 9 ) and ( 3 ), and ( 10 ) and ( 2 ), respectively . at the end of this portion of the cycle , the process is reversed so that , for example , complex at ( 1 ), now desorbed , is lowered in temperature and pressure to the conditions at ( 10 ) for adsorption . the complex at ( 10 ), which is now adsorbed , is increased in temperature and pressure to the conditions of ( 1 ), as are complex compounds in the other three reactors . thus , the output from the cycle , depending on the intended application , may be used for cooling obtained from ammonia evaporation at ( 6 ), or the heat released from the process at ( 5 ) and ( 7 ) in a quasi - continuous mode . referring again to the example using four aforesaid complex compounds and points ( 1 )-( 10 ) in fig2 the following table illustrates the different temperatures and pressures at which the complex compounds adsorb and desorb the ammonia ligand . table i______________________________________ desorb adsorb ( 16 . 28 bar ) ( 4 . 6 bar ) nh . sub . 3 temp . ° k . ______________________________________mgbr . sub . 2 . 2 / 6 ( 1 ) 604 544 ( 10 ) mgcl . sub . 2 . 2 / 6 ( 2 ) 495 449 ( 9 ) srbr . sub . 2 . 2 / 8 ( 3 ) 432 391 ( 8 ) srcl . sub . 2 . 1 / 8 ( 4 ) 374 342 ( 7 ) ______________________________________ from this example of a set or series of complex compounds it is shown that the temperature of adsorption of the low vapor pressure salt , at the low adsorbing pressure , is higher than the desorption temperature of the next higher vapor pressure salt . observing fig2 this critical feature will be evident from the complex compounds in the table noting the points of the cycle stages which correspond to the phase diagram numbers . referring to fig3 a three reactor apparatus utilizing a system according to the invention is shown . examples of suitable compounds for use in such an apparatus for carrying out a discrete constant pressure adsorption / desorption process is shown in tables ii and iii together with the desorption and adsorption temperatures and pressures . the compounds are listed in their ascending order from the lowest to the highest ammonia vapor pressure . in the example of fig3 instead of using an evaporator and condenser illustrated in fig1 nabr or bacl 2 in reactors 55 and 57 is used to desorb and adsorb the ammonia from and to reactors 72 , 74 and 76 . in this example , in each of the respective reactors , a different one of the salts forming the complex compounds of table ii or iii is placed in each of the reactors , so that the compound having the lowest gas vapor pressure is in first reactor 72 , and compounds of successively higher gaseous reactant vapor pressures in the successive reactors 74 and 76 . again , this successive positioning of compounds based on ascending vapor pressures in corresponding successive reactors or reaction regions as illustrated in the drawing and previously described , is critical to the invention . burner 71 and heat exchanger 70 are utilized in a manner as previously described in fig1 ( for burner 20 and heat exchanger 22 ). heat is also exchanged externally with heat transfer fluid flowing through reactors 55 and 57 . these reactors alternatively provide heating and cooling . during one half - cycle , reactor 57 provides cooling while 55 is heating , and in the other half - cycle 55 is cooling and 57 is heating . the advantages of using the sodium bromide , or other solid reactant , for adsorbing / desorbing the gaseous reactant as opposed to the condenser / evaporator equipment include ( 1 ) higher energy density in the adsorption / desorption reactions as compared to evaporation and condensation of the gas , resulting in higher coefficients of performance and less system mass , and ( 2 ) the ability to reject heat at high temperature with lower system pressure than would be required using refrigerant condensation . for continuous cooling two or more subsystems can be operated in a phase shifted mode . table ii______________________________________ desorb adsorb ( 16 . 28 bar ) ( 4 . 6 bar ) nh . sub . 3 temp . ° k . ______________________________________mgbr . sub . 2 . 2 / 6 604 544cocl . sub . 2 . 2 / 6 495 449srcl . sub . 2 . 1 / 8 374 342______________________________________ table iii______________________________________ desorb adsorb ( 7 . 31 bar ) ( 1 . 44 bar ) nh . sub . 3 temp . ° k . ______________________________________mgbr . sub . 2 . 2 / 6 562 502cocl . sub . 2 . 2 / 6 461 416cacl . sub . 2 . 2 / 4 356 320______________________________________ the process and system of the invention may also be used as a thermal compressor , which is a subsystem of a heat activated heat pump . for example referring to fig1 by removing condenser 26 , evaporator 24 , and valve 31 , the resulting sub - system apparatus is a thermally activated compressor which receives low pressure vapor through conduit 43 and delivers high pressure vapor through conduit 45 . such a thermal compressor may be used as a less expensive alternative to an electrically driven compressor for obtaining pressurized gaseous reactants . thus , constant pressure staging of appropriate compounds can provide efficient thermal compression of any gaseous reactant , such as water , ammonia , carbon dioxide , sulfur dioxide , methanol and other lower alkanols , alkylamines , polyamines , and phosphine . hydrogen can also be compressed by use of hydrides in the reactors in place of complex compounds while carbon dioxide can be used with metal oxide / metal carbonate reactants , and water can be used with metal oxide / metal hydroxide or complex compound reactants . such thermal compression using a process of the present invention is more efficient than conventional thermal compressors because heat is cascaded through several stages and high pressure vapor is generated at each stage . the constant pressure staging process of the invention may also be used in a heat pump which receives high pressure refrigerant vapor , discharges low pressure vapor , and produces cooling or heating . the high pressure refrigerant vapor can be provided by a mechanical compressor , thermal compressor , for example a constant pressure staged thermal compressor described above , or other source . the constant pressure staged heat pump is most advantageous when coupled with a mechanical compressor , because efficiency and reliability of mechanical compressors increase as compression ratio is decreased . such an apparatus is illustrated in fig4 and process conditions shown in fig5 . compounds a , b , c and d are contained in reactors 104 , 105 , 106 , and 107 , respectively . during the first half - cycle , valve 101 is positioned such that high pressure vapor delivered through conduit 113 from compressor 100 is directed to reactors 104 and 106 . compound a in reactor 104 and complex c in reactor 106 are initially at high pressure p2 in the first half - cycle , and b and d in reactors 105 and 107 are at low pressure p1 . compound a adsorbs at high pressure point ( 5 ), releasing heat which drives desorption of compound b at low pressure point ( 2 ); compound c adsorbs at high pressure ( 7 ), releasing heat which drives desorption of compound d at low pressure ( 4 ). vapor generated during desorption of compounds b and d is routed through valve 101 and conduit 114 to the inlet ( low pressure ) side of compressor 100 . during the second half - cycle , compounds a and c are at low pressure , and compounds b and d are at high pressure . valve 101 is positioned to direct high pressure vapor from the compressor to compounds b and d in vessels 105 and 107 , and to direct low pressure vapor from reactors 104 and 106 to the inlet side of compressor 100 . during this half - cycle , compound , a desorbs at low pressure ( 1 ) producing refrigeration at temperature t1 . compound b adsorbs at high pressure ( 6 ), and heat released is used to drive the desorption of complex c at low pressure ( 3 ). compound d desorbs at high pressure ( 8 ), delivering heat at temperature t8 . cooling at t1 , heating at t8 , or both , are the useful products of the heat pump operation . continuous cooling or heating is provided by utilizing two or more banks of reactors , operating out of phase . the number of compounds used can be two or greater . the lowest temperature compound ( a in fig5 ) may be replaced by evaporation and condensation of the gaseous reactant . the utility and improvement of the invention is evident from fig5 . heat is lifted from temperature t1 to t8 while operating between pressures p1 and p2 . use of only compound a ( or refrigerant condensation / evaporation ) would only lift heat to t3 at the same pressures . a peak pressure of p3 , several orders of magnitude higher than p2 , would be required to obtain temperature lift to t8 . compounds and operating conditions are selected such that the high pressure compounds always adsorb at sufficiently high temperature so heat released can be used to drive the next description . specifically , referring to fig5 t3 must be greater than t2 , t5 greater than t4 , and t7 greater than t6 . thus , in this embodiment , the successive compounds in the set or group are selected so that the higher temperature adsorbing compound , i . e ., the compound that adsorbs at a higher temperature , at high pressure , has an adsorption temperature higher than the desorption temperature of the next succeeding , compound at low pressure . the compounds are located into successive reactors in this ascending adsorption temperature order . selection of such compounds and high and low reaction pressures will be understood by those skilled in the art . although the reactions described and shown herein will normally involve the next successive higher vapor pressure compound , in certain instances , such as heat pump operations under extreme temperature conditions , or multiple temperature level operations , it may be desirable to skip one or more compounds in any specific cycle . the discrete constant pressure staging cycle process disclosed herein has a number of advantages over previously known heat pump cycles , thermal compressors , and thermal storage . as a heat activated heat pump or thermal compressor , the process of the present invention delivers high coefficient performance , and takes thermodynamic advantage of high driving temperatures , limited only by the stability of the lowest vapor pressure compounds . multiple staging is performed within the hardware of single staged systems , and results in lower cost than is possible with other two or multi - stage cycles . between half - cycles , the complex in each stage is heated by drawing heat from the next hotter stage , making regeneration of sensible heat efficient and simple , and improving cycle efficiency as compared to other solid - vapor heat pumps and thermal compressors . operating as a mechanical or thermal compressor heat pump , the system of the invention makes high temperature lift and low pressure ratios possible . although separate reactors are shown in the drawings for the different reaction sites the reactions may be carried out in reaction sites or chambers of a single reactor . thus , as used herein , the term reactors is intended to include one or more reaction sites or chambers in a single reactor as well as multiple reactors . constant pressure staging of the invention can also be used to receive or deliver vapor at more than one pressure level . this capability allows for multiple temperature refrigeration , multiple temperature heat delivery from a heat pump , thermal storage at different temperature levels , or thermal compression simultaneously operating at more than one compression ratio . the number of different pressure ratios possible is equal to the number of stages in the cycle . fig6 is a phase diagram illustrating an example of a six stage cycle for providing refrigeration at two different temperatures . refrigeration temperatures t1 and t2 establish system pressures p1 and p2 , according to the vapor pressure function of the heat pump working media , which can be a pure refrigerant undergoing phase change , or refrigerant involved in any sorption process . heat rejection temperature t3 at pressure p3 is also on the heat pump media vapor pressure line . the cycle operates in the manner as described previously . heat is input at a temperature t4 , which is relatively high compared to t3 . energy input at state point ( 1 ) drives desorption of compound a . adsorption at point ( 15 ) releases heat to drive desorption at point ( 2 ), and so on for compounds b - f . heat input at point ( 1 ) is effectively cascaded through the cycle , in the state point sequence of 1 - 15 - 2 - 14 - 3 - 13 - 4 - 12 - 5 - 11 - 6 - 10 . heat release during adsorption at state point 10 is rejected external to the heat pump cycle . the advantage and unique feature of this cycle embodiment is that adsorptions occur at two different pressure levels . gaseous reactant vapor generated to provide cooling at t1 is at pressure p1 and is adsorbed at state points 10 , 12 , and 15 , while the vapor generated to provide cooling at t2 is at pressure p2 and is adsorbed at points 11 , 13 , and 14 . the selection of pressures for the different stages is dependent on the desired or available media , i . e ., solid - vapor , liquid - vapor , etc ., and on the amount of cooling to be achieved at each temperature level . it is desirable to maximize the number of stages in a cycle while maintaining adequate heat transfer approach temperatures ( temperature differentials ) for heat exchange between stages . moreover , more than two temperature and pressure levels may also be used . heat may be directed between any state point ( reaction chamber ) and external heat exchange means in order to input or to take advantage of the multiple cooling and heating temperatures of such a system . for example , such a system may be used in cascaded refrigeration , air heating and hot water supply , as well as in applications with cogeneration systems where excess waste heat is available at multiple temperature levels . a heat pump incorporating multiple heat rejection temperatures , or thermal compressor using multiple delivery pressures , operates in the same manner although some stages of sorption operate below the intermediate pressure level ( s ). multiple adsorption and desorption pressures may also be used in a single system . although not intended as part of the present invention , the constant pressure staging system may be operated with bivariant media in which the adsorbent vapor pressure is also a function of the refrigerant concentration . each individual vapor pressure line is replaced by a solution field over which the specific media operates . the resulting system is less practical for use with bivariant solid vapor media , for example zeolites or activated carbon , because solution fields , of reasonable refrigerant concentration spread in the media , are quite wide . since no overlap of solution fields is acceptable , only a portion of the theoretical solution field and very few stages may be used . moreover , the large thermal masses and ineffective staging results in low efficiency . additionally , during shutdown all refrigerant will migrate to the lowest vapor pressure media , further reducing efficiency for cyclic operation . use of liquid absorbents overcomes some of these bivariant media problems . each stage of the constant pressure staged cycle would be a narrow concentration range of the media . media may be pumped from stage to stage such that as it is desorbed and vapor decreased , it moves to a higher temperature stage , and as fluid absorbed refrigerant it moves to a lower temperature stage . temperature change between stages may be accomplished recuperatively .

a method of transferring and recovering energy comprises placing in different reactors two or more different solid adsorbents having a gaseous reactant adsorbed thereon and each having a different gaseous reactant vapor pressure , in a first reaction cycle , pressurizing a first portion of the reactors at a first pressure to desorb the gaseous reactant in an endothermic reaction , and pressurizing a second portion of the reactors at a second pressure to adsorb the gaseous reactant in an exothermic reaction , and in a second reaction cycle , pressurizing the first portion of the reactors at the second pressure to adsorb the gaseous reactant in an exothermic reaction , and pressurizing the second portion of the reactors at the first pressure to desorb the gaseous reactant in an endothermic reaction , and directing at least a portion of the heat released during the exothermic reactions or at least a portion of heat adsorbed during the endothermic reactions to heat exchange means for energy recovery . the invention includes apparatus having means for carrying out the process .

referring to fig1 , shown is a double hung window assembly 100 in which a block and tackle window balance constructed in accordance with the teachings of the present invention can be used . the double hung window assembly 100 includes a window frame 102 , a lower window sash 104 , an upper window sash 106 , and a pair of window jambs 107 . within each window jamb 107 , jamb pockets 108 are defined . the lower window sash 104 and upper window sash 106 slide vertically within the jamb pockets 108 . generally , window balances are attached to the lower and upper window sashes 104 , 106 to balance the weight of the window sashes at any vertical position within the jamb pockets 108 . fig2 a , 2 b , and 3 show perspective views of a prior art block and tackle window balance 200 . fig2 a shows the prior art block and tackle window balance 200 in full , whereas fig2 b shows the prior art block and tackle window balance 200 with one side wall of a rigid u - shaped channel 205 cut away so that components within the window balance 200 are more visible . fig3 shows a rear view of the window balance 200 . the block and tackle window balance 200 includes a spring 220 , a translatable pulley unit 230 , a fixed pulley unit 235 , a roller 239 , and a cord 240 all housed with the rigid u - shaped channel 205 . attached to the two ends of the rigid u - shaped channel 205 with fasteners 212 , 216 are a top guide 210 and a bottom guide 215 that are used to connect the window balance 200 to either the upper or lower window sashes 104 , 106 and to help guide the vertical motion of the window balance 200 within the jamb pockets 108 . the top guide 210 includes an upper portion 202 and a lower portion 203 . the upper portion 202 of the top guide 210 is angled and is sized to be received by a member attached to a window sash , such as a cam . the bottom guide 215 includes a back portion 213 , best seen in fig3 , that encases a portion of the rigid channel 205 . within the back portion 213 of the bottom guide 215 is a channel 214 sized to receive a portion of a window sash . the rigid u - shaped channel 205 has a back wall 206 and two side walls 207 , 208 that in combination form the u - shape . the rigid u - shaped channel 205 serves as an external frame to which the components of the window balance 200 can be secured . the rigid u - shaped channel 205 also keeps components located within the rigid u - shaped channel 205 free of debris and particulate matter . the spring 220 , the translatable pulley unit 230 , the fixed pulley unit 235 , and the roller 239 are located inside the rigid u - shaped channel 205 . both of the translatable pulley unit 230 and the fixed pulley unit 235 include one or more pulleys rotatable around respective axles . components within the rigid u - shaped channel 205 work in combination to create a force to counterbalance the weight of the attached sash at any vertical position within the window frame 102 . these components are attached to each other such that a first end 219 of the spring 220 is connected to the translatable pulley unit 230 , and the translatable pulley unit 230 is connected to the fixed pulley unit 235 and the roller 239 via the cord 240 . a pulley in the fixed pulley unit 235 and the roller 239 may be contained in a frame 236 . to secure the components within the rigid u - shaped channel 205 , the second end 221 of the spring 220 and the frame 236 are fixed to opposite ends of the rigid u - shaped channel 205 via respective fasteners 218 , 243 . the frame 236 is also used to secure a pulley axle 237 and a roller axle 238 , around which the pulley in the fixed pulley unit 235 and the roller 239 respectively rotate . a first distance “ aa ” 275 is defined by a length extending between the upper portion 202 of the top guide 210 and the roller axle 238 . the spring 220 and the translatable pulley unit 230 are connected together by hooking the first end 219 of the spring 220 through an upper slot opening 229 in a frame 225 . the frame 225 houses the translatable pulley unit 230 and a pulley axle 232 around which a pulley in the translatable pulley unit 230 rotates . the cord 240 , which can be a rope , string , or cable , has a first end 241 and a second end 242 . the first end 241 of the cord 240 is secured to the frame 225 and the second end 242 , which is a free cord end , is threaded through the translatable pulley unit 230 , the fixed pulley unit 235 , and the roller 239 , thereby connecting all three components together . after the cord 240 connects the three components together , a jamb mounting attachment 245 is secured to the second end 242 of the cord 240 . when the prior art window balance 200 is located in the jamb pocket 108 , the jamb mounting attachment 245 engages an opening 430 ( fig5 ) within one of the jamb pockets 108 , securing the window balance 200 to the window jamb 107 . the spring 220 provides the force required to balance the sashes . the spring 220 is extended when the second end 242 of the cord 240 with the jamb mounting attachment 245 is pulled , causing the frame 225 to move within the rigid u - shaped channel 205 towards the frame 236 , which is fixed . as the frame 225 moves towards the frame 236 , the spring 220 is extended . fig4 a and 4b show an embodiment of a block and tackle window balance 300 in accordance with the teachings of the present invention . the window balances 300 act to counterbalance the weight of the window sashes 104 , 106 at any vertical position within the window frame 102 . fig4 a show one perspective view of the window balance 300 and fig4 b shows another perspective view of the same balance , but with a side wall of the rigid u - shaped channel 305 removed . the window balance 300 includes the rigid u - shaped channel 305 , a top guide 310 , a bottom guide 315 , a spring 320 , a translatable pulley unit 330 , a fixed pulley unit 335 , a bottom guide roller 350 , and a cord 340 . the top guide 310 and the bottom guide 315 are fixed to the rigid u - shaped channel 305 by fasteners 312 , 316 . the top guide 310 is used to help connect the block and tackle window balance 300 to the window sash 104 , 106 and to help guide the movement of the block and tackle window balance 300 within the jamb pocket 108 . the top guide 310 may include a top angled portion 302 and a bottom portion 303 as shown in fig4 a and 4b . the bottom guide 315 is also used for connection and guidance purposes , but the bottom guide 315 further serves as a frame for housing the bottom guide roller 350 . the bottom guide 315 extends beyond the rigid u - shaped channel 305 and , therefore , the bottom guide roller 350 is located outside of the rigid u - shaped channel 305 . a back portion 313 of the bottom guide 315 may include a channel 314 for receiving a portion of the window sash , as depicted in fig5 . some windows have a groove running along a bottom rail of the sash . on conventional balances , the bottom guide can drop into this groove so a manufacturer needs to use a shorter balance to avoid dropping into the groove . this effectively reduces the amount of travel , because shorter balances have to be used . the bottom guide 315 of the present invention is configured so the contact point of the bottom guide 315 to the sash is higher on the balance 300 so the groove is avoided and a longer balance with a greater spring force can be used . this can afford increased force for balancing the sash at any vertical position , as well as increased amount of travel resulting from the longer balance . the spring 320 , the translatable pulley unit 330 , and the fixed pulley unit 335 are located within the rigid u - shaped channel 305 . in the embodiment shown in fig4 a and 4b , the translatable pulley unit 330 includes two pulleys 326 , 327 that are rotatable about a single pulley axle 328 , however , in other embodiments , the translatable pulley unit 330 may contain one or more pulleys rotatable about the pulley axle 328 . similarly , the fixed pulley unit 335 , as shown in fig4 a and 4b , includes two pulleys 331 , 332 that rotate about a single pulley axle 333 ; however , in other embodiments , the fixed pulley unit 335 may contain one or more pulleys that rotate about the pulley axle 333 . a first end 319 of the spring 320 is fixed with respect to the rigid u - shaped channel 305 via a fastener 318 . in the disclosed embodiment , the fastener is a rivet ; however the fastener could also be a support member welded between the two side walls of the rigid u - shaped channel 305 , a hook secured to or formed in the rigid u - shaped channel 305 , or any other device which secures the first end 319 of the spring 320 to the rigid u - shaped channel 305 . the second end 321 of the spring 320 is attached to a frame 325 , which houses the translatable pulley unit 330 . to connect the spring 320 to the frame 325 , the second end 321 of the spring 320 hooks through an opening 329 in the frame 325 . the cord 340 has a first end 341 and a second end 342 . the first end 341 of the cord 340 is attached to the frame 325 through a frame opening 322 . the second end 342 is attached to a jamb mounting hook 345 . the cord 340 is threaded through the translatable pulley unit 330 , the fixed pulley unit 335 , and around the bottom guide roller 350 , connecting the three components together . the cord 340 in the disclosed embodiment is a string , however it may also be a rope , or a cable . both the fixed pulley unit 335 and the bottom guide roller 350 are fixed with respect to the rigid u - shaped channel 305 . the fixed pulley unit 335 is housed within a frame 336 and rotates around the pulley axle 333 . the frame 336 is secured within the rigid u - shaped channel 305 with a fastener 337 . in an alternative embodiment , the frame 336 is not required , the fixed pulley unit 335 rotates around an axle supported between side walls of the rigid u - shaped channel 305 . in yet another alternative embodiment , the fixed pulley unit 335 can be integral with the bottom guide 315 and as a result , fasteners 337 and 316 can be eliminated because tension of the spring 320 will keep the bottom guide 315 engaged with or connected to the rigid u - shaped channel 305 . the bottom guide roller 350 is located within the bottom guide 315 and rotates around a bottom guide axle 352 . a second distance “ bb ” 375 is defined as the length extending between the top angled portion 302 of the top guide 310 and the bottom guide axle 352 . it should be noted that the second distance “ bb ” 375 is greater than the first distance “ aa ” 275 of the window balance 200 . to use the block and tackle window balance 300 within the window assembly , the balance is connected to both the widow jamb 107 and to either the lower window sash 104 or the upper window sash 106 . substantially vertical front portions 301 , 311 of the top guide 310 and the bottom guide 315 , respectively , help guide movement of the balance 300 when installed in the jamb pocket 108 . referring to fig5 , the block and tackle window balance 300 is attached to the window jamb 107 via the jamb mounting hook 345 . the jamb mounting hook 345 is secured within an opening 430 within the jamb pocket 108 . the window balance 300 is then connected to a window sash by inserting a portion of the window sash into the channel 314 ( formed from walls having an angled portion 317 ) of the bottom guide 315 and connecting a cam 405 mounted on the top of the window sash 400 to the top angled portion 302 of the top guide 310 , as shown in fig6 . the spring 320 of the window balance 300 creates the force required to counterbalance the weight of the window sash . however , because the bottom guide roller 350 is located in the bottom guide 315 , instead of within the rigid u - shaped channel 305 as in prior art balances , window sashes with the block and tackle window balances 300 as disclosed in this application provide greater travel distance . fig7 a is an illustration of a window assembly 500 with two prior art window balances 200 attached to a lower window sash 504 . in fig7 a , the lower window sash 504 is in a closed position . fig7 b shows the window assembly 500 , but with the lower window sash 504 in a fully open position . the standard travel distance of a window sash attached to the prior art window balance 200 is labeled “ cc ” 520 in fig7 b . the window sash 504 , as shown in fig7 a and 7b , is prevented from achieving a greater travel distance by the roller 239 , located within the rigid u - shaped channel 205 , hitting the jamb mounting hook 245 . fig8 a and 8b show a schematic of the window assembly 600 with block and tackle balances 300 of the present invention . fig8 a shows the window assembly 600 in the closed position , while fig8 b shows the window assembly 600 in the fully open position . because the bottom guide roller 350 is mounted within the bottom guide 315 instead of within the rigid u - shaped channel 305 , the window sash 604 can travel a greater distance before the bottom guide roller 350 hits the jamb mounting hook 345 , resulting in a greater travel distance , labeled “ dd ” 530 in fig8 b . it should be noted that the distance “ dd ” 530 is greater than the distance “ cc ” 520 . the greater travel distance is an important feature , because it allows for an increased window clearance that will help persons who are using the window assembly as an emergency exit . variations , modifications , and other implementations of what is described herein will occur to those of ordinary skill in the art without departing from the spirit and the scope of the invention as claimed . accordingly , the invention is to be defined not by the preceding illustrative description but instead by the spirit and scope of the following claims .

