bluuebunny/crossref_metadata_2025 huggingface dataset:
THE DISCRETENESS-OF-CHARGE EFFECT IN ELECTRIC DOUBLE LAYER THEORY
Authors: Levine S. , Bell G. M. , Calvert D.
Published: May 2006

The Stern–Grahame–Devanathan theory of the electrical double layer in aqueous systems is modified to include the so-called discreteness-of-charge effect of Esin and Shikov and Ershler. This provides an explanation of a number of phenomena which are at variance with the Stern theory. A simple method of incorporating the above effect into the Stern theory is suggested by the work of Grahame and is equivalent in principle to the discrete-ion approximation employed by the Russian authors. It is shown that the effect can be interpreted in terms of a 'self-atmosphere' potential at the counterions adsorbed in the Stern layer. This provides a new term in the energy of an adsorbed ion, which is very nearly proportional to the surface density of these ions and which had hitherto been included in the specific adsorption potential in the Stern adsorption isotherm. This energy is not small and accounts for the conclusion reached by Grahame that the adsorption potential varies strongly with the surface charge. Grahame found that the potential at the plane separating the compact and diffuse parts of the double layer in the solution phase (i.e. the outer Helmholtz plane) at the mercury –aqueous electrolyte interface displays a maximum as the potential across the interface is varied, and this property is reproduced by the theory. The effect of ion size on the adsorption isotherm is also considered.
HIGH-PRECISION VOLUME TITRIMETRY
Authors: Dean G. A.
Published: May 2006

Ways in which the ultimate limit of volume titrimetry may be reached are analyzed: the most suitable approach, based essentially upon the use of a bulb burette, allows, in theory, a mechanical precision better than that of the best weight techniques to be obtained, and the various factors influencing this precision are detailed. Several end-point systems potentially sensitive to considerably better than 1 part per million (p.p.m.) are discussed. An attempt at high precision with the iron(II)/dichromate titration, using refined equipment and an amperometric end point, is described: the observed precision was 0.7–1.1 p.p.m. for two experiments of about eight titrations each; the calculated precision, estimated from the resultant of the component precisions, was about 0.9 p.p.m. The ultimate limit of precision of any titrimetric operation, whether by weight or by volume, is shown to be about 0.1 p.p.m.
THE DECARBOXYLATION OF RING-SUBSTITUTED INDOLE-2(AND 3)-CARBOXYLIC ACIDS
Authors: Piers E. , Brown R. K.
Published: May 2006

not available
N,N-BRIDGED DERIVATIVES OF ADENINE
Authors: Burstein Sumner H. , Ringold H. J.
Published: May 2006

not available
DIMETHYLPHENYLBENZYLAMMONIUM CHLORIDE AS A REAGENT FOR PLATINUM
Authors: Ryan D. E.
Published: May 2006

not available
FURFURALDEHYDE FROM THE ALDOBIURONIC ACID 2-O-(4-O-METHYL-α-D-GLUCOPYRANOSYL URONIC ACID)-D-XYLOPYRANOSE
Authors: Sen S. K. , Gupta P. C. Das
Published: May 2006

not available
DERIVATIVES OF MONOGERMANE: PART I. THE VIBRATION–ROTATION SPECTRA OF GERMYL FLUORIDE AND BROMIDE
Authors: Griffiths J. E. , Srivastava T. N. , Onyszchuk M.
Published: May 2006

The vibration–rotation infrared absorption spectra of germyl fluoride and bromide have been observed. All of the fundamentals in GeH3F were located, and the rotational structure of the E-type bands were resolved and analyzed. The low-frequency band, ν3(a1), in GeH3Br was not observed but an estimate of its position was made from the frequencies of the combination band ν3 + ν6 and of ν6. The rotational constant A″ and the Coriolis constants ζ4, ζ5, and ζ6 were calculated for both molecules, and agreement with microwave A″ values was satisfactory. Thermodynamic functions based upon a rigid-rotator, harmonic-oscillator model have been evaluated for germyl fluoride and bromide.
THERMAL CONDUCTION IN A TIAN–CALVET MICROCALORIMETER
Authors: Benjamin L. , Benson G. C.
Published: May 2006

The transfer of heat in a Tian–Calvet microcalorimeter is treated theoretically. Although quantitative agreement between predicted behavior and experimental observation is not obtained, the qualitative features brought out by the considerations should be helpful in the design and use of this type of calorimeter.
INFRARED SPECTRA AND PHASE CHANGES OF SOLID ANILINIUM HALIDES
Authors: Cabana A. , Sandorfy C.
Published: May 2006

The infrared spectra of anilinium chloride, bromide, and iodide, measured at 22 °C and at −190 °C, are presented. The spectrum of the chloride is essentially the same at both temperatures but the spectra of both the bromide and the iodide exhibit changes indicating a crystalline phase transition, in accordance with recent X-ray determinations of the crystal structures of these compounds.
NITROGEN-FREE DERIVATIVES OF ATISINE: AN EXTREMELY HINDERED CARBOXYLIC ACID
Authors: ApSimon J. W. , Edwards O. E. , Howe R.
Published: May 2006

The action of nitrous acid on azomethines derived from the alkaloid atisine gave a good yield of nitrogen-free hemiacetal, thus providing the first means of removing the nitrogen from the diterpenoid alkaloids. Transformation products of the hemiacetal, including the most hindered carboxylic acid hitherto known, are described. The internal oxidation–reduction reactions encountered in this and related work are discussed.
SOLUTIONS OF SULPHUR TRIOXIDE IN FLUOROSULPHURIC ACID AND CHLOROSULPHURIC ACID: RAMAN AND N.M.R. SPECTROSCOPIC EVIDENCE FOR THE FORMATION OF HALOGENOPOLYSULPHURIC ACIDS
Authors: Gillespie R. J. , Robinson E. A.
Published: May 2006

The Raman spectra of solutions of sulphur trioxide in fluorosulphuric acid and chlorosulphuric acid have been examined. By comparing the spectra with those of the polysulphuryl halides and the polysulphuric acids the formation of the halogen-substituted polysulphuric acids HS2O6F, HS3O9F, HS2O6Cl, and HS3O9Cl is proved and some evidence is obtained for higher polyacids such as HS4O12F and HS4O12Cl. The fluorine n.m.r. spectra of solutions of sulphur trioxide in fluorosulphuric acid have also been investigated: they provide supporting evidence for the formation of fluoropolysulphuric acids. Vibrational frequencies diagnostic of the ions S2O6F− and S2O6Cl− have been obtained from the Raman spectra of fluorosulphuric acid solutions containing both sulphur trioxide and sodium fluorosulphate, and chlorosulphuric acid solutions containing both sodium chlorosulphate and sulphur trioxide.
THE CRYSTAL STRUCTURE OF Ag3Ca5
Authors: Rand R. P. , Calvert L. D.
Published: May 2006

