Patent Application: US-201013516359-A

Abstract:
a container used for chromatographic sample analysis has at least one silica uppermost layer , which is deposited onto the container using a liquid phase deposition process , and , optionally , at least one indicator present in at least part of the at least one silica uppermost layer for visually distinguishing the container from other containers , and / or determining the “ use status ” of the container , and / or identifying the proper orientation of the container when it is to be put in use , and / or providing a means of decoration , identification , or counterfeit detection . in one preferred embodiment , the indicator is thermochromic . in another preferred embodiment , the indicator is photochromic .

Description:
in one preferred embodiment of this invention as illustrated in fig3 c , a container such as a borosilicate liner or vial is leached with diluted hydrochloric acid to remove the accessible boric and alkali metal oxides , and then washed to neutrality with deionized water . the article is then immersed in a silica saturated ( or supersaturated ) solution of fluorosilicic acid , optionally containing additives or indicators so as to impart the desired properties in the finished product . the temperature may optionally be raised to accelerate the silica deposition rate . at the conclusion of treatment , the article is removed from the solution and rinsed thoroughly with deionized water . it is then placed in a vessel and while purged with an inert gas , it is heated to as high as 550 ° c . from several minutes to several hours before cooling . the resulting liner or container is thus coated with a film exhibiting the properties shown in table 1 , and is finally deactivated with silanes using procedures described in the art . in fig2 a - 2i , sectional views of various sample inlet liner configurations known in the art are illustrated . fig2 a is an example of a straight through sample inlet liner 10 . fig2 b illustrates a liner 20 , comprising the liner 10 incorporating a matrix 21 , which may be comprised of wool , particles , wire bundles , or other materials know in the art , fig2 c illustrates a single taper liner configuration 30 , fig2 d illustrates a liner 40 having the same configuration as in liner 30 , with the addition of a matrix 41 , similar in composition to that designated as 21 in fig2 b . fig2 e illustrates a sample inlet liner 50 with dimples or constrictions extending into the inner bore . fig2 f illustrates a liner configuration 60 with two sets of internal dimples or constrictions ; and fig2 g represents the same type of liner , with the same two sets of dimples or constrictions 70 , but with the addition of a matrix 71 described above that is supported within the zone created by said dimples or constrictions . fig2 h illustrates a liner 80 having a straight through sample inlet liner with yet three sets of internal dimples or constrictions ; and fig2 i illustrates a sample inlet liner 90 with multiple sets of interior baffles . in fig4 , 401 is an example of the present invention and is fabricated from borosilicate glass . in the enlarged view of a portion of this figure , 405 represents the inner region of the liner tube , with 406 being the outer . region 404 represents the borosilicate glass body from which the liner is fabricated , with 403 illustrating a thin film of silicon dioxide deposited on the inner and outer walls using the process of this invention . in order to eliminate absorptive activity towards analytes , the liner is coated with a final layer of a deactivant that is usually silane or siloxane in nature , but may be comprised of other moieties as known in the art , and designated as 402 . fig5 is a rendering of a borosilicate or quartz liner with the main body shown as 501 , and the wall view expanded as 505 and the inner and outer regions designated 508 and 509 , respectively . section 504 represents a film of silicon dioxide deposited on the glass surface using the lpd process and containing one or more types of dye molecules 506 co - deposited at the same time , and fully encapsulated within the film . the liner is coated inside and out with a deactivant as in fig2 and designated in this figure as 502 . fig6 illustrates a borosilicate or quartz liner 601 as in the preceding figure , and expanded as 605 , but with the addition of a second silica deposition layer 603 containing one or more dye molecule families ( 604 ) that may be the same or different from those ( 606 ) deposited in the first silica layer 607 . again , the inner and outer wall regions are designated in this figure as 608 and 609 , respectively . the liner is coated inside and out with a deactivant as in the preceding . figure and designated