disclosed are apparatus for a block and tackle window balance to be incorporated in single and double hung window assemblies . in one embodiment the block and tackle window balance includes a roller secured within a bottom guide to increase range of travel of a window sash .

the heat absorbing window shown generally at 10 includes an outer frame member 12 which retains a number of window panes . the exterior most pane 14 is formed of non - heat absorbing material and typically of standard clear glass . the pane 14 receives solar energy and transmits substantially all of the energy ; both its heat and its illumination . spaced from the first pane 14 is a second window pane 16 formed of heat absorbing material . the area 18 between the panes 14 and 16 define an insulation space therebetween . the insulation space 18 can either contain dry gas at atmospheric pressure or other transparent insulation material . however , this section should not impede the passage of the solar radiation into the rest of the window . spaced from the second window pane 16 and positioned internally of the window frame , is a third window pane 20 . the space between the window panes 16 and 20 defines a fluid channel 22 in which the working fluid flows for transporting the heat energy to a heat exchanger . the process involved is as follows : solar energy , generally in the form of sunlight , contains both heat and illumination energy . the solar energy falls on the exterior pane 14 and passes through that into the insulation space 18 . the solar energy retains a high percentage of its solar heat and substantially all of its illumination . the sunlight then strikes the second window pane 16 formed of heat absorbing material . a large amount of the heat is retained by this window pane . the illumination portion , however , passes through the window pane 16 and on through the fluid contained in the fluid channel 22 . the fluid is of such a quality that it does not impede the passage therethrough of the illumination . the illumination , in the form of light , continues to pass through the last window pane 20 . this window pane can either be of clear material or of heat absorbing material . in either case , it will permit the illumination to pass through that pane . thus , the light striking the first pane 14 will provide illumination through the entire window to be used inside the building structure on which is positioned the improved window . however , the heat will be absorbed by the window pane 16 , and if the pane 20 is also of absorbing material , it will also aid in the retention of the heat . as the fluid passes through the fluid chamber 22 , it will be heated by the window panes 16 and 20 defining and bounding the fluid channel 22 . the heat transmitted to the fluid will then be conveyed as the fluid is taken out of the fluid chamber 22 . by providing a continuous flow of fluid through the fluid chamber 22 , the heat can continuously be removed and provided for useful purposes . it will thus be appreciated , that the first window pane 14 serves a dual purpose . firstly , it acts as the exterior window pane of the window . at the same time , it defines one side of an insulation chamber . in a similar manner , the window pane 16 also serves as both a dual function as the heat absorbing member and at the same time defining a fluid channel on one side and the insulation channel on the other side . finally , the interior window pane 20 also serves as both a regular window pane of the window inside the structure , and to define the other part of the fluid chamber . the window panes are maintained in the frame member 12 by means of a support such as a homogeneous , pliable gasket , or glazing compound 24 . additionally , a rectangular tubing 26 can be provided on all sides of the frame and spaced between the peripheral edges of the first and second window panes 14 , 16 . the rectangular tubing 26 can contain desicant material or other type of drying agents to avoid moisture accumulation in the window panes . additionally , the gasket material can also contain water resistant materials . the panes can be attached by means of an adhesive sealant that resists separation due to thermally caused motion , including expansion and contraction . the materials are also of a type which will not deteriorate under sunlight and which maintain the integrity of the insulating space . the gasket or other glazing support material 28 is also provided as a support for the third window pane 20 positioned at the interior side of the window . an opening or slot 30 is provided in the window frame member 12 to permit entry and exit of the working fluid into the fluid chamber 22 as will hereinafter be described . the windows are arranged in series one adjacent to the other with the working fluid provided at one end , and moving to the opposite end , and then to the next adjacent window frame . the movement is generally provided in an upward direction in accordance with the natural flow of heated substances . thus , fluid is initially provided at the bottom entry port of one window frame and is heated as it passes through the frame and then passes out through the exit port at the upper end of that frame . it is then directed into the next adjacent window frame in that series , and so continues all through the plurality of interconnected window frames of a single series . in order to provide an interconnection between adjacent window frames , there is included a connecting link , or connecting manifold between adjacent windows . referring now to fig3 there is shown one such embodiment of a connecting manifold which connects a first window , typically a lower window 10 shown on the left , with the next adjacent window , typically an upper window 10 &# 39 ;, and shown on the right . the lower window includes the three window panes 14 , 16 , 20 , as heretofore described and held by means of the material 24 and 28 . the next adjacent upper frame 10 &# 39 ; also includes panes 14 &# 39 ;, 16 &# 39 ;, 20 &# 39 ;, and is also interconnected by means of the support material 24 &# 39 ; and 28 &# 39 ;. the interconnecting manifold includes a first interconnecting bracket member 30 which fits over their interior section of the two adjacent windows and is positioned respectively over the innermost window panes 20 and 20 &# 39 ;. a second bracket member 32 includes arms which fit over the first two window panes of each window and extends into the fluid channels 22 , 22 &# 39 ; of the respective adjacent windows . the two brackets 30 , 32 provide an interconnecting chamber 34 in fluid communication between the fluid chamber 22 of the window 10 , and the fluid chamber 22 &# 39 ; and the window 10 &# 39 ;. thus , fluid flowing upward from the lower window 10 can pass through the interconnecting chamber 34 and continue onward to the upper fluid chamber 20 &# 39 ; of the next adjacent window , 10 &# 39 ;. it is noted , that the brackets 30 , 32 include inwardly directed center sections within the bracket which provide support , as well as other improved results . on the exterior of the window is provided a securing brace 36 which serves as a front plate for the interconnection and fits between the adjacent windows . arms 38 , of the brace 36 space the adjacent windows and provide a brace for the brackets . the space between the brace 36 and the bracket 32 is filled with insulation material 40 such as foam , or other such insulation , and provides a moisture barrier as well . an alternate embodiment of an interconnecting manifold is shown in fig4 and includes a self - locking feature . in the embodiment shown in fig4 the first lower window 10 has opposing brackets 44 and 46 positioned against its window frames . bracket 44 includes a single leg 48 covering the two window panes 14 and 16 with a portion of the leg 50 extending into the fluid channel 22 . the bracket 46 includes a lower u shaped member 52 which fits over the window pane 20 . the extending arms of the bracket 44 , 46 define a first channel 54 . the remote ends of the channel walls have outwardly directed flanges 56 , 58 , respectively . the adjacent upper window 10 &# 39 ; includes similarly positioned brackets which are identified by means of primed numbers . it should be noted , however , that the remote ends of the second brackets 56 &# 39 ;, 58 &# 39 ;, have inwardly directed flanges . the flanges 56 , 56 &# 39 ;, as well as 58 , 58 &# 39 ;, define a closed space 60 which actually extends peripherally around the transverse section of the window at its point of interconnection . gaskets 62 are placed within the openings 60 . a spring 64 is positioned between the two brackets and biases the flanges towards each other so that the flanges will compress the gasket 62 therebetween and provide a self - closing and self - locking seal therebetween . it should be noted that the inter - connecting chambers 54 , 54 &# 39 ; are in fluid flow communication with each other , and with the fluid chambers 22 , 22 &# 39 ; of the adjacent windows . thus , fluid flowing outward of the lower window 10 can pass through the interconnecting chamber 54 , 54 &# 39 ; and continue through the chamber 22 &# 39 ; of the next adjacent window . thus , in the embodiment of fig3 there is provided a static type manifold which includes the necessary glazing supports , fluid channel interconnection , insulation , caps , etc . in the embodiment shown in fig4 there is provided a self - locking manifold which adds the spring closing device and water seals within the sliding sleeves of the interconnecting channels . in fig4 there is also provided a front brace 66 and rear brace 68 whose legs space apart the brackets and accordingly , the windows . the chambers formed between the braces and the brackets are filled with insulating material 70 . referring now to fig5 there is shown a complete solar system incorporating a plurality of individual windows 10 interconnected by means of the connecting manifolds 72 . at the ends of this series of windows , there are provided end manifolds 74 which are substantially one half of the individual manifolds shown in fig3 and 4 . conduits 76 lead from the windows past the valves 78 and through a drive means shown as the impeller 80 towards a heat exchanger 82 . the heated fluid passes through the exchanger and continues through additional conduit 84 and further valves 86 back to the input end of the series of windows . the additional valves and conduits which are shown would interconnect to other series of windows . another fluid would be sent into the heat exchanger 82 passing therein along line 88 and back out through line 90 . such other fluid can be sent to domestic heating supplies , space heaters , as well as being used for other types of heating within the housing unit . the valves are one way valves and permit directional flow only in one direction through the system . it is noted that separate valves are provided for each series of windows , so that should a leak occur within a particular window or series of windows , that series can be disconnected by closing the valves at the input and output of that series without effecting the remaining flow through the other series of windows . the type of heat exchanger utilized as well as the remaining heating system , is of standard construction , and is well known in the art . the type of fluid utilized to pass through the heat absorbing windows can be either air or liquid . preferably , the working fluid will be a mixture of water with an antifreeze additive , such as approximately 10 % propyleneglycol or similar substance . however , the system can also utilize air as the flowing medium . in an air activated system , the fluid channel would probably be larger , as for example a fluid channel of 3 inches by 24 inches . the working fluid being a as would require a simpler interconnecting manifold of a similar nature to those described . the manifold would probably appear as a rectangular tube that interlocks with the glazing panels at the fluid portals . when the fluid is a liquid , such as water , then the fluid system should preferably be a closed system as shown in fig5 . with an air system it could as well be an open system , where the air would not be reused but would continuously be freshly supplied from the environment . the edges of the device are generally sealed with a semi - flexible rubber gasket as heretofore described . the fluid portals , however , at the surfaces of the channel would be opened . the gasket is secured by the metal guard frame at the outermost edges of the device , which in turn is continuous except for at the fluid portals at which point , the guard extends sufficiently into the fluid channel to protect the edges of the glass . with various special requirements of building codes , minor variations of the present absorbant system may be necessary . for example , with building codes that require glass which protects from shattering , it may be necessary to utilize wired safety glass rather than laminated glass . lamination glass would probably reduce the solar transmission of the device , while the wired safety glass would satisfy the building codes and yet still maintain the novel features of the invention . however , it should be noted that such wired safety glass would only need be in the exterior sheet alone . it should be further appreciated that the exterior most pane of glass 14 need not always be provided . for example , in exceedingly warm climates where no heat insulation is needed , the outermost pane can be completely eliminated and only the two panes defining the fluid chamber need be provided . while certain novel features of this invention have been shown and described and are pointed out in the annexed claims , it will be understood that various omissions , substitutions and changes in the forms and details of the device illustrated and in its operation can be made by those skilled in the art without departing from the spirit of the invention .

a heat absorbing window which can receive solar energy and transmit the illumination part of the solar energy , while utilizing the heat part of such energy to provide a source of heat for useful purposes . the window includes a frame with three window panes . the outermost pane faces the exterior and is of non - heat absorbing material . the middle pane is of heat absorbing material , and the innermost pane can be either clear or of absorbing material . the space between the first and middle window panes defines an insulation space therebetween . the space between the middle and the inner window panes defines a fluid chamber wherein a fluid is passed . while in the chamber , the fluid is heated from the heat absorbed by the abutting heat absorbing window panes . the heated fluid is sent to a heat exchanger to extract the heat and provide useful heating purposes .