Ag3Ca5 is tetragonal, a = 8.039 ± 5 Å, c = 15.011 ± 15 Å, c/a = 1.87, space group I4/mcm. The structure is of the D8l type with 4 AgI in 4(a); 8 AgII in 8(h), x = 0.378 ± 5; 4CaI in 4(c); and 16 CaII in 16(l), x = 0.164 ± 5 and z = 0.150 ± 5. The structure is characterized by sheets of closely linked Ag and Ca atoms parallel to (001). An indexed powder pattern is given. NH4Pb2Br5, RbPb2Br5, and KPb2Br5 also have the same structure and should be included together with B3Cr5, Ge3Ta5, Si3Ta5, and Si3Nb5 in the D8l group.
COMPLEXES BETWEEN LAMELLAR STRUCTURES AND BROMINE, IODINE CHLORIDE, AND CHROMYL CHLORIDE
Authors: Hooley J. G.
Published: May 2006

Isotherms of Br2 on four sizes of natural graphite crystals were measured with a recording vacuum balance. For 0.02- to 2-mm crystals, capillary condensation near saturation was small but significant, surface adsorption was negligible, and the composition C16Br2 was independent of pressure from 0.9 to 0.5. For the 0.002- to 0.01-mm crystals capillary condensation near saturation and surface adsorption were much greater, there was less intercalation than in the larger crystals, and there were no pressure-independent compositions. These effects of crystal size on the isotherm are believed to account for many of the variations in the reported compositions of lamellates in general and show that the complete isotherm on natural crystals at least 0.02 mm across should be determined. When this was done, there were pressure-independent compositions of C16Br2, C16ICl, C8ICl, and about C40CrO2Cl2. In the latter case the longer the intercalated material remained in the structure the less of it diffused out on reducing the pressure to zero, until finally, none left. For these three adducts there were threshold partial pressures below which no intercalation occurred of 0.05 for Br2, 0.03 for ICl, and 0.25 for CrO2Cl2 at 20 °C. The adsorption curves above these pressures gave isosteric heats of 11, 12, and 13 kcal mole−1. For a mixture of 0.02- to 2-mm crystals the rate of absorption of Br2 or ICl at saturation was inversely proportional to composition for the first third of the reaction and was reproduced in subsequent runs on the same sample. The diffusion coefficient for this initial portion for ICl was three times the value for Br2.Isotherms of the three adducts on BN and MoS2showed no conclusive evidence for intercalation.
MANGANESE (III) COMPLEXES WITH ETHYLENEDIAMINETETRAACETIC ACID
Authors: Yoshino Y. , Ouchi A. , Tsunoda Y. , Kojima M.
Published: May 2006

Manganese(III) ethylenediaminetetraacetic acid complex has been prepared by various methods. The solid having a composition of KMnY.2.5H2O is obtained as deep red crystals when the manganese dioxide suspension reacts with free ethylenediaminetetraacetic acid (H4Y). The manganese was shown to be trivalent from its redox equivalent in its reaction with acidified iodide solution, and its magnetic moment, which was 4.89 Bohr magnetons, corresponding to four unpaired electron spins. The complex ion has an absorption maximum at 500 mμ (log ε = 2.67) in a slightly acidic medium. The variation of the visible spectra with pH has been studied by the spectrophotometric method, the value [Formula: see text] being obtained between the red and the yellow species. Observations have been made on the type of bond between the metal and carboxylate groups by the infrared spectral method. From its ion-exchange and pH titration behavior a formula, K[Mn(OH2)EDTA].1.5H2O, was suggested.
TERPENOIDS: I. THE CONSTITUTION AND STEREOCHEMISTRY OF CEANOTHIC ACID
Authors: Mayo P. De , Starratt A. N.
Published: May 2006

Ceanothic acid, a substance previously isolated by Julian, Pikl, and Dawson (J. Am. Chem. Soc. 60, 77 (1938)), has been shown to be a triterpenoid related to the lupeol–betulin group, but in which ring A is five-membered. It has been degraded to the keto ester A norbetulonic acid methyl ester, a substance of defined constitution and stereochemistry. The hydroxyl and carboxyl groups attached to ring A have been shown by spectroscopic studies to be trans, the stereochemistry of ceanothic acid being that represented by (XII).
A KINETIC STUDY OF THE METATHETICAL AND ADDITION REACTIONS CHARACTERISTIC OF ALLYL POLYMERIZATION
Authors: Brown A. C. R. , James D. G. L.
Published: May 2006

The rate constants of the reactions[Formula: see text]have been measured in the gas phase between 50° and 142 °C:[Formula: see text]where ki is the (known) rate constant for the reaction[Formula: see text]The significance of these values is discussed in relation to the propagation and chain transfer processes in the polymerization of allyl alcohol. A consideration of the rates of addition of free radicals to a series of monomers of diverse reactivity reveals that a correlation exists between the rate constants for the addition of the ethyl radical in the gas phase and of certain polymer radicals in the liquid phase.An application of the general equation proposed by Bamford, Jenkins, and Johnston for radical reactivity leads to the conclusion that kp ≈ 2k7 and that kP/kf ≈ k7/k6 = 1.8 for allyl alcohol at 60 °C. Predictions based upon these relationships are compared with experimental data for the propagation and degree of homopolymerization of allyl alcohol and for inhibition and propagation in copolymerization; reasonable agreement is found in all cases.
ORGANIC PEROXIDES: IV. CATALYSIS OF AROYL PEROXIDE REACTIONS BY ALUMINUM CHLORIDE: THE DIRECT INTRODUCTION OF O-AROYL GROUPS INTO AROMATIC NUCLEI
Authors: Edward J. T. , Chang H. S. , Samad S. A.
Published: May 2006