in this figure as 602 . the liner represented in fig7 as 701 and the core glass or quartz wall designated as 703 , contains a selected region that is coated with a silica film 705 and containing one or more dye molecule families 706 co - deposited and fully encapsulated within the film . selected deposition may be accomplished by partial immersion into a silica saturated fluorosilicic acid solution containing the desired dye ( s ) or by masking off of regions where solution contact is to be prevented . again , a suitable deactivant film 702 is shown applied on the inner 704 and outer 707 walls of the liner to minimize analyte interaction with residual active sites . the liner illustrated in fig8 and represented by 801 and body 804 contains a layer of liquid phase deposited silica 807 in a selected region only and optionally containing one or more types of dye molecules 806 . this layer is shown on both inside 805 and outside 808 surfaces of the tube , but may be selectively placed on only one , or with myriad gaps as desired according to the masking / immersion method used . the lpd layer first placed on the tube and the remaining surfaces are coated with a second silica film using the methods of this invention 803 that totally encapsulates the liner . in this figure , the second coating of silica is clear and is intended to illustrate a barrier layer capable of barring passage or diffusion of any buried atoms . a deactivant layer 802 is shown as a final coating to mask silanol sites or other residual reactive regions . the liner illustrated in fig9 and represented by 901 and body 905 contains a layer of liquid phase deposited silica 907 in a selected region only and optionally containing one or more types of dye molecules 908 . this layer is shown on both inside 906 and outside 909 surfaces of the tube , but may be selectively placed on only one , or with myriad gaps as desired according to the masking / immersion method used . the lpd layer first placed on the tube and the remaining surfaces are coated with a second silica film using the methods of this invention 903 that totally encapsulates the liner . in this figure , the second coating of silica also contains one or more families of dye molecules 904 intended to both shield the underlying surface from exposure to the environment and impart a secondary visual effect . a deactivant layer 902 is shown as a final coating to mask silanol sites or other residual reactive regions . the tube in fig1 as illustrated as 1001 is a representation of another aspect of the embodiment of this invention , with an expanded view as 1004 . the region 1008 shows the presence of “ through pores ”, or pores providing fluidic communication between the inner 1009 and outer 1007 walls of the liner , such as would be found with porous vycor glass as the substrate material . these pores are not initially present in the tube , but result from an acid leaching process wherein interconnected regions of borate - rich glass that permeate through the glass are selectively solubilized and removed . the section identified as 1002 is a superficial pore that extends inward from either the interior 1009 or exterior 1007 surface of the tube . this type of pore exists in vycor type glasses , but they also are prevalent on the surface of acid leached borosilicate glasses ( including pyrex and other brands ) that have not undergone phase separation into continuous regions . these pores are generally small and don &# 39 ; t penetrate more than a few tenths of microns from the surface , but their physical presence is easily noted as an increased surface roughness after acid leaching compared to that of the initial glass . all pores contribute to an increased surface area over that of the solid body [ 18 - 23 ]. the present illustration shows the presence of a film of lpd silica that fills both superficial and through - hole pores and covers the exposed surfaces of the tube . it optionally can contain one or more families of dye molecules 1003 that are encapsulated within the clear film 1005 to impart the desired optical properties to the object . this film also accomplishes a hole - plugging task that effectively eliminates fluidic communication between the inner and outer surfaces of the tube . the liner may be deactivated with a suitable film shown as 1006 to provide inertness toward analytes . fig1 depicts a section of a chromatogram of a pesticide mixture that was obtained from ultra scientific . the key areas illustrated show the elution region of endrin and its typical breakdown products endrin aldehyde and endrin ketone . it also shows the presence of ddt , another chlorinated pesticide . the chromatogram was acquired using cold on - column injection of 1 μl to eliminate injection port liner contributions to analyte breakdown , and used a 15 meter , 0 . 