referring now to fig1 a , 1b and 2 , a preferred embodiment of transfer system 10 of the present invention is illustrated . transfer system 10 comprises a box frame 11 which is shaped to provide a base 200 which fits between a mattress 16 and a foundation 18 such as box springs or a bed platform . so positioned , frame 11 rests on its base , extending from one edge of the base around an edge of the mattress 16 , preferably the end of the mattress located at the foot of a bed . from the exposed edge of the base frame 11 rises vertically for a distance and then bends back over mattress 16 . the end of frame 11 opposite the base is thus suspended over mattress 16 . on the end of frame 11 over mattress 16 , a handle 12 and a support brace 14 are positionable for the use of a person getting into and out of bed . normally , a person lying on mattress 16 can grab handle 12 when extended and be pulled to a sitting position by the handle as it is retracted . for individuals with limited use of their arms , a harness 92 may be attached to handle 12 by straps 93 and 95 . the individual can than fit harness 92 around their back with the straps 93 and 95 extending from under their arms to be pulled to a sitting position . alternatively , handle 12 can be removed and harness 92 fitted directly to the linkages used for attachment of the handle to frame 11 . the upper section of frame 11 , corresponding in part to arms 23 and 27 , slants downwardly from a location over the end of the mattress 16 toward the head of the bed . handle 12 is movable on frame 11 from the end of the frame over the bed in the directions indicated by double arrow “ a ”. handle 12 thus may be extended somewhat downwardly toward the head of the bed ( illustrated in fig4 ) and retracted back into frame 11 . handle 12 is disposed on rods which extend from within frame tubes 20 and 24 and which are spring biased to urge the handle outwardly from frame 11 out over mattress 16 toward the head of the bed . a handle retraction motor 111 is mounted to frame 11 on cross member 32 and is connected to handle 12 by a flexible tether 113 set on a pulley ( illustrated below ). tether 113 provides for retracting handle 12 into frame 11 with sufficient force to overcome the bias of the spring . when the weight of a person &# 39 ; s torso hangs from handle 12 the person is gently lowered onto the bed from a sitting position and can , from a recumbent position , pull the handle towards themselves . handle 12 is also rotatable in the directions indicated by double arrow “ b ” on an axis which is parallel to the upper major surface of mattress 16 to allow the handle to be pushed out of the way or pulled to a more convenient position . a support brace 14 is also mounted to a cross member 34 near the upper end of frame 11 . support brace 14 may be rotated in the directions indicated by double arrow “ c ” about an axis substantially perpendicular to the upper major surface of mattress 16 . brace 14 may be moved out over one of the major edges of mattress 16 to provide support to a person moving from a standing position along side the bed to a sitting position on mattress 16 , or from a sitting position on the mattress to standing alongside the bed . frame 11 is constructed from two tubular members 20 and 24 , and a plurality of transverse cross members 28 , 30 , 32 and 34 . each tubular member has , in turn , three major sections corresponding to the principal parts of the frame 11 . for tubular member 20 there is a base leg 21 , an upright 22 and a positioning arm 23 . tubular member 20 is preferably formed from a single tube with curved transition sections between the major sections . similarly , tubular member 24 has a base leg 25 , an upright 26 and a positioning arm 27 . frame 11 has three major sections , defined by their respective functions , which are : as a base or foundation for the frame ; as a riser disposed between the base and an upper support platform to allow positioning of the frame around an edge of the bed ; and as a platform positioned above the bed for the active elements of the support system 10 . frame 11 stands on one side of the frame , comprising base legs 21 and 25 and cross member 28 , which form the base . the base is illustrated as positioned below a mattress 16 , which stabilizes frame 11 on a box spring or platform 18 . the riser corresponds to vertical uprights 22 and 26 and cross member 30 . the platform to position patient aid braces and handles within easy reach of a patient is formed by arms 23 and 27 along with cross members 32 and 34 . vertical support for arms 23 and 27 is provided by vertical uprights 22 and 26 , respectively . uprights 22 and 26 are braced against on one another be cross member 30 . positioning arms 23 and 27 depend from uprights 22 and 26 , respectively , and are linked to one another by cross members 32 and 34 . cross members 28 , 30 , 32 and 34 are attached to tubular members 20 and 24 by suitable fastening means . for cross members 28 , 30 and 32 these may include penetration of the tubular members 20 and 24 by the ends of the cross members coupled with screws through the bodies of the tubular members into the cross members . cross member 34 serves other functions and is attached to tubular members 20 and 24 somewhat differently as is described below . frame 11 generally defines a u - shaped frame , which can be fitted around one edge of bed mattress and which is held in place by the mattress . specific construction elements , such as tubular frames , joints , bends and cross members , including consideration of their size and material may vary upon specific application of the device , for example in houses or health care facilities , or the type of bed used . spring types , fasteners and the like may be chosen based on cost considerations or the desire for the highest refinement of the tool . the basic design concept would be unchanged . for example , hospital and nursing home beds are different than beds normally found in individual houses or apartments in that a spring grid is all that is provided immediately under the top level bedding element . no box spring is provided and as a result no integral surface exists as a base . in such an application a tubular frame base would not be appropriate . in some applications welded joints joining distinct tubes may be used in place of a single bent tubes , or rectangular tubing may be used instead of circular cross - section tubing to enhance rigidity . the retraction motor is preferably of a type generating high torque at low rotational speeds , such as provided by vehicle windshield wiper motor . [ 0029 ] fig2 is a side elevation of frame 11 illustrating more fully tubular member 20 and the position relative thereto of handle 12 . brace 14 swings on a pivot axis 70 which is perpendicular to the upper major surface of mattress 16 . a plurality of screws 80 are set in tubular member 20 hold cross members 28 , 30 and 32 in place . similar screws ( not shown ) join the cross members 28 , 30 and 32 to tubular member 24 . referring now to fig3 a - b and 4 , the mechanical details relating to positioning of handle 12 are illustrated . handle 12 is mounted on co - axial pivoting mounts 42 and 44 , which are provided by rods 50 and 52 to position a gripping section 36 within easy reach of a person laying in a bed . rods 50 and 52 are mounted in cylinders 46 and 48 with rod exerts 54 and 56 extending from the cylinders to mate with holes through handle arms 38 and 40 , respectively . appropriate threaded nuts or other fastening elements may be used to hold handle 12 on rod exerts 54 and 56 . retraction of handle 12 is powered by a motor 111 , which is mounted on a platform 123 which in turn is set on cross rod 32 . motor 111 is turned on by depression of either of switch pads 115 which may be placed on handle 12 to be easily reached by a user . the position indicated for switch pads 115 is illustrative only and many other locations may be used for the control switch such as a free box which may be placed on an adjacent table . typically the switches will be spring loaded and will cut off if continuous pressure is not applied . motor 111 turns a shaft 127 which in turn drives a constant rotation direction pulley 125 . tether system 113 is connected to retract a cable between pivot mounts 42 and 44 and the constant rotation direction payout pulley 125 to effect retraction of handle 12 . tether system 113 comprises a base cable 121 which winds on pulley 125 . cable 121 divides into two parts , 117 and 119 which are looped through holes 97 and 99 in extensions 83 and 85 , which depend from mounts 42 and 44 , respectively . tether segments 117 and 119 feed though openings 150 and 152 through cross member 34 . extension and retraction of handle 12 relative to frame 11 is supported on piston rods 62 and 64 , which extend from the bases of mounting cylinders 46 and 48 , respectively , and which are partially inserted into the open ends of positioning arms 23 and 27 . rods 62 and 64 are free to move in and out of positioning arms 23 and 27 except as limited rod ends 67 and 69 and by restraining caps 78 and 80 . restraining caps 78 and 80 close the open ends of positioning arms 23 and 27 save for annular openings sized to pass rods 62 and 64 . restraining caps 78 and 80 are of smaller diameter than the width of rod ends 67 and 69 . this allows the free traversal of the rods 62 and 64 . referring to fig4 a cross sectional view of arm 27 illustrates a spring biasing mechanism applicable to both arms . compression spring 68 biases rod 64 outwardly from the tube forming positioning arm 27 toward an extended position . compression spring is located between a piston rod shoulder stop 76 located around piston rod 64 and a screw 220 which positions one end of cross member 32 . if desired , the force generated by spring 68 may be adjusted by building up shoulder 76 , or by selecting a spring with a different spring constant . for a patient with minimal upper body strength and no abdominal strength , handle 12 should be easily drawable , if speed limited , the retractive force applied by the tether 113 balancing the outward force supplied by spring 68 and a comparable spring in arm 23 . retractive force , overcoming the spring forces and supporting the weight of the patient is supplied by motor 111 . the maximum speed of extension may be set by limiting the speed at which constant rotation direction payout pulley 125 can turn . brace 14 is pivotally mounted to an extension of cross member 34 , which positions the pivot 70 for the brace at a point horizontally displaced from the upper or positioning section of frame 11 toward an edge of the bed . a pivot stop 72 limits travel of brace 14 toward the center of the bed and allows the infirm user of the apparatus to pull him or herself around to bring their legs over the edge of the bed . brace 14 may then be pivoted outwardly over the edge of the bed , or to other convenient positions , to provide a support for the individual as he or she stands . it should be apparent that brace 14 and handle 12 may be used to reverse the process as well . [ 0036 ] fig5 illustrates a simple series circuit suitable forproviding energization of motor 111 . a power supply 131 may be connected to motor 111 by simple closure of switch 115 . as stated above , switch 115 is biased open . wires for switch 115 are typically snaked through the tubing of the handle and of frame 11 to reach motor 111 . where handle 12 is removed for a harness an independent switch box may be provided . the present invention aids the infirm in getting into and out of bed , generally without assistance of another individual , or in the case where two elderly persons live together , eases the task of helping another person out of bed . the preferred embodiment is readily installed on most beds , requiring no permanent physical modification of the bed , and is readily removed if desired . when positioned with a bed the apparatus does not limit access to the bed by blocking the major sides with rails . while the invention is shown in only one of its forms , it is not thus limited but is susceptible to various changes and modifications without departing from the spirit and scope of the invention .

a patient self - assist transfer aid provides an open box frame having a base for fitting beneath a mattress of a bed , a riser section extending upwardly from the base for extending around an edge of the mattress and a positioning section for extending out over the mattress from the riser section . the open box frame may be positioned around the mattress end at the foot of the bed to leave the major sides of the bed open for ease of access . a linkage is fitted to the positioning section of the open box frame and may be extended therefrom to position a handle within easy grasp of a person laying in the bed . a spring system urges the linkage outwardly , but is balanced by a motor and pulley system . a handle is pivotally attached to the linkage and for grasping by a patient recumbent in the bed for raising himself with motor assistance or for lowering himself into bed .

in the discussion of the figures the same reference numerals will be used throughout to refer to the same or similar components . in the interest of conciseness , various other components known to the art , such as hydraulic jacks , and the like , preferred or necessary for the operation of the invention , have not been discussed in detail . it is noted that references herein to “ metal ” refer to metallic material , such as , by way of example , conventional carbon steel , but may include any of a number of different materials effective for implementing the invention described herein . referring to fig1 of the drawings , the reference numeral 10 generally designates an apparatus embodying features of the present invention for bending metal . the apparatus 10 preferably includes a base member 12 comprising a metal plate supported by two angle irons 14 positioned on a flat surface 15 , such as ground or a floor . as viewed in fig1 , two posts 16 are secured ( e . g ., by welding ) at their lower ends to the base member 12 , and at their upper ends to a horizontal cross member 18 that spans across the upper ends of the posts 16 . as viewed in fig1 and 2 , a vertical cross member 19 is secured ( e . g ., by welding ) across the horizontal cross member 18 , and a handle 20 is secured ( e . g ., by welding ) to the top of the vertical cross member 19 to facilitate portably carrying the apparatus 10 . it is noted that the cross members 18 and 19 form a t - bar , and alternatively a t - bar may be substituted therefor . a cylindrical receiver 21 is centrally secured ( e . g ., by welding ) on a bottom side of the horizontal cross member 18 , for purposes discussed below . sleeves 22 are slidably positioned on the posts 16 , and springs 17 are positioned on the posts 16 between the sleeves 22 and the base member 12 . a wedge 26 is secured ( e . g ., by welding ) between the sleeves 22 , such that , as most clearly viewed in fig2 , a pointed or angled end 26 a is directed downwardly toward the base member 12 . a wedge plate 27 is preferably positioned ( e . g ., by welding ) on top of the wedge 26 . a jack 28 , such as a hydraulic jack ( shown in fig1 ) or the like , is positioned on the wedge plate 27 . jacks are considered to be well - known in the industry and , therefore , will not be discussed in further detail herein , except insofar as necessary to describe the present invention . the jack 28 includes a jack body 30 positioned on the wedge plate 27 , and a piston extension portion 32 extending into the receiver portion 21 . the jack 28 also includes a conventional operational mechanism 34 for receiving a lever 36 ( shown in dashed outline ) configured for applying activating force to the jack 28 . two blocks 40 and 41 are positioned and secured ( e . g ., by welding ) on the base member 12 , and a stop 44 , such as a bolt , or the like , is secured to the base member 12 . the stop 44 is preferably centrally positioned between the two blocks 40 and 41 , substantially directly beneath the pointed end 26 a of the wedge 26 . the blocks 40 and 41 are sized , configured , and positioned on the base member 12 to facilitate bending sheet metal at a predetermined angle , as discussed in further detail below . in the operation of the metal bending apparatus 10 , as most clearly depicted in fig3 a , 3 b , and 3 c , a sheet of metal 60 is inserted into the apparatus between the blocks 40 and 41 and the wedge 26 , the wedge being maintained in an elevated position by the springs 22 which urge the sleeves 22 , and hence the wedge 26 , upwardly . the lever 36 is then inserted in the operational mechanism 34 and a user applies force through the lever 36 to the jack 28 in a conventional manner to cause the piston extension portion 32 to extend outwardly from the jack body 30 , causing the wedge 26 to move downwardly and compress the springs 17 , as shown in fig3 b . as the wedge 26 moves downwardly , the pointed end 26 a of the wedge 26 engages the sheet metal 60 . as the wedge 26 continues to move downwardly , the sheet metal 60 deforms , bending at the point of contact with the pointed end 26 a of the wedge 26 , as shown in fig3 c . the wedge 26 may continue to be moved downwardly in such manner until further deformation of the sheet metal 60 is resisted by the stop 44 , at which point the operation of bending the sheet metal 60 is complete , and the sheet metal may be removed therefrom . it may be appreciated that the angle of the bend ( typically about 90 °) in the sheet metal 60 , deformed as described above , may be controlled by the size , configuration , and position of the blocks 40 and 41 , stop 44 , and the angle of the pointed end 26 a of the wedge 26 , all of which are design decisions , the determination of which are considered to be apparent to a skilled artisan upon a review of the present description of the invention and , therefore , will not be discussed in further detail herein . by use of the present invention , sheet metal may be consistently bent at a precise predetermined angle . the precise position of the sheet metal 60 in the apparatus 10 may also be controlled , for example , by measuring and controlling the distance of an edge of the sheet metal 60 from a block 40 or 41 . additionally , the apparatus may be readily transported to a work site where needed . it is understood that the present invention may take many forms and embodiments . accordingly , several variations may be made in the foregoing without departing from the spirit or the scope of the invention . for example , the stop 44 may comprise a bolt that is threaded into the base member 12 and may be adjusted by being screwed in or out , and thereby control the amount of downward movement of the wedge 26 and , hence , of the angle of bend in the sheet metal 60 . the stop may be replaced with blocks that rest on the base member 12 and may be readily replaced with blocks of differing sizes ( preferably smaller than the blocks 40 and 41 ), including combinations of blocks and bolts , to thereby control the angle of bend induced in the sheet metal 60 . depending on the stop utilized , the angle irons 14 may not be needed . depending on the size of the blocks 40 and 41 and the angle of bend desired in the sheet metal 60 , the wedge 26 may move downwardly until it is stopped by the base member 12 , and the stop 44 may therefore not be needed . the jack 28 may be hydraulic , pneumatic , electric , mechanical , a screw mechanism , or the like , effective for urging the wedge toward the base member 12 . depending on the type of jack utilized , the springs 17 may not be needed . while various components of the metal bending apparatus 10 are welded together , they may be secured together via screws , or like fasteners . the invention may also be used in a number of applications other than bending sheet metal . for example , the apparatus 10 may be utilized in the cutting or breaking of tile . having thus described the present invention by reference to certain of its preferred embodiments , it is noted that the embodiments disclosed are illustrative rather than limiting in nature and that a wide range of variations , modifications , changes , and substitutions are contemplated in the foregoing disclosure and , in some instances , some features of the present invention may be employed without a corresponding use of the other features . many such variations and modifications may be considered obvious and desirable by those skilled in the art based upon a review of the foregoing description of preferred embodiments . accordingly , it is appropriate that the appended claims be construed broadly and in a manner consistent with the scope of the invention .

a metal bending apparatus which has a base member and a cross member connected together by two posts extending therebetween . a spring and sleeve are slidably positioned on each post , and a wedge is secured between the sleeves , the wedge includes a pointed end directed toward the base member . a stop is secured on the base member substantially directly under the pointed end of the wedge , and two blocks are positioned on the base member substantially parallel to each other and equidistant from the stop . a jack is positioned between the wedge and the cross member for urging the wedge toward the base member , and for bending a sheet of metal interposed between the wedge and the two blocks .