In inert solvents in the presence of aluminum chloride, aroyl peroxides decompose to esters and carbon dioxide. In highly nucleophilic solvents such as anisole or mesitylene, p,p′-dinitrobenzoyl peroxide effects a Friedel–Crafts type of substitution of the solvent molecule. Both decomposition and substitution reactions probably depend on a heterolytic fission of the peroxide linkage catalyzed by aluminum chloride.
5-BROMOPENTANOIC ACID AND 2,5-DIBROMOPENTANOIC ACID
Authors: Isenberg N. , Leibsohn J. B. , Merola V. E.
Published: May 2006

not available
BIOSYNTHESIS OF SUGARS FOUND IN BACTERIAL POLYSACCHARIDES: PART I. BIOSYNTHESIS OFL-RHAMNOSE
Authors: Jones J. K. N. , Perry M. B. , Stoodley R. J.
Published: May 2006

Azotobacter indicum was grown on media which contained D-glucose-1-C14, D-glucose-2-C14, D-glucose-6-C14, D-mannose-1-C14, or D-galactose-1-C14. The radioactive polysaccharides produced were hydrolyzed and the specific activities of the isolated D-glucose and L-rhamnose were measured. The sugars were degraded and the distribution of activity in the individual carbon atoms was determined.The results suggest that some L-rhamnose is formed from D-glucose by a pathway which involves the breakdown of the glucose carbon skeleton.
TRYPTAMINES, CARBOLINES, AND RELATED COMPOUNDS: PART X. AN ALTERNATIVE SYNTHESIS, AND THE NITRATION, OF δ-CARBOLINE
Authors: Abramovitch R. A. , Adams K. A. H.
Published: May 2006

δ-Carboline, together with β-carboline, has been synthesized in reasonably good yield by the Fischer cyclization of cyclohexanone 3-pyridylhydrazone followed by dehydrogenation of the separated tetrahydro derivatives. The isomer ratios of products formed in this and similar reactions are discussed. Nitration of δ-carboline gives a mixture of the 6- and 8-nitro derivatives, the latter being the predominant product. The magnitude of the dipole moment of δ-carboline is appreciably higher than that predicted from molecular orbital calculations (15).
THE BASE-CATALYZED REARRANGEMENT OF N-ALKYL TRIPHENYLISOXAZOLIUM SALTS
Authors: King J. F. , Durst T.
Published: May 2006

The action of base on trisubstituted N-alkyl isoxazolium salts, first described by Kohler and co-workers (1, 2), has been reinvestigated. On the basis of photochemical and spectroscopic studies it is concluded that the reaction of the N-methyl triphenylisoxazolium ion (Ia) with aqueous sodium hydroxide leads to 4,5,6-triphenyl-2H-1,3-oxazine (III), a derivative of a heterocycle previously known only in benz-fused systems.
THE THERMAL DECOMPOSITION OF HEXAFLUOROAZOMETHANE
Authors: Leventhal Elizabeth , Simonds Charles R. , Steel Colin
Published: May 2006

The pyrolysis of hexafluoroazomethane has been studied in a static system between 0.3 mm and 73 mm and 572 °K and 634 °K by measuring the rate of nitrogen formation. The rate constant of the high-pressure homogeneous reaction is given by k = 1016.17±0.15 exp (−55,200 ± 400/RT) sec−1
HYDRODESULPHURIZATION OF THIOPHENE: II. REACTIONS OVER A CHROMIA CATALYST
Authors: Owens P. J. , Amberg C. H.
Published: May 2006

The hydrodesulphurization of thiophene to butane and H2S over chromia has been studied by flow and microreactor techniques. The sulphided, i.e. mixed oxide–sulphide, catalyst showed improved desulphurization activity compared to pure chromia, while butene hydrogenation activity was reduced by a factor of at least 103. The apparent activation energy of the flow reaction was 24–25 kcal/mole. No organosulphur compounds were found among the products. The reaction proceeded predominantly via butadiene and butene intermediates, with a preference for 1-butene; their rates of hydrogenation as well as the rates of isomerization of the butenes have been compared as a function of temperature. The reaction also partly went to completion at the original desulphurization site, without the desorption of intermediates, presumably by a series of analogous steps on the surface.
HYDROGEN BONDING IN PHENOL, ANILINE, AND THIOPHENOL BY NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY AND CRYOSCOPY
Authors: Rao B. D. Nageswara , Venkateswarlu Putcha , Murthy A. S. N. , Rao C. N. R.
Published: May 2006

Hydrogen bonding in phenol, aniline, and thiophenol has been investigated by n.m.r. spectroscopy and cryoscopy. While phenol shows evidence for the presence of monomer–dimmer–polymer equilibrium, thiophenol only indicates low monomer–dimer equilibrium. The extent of association in these three systems decreases in the order phenol, aniline, thiophenol.
THE PHOSPHORYLATION OF 2-METHYL-Δ2-OXAZOLINE
Authors: Greenhalgh R.
Published: May 2006

In common with other acylating agents, diisopropyl phosphorochloridate reacts with 2-methyl-Δ2-oxazoline in aqueous and ethereal media to yield N-phosphoryl derivatives. In both media, phosphorylation is followed by ring opening between positions 1 and 5, as shown by the isolation of diisopropyl N-acetyl-N-2-chloroethylphosphoramidate and diisopropyl N-acetyl-N-2-hydroxyethylphosphoramidate. The latter compound undergoes further rearrangement, being slowly converted to diisopropyl N-2-acetoxyethylphosphoramidate in aqueous bicarbonate solution.Nuclear magnetic resonance studies of 2-methyl-Δ2-oxazoline in aqueous bicarbonate solution (pH 8.5) reveal that it is all transformed to N-acetylethanolamine within 23 hours. This short lifetime allows speculation regarding the origin of 2-acetamidoethyl diisopropyl phosphate isolated from the reaction of the base with diisopropyl phosphorofluoridate.
LE SPECTRE INFRAROUGE DE L'ANHYDRIDE PERCHLORIQUE Cl2O7
Authors: Savoie Rodrigue , Giguère Paul A.
Published: May 2006

not available
THE ACTION OF ANHYDROUS ACIDS ON ATP:CREATINE PHOSPHOTRANSFERASE
Authors: Quiocho Florante A. , Friedberg Felix
Published: May 2006