53 mm id , 1 um film , rxi - 5ms column for the separation . the run conditions were : inlet : 50 ° c . ( hold 0 . 5 min ) to 280 ° c . @ 20 ° c ./ min ( hold 3 min ), constant flow @ 5 ml / min ( he ); oven : 45 ° c . ( hold 0 . 5 min ) to 275 ° c . @ 20 ° c ./ min ( hold 3 min ); detector : uecd , 310 ° c ., n 2 make - up gas flow of 60 ml / min . the peaks are identified on the chromatogram with their absolute area counts in parentheses , and the bulk endrin and ddt concentrations in the test mixture were 50 and 100 pg / μl respectively . the identification of the eluted peaks and their absolute area counts was based on previous studies with internal standards . in this experiment , the endrin breakdown was found to be 0 . 62 %, which may be considered a baseline value for this particular standard using the separation column and conditions indicated . fig1 illustrates a chromatogram of a commercial single gooseneck style liner containing borosilicate wool , and manufactured according to typical procedures reported in the art , with the analytical conditions listed below and using the mixture in fig1 : inlet temperature : 250 ° c ., splitless injection , at 20 ml / min @ 0 . 5 min , constant flow @ 1 . 5 ml / min , helium carrier oven : 150 ° c . to 240 ° c . @ 20 c / min to 265 ° c . @ 6 ° c ./ min detector : μecd , 300 ° c ., n 2 make - up gas flow of 60 ml / min the same analytical standard was used for the analysis , and 1 μl was injected . the endrin breakdown level was found to be 15 . 8 % and that of ddt to be 4 . 3 %. the difference in breakdown levels from those found in fig1 may be attributed to analyte breakdown in the heated injection port liner . fig1 shows a chromatogram using the best competitive liner available as determined by exhaustive benchmark testing . it was tested using the mixture from fig1 with the following conditions : inlet temperature : 220 ° c ., splitless injection , 15 sec . hold time , 20 ml / min purge flow , column flow @ 1 . 5 ml / min , helium carrier oven : 120 ° c . ( hold 1 min .) to 225 ° c . @ 20 ° c ./ min to 280 ° c . @ 6 ° c ./ min . ( hold 7 min ) detector : μecd , 290 ° c ., n 2 make - up gas flow of 60 ml / min the endrin breakdown level was found to be 2 . 8 % and that of ddt to be 1 . 2 %. the difference in breakdown levels from those found in fig1 may be attributed to analyte breakdown in the heated injection port liner . fig1 illustrates a chromatogram obtained in the analysis on the pesticide mixture in fig1 with an injection port liner fabricated with a liquid phase deposition layer of silica containing rhodamine b dye below the deactivation layer , and prepared according to this invention . the analytical conditions for this run were the same as fig1 . the endrin breakdown level was found to be 1 . 9 % and that of ddt to be 1 . 0 %. the difference in breakdown levels from those found in fig1 may be attributed to analyte breakdown in the heated injection port liner . it should be noted that this improved inertness toward analyte breakdown was achieved with the prototype liner of the invention compared to the prior art liner used in connection with fig1 , even though the temperature of the injection port was 30 ° c . higher here than in the prior case ( fig1 ). increasing the injection port temperature is known to increase the amount of endrin and ddt breakdown in an analysis . the chromatogram depicted in fig1 was generated to quantitate a typical level of loss of 2 , 4 - dinitrophenol , which is an acidic analyte shown to be sensitive toward active sites in gc injection port liners . its response is reported relative to the internal standard acenaphthene using cold on - column injection analysis , and the value indicating no absorptive losses is 0 . 31 . this single gooseneck liner containing wool gave a response factor of 0 . 049 , when run under the following conditions : inlet : 250 ° c ., constant pressure at 50 psi , splitless injection , split flow @ 20 ml / min @ 1 min detector : fid , 300 ° c ., h 2 @ 40 ml / min , air @ 450 ml / min , n 2 @ 45 ml / min the sample was 1 μl , of a 10 ng / μl solution of 2 , 4 - dinitrophenol and 10 ng / μl of acenaphthene fig1 shows a chromatogram using the best competitive liner available as determined by exhaustive benchmark testing for the analysis of 2 , 4 - dinitrophenol . the conditions and the sample were the same as in fig1 , and the response factor for 2 , 4 - dinitrophenol was 0 . 298 relative to acenaphthene . fig1 illustrates a chromatogram obtained in the analysis of 2 , 4 - dinitrophenol with an injection port liner of the invention fabricated with a liquid phase deposition layer of silica containing rhodamine b dye below the deactivation layer , and prepared according to this invention . the conditions and the sample were the same as in fig1 , and the response factor for 2 , 4 - dinitrophenol was , 0 . 