the desgly 9 compounds of the invention are illustrated by the following structural formula : ## str1 ## in which : p is phe or phe ( 4 &# 39 ;- alk ); x is d - phe , d - val , d - nva , d - leu , d - ile , d - aile , d - pba , d - nle , d - cha , d - abu , d - met d - chg , d or l - tyr or d or l - tyr ( alk ); a is val , ile , abu , ala , gly , lys , cha , nle , phe , leu , chg or nva ; n is 0 , 1 or 2 , or a pharmaceutically acceptable salt , ester prodrug or complex thereof . a subgeneric group of compounds of this invention comprises compounds of formula i in which x is d - tyr , d - cha , d - phe , d - ile , d - leu , d - val or d - tyr ( et ); p is phe or phe ( 4 &# 39 ;- et ), a is as defined above , y is nh 2 ; w is pro , z is arg and n is 1 . the compounds of formula i in which x is d - tyr ( et ) are particularly active adh antagonists as are the amide 8 congeners . individual compounds of interest are [ 1 -( β - mercapto - β , β - cyclopentamethylenepropionic acid )- 2 - d - tyrosine - 4 - valine - 8 - arginine - 9 - desglycine ] vasopressin , [ 1 -( β - mercapto - β , β - cyclopentamethylenepropionic acid )- 2 - d - tyrosine - 4 - valine - 8 - arginine - 9 - desglycinamide ] vasopressin and , especially , [ 1 -( β - mercapto - β , β - cyclopentamethylenepropionic acid )- 2 -( o - ethyl - d - tyrosine )- 4 - valine - 8 - arginine - 9 - desglycine ] vasopressin . also included in this invention are various derivatives of the compounds of formula i such as addition salts , prodrugs in ester or amide form and complexes . the addition salts may be either salts with pharmaceutically acceptable cations such as nh 4 . sup .⊕, ca . sup .⊕⊕, k . sup .⊕ or na . sup .⊕ at the terminal acid group ( y = oh ) or with a pharmaceutically acceptable salt at a basic center of the peptide ( as in the arg units ). the acetate salt forms are especially useful although hydrochloride , hydrobromide and salts with other strong acids are useful . the compounds , also , form inner salts or zwitter ions as when y is oh . the ester prodrug forms are , for example , lower alkyl esters of the acids of formula i which have from 1 - 8 carbons in the alkyl radical or aralkyl esters such as various benzyl esters . other latentiated derivatives of the compounds of formula i will be obvious to those skilled in the art &# 34 ; complexes &# 34 ; include various solvates such as hydrates or alcoholates or those with supporting resins , such as a merrifield resin . the compounds of formula i are prepared by cyclizing a linear octapeptide by means of the two mercapto groups , at the cysteine unit ( cys ) at position 6 and at the β - mercapto - β , β - cycloalkylenepropionic acid unit ( cap ) at position 1 . the cyclization reaction occurs readily in the presence of a mild oxidizing agent capable of oxidizing a mercaptan to a disulfide . the reaction is represented as follows : ## str2 ## in which : x , p , a and y are as defined for formula i , above ; z is as defined for formula i above or also may be a single bond whenever y is oh ; w is as defined for formula i above or also may be oh whenever z and y are absent ; and q 1 and q 2 are , each , hydrogen or a displaceable group . the intermediates of formula ii are new compounds and are a part of this invention . the compounds of formula iii in which either or both w and z are absent are also new compounds useful as intermediates as described below . the latter have vsp antagonist activity at a lower level than that of the octapeptides . the cyclization reaction of this reaction sequence is most usefully carried out by oxidation . any oxidizing agent known to the art to be capable of converting a dimercaptan to a disulfide may be used . exemplary of such agents are an alkali metal ferricyanide , especially potassium or sodium ferricyanide , oxygen , gas , diiodomethane or iodine . as an example , potassium ferricyanide is added to the dimercaptan of formula ii dissolved in a suitable inert solvent , for example , water or aqueous methanol at temperatures of from 0 °- 40 °. often , oxidation is at a ph of 7 - 7 . 5 at ambient temperature in dilute solution gives good yields , 40 - 50 %, of the cyclic compound . the compounds of formula iii which are the cys ( oh ) 6 or pro ( oh ) 7 compounds are reacted with a dipeptide , a protected ( nh 2 )- wzy , or an amino acid , ( nh 2 )- z - y , respectively , as described hereafter . the linear mercaptan starting material may or may not have displaceable or protective groups common to the art ( q 1 and q 2 ) present at the various amino acid units . such protective groups include benzyl , p - methoxybenzyl , 1 - adamantyl , t - butyl , p - nitrobenzyl , trityl , benzylthiomethyl , ethylcarbamoyl or acetamidomethyl . benzyl , adamantyl or t - butyl are removed by mercuric ( halo ) acetate salts in aqueous methanol at 0 °- 80 °. the protective group is usually removed before cyclization such as during the hydrogen fluoride splitting of the peptide from the supporting resin . it may , however , be removed either during the cyclization or , in situ , before cyclization . the s - acetamidomethyl groups are especially useful . for example , s - acm - pmp - d - tyr ( et )- phe - val - asn - s - acm - cys - pro - obzl was treated with potassium carbonate in aqueous methanol to give the pro acid linear peptide in 78 - 84 % yield . this was , then , oxidatively cyclized using iodine in aqueous methanol to give the desired pro ( oh ) 7 product in 65 - 70 % yield . alternatively , the protected product was cyclized under the same conditions with initial iodine treatment followed by potassium carbonate removal of the protective ester radical . the pro 7 acid was , then , condensed with arg ( nh 2 ), using dcc and dmap in dmf at 0 °- 20 ° to give the ## str3 ## in 45 % yield . iodine , therefore , removes the s - protective group , especially the acm group , and cyclizes the intermediate . mercuric acetate or lead acetate also remove the acm group to yield a metal mercaptide . this is converted to the thiol in situ by treatment with hydrogen sulfide and , then , oxidized in a separate step . the desired cyclic octapeptide of formula i can be conveniently isolated by acidifying the aqueous oxidation mixture , such as using glacial acetic acid , and passing the reaction mixture over an ion - exchange chromatographic column , for example , over a weakly acid , acrylic resin column with acid elution , or by gel filtration over a bead - formed gel prepared by cross - linking dextran with epichlorohydrin . as an alternative to the cyclization of the linear intermediates of formula ii suggested above , the cyclized 6 - cys acids or 7 - pro acids ( those of formula i in which either both tail units , w and z , or only one tail unit , z , are absent ) are condensed with a protected dipeptide , w - z - y , or with an amino acid , z - y , respectively . the reaction of the cys acid or the pro acid with a suitably protected dipeptide or amino acid is carried out using any amide forming reaction common to the peptide art . usually , substantially equimolar quantities of the starting materials are reacted in the presence of a carbodiimide , such as dicyclohexylcarbodiimide , plus 1 - hydroxybenzotriazole or dimethylaminopyridine in an organic solvent at from 0 °- 35 °, preferably , from ice to room temperature . the protective groups are removed by a reaction which will not split the disulfide bond of the hexapeptide ring , for example , mild alkali . the important intermediates of formula ii are conveniently prepared using solid - phase methods of peptide synthesis as discussed in m . manning et al ., j . med . chem . 25 46 ( 1982 ). a commercial benzhydrylamine support resin ( bhr ) is used to prepare the end products of formula i in which y is nh 2 ( the des - glycines ) and a chloromethyl support resin ( cmr ) is used to prepare the compounds of formula i in which y is oh ( the des - glycinamides ). the peptide chain of the linear peptides of formula ii is built up , stepwise , proceeding from unit 8 working toward unit 1 . each unit is properly protected as known in the peptide art and as described below . alternatively , various oligopeptides may be built up using liquid or support reactions , then condensed as a last step in the reaction sequence for preparing the dimercapto intermediates . the preferred sequence of resin supported step reactions is conveniently carried out in a beckman 990b peptide synthesizer without isolation of each intermediate peptide . the details of the procedure are in the working examples presented hereinafter . solution or enzyme reaction conditions are applicable here as known to the art . the various amino acids , which are consecutively added to the resin supported chain are protected as known to the art . for example , the boc protecting group is used for an amino group especially at the α - position ; an optionally substituted benzyl , for the mercapto groups at the pmp and cys units ; tosyl , for the arg unit ; and an optionally substituted carbobenzoxy ( z ) for the tyr or lys units . the protective groups should , most conveniently , be those which are easily removed , that is , using acid treatment for the tert .- butyloxycarbonyl group , sodium - liquid ammonia or catalytic hydrogenation for the benzyl or carbobenzoxy groups where the removal reaction conditions are not conducive to reaction at other portions of the peptide such as the disulfide bond . as other examples of protecting groups , the amino group of an amino acid or oligopeptide is protected conventionally by an acyl group such as formyl , trifluoroacetyl , phthaloyl , p - toluenesulfonyl or o - nitrophenylsulfonyl group ; a benzyloxycarbonyl group such as benzyloxycarbonyl , o - bromobenzyloxycarbonyl , p - bromobenzyloxycarbonyl , o - or p - chlorobenzyloxycarbonyl , p - nitrobenzyloxycarbonyl or p - methoxybenzyloxycarbonyl , an aliphatic oxycarbonyl group such as trichloroethyloxycarbonyl , t - amyloxycarbonyl , t - butoxycarbonyl or diisopropylmethoxycarbonyl , or an aralkyloxycarbonyl group such as 2 - phenylisopropoxycarbonyl , 2 - tolylisopropoxycarbonyl or 2 - p - diphenylisopropoxycarbonyl . amino groups are also protected by forming enamines by reaction with a 1 , 3 - diketone such as benzoylacetone or acetylacetone . the carboxyl groups can be protected by amide formation , hydrazide formation or esterification . the amide group is substituted , if necessary , with a 3 , 4 - dimethoxybenzyl or bis -( p - methoxyphenyl )- methyl group . the hydrazide group is substituted with a benzyloxycarbonyl , trichloroethyloxycarbonyl , trifluoroacetyl , t - butoxycarbonyl , trityl or 2 - p - diphenyl - isopropoxycarbonyl group . the ester group is substituted with an alkanol such as methanol , ethanol , t - butanol or cyanomethylalcohol ; an aralkanol such as benzylalcohol , p - bromobenzylalcohol , p - chlorobenzylalcohol , p - methoxybenzylalcohol , p - nitrobenzylalcohol , 2 , 6 - dichlorobenzylalcohol , benzhydrylalcohol , benzoylmethylalcohol , p - bromobenzoylmethylalcohol or p - chlorobenzoylmethylalcohol ; a phenol such a 2 , 4 , 6 - trichlorophenol , 2 , 4 , 5 - trichlorophenol , pentachlorophenol , p - nitrophenol or 2 , 4 - dinitrophenol ; or a thiophenol such as thiophenol or p - nitrothiophenol . the hydroxy group in tyrosine is optionally protected by esterification or etherification . a group protected by esterification is , for example an o - acetyl group ; a o - benzoyl group , o - benzyloxycarbonyl or o - ethyloxycarbonyl . a group protected by etherification is , for example , an o - benzyl , o - tetrahydropyranyl or o - t - butyl group . the amino group in the guanidino group in arginine can be protected by a salt forming , nitro , tosyl , benzyloxycarbonyl or mesitylene - 2 - sulfonyl group . however , it is not always necessary to protect the guanidino group . the protected linear peptide intermediate is split from the carrying resin matrix , for example , by using ammonia in an alcoholic solvent , and , then , is treated to remove the protective groups , such as by using sodium - liquid ammonia . this procedure gives the amide derivative of the linear octapeptide . more conveniently , the two steps are combined by treating the resin supported peptide with anhydrous hydrogen fluoride in the presence of a suitable cation scavenger as known to the art , such as anisole , to give the octapeptide intermediate of formula ii , in dimercaptan form , and in good yield . the compounds of this invention have potent vasopressin antagonist activity . vasopressin is known to contribute to the anti - diuretic mechanism of action within the kidney . when the action of these compounds antagonizes that of the natural anti - diuretic hormone ( adh ), the body excretes water due to an increased permeability of the terminal portions of the renal tubule . we believe the mechanism of action is at the vasopressin receptors ( v 2 - receptors ) located on the plasma membrane of certain renal epithelial cells . the most notable pharmocodynamic effect of the adh antagonists of the invention is that of a water diuretic rather than of a natriuretic such as a thiazide . any patient suffering from the syndrome of inappropriate antidiuretic hormone secretion ( siadh ) or from an undesirable edematous condition is a target for the claimed compounds . examples of clinical conditions indicated for the compounds of this invention include hypertension , hepatic cirrhosis , congestive heart failure or a component of any traumatic condition resulting from serious injury or disease in which the agonism of naturally occurring vasopressin at the vsp - mediated receptor sites is a contributing factor . the second group of vasopressin receptor sites are the vascular pressor sites ( v 1 - receptors ) located within the cardiovascular system itself . for example , compound 5 of table i below was tested in the dyckes protocol ( u . s . pat . no . 4 , 367 , 255 ) for inhibition of vasopressin - induced vasoconstriction in the rat ; in vitro ( pa 2 8 . 40 ) and in vivo ( pa 2 7 . 71 ). antagonism at the v 2 receptor sites results in vasodilation with an end result of anti - hypertensive activity . treatment of dysmenorrhea is another utility for the compounds of this invention when administered intravenously or intranasally . the compounds of this invention , therefore , are used to treat edema or to expell water in patients in need of such treatment by administering parenterally or by insufflation a nontoxic but effective quantity of the chosen compound , preferably combined with a pharmaceutical carrier . dosage units of the active ingredient are selected from the range 0 . 01 to 10 mg / kg , preferably 0 . 01 to 5 mg / kg , based on a 70 kg patient . the dosage units are applied from 1 to 5 times daily . the pharmaceutical composition for inducing vasopressin antagonism contains an active ingredient of formula i in the form of a dosage unit as described above dissolved or suspended in a standard liquid carrier . a standard carrier is isotonic saline , contained in an ampoule or a multiple dose vial which is suitable for parenteral injection such as for intravenous , subcutaneous or intramuscular administration . a composition for insufflation is similar but is usually administered in a metered dose applicator or inhaler . pulverized powder compositions may , also , be used , along with oily preparations , gels , buffers for isotonic preparations , emulsions or aerosols , as standard composition forms . the compounds of this invention have been demonstrated to have unique antagonistic activity toward the natural antidiuretic hormone ( anti - adh activity ), in vitro , in the medullary tissue of hog or human kidney and , in vivo , in the hydropenic rat or the hydropenic monkey . details of the in vitro protocols are in f . l . stassen et al ., j . of pharm . exp . ther . 233 , 50 - 54 ( 1982 ) but the calculations of cyclase activity and binding potential at the receptor site are as follows : in each experiment the amount of 32 p / camp formed in the absence of medullary membrane is determined ( blank ). the blank value is subtracted from all experimental data . the compound is tested for its effect on basal adenylate cyclase activity and / or on vasopressin stimulated activity . each determination is carried out in triplicate . the ka value is derived from a lineweaver - burke plot . rel . v max =( v max drug / v max vasopressin )× 100 . k i = i /[( ka &# 39 ;/ ka )- 1 ] where i is the concentration of the antagonist , and ka &# 39 ; and ka are the concentrations of vasopressin required to give half - maximal activity of adenylate cyclase in the presence and absence of antagonist , respectively . test procedure for binding assay : in each experiment , the amount of 3 h - vasopressin bound in the absence and in the presence of an excess of vasopressin ( 7 . 5 × 10 - 6 m ) is measured in triplicate . these values represent total and non - specific binding , respectively . the k b of a compound is derived from the equation for competitive inhibition : k b = ic 50 /( 1 + l / k d ), where ic 50 is the concentration required for 50 % inhibition of specific 3 h - vasopressin binding , l is the concentration of the ligand , and k d is the dissociation constant of 3 h - vasopressin ( k d = 3 . 6 × 10 - 9 m ; 1sd = 0 . 4 × 10 - 9 m ). this is the average k d value determined on 3 preparations of hog kidney membranes . food and water are removed from male rats approximately 18 hours prior to testing . animals are housed 4 per metabolism cage . at 0 hour , the test compound is administered intraperitoneally to the test group and an equivalent volume of vehicle is administered to both control groups ( fasted and non - fasted ). urine volume and osmolality are measured every hour for 4 hours . test values are recorded as ml of urine excreted ( cumulative ), meq / rat electrolyte excreted , mg / rat urea excreted , and osmolality in milli - osmoles / kg h 2 o . a tolerance test is used to determine significance . ed 300 is defined as the dose of compound ( μg / kg ) required to lower urine osmolality to 300 m - osmoles / kg . ed 500 is defined as the dose of compound ( μg / kg ) required to lower urine osmolality to 500 m - osmoles / kg . the hydropenic monkey protocol is similar . table i______________________________________ ## str4 ## anti - adh activity in vivo ( rat ) in vitro ( pig ) ed . sub . 300 ki k . sub . bx y a ( μg / kg )* ( nm ) ( μm ) ______________________________________1 . -- d - tyr glynh . sub . 2 val 32 30 0 . 0822 . -- d - tyr nh . sub . 2 val 63 27 0 . 0653 . -- d - tyr oh val 156 160 0 . 354 . -- d - tyr ( et ) glynh . sub . 2 val 9 . 9 5 . 9 0 . 0115 . -- d - tyr ( et ) nh . sub . 2 val 5 . 8 3 . 0 0 . 00786 . -- d - tyr ( et ) nh . sub . 2 abu 13 7 . 6 0 . 018______________________________________ * estimated dose of peptide delivered ip stat ( μg / kg ) which results in reduction of u . sub . osm from hydropenic levels to 300 mosmoles / kg h . sub . 2 o . table i demonstrates , in the described protocols , the anti - vasopressin activity of selected representative compounds whose octapeptide structures have the desgly dipeptide tail which is characteristic of the compounds of this invention . presence of substantial antagonistic activity is unexpected because , in the agonist series , the des - gly - oxytocin has an opposite effect on blood pressure compared with oxytocin itself ( see b . berde at al ., loc . cit .) and shortening the linear tail of oxytocin and vasopressin result is known in the art to cause &# 34 ; a striking decrease of the typical biological activities of the substances &# 34 ; ( see t . barth et al ., loc . cit .). compound 5 of table i , furthermore , has proven to be a compound of exceptional antagonist activity across the various testing protocols in hog or human tissue in vitro tests as well as in hydropenic rat and monkey tests . its anti - adh activity , manifested as the dose required to decrease urine osmolality to 300m osm / kg water in the conscious hydropenic squirrel monkey test , is ed 300 = 8 . 6 nmoles / kg ( i . p .). that of compound 4 of table i is 33 . 1 nmoles / kg . the 2 - d - phe analog of the latter compound is 319 . 0 nmoles / kg . the following examples are intended solely to teach the preparation of the compounds of this invention . all temperatures are in degrees centigrade . for the solid - phase synthesis of the titled resin supported peptide , boc - arg ( tos ) resin ( 3 mmol / 5 . 4 grams of resin ) was used as starting material . the appropriately protected amino acids were coupled sequentially onto the boc - arg ( tos ) resin , prepared by reacting boc - arg ( tos ) as the cesium salt with commercial merrifield resin ( cl - ch 2 resin ) as known to the art , by using a manual program as described in the following steps : 2 . prewashed with 33 % trifluoroacetic acid in methylene chloride with 1 % indole ( 1 time , 1 minute ). 3 . deprotection with 33 % trifluoroacetic acid in methylene chloride with 1 % indole ( 20 minutes ). 5 . prewashed with 10 % triethylamine in methylene chloride ( 1 time , 1 minute ). 8 . protected amino acid ( 10 mmol ) in triethylamine in methylene chloride and 0 . 5m n , n &# 39 ;- dicyclohexylcarbodiimide in methylene chloride ( 20 ml ) were added . in the case of the coupling of the asn moiety , 1 - hydroxybenzotriazole ( hbt , 10 mmol ) was added with boc - asn in dry dimethylformamide . dry dimethylformamide ( dmf ) was also used as solvent when pmp ( bzl ) was coupled onto the peptide resin , using 4 - dimethylaminopyridine ( 10 mm ). completion of each coupling reaction was monitored by the ninhydrin test . the 4 - methoxybenzyl group was used to protect the thiol group of cys and the 2 - bromo - carbobenzoxy group was employed to block the phenolic hydroxyl of d - tyr . the resulting protected pmp ( bzl )- d - tyr ( br - z )- phe - val - asn - cys ( ome - bzl )- pro - arg ( tos )- resin was washed well with methylene chloride and methanol , respectively . after drying in vacuo overnight , 8 . 4 grams of the titled protected resin intermediate was collected . pmp ( bzl )- d - tyr -( p - bromocarbobenzoxy )- phe - val - asn - cys ( ome - bzl )- pro - arg ( tos ) resin ( 4 g , ca . 1 . 5 mmol ) was subjected to ammonolysis using saturated ammonia / methanol solution ( 200 ml ) in dry dimethylformamide ( 50 ml ) at room temperature for 48 hours . after evaporation to dryness , the residue was precipitated by ethyl acetate / n - hexane and filtered to give the protected octapeptide amide ( 1 . 54 g ). this crude peptide was dissolved in liquid ammonia ( 250 ml ) and treated with sodium / liquid ammonia solution to give pmp - d - tyr - phe - val - asn - cys - pro - arg - nh 2 which was , then , oxidized using 0 . 01m potassium ferricyanide solution in 4 l . of aqueous solution at ph 7 - 7 . 5 . after the completion of oxidation reaction , the ph of aqueous solution was adjusted to ph 4 . 5 by adding glacial acetic acid . this solution was passed through a weakly acid acrylic resin ( bio - rex 70 ) column ( 11 × 2 . 5 cm , h + form ) slowly . the column was eluted with 5 % and 50 % acetic acid solution , respectively . crude cyclized ## str6 ## was collected from 50 % acetic acid solution fractions ( 860 mg ). ______________________________________purification of ## str7 ## ______________________________________1 . counter - current distribution : sample : 860 mg crude , n - buoh / hoac / h . sub . 2 o ( 4 : 1 : 5 ) 250 transfers ( a ) fr . 186 - 204 , 436 mg ( b ) fr . 182 - 185 & amp ; 205 - 218 , 219 mg2 . partition chromatography : sample : 250 mg ( from 1 - a ), g - 25 fine ( 2 . 5 × 55 cm ), n - buoh / hoac / h . sub . 2 o ( 4 : 1 : 5 )( a ) fr . 32 - 46 222 mg3 . preparative hplc : sample : 40 mg ( from 2 - a ); alltech c18 , 3000 psig . flow rate : 3 . 0 ml / min . buffer a : 0 . 1 % tfa buffer b : 0 . 25 % tfa / ch . sub . 3 cn ( 4 : 6 ) 60 % b ; isocratic ; 235 nm ( 2 . 0 aufs ) injection : 10 mg / 0 . 5 ml . buffer a 17 mg of pure titled compound . 4 . ion - exchange chromatography : sample : 365 mg ( from 1 - a & amp ; 2 - a ); cmc ; 0 . 01m nh . sub . 4 oac to 0 . 1m nh . sub . 4 oac linear gradient ( a ) fr . 51 - 70 93 . 3 mg ( b ) fr . 71 - 89 86 . 5 mg ( c ) fr . 91 - 110 65 mg ( d ) fr . 111 - 121 24 . 5 mg______________________________________ pmp ( bzl )- d - tyr ( br - z )- phe - val - asn - cys ( ome - bzl )- pro - arg ( tos )- resin ( 4 . 2 g , 1 . 5 mmol ) from example 1 , in 4 . 5 ml distilled anisole , was reacted with anhydrous hydrogen fluoride ( 40 ml ) at 0 ° for one hour . after treatment as described above and evaporation in vacuo to dryness , the residue was treated with anhydrous ether and filtered off to give 1 . 33 g crude peptide . the completion of removal of the bzl group from the pmp moiety was carried out using the sodium in liquid ammonia reaction as described in example 1 . the resulting unprotected octapeptide was cyclized using 0 . 01m potassium ferricyanide solution at ph 7 - 7 . 5 until color persisted for 30 minutes again as described above in the preparation of the amide . desglycinamide octapeptide ( 600 mg ) was collected after acidifying the oxidation solution with acetic acid to ph 4 . 5 and passing the reaction mixture over a bio - rex - 70 column with 1 l . of 5 % acetic acid as eluent . ______________________________________purification of ## str9 ## ______________________________________1 . counter - current distribution : sample : 600 mg from bio - rex 70 . n - buoh / hoac / h . sub . 2 o ( 4 : 1 : 5 ); 200 transfers ( a ) fr . 150 - 161 169 mg ( b ) fr . 133 - 149 & amp ; 162 - 1632 . preparative hplc : sample : 52 mg ( from 1 - a ); alltech c18 ( 25 cms 10 mm , 10 micron ); buffer a : 0 . 1 % tfa buffer b : 0 . 25 % tfa / ch . sub . 3 cn ( 4 : 6 ) 60 % b , isocratic ; 3000 psig ; 3 . 0 ml / min . injection : 10 mg / 0 . 6 ml in buffer a 235 nm ( 2 . 0 aufs ). ( a ) 24 mg ( b ) 7 . 3 mgcombine 2 - a and 2 - b , repurified on hplc to give 15 mgpure peptide . 3 . partition chromatography : sample : 117 mg ( from 1 - a ), g - 25 fine ( 2 . 5 × 55 cm ) n - buoh / hoac / h . sub . 2 o 4 : 1 : 5 ( a ) fr . 32 - 36 83 mg of pure product______________________________________ the titled compound was prepared by the solid phase method on benzhydrylamine resin ( bha ). thus , 1 . 0 g bha resin ( 1 . 13 mmol nh 2 / g resin ) was reacted with 1 . 5 equivalents of boc - arg ( tos ), 1 . 5 equivalents of dcc and 3 . 0 equivalents of hbt which were made up in dimethylformamide to be 0 . 1m in boc - arg ( tos ). deblocking was performed with 50 % tfa / methylene chloride and neutralization with 5 % diea / methylene chloride . the peptide was elongated , stepwise , by coupling , using preformed boc aminoacyl symmetrical anhydrides in dmf ( 0 . 1m ). boc - asn , boc - d - tyr ( et ) and pmp ( mbz ) were successively coupled using dcc and hbt in dmf . completeness of coupling was monitored by the qualitative ninhydrin test and recoupling was performed as necessary . the completed pmp ( mbz )- d - tyr -( et )- phe - val - asn - cys ( mbz )- pro - arg ( tos )- bha resin was washed with methylene chloride and dried to constant weight , 2 . 