Treatment of ATP:creatine phosphotransferase with anhydrous sulphuric acid permits transposition of 24% of the threonine residues and 69% of the serine residues. Treatment with anhydrous phosphoric acid yields similar results: 41% of the threonine residues and 60% of the serine residues are rearranged. Anhydrous formic acid does not induce an N- to O-acyl migration in the protein.Non-specific hydrolysis of peptide bonds or destruction of certain amino acids that might have occurred simultaneously with rearrangement during the anhydrous sulphuric or anhydrous phosphoric acid appears to be very slight. When the protein is treated with anhydrous sulphuric acid, however, phenylalanine "disappears" almost completely from the chromatogram.
NEAR-INFRARED SPECTRA OF ALIPHATIC ALDEHYDES
Authors: King J. F. , Vig B.
Published: May 2006

not available
UREA AND SODIUM CHLORIDE WHISKERS
Authors: Calvert L. D. , Sirianni A. F. , Puddington I. E.
Published: May 2006

not available
SECONDARY ISOTOPE EFFECT IN THE ADDITION OF HYDROGEN ATOMS TO PROPYLENE-d6
Authors: Takahasi M. , Cvetanović R. J.
Published: May 2006

not available
A RADIOCHEMICAL METHOD FOR THE ESTIMATION OF THE SULPHYDRYL-TO-DISULPHIDE RATIO IN WHEAT GLUTEN
Authors: Lee C. C. , Samuels E. R.
Published: May 2006

not available
THE PHOTOIONIZATION OF NITROGEN DIOXIDE
Authors: Frost D. C. , Mak D. , McDowell C. A.
Published: May 2006

The ionization of nitrogen dioxide by photons has been studied using a photoionization mass spectrometric technique and also by the ordinary electron impact method. The photoionization results show a large variation in the relative ionization efficiency within the energy range 9–14 ev, and help to explain the differences between previously reported values for the first ionization potential of this compound. The photoionization efficiency curve indicates the first ionization potential to lie at 9.8 ev and inner ionization potentials to lie at about 11.1 and 12.7 ev.The electron impact ionization efficiency curve for the NO2+ ion exhibits a low ion intensity near the threshold. This confirms the viewpoint that previous determinations of the first ionization potential have employed threshold energy measuring techniques not properly suited for the type of molecule such as nitrogen dioxide which radically changes symmetry on ionization.
NUCLEAR MAGNETIC RESONANCE STUDIES: PART I. THE CHEMICAL SHIFT OF THE FORMYL PROTON IN AROMATIC ALDEHYDES
Authors: Klinck R. E. , Stothers J. B.
Published: May 2006

Chemical shift data for the formyl proton in some 30 aromatic aldehydes are reported. It was found that meta- and para-substituted benzaldehydes exhibited this peak in the range 9.65–10.20 δ, while ortho-substituted compounds appear at lower field, 10.20–10.50 δ; the former shifts show an approximate correlation with the Hammett sigma parameter. Evidence for steric inhibition of resonance is presented for some ortho-substituted compounds and some interesting solvent effects are discussed.
THE REACTIVE SPECIES IN ACTIVE NITROGEN
Authors: Wright A. N. , Nelson R. L. , Winkler C. A.
Published: May 2006

A study has been made of the discrepancy between the N-atom content of active nitrogen as inferred from the maximum HCN production from the reaction of many hydrocarbons, and that indicated by the extent of NO destruction. The HCN production from several hydrocarbons was similar at high reaction temperatures in a spherical reaction vessel, and was independent of reaction temperature in a cylindrical reaction vessel. The ratio (NO destroyed)/(HCN produced) was found to be independent of the mode of excitation òf the molecular nitrogen and of the N-atom concentration, and to be unaffected by the addition, upstream, of N2O or CO2. Although NH3 was found to be a minor product of the hydrocarbon reactions, HCN accounted for at least 96% of the N-atom content of the products under conditions where its formation is considered a measure of the N-atom concentration. The NO "titration" value, the maximum extent of HCN production from C2H4, and the destruction of NH3 after different times of decay of active nitrogen gave evidence that part of the NO reaction occurred, as does the NH3 reaction, with excited nitrogen molecules. The long lifetime of the N2* species capable of reaction with NO or NH3, as calculated from the above data, strongly favors its identification as low vibrational levels of the N2(A3∑u+) molecule. A consideration of the values for the NO/HCN, NH3/HCN, and NH3/NO ratios, after different times of decay, for poisoned and unpoisoned systems, suggested that the N2* responsible for the NH3 reaction is formed only during homogeneous recombination of N atoms, while the N2* responsible for reaction with NO might be produced by wall recombination as well. Possible reactions of excited molecules present in the active nitrogen – NO system that might lead to decomposition of NO without consumption of N atoms are discussed.
A PROTECTED ANGIOTENSIN II
Authors: Mazur Robert H.
Published: May 2006

The preparation of an octapeptide, carbobenzoxy-(β-benzylester)-L-aspartyl-nitro-L-arginyl-L-valyl-L-tyrosyl-L-isoleucyl-(im)benzyl-L-histidyl-L-prolyl-L-phenylalanine methyl ester, a derivative of angiotensin II, is described.
GAS–LIQUID CHROMATOGRAPHY OF SOME FLAVONOID COMPOUNDS AND HYDROXY DIPHENYLS
Authors: Narasimhachari N. , Rudloff E. Von
Published: May 2006

Gas–liquid chromatography of the methyl ethers of 36 flavones, flavanones, isoflavones, and chalkones, 2 chromones, and 9 hydroxy diphenyls was carried out, using SE-30 silicone polymer as liquid phase. The results obtained show that this technique can be used for the separation, isolation, and identification of milligram amounts of these compounds. The influence of methylation, acetylation, and hydrogen bonding was demonstrated and is discussed. Dehydration of a 2-hydroxyisoflavanone to the corresponding isoflavone and isomerization between some flavanones and chalkones were encountered. No linear relationship between the number of substituents and retention time was obtained, indicating that substituents at different positions of a flavonoid nucleus influence the retention characteristics in a different manner. This was especially noticeable with some 3- and 5-substituted flavones, but in other instances the difference in retention times was also sufficient to differentiate between position isomers.
METHYLATION OF SUGAR DITHIOACETALS: III. D-GALACTOSE DIETHYL DITHIOACETAL
Authors: Dutton G. G. S. , Tanaka Y.
Published: May 2006