301 relative to acenaphthene , showing at least comparable results to those in fig1 , and a considerable improvement over the results with the liner tested in fig1 . the following examples are presented to show various aspects of the process of the invention . in this example , simple coloration of a single gooseneck borosilicate glass liner , illustrated in fig2 c is described . silica powder was added in intervals to a 3 . 2m solution of fluorosilicic acid and stirred magnetically until no more dissolved . the suspension was then placed in a freezer at − 9 ° c . overnight . a portion of the suspension was taken and diluted 1 : 1 with a 0 . 2 % solution of rhodamine bin water . after brief mixing , the suspended silica was removed by filtration through a 0 . 45 μm ptfe filter . a 4 mm id single gooseneck borosilicate glass liner suitable for use in an agilent 6890 gas chromatograph was rinsed with acetone , dried , and then immersed in the freshly filtered solution . the vessel was capped , and periodically mixed . after 4 hours , the liner was removed from the solution and rinsed well with water . it exhibited a transparent dark pink / purple color that was uniform throughout . a non - cationic dye was utilized as a colored indicator , even though it has limited water solubility in its acid form , but still exhibiting an intense fluorescence . a silica saturated fluorosilicic acid ( ssfa ) solution prepared as in example 1 above was filtered and diluted with an equal volume of an aqueous solution saturated with fluorescein . a liner as in example 1 was immersed in the solution and agitated periodically over 16 hours . the liner was removed from the solution , rinsed well with water and dried . it appeared almost colorless , but exhibited some visible fluorescence when illuminated with ultraviolet light . a ssfa solution prepared as in example 1 above was filtered and diluted and mixed with an equal volume of a 0 . 2 % solution of crystal violet dye in water . crystal violet is a member of the family of triphenylmethane cationic dyes , whose color is a function of the local ph . a liner was treated with this solution as in example 2 . it exhibited a transparent light blue color . the liner was rinsed well with water until neutral ph was achieved and no dye was extractable from the glass surface . the liner was then dried in a forced air oven . after overnight treatment at 200 ° c ., the color was as before , with no visible change having occurred . a liner was treated as in example 3 above , but with malachite green oxalate ( another cationic dye from the triphenylmethane family ) as the dye . it exhibited a transparent dark green color . the liner was rinsed well with water until neutral ph was achieved and no dye was extractable from the glass surface . the liner was then dried in a forced air oven . after overnight treatment at 200 ° c ., the color was as before , with no visible change having occurred . examination of less thermally stable dyes as thermochromic indicators was demonstrated in this example . a borosilicate glass liner was treated as in example 3 above , but with the phenothiazine compound methylene blue hydrate as the dye . it exhibited a transparent dark blue color . the liner was rinsed well with water until neutral ph was achieved and no blue dye was extractable from the glass surface . the liner was then dried in a forced air oven . after overnight treatment at 200 ° c ., the color was gone , leaving the liner clear and colorless . a liner was treated as in example 3 above , but with anionic methyl orange as the dye . it showed no visible evidence of dye incorporation . this result is consistent with reports in the literature that cationic dyes are more likely to be incorporated in the growing silica film than anionic ones . a liner was treated as in example 3 above , but with another anionic compound , trypan blue as the dye . it showed , no visible evidence of dye incorporation . this result is consistent with reports in the literature that cationic dyes are more likely to be incorporated in the growing silica film than anionic ones . dyes with higher thermal stability and thermochromic behavior as indicators were utilized in the following example . a borosilicate glass liner was treated as in example 3 above , but with neutral red as the dye . it exhibited a transparent brick red color . the liner was rinsed well with water until neutral ph was achieved and no dye was extractable from the glass surface . the liner was then dried in a forced air oven . after overnight treatment at 200 ° c . in air , the color was as before , with no visible change having occurred . the temperature was increased to 400 ° c . and the liner was examined after 1 hour exposure . it had turned a transparent light brown color . heating was continued at 400 ° c . in air and the liner periodically examined for color change . none occurred and the experiment was terminated after 72 hours accumulated heating time at 400 ° c . the effect of the lpd process with wool present inside the liner , along with annealing and deactivation were demonstrated in the following example . a single gooseneck borosilicate glass liner was loaded with 6 mg of 4 μm ( nominal fiber diameter ) fused quartz wool and leached with 3m hcl solution for 30 minutes . the acid was removed by rinsing with water until the ph was neutral . the liner was then oven dried at 120 ° c . for 30 minutes . the initially smooth glass surface was noticeably rougher after the acid leaching process as determined by physical feel . silica saturated fluorosilicic acid solution prepared in example 1 was allowed to warm to room temperature and was held for 24 hours . the excess silica was removed by filtration and 20 ml of this solution was placed in a plastic tube . the solution was diluted with 20 ml of water that had 2 drops of a 0 . 2 % rhodamine b solution added to it . after mixing well , the acid leached liner was immersed in the solution and allowed to stand 6 hours with occasional swirling . the liner was then removed from the solution and rinsed with water until the ph was neutral . a faint pink transparent coloration of the glass was observed , with more intensity of color on the wool surface . the rough surface had also developed a very smooth feel as a result of the deposition treatment . the liner was placed in a stainless steel vessel , purged with helium , and heated to 250 ° c . for 5 hours to anneal the freshly deposited silica and reduce the overall fluoride content . the liner was then deactivated using standard reagents and processes and evaluated for inertness by gas chromatography . results are shown in fig1 and 17 . a ssfa solution prepared as in example 1 above was filtered , diluted and mixed with an equal volume of water . two drops of rhodamine b solution ( 0 . 2 % in water ) was added , and a single gooseneck liner was immersed in the solution and the plastic vessel containing it was closed . the vessel was placed in an oven at 35 ° c . and within 2 hours pink particles had formed and coated both the inside of the vessel and the liner . the liner itself showed a pink coloration similar to the liner from example 9 after water rinsing and drying , but with a significant haze . the surface of the liner was also much rougher in feel than the liner from example 9 . this example demonstrated the effect of combined dilution and heating in one step . homogeneous nucleation occurred from the supersaturation level being too high , such that particle formation competed with film growth . in this example , the lpd solution was not diluted with an equal volume of water , but was heated in order to effect silica supersaturation . a ssfa solution prepared as in example 1 above was filtered and mixed with two drops of rhodamine b solution ( 0 . 2 % in water ). a single gooseneck liner was immersed in the solution in a closed plastic vessel . the vessel was placed in an oven at 35 ° c . and allowed to heat overnight . the vessel was cooled and the liner rinsed well with water until ph neutral . the liner was transparent with a transparent light pink color and exhibited no sign of haziness , indicating that only film formation occurred without homogeneous nucleation . the liner surface was shiny and smooth . physical blocking of the glass surface by a hydrophobic mask was used in this example to demonstrate the need for lpd solution contact with the glass surface for film formation to occur . a single gooseneck liner was immersed to a depth of 1 inch into melted paraffin wax and then removed . after the wax had hardened , the liner was immersed into an ssfa solution as in example 3 , but containing rhodamine b as the dye . after the deposition treatment , the liner was rinsed with water , and then hot toluene . the pink clear coating was only present where the contact with the wax had not occurred , the latter having served as an effective mask against silica deposition . multiple thermochromic indicators in multiple deposition steps were used in this example . the partially coated liner from example 12 was immersed in an ssfa solution containing methylene blue as in example 3 , but with about 10 % of the dye concentration . the liner was then rinsed well with water and dried . the liner exhibited a blue color in the region where the wax mask had originally been , and a purple color where the