34 g . the peptide was deblocked and cleaved from the resin by treatment with anhydrous liquid hydrogen fluoride ( 30 ml ) in the presence of anisole ( 4 ml ) at 0 ° for one hour . after evaporation to dryness under vacuum , the resin was washed with ethyl ether , air dried and , then , extracted with degassed dimethylformamide ( 3 × 20 ml ) and 20 % acetic acid ( 4 × 20 ml ). the dmf and acid extracts were added to 4 l of water ( ph 4 . 5 with acetic acid ). the ph was adjusted to 7 . 2 with ammonium hydroxide and the solution was titrated with 0 . 01m potassium ferricyanide under argon with stirring until a yellow color persisted ( 85 ml ). the ph was brought to 4 . 8 with glacial acetic acid . the mixture was filtered and the filtrate passed over a bio - rex 70 column ( h . sup .⊕). after washing the column with water ( 200 ml ) the crude peptide was eluted with 300 ml of pyridine / acetic acid / water ( 30 : 4 : 66 v / v ). the eluant was evaporated under vacuum at 30 °. the residue was dissolved in 100 ml of 0 . 2n acetic acid , then , lyophilized , yielding 507 mg of the crude titled octapeptide . ______________________________________purification of ## str11 ## ______________________________________1 . counter - current distribution : sample : 607 mg crude , n - buoh : hoac : h . sub . 2 o , 4 : 1 : 5 , 240 transfers ( a ) fr . 154 - 170 & amp ; 190 - 192 71 mg ( b ) fr . 171 - 189 230 mg2 . gel filtration sample : 123 mg of sample ( b ), g - 15 ( 2 . 5 × 55 cm ) using 0 . 2 n hoac , 25 ml / hr ( a ) fr . 46 - 50 ˜ 20 mg ( b ) fr . 51 - 77 60 mg pure peptide______________________________________ a mixture of 0 . 1 mmole of ( pmp 1 - d - leu 2 - val 4 - desglynh 2 ) avp , prepared as described above but using boc - d - leu at position 2 , and 0 . 1 mmole of n - propylamine in 20 ml of dmf was reacted with 23 mg ( 0 . 11 mmol ) of dcc and 14 mg ( 0 . 11 mmol ) of hbt at room temperature for 2 hours . the volatiles were evaporated to give an oily product residue . the product was purified as described above using : ( 1 ) gel filtration over g - 10 - sephadex eluted with 0 . 2n acetic acid ; ( 2 ) high pressure liquid chromatography using 0 . 05 % tfa in 39 % acetonitrile in water ; and , again , ( 3 ) gel filtration to give 20 mg of the pure octapeptide of the title . amino acid analysis : asp 0 . 88 , pro 0 . 93 , val 1 . 00 , leu 1 . 09 , phe 0 . 88 , arg 1 . 07 . hplc = 95 % major peak at 11 . 33 with 40 % aqueous acetonitrile with 0 . 05m kh 2 po 4 as buffer . k bind = 12 . 1 % inhibition at 10 - 5 m . using ( pmp 1 - d - tyr ( et ) 2 - val 4 - desglynh 2 )- avp prepared as in example 2 above and benzylamine gives ## str13 ## other n - alkylated derivatives are prepared similarly . for the solid phase synthesis of the title resin - supported peptide , boc - arg ( tos ) bha resin ( 1 . 19 mmol / g of resin ) was used as a starting material . it was prepared by reaching boc - arg ( tos ), 3 mmol , with the benzhydrylamine resin , 1 . 0 mmol , in dimethylformamide for two hours . the benzhydrylamine resin as the hydrochloride salt was covered with methylene chloride overnight . it was , then , washed with methylene chloride ( 4 × 1 min ), neutralized with 7 % diisopropylethylamine in methylene chloride ( 2 × 2 min ), then , 6 × 1 min with methylene chloride alone and , finally , 2 × 1 min with predried dimethylformamide . the loading of boc - arg ( tos ) on the resin was carried out twice on the shaker using 1 - hydroxybenzotriazole ( hbt , 6 mmol ) and dicyclohexylcarbodiimide ( dcc , 3 mmol ). a quantitative ninhydrin test and amino acid analysis were performed routinely after loading to determine the percentage loading on the resin . loading in this particular run was 62 . 66 %, i . e . 0 . 74 mmol / g of resin was available . the subsequent amino acid , boc - pro , was coupled on the shaker using the following protocol . ( 2 ) prewashed with 50 % tfa in methylene chloride ( 1 time , 1 min ). ( 5 ) prewashed with 7 % diea in methylene chloride ( 1 time , 1 min ). ( 9 ) added protected amino acid ( 3 mmol ) and hbt , 6 mmol , in dmf , followed by the addition of dcc in methylene chloride , 3 mmol , and coupling for 2 hours . the subsequent amino acids were coupled sequentially using beckman peptide synthesizer 990 - b . the program used for each coupling except bocasn and pmp ( 4 - mebzl ) was as follows . ( 2 ) prewashed with 50 % tfa in methylene chloride ( 1 time , 1 min ). ( 5 ) prewashed with 7 % diea in methylene chloride ( 1 time , 1 min ). ( 6 ) neutralized with 7 % diea in methylene chloride ( 1 time , 10 min ). ( 8 ) protected amino acids ( 3 mmol ) in methylene chloride , followed by addition of dcc , 3 mmol , 10 ml of 0 . 3m in methylene chloride , and coupling for two hours . in case of coupling of asn moiety , 1 - hydroxybenzotriazole ( hbt , 6 mmol ) was used , 10 ml of 0 . 6m dimethylformamide . dry dimethylformamide was also used as solvent when pmp ( 4 - mebzl ) was coupled onto the peptide resin , using 4 - dimethylaminopyridine ( 3 mmol ). completion of each coupling reaction was monitored by the ninhydrin test . the 4 - methylbenzyl ( 4 - mebzl ) group was used to protect the thiol groups of the cys and pentamethylene mercaptopropionic acid ( pmp ) moieties . pmp ( 4 - mebzl )- d - tyr ( et )- phe - abu - asn - cys -( 4 - mebzl )- pro - arg ( tos ) bha - resin , 1 . 25 g , ( 0 . 37 mmol ) in 2 ml of anisole , was reacted with anhydrous hydrogen fluoride ( 20 ml at 0 ° for 50 min ). after evaporation of hf in vacuo , the residue was washed with anhydrous ether , 4 × 20 ml , and the crude peptide was extracted with dimethylformamide ( 50 ml ) and 33 % acetic acid ( 50 ml ) into 2 liter of degassed water previously adjusted to ph 4 . 5 . the aqueous diluted disulfhydryl octapeptide was cyclized using 0 . 01m potassium ferricyanide solution at ph 7 . 2 until the yellow color persisted for 30 minutes ( 50 ml ). the ph was adjusted to 4 . 5 using glacial acetic acid and the solution was passed through a weakly acid acrylic resin ( bio - rex - 70 ) column ( 2 . 5 × 12 , r . sup .⊕ form ), slowly . the column was eluted with pyridine - acetate buffer ( 30 : 4 : 66 ; pyridine / glacial acetic acid / water ). the pyridine acetate solution was removed by distillation in vacuo . the residue was lyophilized from 10 % acetic acid to give 300 mg ( 76 %) of crude titled peptide . ______________________________________purification of ## str14 ## ______________________________________1 . counter - current distribution : sample : 300 mg , n - buoh / hoac / h . sub . 2 o , 4 : 1 : 5 , 240 transfers . ( a ) fr . 176 - 186 , 99 . 6 mg of pure peptide ( b ) fr . 170 - 175 and 187 - 210 , 117 . 24 mgyield of purified material , 216 . 84 mg ( 55 %) 2 . molecular formula : c . sub . 50 h . sub . 72 n . sub . 12 o . sub . 10 s . sub . 2 molecular weight : 1064 . 53 amino acid analysis : asp ( 1 . 00 ), abu + cys ( 1 . 70 ), tyr ( 0 . 64 ), phe ( 0 . 98 ), arg ( 0 . 91 ) peptide content : 68 . 06 - 91 . 52 % from amino acid analysis 87 . 33 % from nitrogen analysis3 . chromatography data : solvent r . sub . ftlc n - buoh / hoac / h . sub . 2 o / etoac 0 . 56 ( 1 : 1 : 1 : 1 ) n - buoh / hoac / h . sub . 2 o / 0 . 42 ( 4 : 1 : 5 ) upperhplc c . sub . 18 - column k &# 39 ; isocratic h . sub . 2 o / ch . sub . 3 cn / tfa , 3 ( 60 : 40 : 0 . 25 ) 0 . 05 mkh . sub . 2 po . sub . 4 : 7 . 33 acetonitrile ( 60 : 40 ) gradient h . sub . 2 o / ch . sub . 3 cn / tfa , 8 . 82 80 : 20 : 0 . 25 to 50 : 50 : 0 . 25fast atom bombardment ( fab ): m / z 1065 ( m + h ). sup .+ ; 1063 ( m - h ). sup .- ______________________________________ the tetrapeptide supported resin , boc - asn - cys ( 4 - mebzl )- pro - arg ( tos )- bha , 0 . 72 g ( 0 . 36 mmol ), was synthesized on beckman 990 - b peptide synthesizer , starting from the boc - arg ( tos ) benzhydrylamine resin ( 0 . 72 mmol / g ) using a protocol like that of example 5 . the subsequent amino acids were coupled sequentially on the shaker using hbt and dcc for 2 hours in a similar fashion . after coupling of the last residue , i . e , pmp ( 4 - mebzl ), the resin containing peptide was washed as usual , dried to give 0 . 88 g of the titled intermediate . pmp ( 4 - mebzl )- d - tyr ( et )- phe - ala - asn - cys ( 4 - mebzl )- pro - arg ( tos )- bha - resin , in 2 ml of anisole , was reacted with anhydrous hf , 20 ml , at 0 ° for 50 minutes . the work up was done as usual and the uptake of k 3 fe ( cn ) 6 was 45 ml to give 230 mg ( 60 . 8 %) of crude titled peptide . ______________________________________purification of ## str16 ## ______________________________________1 . counter - current distribution : sample : 230 mg , n - buoh / hoac / h . sub . 2 o , 4 : 1 : 5 , 240 transfers ( a ) fr . 160 - 178 , 105 . 2 mg pure product ( b ) fr . 179 - 190 and 150 - 159 , 49 . 5 mgyield of purified material , 154 . 7 mg ( 41 %). 2 . molecular formula : c . sub . 49 h . sub . 70 n . sub . 70 o . sub . 10 s . sub . 2 molecular weight : 1050 . 449 amino acid analysis : asp ( 1 . 00 ), pro ( 1 . 03 ), ala ( 0 . 94 ), cys ( 0 . 46 ), tyr ( 0 . 65 ), phe ( 0 . 91 ), arg ( 0 . 92 ). peptide content : 59 . 18 - 81 . 77 % from two analyses . 3 . chromatography data : solvent r . sub . ftlc mbuoh / hoac / h . sub . 2 o / etoac 0 . 64 ( 1 : 1 : 1 : 1 ) hplc c . sub . 18 - column k &# 39 ; isocratic h . sub . 2 o / ch . sub . 3 cn / tfa , 2 . 18 60 : 40 : 0 . 1gradient h . sub . 2 o / ch . sub . 3 cn / tfa , 6 . 47 60 : 40 : 0 . 1 to 50 : 50 : 0 . 1fast atom bombardment ( fab ): m / z 1051 ( m + h ). sup .+ ; 1049 ( m - h ). sup .- ______________________________________ the titled resin - supported peptide was prepared from boc - arg ( tos ) bha resin ( 0 . 4 mmol / g ) on a shaker using a protocol used before i . e . deprotection - coupling using hbt and dcc for 2 hours , up to boc - val - asn - cys -( 4 - mebzl )- pro - arg ( tos )- bha resin . the next two amino acid residues were coupled using the beckman peptide synthesizer 990 - b . the pmp ( 4 - mebzl ) was coupled manually using dmap - dcc overnight . the resin - containing peptide was washed and dried as usual to give 2 . 00 g of the titled intermediate . pmp -( 4 - mebzl )- d - tyr ( et )- phe ( 4 - et )- val - asn - cys - 4 - mebzl )- pro - arg ( tos )- bha resin , in 3 ml of anisole was reacted with 30 ml of anhydrous hydrogen fluoride at 0 ° for an hour . the work up was done as described above , with 38 ml of k 3 fe ( cn ) 6 taken up . about 50 mg of crude peptide was obtained from the bio - rex column and 139 mg was precipitated out of solution , total yield 189 mg ( 42 . 7 %) of titled peptide . ______________________________________purification : ______________________________________1 . partition column chromatography , sephadex , g - 25 : sample : 50 mg , n - buoh / hoac / h . sub . 2 o , 4 : 1 : 5 ,( a ) fr . a , 23 . 86 mg ( b ) fr . b , 18 . 5 mgpreparative hplc sample : 43 mg ( from 1 , fr . a + fr . b ), altex ods , 10 mm × 25 cm , 5μ , flow rate 4 ml / min ., water / acetonitrile / tfa ( 50 : 50 : 0 . 25 ), isocratic , 229 nm ( 2 . 0 aufs ), injection 2 . 0 mg / 300 μl and 4 . 0 mg / 420 ml to give 30 . 0 mg of pure peptide . 2 . physical data : molecular formula : c . sub . 53 h . sub . 78 n . sub . 12 o . sub . 10 s . sub . 2 molecular weight : 1106 . 47 amino acid analysis : asp ( 1 . 00 ), pro ( 0 . 78 - 0 . 84 ), cys ( 0 . 45 ), val ( 1 . 02 ), tyr ( 0 . 63 ), phe ( p - et ) ( 1 . 50 ), arg ( 1 . 00 - 0 . 96 ) peptide content : 73 . 3 - 89 . 6 % 3 . chromatography data : solvent r . sub . ftlc nbuoh / hoac / h . sub . 2 o / etoac , 0 . 70 1 : 1 : 1 : 1 nbuoh / hoac / h . sub . 2 o , 0 . 299 4 : 1 : 5 upperhplc c . sub . 18 column k &# 39 ; isocratic h . sub . 2 o / ch . sub . 3 ch / tfa , 4 . 43 55 : 45 : 0 . 1gradient h . sub . 2 o / ch . sub . 3 cn / tfa , 8 . 7 60 : 40 : 0 . 1 to 50 : 50 : 0 . 1fab m / z 1107 ( m + h ). sup .+ ; 1105 ( m - h ). sup .- ______________________________________ one millimole of boc - asn - cys ( 4 - mebzl )- pro - arg -( tos )- bha resin was prepared using 1 mmole of boc - arg ( tos )- 4 - methylbenzhydrylamine ( mbha ) resin as starting material by coupling sequentially with the appropriate t - boc - protected amino acids in a beckman 990 - b peptide synthesizer , 990 - b . 1 . 83 grams of the protected peptide resin was obtained and was divided into two equal parts of 0 . 915 g each . one part of the protected peptide resin from above was further sequentially coupled with 1 . 5 mmoles of the appropriate boc amino acids and β -( s - mebzl )- pmp - oh to give 1 . 16 g of the final protected peptide resin . pmp ( s - mebzl )- d - tyr ( et )- phe - gly - asn - cys ( 4mebzl )- pro - arg -( tos ) mbha resin was obtained and dried in vacuo . this protected resin was treated with 1 . 5 ml of anisole and 25 ml of anhydrous hydrogen fluoride at 0 ° for 1 hour . the deprotected peptide was treated with 0 . 01 mole of potassium ferricyanide solution at ph 7 . 2 in 2 liters of water . 53 ml of the oxidizing agent was used . the resulting solution was passed through a c 18 flash column . the column was eluted with 50 % of acetonitrile with 0 . 25 % trifluoroacetic acid in 20 ml per fraction . 325 mg crude product was isolated from the fractions . further purification of the product by ccd ( b / a / w , 4 : 1 : 5 ) to obtain 188 mg of 99 % pure titled product . ______________________________________amino acid analysis : ______________________________________peptide content 82 % asp 1 . 04 tyr 0 . 92pro 1 . 15 phe 1 . 01gly 1 . 00 arg 0 . 91cys 0 . 54fab / ms = m / z ( m + h ). sup .+ 1037______________________________________ one part of the protected peptide resin from example 8 was further sequentially coupled with 1 . 5 mmoles of the appropriate boc amino acids and β -( s - 4 - mebzl )- pmp - oh to give 1 . 06 g of the final protected peptide resin , pmp ( s - 4 - mebzl )- d - tyr ( et )- phe - chg - asn - cys ( s - 4 - mebzl )- pro - arg -( tos ) mbha resin , obtained after drying in vacuo . this protected peptide resin was treated with 1 . 5 ml of anisole and 25 ml of anhydrous hydrogen fluoride . following the usual oxidation by potassium ferricyanide and isolation over a c 18 column , 165 mg crude titled product was obtained . further purification by ccd g - 15 and p - 2 gel filtration as described above gave 55 mg hplc pure titled product . preparation of ## str20 ## and its use for preparing the compound of example 3 4 . 87 g ( 15 mmol ) of the boccys ( 4mebzl ) was dissolved in 30 ml of ethanol and 10 ml of water added . the ph was then adjusted to 7 . 1 with an aqueous solution of cesium bicarbonate . the mixture was concentrated and the residue evaporated three times from 50 ml of toluene . this residue was , then , placed under high vacuum at ambient temperature overnight . the salt was dissolved in 35 ml of dimethylformamide and 5 g of commercial chloromethylphenyl resin added . the mixture was stirred at 53 ° under argon overnight . the mixture was filtered and the resin washed with dimethylformamide ( 5 × 60 ml ), dmf / water , 9 : 1 , ( 5 × 60 ml ), dmf ( 5 × 60 ml ) and ethanol ( 6 × 60 ml ). it was , then , dried under high vacuum at ambient temperature over the weekend . the peptide chain was built up in a beckman synthesizer as described above using the boc derivatives of asn , val , phe , d - tyr ( et ) and the s -( 4 - mebzl ) pmp derivative . the resin was removed and placed in a manual shaker . 0 . 86 g of the peptide resin was treated with 1 . 5 ml of anisole and stirred for 60 min at 0 ° in 15 ml of hydrogen fluoride . the hydrogen fluoride was , then , removed under aspirator pressure at 0 °. the residue was then washed with 3 × 25 ml of ether ( discarded ) and the peptide eluted with dimethylformamide and 30 % acetic acid ( 4 × 10 ml ). this solution was added to 21 of degassed water and the ph adjusted to 7 . 0 with ammonium hydroxide . a 0 . 01m potassium ferricyanide solution was added slowly ( 35 ml ). the ph was then adjusted to 4 . 5 with acetic acid and the mixture stirred for 30 minutes with 25 g ( wet ) of a weakly basic ion exchange resin ( ag - 3 × 4 1r - 4s ). the suspension was filtered and the resin washed with 2 × 400 ml of 30 % acetic acid . the filtrate was , then , passed thru a c 18 flash column ( 7 × 16 mm ). the column was then washed with water ( 3 × 400 ml ) and the peptide eluted with acetonitrile / water / tfa , 50 : 50 : 0 . 25 ). fractions 30 → 36 were combined , concentrated and lyophillized to yield 25 mg of the titled free cys ( oh ) cyclic intermediate . fab mass spectrum in glycerol : 827 ( m + h ) + , 825 ( m - h ) - . the cys acid ( 20 mg ) is reacted with one equivalent of pro - arg ( nh 2 ) hcl ( prepared from the commercial dihydrochloride by treatment with 1 equivalent of triethylamine ) in the presence of dcc and hbt in dimethylformamide to produce the compound of example 3 . similarly , pro ( ome ) is attached to the cys acid , hydrolyzed with mild sodium hydroxide to give the pro acid which is , then , reacted with arg ( hcl )( ome ) to give the acid parent of the compound of example 3 after mild hydrolysis of the ester . this compound is isolated as the potassium salt if desired . see example 12 below . alternatively , the pro - arg ( nh 2 ) is used in the condensation directly . a mixture of 4 . 5 mg of pmp - d - tyr ( et )- phe - val - asn - cys - oh prepared as above and 1 ml of methanol was treated with ethereal diazomethane and purified by preparing hplc ( 50 % ch 3 cn / 50 % h 2 o / 0 . 1 % tfa ) to yield 4 . 3 mg of the methyl ester ( 94 %), fabms m / z 841 ( m + h ) + , homogeneous by hplc and tlc . bocpro - merrifield resin was made by coupling bocpro to merrifield resin using the cesium salt method to give boc - pro - och 2 - c 6 h 4 - resin which was used as the starting material for the synthesis . the synthesis was carried out on the beckman 990 - b peptide synthesizer using the following protocol . three equivalents of the amino acids were dissolved in their appropriate solvents [ the boc derivatives of 4mebzl - cys , val , phe in methylene chloride , asn in dimethylformamide , x such as d - tyr ( et ) or brbz - d - tyr in 1 : 1 methylene chloride / dimethylformamide and 4mebzl - pmp in methylene chloride ] and were coupled using an equimolar amount of dicyclohexylcarbodiimide ( dcc ) and 1 - hydroxybenzotriazole ( hobt ) except for the coupling of 4mebzl pmp where 1 . 0 equivalent of dimethylaminopyridine was used as catalyst . the extent of coupling was determined by qualitative ninhydrin analyses and couplings were repeated when necessary . the boc groups were removed using 1 : 1 trifluoroacetic acid / methylene chloride and after washing the free amine was generated using 5 % diisopropylethylamine / methylene chloride . the sequence of the peptide was checked using solid phase sequencing before the coupling of the 4mebzl - pmp and its homogeneity confirmed . after the final coupling , the resin was dried to give 2 . 24 g of peptide resin in the case of the d - tyr ( et ) 2 - pro 7 compound . 1 . 1 g ( 0 . 5 mmole ) of the d - tyr ( et ) 2 peptide resin with 3 ml of anisole was stirred 60 min . at 0 ° ( ice bath ) in 25 ml of hydrogen fluoride ( hf ). the hf was , then , removed under reduced pressure at 0 °. the residue was washed with ethyl ether ( 4 × 20 ml , discarded ) and the peptide eluted with dimethylformamide 3 × 10 ml , 20 % acetic acid 3 × 10 ml and 0 . 3n ammonium hydroxide 3 × 10 ml . the filtrate was added to 2 l of degassed water and the ph adjusted to 7 . 1 with conc . ammonium hydroxide . a 0 . 01m solution of potassium ferricyanide was then added dropwise with stirring until a faint yellow color persisted ( 41 ml ). this solution was adjusted to ph = 4 . 7 with acetic acid and stored in the cold overnight . the solution was adjusted to ph = 7 with ammonia and stirred for 15 min with 30 g of ag - 3 × 4 bio - rad ion exchange resin ( wet , cl form ). this solution was then filtered slowly through an additional 30 g of resin . the resin was then washed with 4 × 200 ml of 20 % acetic acid and the filtrate stored in the cold overnight . the filtrate was then passed through a flash column ( 5 cm × 10 cm ) of a packing of silica gel coated with a c - 18 silane . the column was then , washed with 350 ml of water and the peptide eluted with 500 ml of 1 : 1 acetonitrile / water ( 0 . 25 % trifluoroacetic acid ) in 20 ml fractions . fractions 11 - 17 were combined and concentrated . the residue was dissolved in conc . acetic acid , diluted with water and lyophillized to yield 189 mg of the d - tyr ( et ) 2 , proline peptide , which was used without further purification for the synthesis of the tail modified peptides . ______________________________________identification of : ______________________________________ ## str22 ## amino acid analysis : peptide content 55 % asp , 1 . 00 ; pro , 1 . 23 ; cys , 0 . 35 ; val ; 1 . 04 , tyr ( et ), 1 . 43 ; phe , 1 . 51 . hplc : satisfactory . ## str23 ## amino acid analysis : peptide content 82 % asp , 0 . 97 ; pro , 1 . 10 ; cys , 0 . 39 ; val , 1 . 05 ; tyr , 0 . 99 ; phe , 0 . 99hplc : satisfactory , 30 % ch . sub . 3 cn / 70 % 0 . 05 m kh . sub . 2 po . sub . 4 , 2 ml / min , 5 uc - 18 , k &# 39 ; = 6 . 14 . ______________________________________ a mixture of 10 mg of the d - tyr ( et )- pro ( oh ) 7 prepared as above , and 1 ml of methanol was treated with ethereal diazomethane and , then , purified by preparing hplc ( 50 % ch 3 cn / 50 % h 2 o / 0 . 1 % tfa ) to yield 7 . 5 mg of the methyl ester ( 74 %), fabms m / z 938 ( m + h + ), homogeneous by hplc and tlc . to a solution of the d - tyr ( et ) 2 - proline heptapeptide , prepared as described above , ( 29 . 7 mg , 0 . 0331 mmol ), and arg ( nh 2 ) ( 0 . 0996 mmol ) in dimethylformamide ( 400 μl ), dicyclohexylcarbodiimide ( 10 . 3 mg , 0 . 05 mmol ) and dimethylaminopyridine ( 0 . 05 mmol ) were added and the reaction mixture was stirred at 0 °- 20 ° for 4 hours . the dimethylformamide was , then , removed under vacuum . the residue was treated as above in example 3 in 45 % yield to give the desired d - tyr ( et ) 2 - val 4 amide . the linear peptidyl resin , pmp ( s - mebzl )- d - tyr ( et )- phe - val - asn - cys ( s - mebzl )- pro - d - arg ( tos )- bha resin , was prepared by the solid phase method using the standard protocol described above . thus , 1 . 5 g benzhydrylamine resin corresponding to 1 . 0 mmol amine was coupled successively with the boc amino acid derivatives in threefold excess using dcc / hobt in methylene chloride / dmf , 1 : 1 . pmp ( s - mebzl ) was coupled with dcc / dmap . completeness of coupling was checked with the kaiser test or a quantitative ninhydrin test . recoupling was performed until the test was negative . the protected peptidyl resin was washed with successive portions of methylene chloride , methanol , ethyl acetate and methylene chloride , and , then , air dried . the peptide was cleaved from the resin with 15 ml of liquid hydrogen fluoride in the presence of 1 . 0 ml of anisole at 0 ° for one hour . after evaporation of the hydrogen fluoride and drying under high vacuum , the resin was washed with 3 × 20 ml of ether and , then , extracted with 2 × 50 ml of 50 % acetic acid , 50 ml of 10 % acetic acid , and 50 ml of water . the combined extracts were diluted to 4 l with water and the ph adjusted to 7 . 2 with 50 % sodium hydroxide solution . the solution was titrated with 0 . 01m k 3 fe ( cn ) 6 solution until a yellow color persisted ( 30 ml ). the ph was adjusted to 4 . 5 with glacial acetic acid and filtered . the filtrate was applied to a cation exchange ( biorex - 70 ) column ( h + form ), washed with water and then eluted with 100 ml of pyridine acetate buffer ( 30 ml of pyridine , 4 ml of acetic acid , 66 ml of water ). the eluant was evaporated to dryness . the residue was dissolved in a small amount of 10 % acetic acid and diluted with water to 1 % acetic acid , then lyophilized , yielding 650 mg of the crude titled peptide . the crude peptide was purified by counter current distribution in n - butanol / acetic acid / water ( b / a / w ) ( 4 : 1 : 5 ) yielding 33 mg partially purified peptide . this was further purified by gel filtration on a sephadex g - 15 column in 1 % acetic acid , yielding 24 . 5 mg pure peptide . amino acid analysis ( hydrolysis in hcl / tfa 2 : 1 , 0 . 005 % phenol for 1 hr .) asp 1 . 00 , pro 0 . 72 , cys 0 . 62 , val 0 . 99 , tyr 1 . 04 , phe 1 . 04 , arg 0 . 95 , 71 % peptide . hplc : ( 40 % acetonitrile / 60 % water / 0 . 01 % tfa ), one peak , k &# 39 ;= 5 . 2 ; ( 45 % acetonitrile / 55 % water / 0 . 1 % tfa ) k &# 39 ;= 3 . 6 ; ( gradient 20 % acetonitrile , 5 &# 39 ;; 20 - 50 % acetonitrile , 20 &# 39 ;; 50 % acetonitrile , 5 &# 39 ;) k &# 39 ;= 8 . 7 , 97 % pure . tlc : rf 0 . 32 ( b / a / w 1 : 1 : 1 ); 0 . 12 ( b / a / w 4 : 1 : 1 ); 0 . 50 ( n - butanol / pyridine / acetic acid / water ), 15 : 10 : 3 : 12 ). the extracted peptidyl resin still contained peptide by amino acid analysis , so it was extracted with 3 × 50 ml of dmf . the dmf was evaporated to dryness and the residue dissolved in 10 % hoac , diluted to 1 % acetic acid and lyophilized , yielding an additional 260 mg of peptide . fab mass spectrometry of this material gave a m / z 1079 which corresponds to m + h for the desired cyclic peptide . substituting a stoichiometric quantity of boc - d - phe for boc - d - try ( br - z ) at the 2 unit of the peptide synthesis of example 1 gives ## str25 ## substituting boc - d - val at the same position using the splitting - oxidation reactions of example 2 gives ## str26 ## substituting β - mercapto - β , β - cyclotetramethylenepropionic acid ( tmp ) for pmp in example 5 gives ## str28 ## β - mercapto - β , β - cyclohexamethylenepropionic acid gives the hmp 1 derivative . substituting in example 1 boc - d - nle at the 2 unit and d - arg ( tos ) at the 8 unit gives ## str29 ## substituting in example 1 boc - α - aminophenylbutyric acid ( pba ) at the 2 unit gives ## str31 ## substituting boc - lys ( clz ) in example 3 for the protected arg gives ## str32 ## other representative compounds which are prepared in like manner are : ## str33 ## a preparation which contains 0 . 5 mg of the cyclic octapeptide of examples 1 or 3 as a sterile dry powder for parenteral injection is prepared as follows : 0 . 5 mg of peptide amide is dissolved in 1 ml of an aqueous solution of 20 mg of mannitol . the solution is filtered under sterile conditions into a 2 ml ampoule and lyophylized . the powder is reconstituted before either intramuscular or intravenous injection to a subject suffering from edema susceptible to anti - adh mechanism of action . the injection is repeated as necessary , from 1 - 5 times daily or in continuous i . v . drug injection . other octapeptides of this invention are made up and used in like manner . 30 mg of finely ground octapeptide of this invention such as the product of example 2 is suspended in a mixture of 75 mg of benzyl alcohol and 1 . 395 g of a suspending agent such as a commercial mixture of semisynthetic glycerides of higher fatty acids . the suspension is placed in an aerosol 10 ml container which is closed with a metering valve and charged with aerosol propellants . the contents comprise 100 unit doses which are administered intranasally to an edematous subject from 1 - 6 times a day .