Partial methylation of D-galactose diethyl dithioacetal in tetrahydrofuran with Purdie's reagents yielded 2-, 3-, and 6-O-methyl-D-galactoses in approximately equal amounts. Poly-O-methyl-D-galactoses were not investigated. These three mono-O-methyl ethers were identified as crystalline 2-O-methyl-D-galactose, 3-O-methyl-D-galactose phenylosazone, and 6-O-methyl-D-galactose phenylhydrazone. Paper çhromatographic separation of all monomethyl-D-galactopyranoses was achieved by addition of borax to the irrigating solvent.
5-METHYL-1,2,3-CYCLOHEXANETRIONETRIOXIME: A COMPARATIVE STUDY WITH SOME vic-DIOXIMES
Authors: Haines R. A. , Ryan D. E. , Cheney G. E.
Published: May 2006

A comparative study has been made of 5-methyl-1,2,3-cyclohexanetrionetrioxime with nioxime and dimethylglyoxime; complexes with nickel, copper, and cobalt have been investigated. Dissociation constants of the three reagents, in aqueous solution, have been determined and formation constants of their copper complexes evaluated. Spectrophotometric and potentiometric studies were used to obtain the results.
ALKOXIDES OF VANADIUM (IV)
Authors: Bradley D. C. , Mehta M. L.
Published: May 2006

A number of tetraalkoxides of vanadium (IV) have been prepared by alcoholysis of tetrakis(diethylamino)vanadium (IV). Volatilities and molecular weights were determined on the new compounds and compared with the properties of the corresponding titanium compounds. Some of the primary alkoxides of vanadium are polymeric and this polymerization affects not only the volatility but also the color of the compound.
CRYSTALLOGRAPHIC DATA FOR DI(PHENYLETHYNYL) MERCURY, POTASSIUM 2,4,6,2′,4′,6′-HEXANITRODIPHENYLAMIDE, AND dl-α-ALANINE HYDROCHLORIDE
Authors: Trotter J.
Published: May 2006

not available
EFFECT OF NUCLEAR SPIN ON THE EMISSION OF THE FORBIDDEN LINE Hg 63P0–61S0
Authors: Kimbell G. H. , Roy D. J. Le
Published: May 2006

not available
THE ACID-CATALYZED CLEAVAGE OF PHENYLSULPHINYLACETIC ACID
Authors: Walker Derek , Leib Joseph
Published: May 2006

A study of the hydrogen peroxide oxidation of phenylmercaptoacetic acid led to a new interpretation of the mechanism of the acid-catalyzed cleavage of phenylsulphinylacetic acid.
THE PHOTODIMERS OF COUMARIN AND RELATED COMPOUNDS
Authors: Anet Ragini
Published: May 2006

The photodimer of coumarin is shown to have the head-to-head cis cyclobutane structure I. An isomer, obtained by the lactonization of o-hydroxy-trans-cinnamic acid, is shown to have the head-to-tail trans structure II. The photodimers of o-methoxy- and o-hydroxy-trans-cinnamic acids have been interrelated.
ISOTOPE RATE EFFECTS IN THE ENOLIZATION OF OXALACETIC ACID
Authors: Kosicki George W.
Published: May 2006

Acid-catalyzed enolization of oxalacetic acid in H2O and D2O gives rise to a constant isotope rate effect [Formula: see text] of 2.4 over the pH (pD) range of 5.5 to 7.5. Base-catalyzed enolization of oxalacetic acid in H2O and D2O gives rise to a constant isotope rate effect [Formula: see text] of 4.5 over the pH (pD) range of 7.0 to 8.0. The percentage of enol form of oxalacetic acid was calculated to be 15.3% at pH 8.0, using the absorption of the enol form in ether at 255 mμ and the absorption of the keto form at pH 0.5 in an aqueous system. The spectrophotometric measurement of the isotope rate effect involved in the enolization of oxalacetic acid gives direct evidence for the rate-determining step in both the acid- and the base-catalyzed reactions without subsequent reactions.
A NUCLEAR MAGNETIC RESONANCE INVESTIGATION OF MOLECULAR COMPLEXES OF POLAR MOLECULES IN AROMATIC SOLVENTS
Authors: Hatton J. V. , Schneider W. G.
Published: May 2006

In order to confirm the existence of specific molecular complexes in solutions of polar solutes in aromatic solvents previously proposed, the temperature variation of the proton resonance shifts of the solutes acetonitrile, p-benzoquinone, and N,N-dimethylformamide in 5 mole% concentration in toluene were measured. The large temperature coefficients of the solute shifts observed strongly support molecular complex formation. For the same solutes dissolved in methylcyclohexane the temperature coefficients were negligibly small. The temperature at which onset of free rotation of the N-dimethyl group of N,N-dimethylformamide occurs is solvent and concentration dependent. These observations are consistent with the proposed geometry of the molecular complex in the aromatic solvents.
THE PYROLYSIS OF TOLUENE
Authors: Price S. J.
Published: May 2006

The pyrolysis of toluene has been studied in a flow system from 913 to 1143 °K. First-order rate constants are independent of the toluene concentration but decrease approximately 9% when the contact time is reduced from 1.0 to 0.41 second. Increasing the contact time from 1.0 second to 2.07 seconds does not affect the rate constant. The overall rate has been resolved into homogeneous and heterogeneous components. It is suggested that the activation energy of the homogeneous process, 85 kcal/mole, may be associated with D(C6H5CH2—H).
PERIODATE-OXIDIZED PHOSPHOMANNAN Y-2448: STRUCTURAL SIGNIFICANCE OF ITS REACTION WITH ALKALI
Authors: Jeanes Allene , Watson P. R.
Published: May 2006

The diesterphosphomannan produced by Hansenula holstii NRRL Y-2448 was shown by periodate-oxidation analysis to have 20% of its D-mannose units linked through carbon-1 only (or carbons-1 and -6), 33% through carbons-1 and -2, and 47% through carbons-1 and -3. Information regarding branching in this macromolecular polysaccharide derivative was not established. The periodate-oxidation product neutralized dilute alkali rapidly at pH 8.5–10.0, with elimination of about 30% of the phosphorus as inorganic orthophosphate. About 80%, inorganic orthophosphate was obtained by longer treatment at pH 10.1–10.5. These observations are shown to support the hypothesis that diesterorthophosphate groups (0.20 mole/mole mannose unit) are held between carbon-6 of units otherwise linked only through carbon-1, and carbon-1 of 60% of the carbon-2-linked units. After periodate oxidation, both phosphoester bonds may undergo β-aldehydo elimination by alkali; the unit having phosphate in hemiacetal linkage and a mannosidic attachment at carbon-2 is presented as the more reactive site. Periodate oxidation also produces sites for β-dealkoxylation by alkali.
THE GAS–LIQUID PARTITION CHROMATOGRAPHY OF CARBOHYDRATE DERIVATIVES: PART II. THE SEPARATION OF METHYL GLYCOSIDES AND OF ACETYLATED DISACCHARIDES
Authors: Jones H. G. , Perry M. B.
Published: May 2006