rhodamine b had already been deposited . it was then placed into an oven exposed to air and heated in increments of 50 ° c ., holding for 30 minutes at each temperature . the first noticeable changes occurred at 200 ° c . the light blue liner had lost the methylene blue dye component , leaving behind a pink rhodamine b color in the originally dyed region . the pink color remained until the temperature testing reached the 400 ° c . hold step , when it became clear and colorless . the stepwise color loss demonstrated an irreversible maximum temperature indicating thermochromic effect . in another example of multiple thermochromic indicators , but co - deposited within the same film , a borosilicate glass single gooseneck liner was immersed in an ssfa solution containing a mixture of methylene blue and neutral red dyes as in example 3 . the liner was then rinsed well with water and dried . it was dark purple in color and smooth . it was placed in an oven and heated gradually to 400 ° c . using the process described in example 13 . at 200 ° c ., the dark blue liner turned much darker , appearing almost black . the dark liner remained black until the hold at 350 ° c . where it turned dark brown . this corresponded to the decomposition of the heavily doped methylene blue dye leaving only the neutral red dye . on continued heating to 400 ° c ., the liner turned a light brown color similar to that seen with the liner in example 8 . the stepwise color change in this example thus demonstrated an irreversible maximum temperature indicating thermochromic effect . the effect of deposition of silica using the process of this invention on surfaces other than silica was shown in this example . a single gooseneck liner was labeled with a silkscreened ceramic glaze decal and heated in a muffle furnace at 550 ° c . for several hours to fuse the pigment into the glass surface . after cooling , the liner was immersed into an ssfa solution as in example 3 above , but with rhodamine b as the dye . it exhibited a pink color . after rinsing and drying , the liner was examined for signs of etching or attack on the inorganic pigment . none was apparent , and the image resolution was not affected . the liner was now smooth over its entire surface , where the image had imparted a rough feel before . microscopic examination revealed the presence of a smooth , conformal pink film over the entire article . a single gooseneck borosilicate glass liner was loaded with 4 μm fused quartz wool and treated the same as the liner in example 9 , but with the omission of the rhodamine b indicator . the treatment provided a very smooth and colorless liner . when tested chromatographically for inertness , this liner gave essentially identical results compared to the performance of the light pink colored liner produced in example 9 . in this example , the interior of a sample vial is deactivated using one preferred embodiment of this invention . a 40 ml borosilicate glass screw cap vial was filled with 3 n hydrochloric acid and allowed to stand for 30 minutes . the solution was removed and the vial was rinsed with deionized water until neutral ph was obtained . silica saturated fluorosilicic acid solution prepared in example 1 was allowed to warm to room temperature and was held for 24 hours . the excess silica was removed by filtration and 20 ml of this solution was placed in the acid leached vial . the solution was diluted with 20 ml of water that had 2 drops of a 0 . 2 % rhodamine b solution added to it . the vial was capped , mixed well , and allowed to stand 6 hours with occasional swirling . the solution was then removed and the vial rinsed with water until the ph was neutral . a faint pink transparent coloration of the glass was observed . the vial was placed in a stainless steel vessel , purged with helium , and heated to 250 ° c . for 5 hours to anneal the freshly deposited silica and reduce the overall fluoride content . the vial was then deactivated using standard reagents and processes . the light pink coating on the vial interior was very smooth and repellant to liquid water . acetone was added to the midpoint of the vial , which was then capped . the solution showed no hint of dye leaching after 3 weeks exposure to the solvent . the references referred to in this application and listed below are hereby incorporated herein by reference . 1 . konrad grob in “ split and splitless injection for quantitative gas chromatography , 4 th ed ., wiley - vch , 2001 . 2 . anal . chem . 2002 , 74 , 10 - 16 “ the two options for sample evaporation in hot gc injectors : thermospray and band formation . optimization of conditions and injector design ” koni grob and maurus biedermann . 3 . u . s . pat . no 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