certain octapeptides , which have structures characterized by being a six unit cyclic peptide ring with a dipeptide tail which lacks a glycine unit at position 9 , have potent vasopressin antagonist activity . the compounds here claimed are in general characterized by having an amino acid unit at position 4 which is other than valine . an important species of the group is - 2 -- 4 - α - aminobutyric acid - 8 - arginine - 9 - desglycine ] vasopressin .

the array 1 shown as an example in fig1 comprises 33 blankets 2 carrying solar cells ( of which fig1 only shows four blankets for the sake of clarity ), an inner current - conducting track system 4 , an outer current - conducting track system 5 , hinges 6 , the solar cells 7 welded to form mini modules 3 , end contacts 14 welded together between the mini modules , a base plate 11 and a pressure plate 12 . in the embodiment shown the blankets 2 comprise a kapton foil with a glass fibre laminate layer , each blanket having a dimension of 3352 mm × 285 mm . on the surface of each blanket 2 there are solar cells 7 of which ten each are contained in a mini module 3 . on each blanket 2 , eighteen mini modules 3 are arranged directly side - by - side so that the direction of the solar cell series connection is parallel to the width of the blankets 2 . in another connection arrangement of the solar cells , another arrangement on the blankets may be necessary . on the two longer margins of each blanket , halves of a piano - type hinge 6 extending along the entire blanket margin are fitted . the hinge halves are designed so that they correspond to the half of the respective adjacent blanket . except for two instances , the spacing between the individual mini modules 3 of a blanket 2 is 1 mm . exceptions are the spacing gaps 15 which are designed to weaken flashover field strengths between mini modules with high potential differences . the current - conducting track systems are also made on flexible blankets whose dimensions correspond to those of the blankets 2 carrying the solar cells . on one longitudinal side , the inner current - conducting track system 4 which is arranged on the inside , directly adjacent to the space vehicle , is mechanically connected to the base plate 11 and on the opposite longitudinal side via hinges 6 to the inner blanket carrying solar cells . the electrical conductor connections between the current - conducting track system 4 and the mini modules 3 of the inner blanket are established in the known way by means of welded - together end contacts of the current - conducting track system and the mini modules . the outer current - conducting track system 5 , which is located in the array 1 at the outer position furthest away from the space vehicle , is accordingly mechanically and electrically connected to the blanket carrying the outer solar cells . the outer longitudinal side of the current - conducting track system 5 is mechanically connected to the pressure plate 12 . for the embodiment , the schematic diagram shown in fig2 shows the design and arrangement of electrically parallel series connections 8 of the solar cells on the array 1 . the series connections 8 in principle comprise a branch a 1 ( b 1 , . . . , h 1 , i 1 ), of solar cells which are electrically connected in series ( in fig2 one branch only is shown in a simplified way as a line ), a second branch a 2 ( b 2 , . . . , h 2 , i 2 ) of solar cells which are electrically connected in series , with opposite polarity arrangement of the solar cells when compared to the first branch , an electric line 10 on the outer current - conducting track system 5 which electrically connects in series the two branches , as well as two electrical lines 9 on the inner current - conducting track system 4 for connecting the series connection 8 to the energy processing system of the space vehicle . the branches with solar cells connected in series extend in the direction of unfolding of the array 1 , in a straight line along all blankets 2 carrying solar cells . in fig2 the polarity direction of the solar cells in the individual branches of the series connections 8 is shown by arrow heads at the branches . those arrow heads point in the direction of increasing potential . in fig2 the area of array 1 comprising solar cells is shown in a simplified way without showing the individual blankets 2 and designated by reference symbol f . according to the details outlined above , in this way the two branches connected in series with the electrical line 10 , form u - shaped series connections 8 . in the embodiment shown , nine series connections 8 are arranged on array 1 , of which for the sake of simplicity , only four series connections 8 are shown . the branches a 1 , . . . , i 2 of the series connections 8 of the embodiment comprise two rows , electrically connected in parallel , each row comprising one hundred and sixty five solar cells 7 connected in series , so that each series connection 8 comprises six hundred and sixty solar cells 7 . depending on the performance required from the solar generator , other connection arrangements are possible . fig3 shows the inner current - conducting track system 4 with the electrical lines 9 applied to the blanket . in the embodiment described here , the branches of the series connections 8 are arranged on array 1 in a particular arrangement . this arrangement is selected such that maximum potential differences between the solar cells of adjacent branches only occur in two places on array 1 . fig3 shows this allocation of the branches ( not shown ) to the interfaces of the electrical lines 9 by means of reference symbols a 1 , . . . , i 2 of the branches . the branches are sequentially arranged on array 1 as follows : a 1 - b 1 - c 1 - d 1 - e 2 - f 2 - g 2 - h 2 - i 2 - a 2 - b 2 - c 2 - d 2 - e 1 - f 1 - g 1 - h 1 - i 1 . using this sequence , maximum potential differences only occur between the pairs of branches d 1 and e 2 as well as between the pairs of branches d 2 and e 1 to the “ inner ” margin of area f comprising solar cells . on the blankets 2 , the mini modules 3 of these pairs of branches are spaced apart from each other by a spacing gap 15 of 1 . 5 mm . a further characteristic of the sequence consists of the branches a 2 , . . . , i 2 being arranged side - by side so that as a result of equipotentiality the electrical lines 9 to these nine branches are taken together to collection lines 16 lead to the energy processing system of the space vehicle . but this is not absolutely necessary . fig4 shows the outer current - conducting track system 5 which is identical in design to the inner current - conducting track system 4 , except to the design of the electrical conductors . each of the electrical conductors 10 connects two of the branches a 1 , . . . , i 2 , which together form a u - shaped series connection 8 . to this effect , the following pairs of branches are taken together : a 1 and a 2 , b 1 and b 2 , . . . , h 1 and h 2 , i 1 and i 2 . allocation of the electrical lines 10 to the branches a 1 , . . . , i 2 of array 1 are shown in fig4 by the reference symbols of the branches ( branches not shown ). fig5 shows the design of a mini module 3 . in the embodiment , ten solar cells 7 taken together , are welded to a mini module via solar cell connectors 13 , and bonded to a common cover glass . in the mini module 3 , the solar cells 7 are arranged in two rows , said rows being arranged side - by - side ; each row comprising five solar cells connected in series . the ends of the two rows are connected to end contacts 14 . the end contacts 14 are designed such that the two rows are connected in parallel in the mini module 3 . in another electrical design of the solar generator , the end contacts can also serve as a series connection only . by means of end contacts 14 , series connection of adjacent mini modules 3 of adjoining blankets 2 is carried out in the known manner as shown in fig6 . the length of a mini module 3 agrees with the short edge length of the blankets 2 so that connection of the end contacts 14 at the fold lines of array 1 takes place in the area of the hinge 6 . the end contacts 14 protrude from the fold lines so that welding together of two end contacts 14 results in the turned up bent shape of the welded - together end contacts 14 , as shown in fig6 . this bent shape provides the advantage in that during folding of the array there are no mechanical loads acting on the end contacts 14 .