Gas–liquid partition chromatography has been used to separate anomeric methyl glycosides and also fully acetylated disaccharides.
HALF-LIVES OF Cs141, Cs142, AND Cs143
Authors: Fritze K.
Published: May 2006

The method of timed precipitations has been used to measure the half-lives of Cs141, Cs142, and Cs143, which were found to be 24 ± 2 sec, 2.3 ± 0.2 sec, and 2.0 ± 0.4 sec respectively.
LIQUID–LIQUID EXTRACTION OF BERYLLIUM: I. A STUDY OF FACTORS AFFECTING EXTRACTION
Authors: Biermann Wendell J. , McCorkell Robert
Published: May 2006

A consideration of factors known to govern the formation of coordination compounds with metal ions led to the conclusion that the best ligands to use in attempting to separate beryllium from other metal ions of inert gas configuration by liquid–liquid extraction would be easily polarizable, monofunctional ligands. It is suggested that the thiocyanate ion, as ammonium thiocyanate, is particularly promising for metallurgical application.The organic solvent was shown to play an active role in the extraction, ketone or hydroxy groups on chains containing six to eight carbons giving good extraction with low solvent loss.
CONSTITUTIONS OF POLYSACCHARIDES FROM SERRATIA MARCESCENS
Authors: Srivastava H. C. , Adams G. A.
Published: May 2006

Constitutional studies of three polysaccharides prepared from Serratia marcescens cells by a sequence of phenol extraction, ultracentrifugation, and fractionation by Cetavlon are described. Methylation of the polysaccharides followed by acid hydrolysis yielded 2,3,4,6-tetra-O-methyl-D-glucose, 2,4,6-tri-O-methyl-D-glucose, 2,4,6-tri-O-methyl-D-mannose, 4,6-di-O-methyl-D-glucose, 2,6-di-O-methyl-D-glucose, and an unidentified di-O-methyl-glucose. The acidic components found were: 2,3,4-tri-O-methyl-D-mannuronic acid, 3-O-(2,3,4-tri-O-methyl-D-mannuronosyl)-2,4,6-tri-O-methyl-D-glucose, and O-2,3,4-tri-O-methyl-D-mannuronosyl-(1 → 3)-O-2,4,6-tri-O-methyl-D-glucosyl-(1 → 3)-2,4,G-tri-O-methyl-D-glucose. The polysaccharides are composed of a main chain of D-glucose and D-mannose residues joined by 1,3-glycosidic bonds. Some glucose residues carry branches at C2 and C4 which terminate in either D-glucose or D-mannuronic acid residues. The three polysaccharides studied had similar chemical structures but varied in the amounts of component sugars and degree of branching.
INFLUENCE OF TEMPERATURE ON THE ELECTROLYTIC SEPARATION FACTOR OF HYDROGEN ISOTOPES
Authors: Roy L. P.
Published: May 2006

An electrolysis cell and a tritium counting system are described for the study of the influence of temperature on the electrolytic separation of hydrogen isotopes on a mild steel cathode in alkaline solution. By careful control of the conditions for electrolysis, the separation factors could be determined with a probable error of ±4%. From the temperature coefficients of the three separation factors α, β, and γ, differences in activation energy of −1680, −2260, and −580 cal/mole have been calculated for electrolysis in the H–D, H–T, and D–T systems respectively. When conditions were less stringently controlled, the separation factor β was found to be a linear function of the separation factor α according to an equation of the form β = Dα−E. This relationship is of importance in the use of deuterium as a tracer in the electrolytic concentration of natural tritium. Some empirical equations showing the temperature influence on the variation of β as a function of α are also included.
DÉCOMPOSITION PYROLYTIQUE DE BORATES D'HEPTYLE
Authors: Lalancette M.
Published: May 2006

not available
THE UNIT CELL, SPACE GROUP, INDEXED X-RAY POWDER PATTERN, AND MAGNETIC SUSCEPTIBILITY OF VCl3•2N(CH3)3
Authors: Calvert L. D. , Pleass C. M.
Published: May 2006

not available
COMPLEX TELLURATES OF COBALT AND MANGANESE
Authors: Lister M. W. , Yoshino Y.
Published: May 2006

Complex tellurates of manganese and cobalt have been prepared by oxidizing mixtures of manganous or cobaltous sulphate with potassium (or sodium) tellurate by means of an alkaline hypochlorite solution. Cobalt gives K3H6Co(TeO6)2•2H2O as a dark green powder. The formula was confirmed by its oxidation equivalent with ferrous sulphate, by its displacement of chloride ions from an anion exchange resin, and by its magnetic susceptibility (−154 × 10−6 e. m. u./g-mol). The behavior of the compound on acidification is reported. Manganese gives K6H8Mn(TeO6)3•5H2O and Na7H7Mn(TeO6)3•5H2O as dark red crystals. The formula was confirmed as for the cobalt complex: its magnetic moment is 3.30 Bohr magnetons, which is reasonable for Mn(IV). The acid–base properties of the compound were examined. The ion is not very stable in solution, as shown by changes in its absorption spectrum; measurements of this gave evidence for the nature of the decomposition, and the equilibrium constant for this reaction. The main reaction is[Formula: see text]for which K = 4 × 10−5 (g-mol/I.)2 at 25 °C.
INVESTIGATIONS IN THE BICYCLOHEPTANE SERIES: PART I. THE ELECTRONIC EFFECT OF METHYL GROUPS ON C6 OF THE NORBORNYL CATION
Authors: McGreer Donald E.
Published: May 2006

The addition of acetic acid to camphenilene has been carried out. The major products are the two expected from normal addition without rearrangement. From the product ratio it is possible to conclude that the difference between the electronic effect of a methyl and a hydrogen at C6 of the norbornyl cation is small.
ANIONIC POLYMERIZATION OF STYRENE EFFECT OF TETRAHYDROFURAN
Authors: Bywater S. , Worsfold D. J.
Published: May 2006