a flexible foldable solar generator having an array of a plurality of blankets carrying solar cells hingeably connected to be folded and unfolded . the solar cells are connected together by branches and the branches are connected by connector lines in inner and outer current conducting tracks system arranged outside the blankets . the branches connect the solar cells with the connecting lines in the outer track to form a u - shaped series connection of the cells and the u - shaped series connected cells are connected in parallel by the connecting lines in the inner track where they can be connected to energy systems of the space vehicle .

in fig1 the centrifuge train c comprises a base support 2 of metal , plastic or the like . mounted on the base 2 is a plenum 4 which is 7 - shaped which includes a horizontal component 6 and a vertical component 8 . the vertical component 8 is attached to the base support 2 . a cyclone separator 10 is mounted to the horizontal plenum component 6 and comprises an air / gas inlet opening 12 into the cylinder 14 of the cyclone separator 10 . the cone 16 of the cyclone separator 10 supports a removable container 18 . the removable container 18 may be removably attached by any conventional means ( not shown ) such as clamps , threading , lugs or the like . mounted on the horizontal component 6 is a differential pressure gauge 20 . also mounted on the horizontal component 6 is a lifting eye 22 which is suitably positioned at the center of gravity of the centrifuge train c to avoid tilting of the centrifuge train c during transport of the centrifuge train c from one position to another . although a lifting eye 22 is disclosed in the drawings , other lifting mechanisms can be utilized and positioned at the center of gravity of the centrifical train c . secured to the rear of the vertical component 8 of the plenum 4 is a roughing filter cartridge and housing 24 which includes a removable filter 26 . the removable filter 26 is accessible for changing through an access door 28 . conventional means ( not shown ) is provided for opening the door 28 either remotely or by manual means as desired . similarly , grappling means ( not shown ) can be provided for disengaging the removable filter 26 from the roughing filter cartridge and housing 24 . above the roughing filter and housing 24 is a differential pressure gauge 30 . the roughing filter cartridge and housing 24 are attached to the vertical component 8 of the plenum 4 by means ( not shown ) such as welding , clamping , and the like . the plenum 4 has an opening in the horizontal component at the bottom thereof leading into the cylinder 14 of the cyclone separator 10 . the cyclone separator 10 is connected to the plenum 4 at the bottom thereof by welding , threading , or the like ( not shown ). the vertical component 8 of the plenum 4 is provided with opening means ( not shown ) which permits air / gas to flow from the plenum 4 into the roughing filter cartridge and housing 24 and through the removable filter 26 . the roughing filter cartridge and housing 24 , may be supported solely by the vertical component 8 of the plenum 4 , or it may be supported directly on the base 2 and secured thereto by means ( not shown ) such as screws , clamps , welding , and the like . adjacent to the roughing filter cartridge and housing is a second filter cartridge and housing 32 . the second filter cartridge and housing 32 is of a high efficiency particle air / gas ( hepa ) filter 34 . an access door 36 is provided in the second filter cartridge and housing 32 permitting removal of the hepa filter 34 . above the second filter cartridge and housing 32 is a differential pressure gauge 38 . the second filter cartridge and housing 32 is secured to the roughing filter cartridge and housing 24 by means ( not shown ) such as welding , clamps , or the like . the second cartridge filter and housing 32 is provided with opening means ( not shown ) to the roughing filter cartridge and housing 24 in series therewith to permit the air / gas exiting from the centrifuge 10 and through the plenum 4 to pass from the roughing filter cartridge and housing 24 through the filter 34 . as best shown in fig2 and 3 , an air / gas outlet 40 is secured to the second filter cartridge and housing 32 for exhausting the air / gas passing through the hepa filter 34 . means for conducting the exiting air / gas from the system to the atmosphere or the like is not shown . it should be noted that the roughing filter cartridge and housing 24 and the second filtered cartridge and housing 32 are positioned vertically adjacent the vertical component 8 of the plenum 4 . both the roughing filter cartridge and housing 24 and the second cartridge and housing 32 may be secured to the base 2 and supported thereby or may be suspended from the vertical component 8 of the plenum 4 by conventional means of fastening or welding or the like . all of the connecting components in the centrifical train c are provided with sealing means ( not shown ) which prevent escape of the air / gas through the centrifuge train c when the cyclone 10 is in operation . in operation , the filter train c is designed to be used primarily to decontaminate radiological and hazardous materials in confined areas where compact equipment is needed and where this equipment is remotely controlled through robotic arms or the like . it has application to various contaminated gases . under normal use in a area where air is to be cleansed from impurities , the air is directed through the inlet 12 into the cyclone separator 10 . heavier particles are drawn down into the waste container 18 . the waste container 18 may be remotely replaceable as before indicated by means ( not shown ). after passing through the cyclone separator 10 , the air is conducted to the horizontal component 6 of the plenum 4 and down the vertical component 8 and through the removable filters 26 and 34 . in the system designed , normal air flow rate is approximately 250 cfm ( cubic feet per minute ). the heavier particles removed in the container 18 are down to approximately 7 microns in size . in the roughing filter 26 , the particles removed are down to about 4 microns in size , and in the hepa filter 34 , the particles are down to approximately 0 . 3 microns in size . the efficiency of the unit runs at 99 . 97 %. the centrifuge train c is designed to be very compact so as to be able to pass through doors without interference with the door frames and also to be positioned in minimal cubic space . the close positioning of the two filters vertically with regard to the plenum and the cyclone is very important to the basic mobility of the unit including the mounting on the platform 2 which dimensionally is kept to a minimum based on the width of the filter cartridge and housing 24 and 32 and the cyclone separator 10 . the pressure differential gauges 20 , 30 , and 38 allow the operator of the centrifuge train c to determine the efficiency of the air flow through the centrifuge train c so as to be able to determine when it is necessary to clean out the plenum 4 or replace the filters 26 and 34 . while this invention has been described as having a preferred design , it is understood that it is capable of further modifications , uses and / or adaptations of the invention following in general the principle of the invention and including such departures from the present disclosure as come within the known or customary practice in the art to which to invention pertains and as may be applied to the central features hereinbefore set forth , and fall within the scope of the invention and of the limits of the appended claims .

a compact cyclone filter train for the removal of hazardous and radiologi particles from a gaseous fluid medium which permits a small cyclone separator to be used in a very small space envelope due to the arrangement of the filter housing adjacent to the separator with the cyclone separator and the filters mounted on a plate . the entire unit will have a hoist connection at the center of gravity so that the entire unit including the separator , the filters , and the base can be lifted and repositioned as desired .

with this method a fine - grain cubic zinc sulfide is already generated during the first step , which is then used as the starting material for the synthesis of the inventive electroluminophores , and the average grain size , grain size distribution and crystal structure of which is essentially maintained by limiting the firing temperature to a maximum of 1000 ° c . and forgoing the use of fluxing agents with a strongly mineralizing effect in step 3 of the inventive process . at the same time the treatment of the luminophore powders obtained after the firing process with inorganic or organic acids according to step 4 together with the process steps 5 and 6 ensures that the electroluminophores synthesized according to this invention have all the composite and structural characteristics required for attaining a high performance despite their small grain sizes . the sequence of the above 4 process steps has now made it possible for the first time to obtain powerful fine - grain electroluminophores with grain sizes of 2 to 20 μm by purely preparative means and in a cost - effective manner without having to subsequently correct the grain size by means of milling , and screening , which would entail serious shortcomings . for screen printing applications , inventive zinc sulfide electroluminophores with average grain sizes of 5 to 20 μm are used . electroluminophores with these dimensions can be advantageously processed into high - performance el lamps with a significantly improved layer structure . inventive fine - grain electroluminophores with average grain sizes between 2 and 5 μm , on the other hand , are particularly suitable for applications in intaglio or offset printing . they permit the implementation of fine electroluminescent graphic structures , e . g ., as security marks in value product printing . these particles are particularly suitable for use in narrow - mesh screens of 120 meshes / inch . in any case , the inventive luminophores are characterized by a brightness - service life relationship that is adapted to the given application and optimal with respect to the adjusted grain size . moreover , studies have confirmed that el elements can be constructed using electroluminophores with average grain sizes of 6 μm produced according to this invention that display levels of brightness and half lives which , under identical operating conditions , are comparable to el films manufactured from commercially available coarse - grained el pigments with grain sizes of 20 to 40 μm . as previously mentioned , the surprisingly high service - life of the electroluminophores produced according to this invention , especially of those el pigments that have average grain sizes of 2 to 5 μm in accordance with this invention , is very likely attributable to their cubic crystal structure , which deviates from the commercially available el pigments . according to the prior art this is considered advantageous for attaining high levels of brightness and stability . the zinc sulfide electroluminophore particles can be coated with thin organic and / or crystalline or amorphous inorganic protective layers so as to increase their service life further . in one embodiment , the protective layer consists of an inner metal oxide film and an outer silicon nitrate film . the zinc sulfide electroluminophore particles are dispersible , and can be used for printing in a halftone photogravure ink , flexographic printing ink , offset printing ink , letterset printing ink , gravure printing ink . the zinc sulfide electroluminophore particles of the present invention can be applied onto thermal transfer films and transferred to printable material by means of transfer printing . alternatively , the zinc sulfide electroluminophore particles are embedded in thermoplastic granule matrices and processed into films by means of extrusion / coextrusion and / or thin film casting . to further improve the stability , the individual crystallites of the inventive electroluminophores may also be provided with suitable protective layers according to the prior art . numerous methods and materials are known for applying such protective layers . further details and advantages of the invention will be explained below based on examples and drawings . 101 of a 1 . 4 molar znso 4 solution are entered into a reaction vessel . the ph of this solution is subsequently adjusted to 1 . 0 under addition of sulfuric acid ( h 2 so 4 ). the precipitation of the fine - grain zinc sulfide takes place by passing h 2 s gas into the prepared solution while stirring ( stirring speed 700 rpm ). the volume flow of the h 2 s gas is 36 l / h , the work is performed at a reaction temperature of 60 ° c . after a reaction time of approximately 500 min . the h 2 s flow is stopped . any h 2 s still remaining in the reaction vessel is exhausted , the obtained zns suspension is decanted , repeatedly washed with deionized water and finally filtered off . the obtained fine - grain zns powder is subsequently dried at a temperature of 120 ° c . curve 1 in fig1 shows the grain size distribution of the fine - grain zinc sulfide prepared in this manner , which was determined with the aid of a coulter counter grain size measuring instrument . what is striking is the very narrow distribution of the zns grain sizes ( the so - called qd value , which is calculated based on the equation qd =( d 75 − d 25 / d 75 + d 25 ), may be regarded as a measure for the range of the distribution , which , in the present case is qd = 0 . 134 ); a d 50 value of 4 . 7 μm was determined for the average grain size of the zns material prepared according to the above described process . in the next step a certain amount of the obtained zinc sulfide is stirred into a copper sulfate solution . after concentrating and drying of this suspension at approximately 120 ° c ., the material , which is now present as a mixture of solids , is once again homogenized dry and subsequently sifted with a 35 μm gauze . the weighed - in quantities of zns and cuso 4 are calculated such as to establish a copper content of 1 . 5 % for the zinc sulfide copper “ activator ”. a comparable process is also used in the preparation of corresponding bii 3 “ activator ”. in the example described here , the bii 3 content of the zns — bii 3 mixture is 8 . 5 %. the preparation of the batch subsequently takes place by a thorough blending of 1 . 65 kg of the fine - grain zinc sulfide , 81 . 5 g of the copper “ activator ”, 7 . 5 g of the zns — bii 3 mixture , as well as 5 . 2 g aluminum fluoride ( alf 3 ). this mixture is entered into covered quartz pans and fired for 2 hours at a temperature of 980 ° c . in an n 2 / h 2 atmosphere with a hydrogen content of 1 . 5 %. after completion of the firing process , the fired material is cooled to room temperature and repeatedly washed with deionized water . this is followed by the acid treatment of the obtained material . for this purpose the washed fired material is entered into an acid bath and 2 l h 2 o and 500 ml of a 37 % hydrochloric acid are added relative to 1 kg of the fired material while stirring . after a retention time of one hour , this is followed by decanting and washing , with deionized water to ph neutrality . the renewed addition of copper sulfate to this aqueous suspension serves to re - dope the luminophore material . the amount of cuso 4 used for this purpose is calculated according to the ratio of 2 g cu per 1 kg luminophore . after concentration by evaporation and drying of the suspension , the dry material is fired in open quartz pans for 2 hours at 600 ° c . in air . this is followed by an acid wash with 10 % hno 3 as well as repeated washing with h 2 o to ph neutrality . this is followed by decanting , filtering and drying . in a concluding process step the obtained material is once again annealed in open quartz pans for 2 hours at 300 ° c . in air and homogenized by sifting after it has cooled off . as a result of these preparation steps a zns - cu luminophore with a green electroluminescence is obtained that is characterized by a high level of brightness and long half - life . the average grain size of the powdery electroluminophore is 5 . 2 μm ( qd = 0 . 265 ). as can be seen from fig1 ( curve 2 ), the average grain size of the el pigment prepared according to the example is only significantly above that of the zns starting material used in this process . as in example 1 , the precipitation of the zinc sulfide takes place after h 2 s gas is passed into a znso 4 solution , however , the reaction parameters are adjusted differently . the reaction is started with a 0 . 25 molar znso 4 solution , the ph is fixed to 1 . 6 , the h 2 s volume flow is 60 l / h and the reaction temperature is 40 ° c . the zinc sulfide that is present in the suspension after completion of the precipitation reaction has an average grain size of 17 . 0 μm ( qd = 0 . 174 , see fig2 , curve 1 ). the obtained zns suspension is washed repeatedly with deionized water and decanted ; afterwards a sufficient amount of copper sulfate is added to establish a copper concentration of the zns material of 200 ppm after the activation . the copper activated zns suspension is transferred to drying pans and dried at 120 ° c . to prepare the starting mixture for the firing process , 1 . 75 kg of the activated zinc sulfide , 0 . 5 g bii 3 , and 2 . 5 alf 3 are thoroughly blended . the firing takes place in covered quartz firing pans at 990 ° c . in air . the firing time is 5 hours . after cooling the fired product to room temperature and washing it with deionized water , a 5 - hour acid treatment is performed with 20 % citric acid . this is followed by decanting and washing with h 2 o to ph neutrality . the re - doping of the luminophore material again takes place through addition of copper sulfate ( 502 . 5 mg per 1 kg luminophore ) to the aqueous zns : cu suspension . after concentration by evaporation and drying of the suspension the dry product is fired in open quartz pans for 3 hours at 700 ° c . in air . this is followed by treatment with 10 % hno 3 and repeated washing with h 2 o ( to ph neutrality ), decanting , filtering and drying . the concluding annealing of the zinc sulfide electroluminophore takes place in open quartz pans for 1 hour at 500 ° c . in air , followed by cooling and sifting . the resulting zns : cu luminophore has an intense blue electroluminescence , as well as a long half - life . as shown by curve 2 in fig2 , the d 50 value of the grain size distribution of the inventive electroluminophore presented in this example , which describes the average grain size , is 14 . 5 μm ( qd = 0 . 156 ) and thus somewhat below the value determined for the corresponding zns starting material .

zinc sulfide electroluminophores are prepared from solutions of zinc salts with hydrogen sulfide . the zinc sulfide compounds are mixed with activator and coactivator compounds to produce luminophores , and the mixtures are fired in the presence of fixing agents . these fired materials are then treated in an acid bath , washed , neutralized , and optionally filtered and dried .