The propagation step in the butyllithium­initiated polymerization of styrene in benzene solution is thought to be due to a small concentration of highly active free ion-pairs in equilibrium with unreactive dimeric ion­pairs. This work shows that these dimers may be broken down by the addition of tetrahydrofuran. Small quantities of tetrahydrofuran form, first, a low concentration of a monoetherate of the ion­pair with a high reactivity, and this augments the propagation reaction without changing the kinetic order with respect to the initiator. This, at higher tetrahydrofuran concentrations, is followed by the complete breakdown of the dimers to give a dietherate in much higher concentration and lower reactivity compared with the initial ion­pair and monoetherate. The kinetic order with respect to the initial initiator species changes from one half to one during this process, and a maximum appears in the rate as the ether concentration increases.
γ-FLUOROGLUTAMIC ACID
Authors: Buchanan R. L. , Dean F. H. , Pattison F. L. M.
Published: May 2006

The synthesis of γ-fluoroglutamic acid, HOOCCHFCH2CH(NH2)COOH, was achieved by two independent methods, both of which involved the Michael reaction: (1) methyl α-fluoroacrylate and diethyl acetamidomalonate gave the transesterified intermediate, which on hydrolysis produced γ-fluoroglutamic acid (31% yield); (2) ethyl α-acetamidoacrylate and diethyl fluoromalonate reacted under mild conditions to give, after hydrolysis, the required amino acid in 56% overall yield. Of the two procedures, the second is preferable, since it is based on more readily available starting materials and gives a higher yield.
ISARIIN, A NEW DEPSIPEPTIDE FROM ISARIA CRETACEA
Authors: Vining L. C. , Taber W. A.
Published: May 2006

One of the metabolic products of the fungus Isaria cretacea has been found to yield four different amino acids and a hydroxyacid on acid hydrolysis. The amino acids were identified as glycine, L-alanine, L-valine, and D-leucine, and a quantitative analysis showed them to be present in the molar ratio of 1:1:2:1, respectively. The hydroxyacid was identified as D-β-hydroxydodecanoic acid. These units appear to be combined in a simple cyclic structure by means of peptide bonds and an ester linkage between the hydroxyl of hydroxydecanoic acid and the carboxyl of the C-terminal amino acid. The sequence valine → β-hydroxydodecanoic acid → glycine has been established.
CLAM POISON: III. PAPER ELECTROPHORESIS OF CLAM POISON
Authors: Bannard R. A. B. , Casselman A. A.
Published: May 2006

In paper strip electrophoretograms on Whatman 3 MM paper, clam poison migrated toward the cathode when formic acid (1 N and 0.1 N), acetic acid (1 N), sodium acetate–acetic acid (0.1 M), monosodium dihydrogen phosphate–disodium monohydrogen phosphate (0.1 M), and sodium tetraborate (0.1 M) were used as electrolytes. Formic acid (1 N) proved the most suitable of these for examination of the quantitative electrophoretic behavior of clam poison. A method of pretreatment for the paper was developed to minimize introduction of extractable impurities into material recovered after electrophoresis by aqueous elution. Pure clam poison, on electrophoresis for 1.75 hours at 900 v on an 8 × 18-in. sheet of pretreated paper, migrated as a single, positively charged, Weber-positive band with apparent mobility 18.1 cm, which exhibited no fluorescence. Recovery was quantitative on both a weight and toxicity basis, and the toxicity, specific rotation, and infrared spectrum of the recovered toxin were identical with those of the starting material, thus providing an additional check on the homogeneity of the sample. Quantitative electrophoresis of toxin from clam poison tailings which had been purified by paper chromatography removed impurities which the latter method was incapable of eliminating, with resultant improvement in both the specific rotation and toxicity. Two such treatments provided toxin possessing a toxicity and specific rotation within the accepted limits for pure clam poison.
THE EXTRACTION OF THORIUM AND SOME LOWER LANTHANIDE NITRATES BY DIBUTYL BUTYL PHOSPHONATE
Authors: Manning P. G.
Published: May 2006

The distribution of thorium and a number of lanthanides between nitric acid and solutions of dibutyl butyl phosphonate in odorless kerosene has been examined as a function of the aqueous nitric acid concentration. Experiments were conducted at trace metal concentration using radioisotopes. Separation factors (denoted by S and defined as the ratio of the distribution coefficients, K, for two metal species) have been measured for some lanthanide–lanthanide couples and also for some thorium–lanthanide couples. Results indicate that separation factors between successive lanthanides (given by S = KZ+1/KZ) at the lower end of the rare-earth series are superior to those obtained with either tributyl phosphate (TBP) (D. Scargill et al. J. Inorg. & Nuclear Chem. 4, 304 (1957)) or trioctyl phosphine oxide (TOPO) (J. M. Schmitt. Oak Ridge National Laboratory. Unpublished data), but as Z increases, SDBBP ~STBP > STOPO. For thorium–lanthanide couples, S′DBBP > S′TBP. Measurements over a range of extractant concentrations indicate that the lanthanides are extracted as trisolvates.
VANADIUM TRIALKOXIDES AND SOME ALCOHOLATES OF VANADIUM TRICHLORIDE
Authors: Bradley D. C. , Mehta M. L.
Published: May 2006

not available
TRANSFORMATION OF ACONITINE TO AN ISOMER OF HYPACONITINE
Authors: Gilman Robert E. , Marion Léo
Published: May 2006

not available
SOME DIELECTRIC PROPERTIES OF CARBONYL CHLORIDE
Authors: Davidson D. W.
Published: May 2006

not available
AN ELECTRON IMPACT STUDY OF CHLOROMETHYL AND DICHLOROMETHYL DERIVATIVES
Authors: Harrison A. G. , Shannon T. W.
Published: May 2006

The appearance potential of the CH2Cl+ ion has been measured from methyl chloride, dichloromethane, bromochloromethane, and ethyl chloride. The results lead to ΔHf(CH2Cl+) = 230 ± 3 kcal/mole. The heat of formation of CHCl2+ is estimated to be 215 ± 3 kcal/mole from the appearance potential of this ion in the mass spectrum of chloroform and of bromodichloromethane. By the indirect mass spectrometric method ΔHf(CH2Cl) = 29 ± 3 kcal/mole and ΔHf(CHCl2) = 15 ± 3 kcal/mole are obtained. The ionization potentials of a number of chlorine-containing compounds have been measured.
DETERMINATION OF FREE FORMALDEHYDE BY VAPOR DIFFUSION TECHNIQUE: A STUDY OF THE GLYCINE–FORMALDEHYDE REACTION
Authors: Morrison John L. , Lee Audrey S. , Moloney Peter J.
Published: May 2006

A vapor diffusion technique has been modified to give absolute values of the free formaldehyde in glycine–formaldehyde mixtures. The equilibrium constant for the formation of the monomethylol addition compound of glycine and formaldehyde was found to be 40, which coincides with that calculated from Levy's measurements which were made with a hydrogen electrode. Values of the equilibrium constant for the formation of the dimethylol compound were variable and much higher than a single value reported by Levy. This uncertainty may be due to polymerization.
HIGH-TEMPERATURE STUDIES OF METALLURGICAL PROCESSES: PART II. THE THERMAL REDUCTION OF CALCINED DOLOMITE WITH SILICON
Authors: Toguri J. M. , Pidgeon L. M.
Published: May 2006

The production of magnesium by the following reaction has been studied:[Formula: see text]The rate of reaction (a) was followed by continuous weight loss measurements of the reactants. Keeping the particle size of the reactants and size and shape of the charge constant, the following factors which affect the yield of magnesium were investigated: (1) temperature, from 1050–1560 °C; (2) pressure, from less than 1 µ to 261 mm of Hg; (3) catalysts, CaF2, BaF2, and MgF2; and (4) ferrosilicon grade, from 18.7% to 96.7% Si.It was found that the yield increased by a factor 1.55 for a 50° increase in temperature over the temperature range investigated. At temperatures below 1300 °C the yield falls linearly with increase in pressure, while at temperatures above 1300 °C the yield remains relatively constant until the pressure exceeds the equilibrium magnesium pressure. All fluoride additions were found to increase the yield, CaF2 being the most effective. The rate of the reaction was also found to have a direct relationship with the silicon activity.
THE HYDROGEN-ABSTRACTION REACTIONS IN THE PHOTOLYSIS OF PENTAFLUOROPROPANAL AND HEPTAFLUOROBUTANAL
Authors: Pritchard G. O. , Miller G. H. , Foote J. K.
Published: May 2006

The main products of the photolysis of the aldehydes at 3130 Å were determined and the rates of H-atom abstraction relative to radical recombination were measured. They are [Formula: see text] for C2F5CHO, and [Formula: see text] for C3F7CHO. The derived Arrhenius parameters are compared with those determined in the photolysis of CF3CHO, and also with the non-fluorinated aldehydes.
THE INHIBITED AUTOXIDATION OF STYRENE: PART I.THE DEUTERIUM ISOTOPE EFFECT FOR INHIBITION BY 2,6-DI-tert-BUTYL-4-METHYLPHENOL
Authors: Howard J. A. , Ingold K. U.
Published: May 2006

Most previous work on the inhibition of autoxidation by phenols has indicated that the reaction involves abstraction of the phenolic hydrogen. However, the apparent absence of any appreciable deuterium isotope effect made it difficult to believe that abstraction could be rate controlling. The present work using styrene as the substrate, 2,6-di-tert-butyl-4-methyl-phenol as the inhibitor, and azo-bis-isobutyronitrile as the initiator has shown that this reaction has an unexpectedly large isotope effect, e.g. ~10.6 at 65 °C. Previous failures to detect an isotope effect are attributed to the rapid exchange of deuterium which takes place between deuterated phenols and traces of moisture or other hydroxyl-containing compounds present in the substrate. Rate constants and activation energies for some of the elementary reactions in the inhibited and uninhibited oxidation of styrene have been measured. It is suggested that a compound which functions in the same way as a weak phenolic inhibitor is formed in the apparently uninhibited oxidation.
FORMATION OF KETENEIMINE LINKS IN ACRYLONITRILE POLYMERIZED UNDER FREE RADICAL CONDITIONS
Authors: Crosthwaite J. C. , McLeskey III J. J. , Smith P.
Published: May 2006

not available
THE STUDY OF HYDROGEN BONDING AND RELATED PHENOMENA BY SPECTROSCOPIC METHODS: PART VII. INTRAMOLECULAR HYDROGEN BONDING AND STERIC INTERACTIONS IN o-NITROBENZALDEHYDE AND RELATED COMPOUNDS
Authors: Forbes W. F.
Published: May 2006

Certain unusual features in the infrared spectra of o-nitrobenzaldehyde have been interpreted either in terms of an intramolecular hydrogen bond or in terms of steric interactions. As an extension of these studies we have investigated the ultraviolet, infrared, and n.m.r. spectra of o-nitrobenzaldehyde and of suitable reference compounds and have re-examined the available other evidence. It is concluded that the observed spectral changes can best be explained in terms of steric interactions rather than in terms of intramolecular hydrogen bonding.
PREPARATION OF ANTIDOTES FOR ANTICHOLINESTERASE POISONING: I. PARPANIT ANALOGUES
Authors: Bannard R. A. B. , Parkkari J. H. , Coleman I. W.
Published: May 2006

Interaction of potassium 1-phenylcyclopentanecarboxylate and 2-diethylaminoethyl chloride in absolute ethanol proved the most satisfactory of four methods examined for the preparation of 2-diethylaminoethyl 1-phenylcyclopentanecarboxylate hydrochloride (Parpanit). This procedure was used to obtain 2-(ethyl-2′-fluoroethylamino) ethyl (I), 2-(ethylisopropylamino) ethyl (II), 2-diisopropylaminoethyl (III), 2-pyrrolidinoethyl (IV), and 2-piperidinoethyl (V) 1-phenylcyclopentanecarboxylate hydrochlorides. 2-Diethylaminoethyl 1-(p-nitrophenyl)-cyclopentanecarboxylate hydrochloride (VI) was also prepared in this way but was obtained more conveniently by direct nitration of 2-diethylaminoethyl 1-phenylcyclopentanecarboxylate. The preparation of intermediates required in these syntheses is described.Preliminary results are given on the potency of these compounds as substitutes for atropine sulphate in the usual oxime and atropine sulphate treatment of mice which have been poisoned with Sarin.