for the purpose of describing the present invention , the following terms have these meanings : “ critical distance ” means the distance separating the anode and cathode at which evolved oxygen forms microbubbles and nanobubbles . “ critical distance ” means the distance separating the anode and cathode at which evolved oxygen forms microbubbles and nanobubbles . “ o 2 emitter ” means a cell comprised of at least one anode and at least one cathode separated by the critical distance . “ metal ” means a metal or an alloy of one or more metals . “ nanobubble ” means a bubble with a diameter less than that necessary to break the surface tension of water . nanobubbles remain suspended in the water , giving the water an opalescent or milky appearance . “ supersaturated ” means oxygen at a higher concentration than normal calculated oxygen solubility at a particular temperature and pressure . “ superoxygenated water ” means water with an oxygen content at least 120 % of that calculated to be saturated at a temperature . “ water ” means any aqueous medium with resistance less than one ohm per square centimeter ; that is , a medium that can support the electrolysis of water . in general , the lower limit of resistance for a medium that can support electrolysis is water containing more than 2000 ppm total dissolved solids . the present invention produces microbubbles and nanobubbles of oxygen via the electrolysis of water . as molecular oxygen radical ( atomic weight 8 ) is produced , it reacts to form molecular oxygen , o 2 . in the special dimensions of the invention , as explained in more detail in the following examples , o 2 forms bubbles which are too small to break the surface tension of the fluid . these bubbles remain suspended indefinitely in the fluid and , when allowed to build up , make the fluid opalescent or milky . only after several hours do the bubbles begin to coalesce on the sides of the container and the water clears . during that time , the water is supersaturated with oxygen . in contrast , the h 2 formed readily coalesces into larger bubbles which are discharged into the atmosphere , as can be seen by bubble formation at the cathode . the first objective of this invention was to make an oxygen emitter with low power demands , low voltage and low current for use with live animals . for that reason , a small button emitter was devised . the anode and cathode were set at varying distances . it was found that electrolysis took place at very short distances before arcing of the current occurred . surprisingly , at slightly larger distances , the water became milky and no bubbles formed at the anode , while hydrogen continued to be bubbled off the cathode . at distance of 0 . 140 inches between the anode and cathode , it was observed that the oxygen formed bubbles at the anode . therefore , the critical distance for microbubble and nanobubble formation was determined to be between 0 . 005 inches and 0 . 140 inches . as shown in fig1 , the oxygen evolving anode 1 selected as the most efficient is an iridium oxide coated single sided sheet of platinum on a support of titanium ( eltech , fairport harbor , ohio ). the cathode 2 is a ( fraction ( 1 / 16 )} inch mesh ( size 8 mesh ) marine stainless steel screen . the anode and cathode are separated by a non - conducting spacer 3 containing a gap 4 for the passage of gas and mixing of anodic and cathodic water and connected to a power source through a connection point 5 . fig2 shows a plan view of the assembled device . the o 2 emitter 6 with the anode connecting wire 7 and the cathode connecting wire 8 is contained in an enclosure 9 , connected to the battery compartment 10 . the spacer thickness is critical as it sets the critical distance . it must be of sufficient thickness to prevent arcing of the current , but thin enough to separate the electrodes by no more than 0 . 140 inches . above that thickness , the power needs are higher and the oxygen bubbles formed at higher voltage will coalesce and escape the fluid . preferably , the spacer is from 0 . 005 to 0 . 075 inches thick . at the lower limits , the emitter tends to foul more quickly . most preferably , the spacer is about 0 . 050 inches thick . the spacer may be any nonconductive material such as nylon , fiberglass , teflon ®. polymer or other plastic . because of the criticality of the space distance , it is preferable to have a non - compressible spacer . it was found that buna , with a durometer measure of 60 was not acceptable due to decomposition . viton , a common fluoroelastomer , has a durometer measure of 90 and was found to hold its shape well . in operation , a small device with an o 2 emitter 1 . 485 inches in diameter was driven by 4aa batteries . the critical distance was held at 0 . 050 inches with a viton spacer . five gallons of water became saturated in seven minutes . this size is suitable for raising oxygen levels in an aquarium or bait bucket . it is convenient to attach a control circuit which comprises a timer that is thermostatically controlled by a temperature sensor which determines the off time for the cathode . when the temperature of the solution changes , the resistance of the thermistor changes , which causes an off time of a certain duration . in cool water , the duration is longer so in a given volume , the emitter generates less oxygen . when the water is warmer and therefore hold less oxygen , the duration of off time is shorter . thus the device is self - controlled to use power most economically . fig3 shows a block diagram of a timer control with anode 1 , cathode 2 , thermistor temperature sensor 3 , timer control circuit 4 and wire from a direct current power source 5 . attempts were made to measure the diameter of the o 2 bubbles emitted by the device of example 1 . in the case of particles other than gasses , measurements can easily be made by scanning electron microscopy , but gasses do not survive electron microscopy . large bubble may be measured by pore exclusion , for example , which is also not feasible when measuring a gas bubble . a black and white digital , high contrast , backlit photograph of treated water with a millimeter scale reference was shot of water produced by the emitter of example 1 . about 125 bubbles were seen in the area selected for measurement . seven bubbles ranging from the smallest clearly seen to the largest were measured . the area was enlarged , giving a scale multiplier of 0 . 029412 . recorded bubble diameters at scale were 0 . 16 , 0 . 22 , 0 . 35 , 0 . 51 , 0 . 76 , 0 . 88 and 1 . 09 millimeters . the last three were considered outliers by reverse analysis of variance and were assumed to be hydrogen bubbles . when multiplied by the scale multiplier , the assumed o 2 bubbles were found to range from 4 . 7 to 15 microns in diameter . this test was limited by the resolution of the camera and smaller bubbles in the nanometer range could not be resolved . it is known that white light cannot resolve features in the nanometer size range , so monochromatic laser light may give resolution sensitive enough to measure smaller bubbles . efforts continue to increase the sensitivity of measurement so that sub - micron diameter bubbles can be measured . depending on the volume of fluid to be oxygenated , the oxygen emitter of this invention may be shaped as a circle , rectangle , cone or other model . one or more may be set in a substrate that may be metal , glass , plastic or other material . the substrate is not critical as long as the current is isolated to the electrodes by the nonconductor spacer material of a thickness from 0 . 005 to 0 . 075 inches , preferably 0 . 050 inches . it has been noticed that the flow of water seems to be at the periphery of the emitter , while the evolved visible bubbles ( h 2 ) arise at the center of the emitter . therefore , a funnel or pyramidal shaped emitter was constructed to treat larger volumes of fluid . fig4 is a cross sectional diagram of such an emitter . the anode 1 is formed as an open grid separated from a marine grade stainless steel screen cathode 2 by the critical distance by spacer 3 around the periphery of the emitter and at the apex . this flow - through embodiment is suitable for treating large volumes of water rapidly . the size may be varied as required . a round emitter for oxygenating a bait bucket may be about 2 inches in diameter , while a 3 - inch diameter emitter is adequate for oxygenating a 10 to 40 gallon tank . the live well of a fishing boat will generally hold 40 to 80 gallons of water and require a 4 - inch diameter emitter . it is within the scope of this invention to construct larger emitters or to use several in a series to oxygenate larger volumes . it is also within the scope of this invention to vary the model to provide for low voltage and amperage in cases where the need for oxygen is moderate and long lasting or conversely , to supersaturate water very quickly at higher voltage and amperage . in the special dimensions of the present invention , it has been found that a 6 volt battery supplying a current as low as 40 milliamperes is sufficient to generate oxygen . such a model is especially useful with live plants or animals , while it is more convenient for industrial use to use a higher voltage and current . table i shows a number of models suitable to various uses . an o 2 emitter was made in a multilayer sandwich embodiment . ( fig5 ) an iridium oxide coated platinum anode 1 was formed into a grid to allow good water flow and sandwiched between two stainless steel screen cathodes 2 . spacing was held at the critical distance by nylon spacers 3 . the embodiment illustrated is held in a cassette 4 which is secured by nylon bolt 5 with a nylon washer 6 . the dimensions selected were : cathode screen 0 . 045 inches thick nylon spacer 0 . 053 inches thick anode grid 0 . 035 inches thick nylon spacer 0 . 053 inches thick cathode screen 0 . 045 inches thick , if a more powerful emitter is desired , it is within the scope of this invention to repeat the sequence of stacking . for example , an embodiment may easily be constructed with this sequence : cathode , spacer , anode , spacer , cathode , spacer , anode , spacer , cathode , spacer , anode , spacer , cathode . the number of layers in the sandwich is limited only by the power requirements acceptable for an application . it is known that oxygen is important for the growth of plants . although plants evolve oxygen during photosynthesis , they also have a requirement for oxygen for respiration . oxygen is evolved in the leaves of the plants , while often the roots are in a hypoxic environment without enough oxygen to support optimum respiration , which can be reflected in less than optimum growth and nutrient utilization . hydroponically grown plants are particularly susceptible to oxygen deficit in the root system . u . s . pat . no . 5 , 887 , 383 describes a liquid supply pump unit for hydroponic cultures which attain oxygen enrichment by sparging with air . such a method has high energy requirements and is noisy . furthermore , while suitable for self - contained hydroponic culture , the apparatus is not usable for field irrigation . in a report available on the web , it was shown that hydroponically grown cucumbers and tomatoes supplied with water oxygenated with a device similar to that described in the &# 39 ; 429 patent had increased biomass of about 12 % and 17 % respectively . it should be noted that when sparged with air , the water may become saturated with oxygen , but it is unlikely that the water is superoxygenated . two small hydroponic systems were set up to grow two tomato plants . circulation protocols were identical except that the 2½ gallon water reservoir for the control plant was eroated with and aquarium bubbler and that for the test plant was oxygenated with a five - inch strip emitter for two minutes prior to pumping . the cycle was set at four minutes of pumping , followed by four minutes of rest . the control water had an oxygen content of about 97 % to 103 % saturation , that is , it was saturated with oxygen . the test water had an oxygen content of about 153 % to 165 % saturation , that is , it was supersaturated . the test plant was at least four times the volume of the control plant and began to show what looked like fertilizer burn . at that point the fertilizer for the test plant was reduced by half . since the plants were not exposed to natural light but to continuous artificial light in an indoor environment without the natural means of fertilization ( wind and / or insects ), the experiment was discontinued after three months . at that time , the test plant but not the control plant had blossomed . a pilot study was designed to ascertain that plants outside the hydroponic culture facility would benefit from the application of oxygen . it was decided to use water treated with the emitter of example 1 as the oxygen carrier . since water so treated is supersaturated , it is an excellent carrier of oxygen . tomato seeds ( burpee “ big boy ”) were planted in one - inch diameter peat and dirt plugs encased in cheese cloth and placed in a tray in a southwest window . controls were watered once a day with tap water (“ control ”) or oxygenated water (“ test ”). both controls and test sprouted at one week . after five weeks , the test plants were an average of 11 inches tall while the controls were an average of nine inches tall . at this time , may 10 , when the threat of frost in minnesota was minimal , the plants were transplanted to 13 inch diameter pots with drainage holes . four inches of top soil was added to each pot , topped off with four inches of scott &# 39 ; s potting soil . the pots were placed outside in a sunny area with at least eight hours a day of full sun . the plants were watered as needed with either plain tap water ( control ) or oxygenated water ( test ). the oxygenated water was produced by use of the emitter of example 1 run for one - half hour in a five - gallon container of water . previous experiments showed that water thus treated had an oxygen content from 160 % to 260 % saturation . the test plants flowered on june 4 , while the controls did not flower until june 18 . for both groups , every plant in the group first had flowers on the same day . all plants were fertilized on july 2 and a soaker hose provided because the plants were now so big that watering by hand was difficult . the soaker hose was run for one half to one hour each morning , depending on the weather , to a point at which the soil was saturated with water . one half hour after the soaker hose was turned off , about 750 ml of superoxygenated water was applied to each of the test plants . the test plants were bushier than the controls although the heights were similar . at this time , there were eight control plants and seven test plants because one of the test plants broke in a storm . on july 2 , the control plants averaged about 17 primary branches from the vine stem , while the control plants averaged about 13 primary branches from the vine stem . as the tomatoes matured , each was weighed on a kitchen scale at harvest . the yield history is shown in table ii . the total yield for the eight control plants was 15620 grams or 1952 grams of tomatoes per plant . the total yield for the seven test plants was 24385 grams or 3484 grams of tomatoes per plant , an increase in yield of about 79 % over the control plants . fig6 shows the cumulative total as plotted against time . not only did the test plants blossom and bear fruit earlier , but that the control plants never caught up to the test plants in the short minnesota growing season . it should be noted that the experiment was terminated because of predicted frost . all fruits , both green and red , were harvested and weighed at that point . in order to apply the findings of example 5 to agricultural uses , an emitter than can oxygenate running water efficiently was developed . in fig7 ( a ) , the oxygenation chamber is comprised of three anodes 1 and cathodes 2 , of appropriate size to fit inside a tube or hose and separated by the critical distance are placed within a tube or hose 3 at 120 ° angles to each other . the anodes and cathodes are positioned with stabilizing hardware 4 . the stabilizing hardware , which can be any configuration such as a screw , rod or washer , is preferably formed from stainless steel . fig7 ( b ) shows a plan view of the oxygenation chamber with stabilizing hardware 4 serving as a connector to the power source and stabilizing hardware 5 serving as a connector to the power source . the active area is shown at 6 . this invention is not limited to the design selected for this embodiment . those skilled in the art can readily fabricate any of the emitters shown in fig4 or 5 , or can design other embodiments that will oxygenate flowing water . one useful embodiment is the “ t ” model , wherein the emitter unit is set in a side arm . the emitted bubbles are swept into the water flow . the unit is detachable for easy servicing . table iii shows several models of flow through emitters . the voltage and flowrates were held constant and the current varied . the dissolved oxygen ( do ) from the source was 7 . 1 mg / liter . the starting temperature was 12 . 2 ° c . but the flowing water cooled slightly to 11 or 11 . 5 ° c . without undue experimentation , anyone may easily select the embodiment that best suits desired characteristics from table iii or designed with the teachings of table iii . * as the apparatus runs longer , the flowing water becomes milky , indicating supersaturation . the one - minute time point shows the rapid increase in oxygenation . the following plants will be tested for response to superoxygenated water : grape vines , lettuce , and radishes in three different climate zones . the operators for these facilities will be supplied with units for drip irrigation . drip irrigation is a technique wherein water is pumped through a pipe or hose with perforations at the site of each plant to be irrigated . the conduit may be underground or above ground . since the water is applied directly to the plant rather than wetting the entire field , this technique is especially useful in arid climates or for plants requiring high fertilizer applications . the superoxygenated water will be applied by drip irrigation per the usual protocol for the respective plants . growth and yield will be compared to the same plants given only the usual irrigation water . pest control and fertilization will be the same between test and control plants , except that the operators of the experiments will be cautioned to be aware of the possibility of fertilizer burn in the test plants and to adjust their protocols accordingly . it is expected that the superoxygenated plants with drip irrigation will show more improved performance with more continuous application of oxygen than did the tomato plants of example 5 , which were given superoxygenated water only once a day . waste water , with a high organic content , has a high bod , due to the bacterial flora . it is desirable to raise the oxygen content of the waste water in order to cause the flora to flocculate . however , it is very difficult to effectively oxygenate such water . using a 4 inch oem ( see table i ) with a 12 volt battery , four liters of waste water in a five gallon pail were oxygenated . as shown in fig8 , the dissolved oxygen went from 0 . 5 mg / l to 10 . 8 mg / l in nine minutes . those skilled in the art will readily comprehend that variations , modifications and additions may in the embodiments described herein may be made . therefore , such variations , modifications and additions are within the scope of the appended claims .

an oxygen emitter which is an electrolytic cell is disclosed . when the anode and cathode are separated by a critical distance , very small microbubbles and nanobubbles of oxygen are generated . the very small oxygen bubbles remain in suspension , forming a solution supersaturated in oxygen . a flow - through model for oxygenating flowing water is disclosed . the use of supersaturated water for enhancing the growth of plants is disclosed . methods for applying supersaturated water to plants manually , by drip irrigation or in hydroponic culture are described . the treatment of waste water by raising the dissolved oxygen with the use of an oxygen emitter is disclosed .

inbred corn line lh185 is a yellow dent corn with superior characteristics , and provides an excellent parental line in crosses for producing first generation ( f 1 hybrid corn . lh185 was developed from the single cross lh59 × lh123ht by selfing and using the pedigree system of plant breeding . selfing and selection were practiced within the above f 1 cross for seven generations in the development of lh185 . some of the criteria used to select ears in various generations include : yield , stalk quality , root quality , disease tolerance , late plant greenness , late season plant intactness , ear retention , pollen shedding ability , silking ability , and corn borer tolerance . during the development of the line , crosses were made to inbred testers for the purpose of estimating the line &# 39 ; s general and specific combining ability , and evaluations were run by the williamsburg , iowa research station . the inbred was evaluated further as a line and in numerous crosses by the williamsburg and other research stations across the corn belt . the inbred has proven to have a very good combining ability in hybrid combinations . the inbred has shown uniformity and stability for all traits , as described in the following variety description information . it has been self - pollinated and ear - rowed a sufficient number of generations , with careful attention to uniformity of plant type to ensure homozygosity and phenotypic stability . the line has been increased both by hand and sibbed in isolated fields with continued observation for uniformity . no variant traits have been observed or are expected in lh185 . inbred corn line lh185 has the following morphologic and other characteristics ( based primarily on data collected at williamsburg , iowa ): lh185 is a line developed from the parents lh59 and lh123 . lh185 as a plant resembles more closely the lh123 parent except lh185 is a shorter plant with a very low ear placement . lh185 is earlier flowering than lh123 . in hybrid combination , the ear type is somewhat like lh123 ( relatively short and girthy ). lh185 has a much greater area of adaptability than lh123 had when lh123 was used commercially . one particular agronomic trait that increases lh185 &# 39 ; s area of adaptation over lh 123 is lh 185 &# 39 ; s improved resistance to summer stalk brittling . this was a particularly limiting problem that was characteristic of lh123 in a number of hybrids . lh185 has very good general combining ability . lh185 &# 39 ; s yield to moisture ratio is improved over either parent . in the tables that follow , the traits and characteristics of inbred corn line lh185 are given in hybrid combination . the data collected on inbred corn line lh185 is presented for the key characteristics and traits . the tables present yield test information about lh185 . lh185 was tested in several hybrid combinations at numerous locations , with two or three replications per location . information about these hybrids , as compared to several check hybrids , is presented . the first pedigree listed in the comparison group is the hybrid containing lh185 . information for the pedigree includes : 2 . a mean for the percentage moisture (% m ) for the hybrid across all locations . 3 . a mean of the yield divided by the percentage moisture ( y / m ) for the hybrid across all locations . 4 . a mean of the percentage of plants with stalk lodging (% sl ) across all locations . 5 . a mean of the percentage of plants with root lodging (% rl ) across all locations . 6 . a mean of the percentage of plants with dropped ears (% de ). 7 . the number of locations indicates the locations where these hybrids were tested together . the series of hybrids listed under the hybrid containing lh185 are considered check hybrids . the check hybrids are compared to hybrids containing the inbred lh 185 . the (+) or (-) sign in front of each number in each of the columns indicates how the mean values across plots of the hybrid containing inbred lh185 compare to the check crosses . a (+) or (-) sign in front of the number indicates that the mean of the hybrid containing inbred lh185 was greater or lesser , respectively , than the mean of the check hybrid . for example , a + 4 in yield signifies that the hybrid containing inbred lh185 produced 4 bushels more corn than the check hybrid . if the value of the stalks has a (-) in front of the number 2 , for example , then the hybrid containing the inbred lh185 had 2 % less stalk lodging than the check hybrid . table 1______________________________________overall comparisons oflh185 × lh195 hybrid vs . check hybrid mean % hybrid yield % m y / m % sl % rl de______________________________________lh185 × lh195 227 20 . 95 10 . 82 1 6 0 ( at 16 loc &# 39 ; s ) as compared to : lh195 × lh212 + 7 -. 67 +. 64 - 3 + 1 0lh132 × lh212 + 16 -. 43 +. 53 - 3 + 1 0lh195 × lh59 + 14 +. 64 +. 36 - 1 + 3 0lh195 × lh184 + 14 +. 67 +. 34 - 1 + 3 0______________________________________ table 2______________________________________overall comparisons oflh185 × lh198 hybrid vs . check hybrid mean % hybrid yield % m y / m % sl % rl de______________________________________lh185 × lh198 221 20 . 54 10 . 78 1 7 0 ( at 21 loc &# 39 ; s ) as compared to : lh132 × lh82 + 29 - 1 . 34 + 2 . 02 - 1 + 1 0lh204 × lh212 + 7 -. 63 +. 65 - 2 + 2 0lh132 × lh59 + 15 -. 37 +. 92 - 1 + 2 0lh205 × lh216 + 21 -. 34 + 1 . 17 0 + 1 0lh198 × lh59 + 12 -. 04 +. 59 0 + 1 0lh198 × lh82 + 27 +. 09 + 1 . 29 - 1 - 4 0______________________________________ table 3______________________________________overall comparisons oflh185 × lh132 hybrid vs . check hybrid mean % hybrid yield % m y / m % sl % rl de______________________________________lh185 × lh132 211 21 . 42 9 . 85 1 6 0 ( at 17 loc &# 39 ; s ) as compared tolh132 × lh212 + 3 -. 86 +. 51 - 1 + 3 0lhe136 × lh82 + 22 -. 03 + 1 . 05 - 1 + 3 0lh132 × lh59 + 17 +. 44 +. 61 - 1 + 1 0lh204 × lh212 + 2 +. 91 -. 37 - 2 + 1 0______________________________________ table 4______________________________________overall comparisons oflh185 × lh74 hybrid vs . check hybrid mean % hybrid yield % m y / m % sl % rl de______________________________________lh185 × lh74 189 20 . 91 9 . 03 3 4 0 ( at 21 loc &# 39 ; s ) as compared tolh74 × lh51 + 1 - 2 . 31 +. 95 - 1 - 1 0lh216 × lh206 + 1 - 1 . 84 +. 76 + 2 0 0lh132 × lh165 + 11 - 1 . 09 +. 96 0 - 1 0lh132 × lh167 + 1 -. 34 +. 18 - 1 - 1 0lh202 × lh82 + 14 -. 08 +. 64 - 4 - 2 0______________________________________ inbred seeds of lh185 have been placed on deposit with the american type culture collection ( atcc ), rockville , md . 20852 , under deposit accession number 75618 on dec . 3 , 1993 . a plant variety protection certificate is being applied for with the united states department of agriculture . although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity and understanding , it will be obvious that certain changes and modifications may be practiced within the scope of the invention , as limited only by the scope of the appended claims .

an inbred corn line , designated lh185 , is disclosed . the invention relates to the seeds of inbred corn line lh185 , to the plants of inbred corn line lh185 and to methods for producing a corn plant produced by crossing the inbred line lh185 with itself or another corn line . the invention further relates to hybrid corn seeds and plants produced by crossing the inbred line lh185 with another corn line .