Kinetics and mechanism of the interaction of DL-methionine with cis-diaquaethylenediamine platinum(II) perchlorate in aqueous medium

The kinetics of the interaction of DL-methionine with [Pt(en)(H2O)2]2+ have been studied spectrophotometrically as a function of [Pt(en)(H2O)22+], [DL-methionine], PH and temperature. The reaction proceeds via a rapid outer sphere association followed by two slow consecutive steps having first order dependence on the aqua ion and methionine concentrations. Activation parameters have been evaluated using the Eyring equation. The low H1 (15.6 kJ mol–1) and large negative value of S1 (–230 J K–1 mol–1) as well as H2 (19.5 kJ mol–1) and S2 (–226 J K–1 mol–1) indicate an associative mode of activation for both the aqua ligand substitution processes in the two consecutive steps.     

Oxidation of [Co(en)2(SOCH2CO2)]+ by S2O82− and by IO4− in binary aqueous solvent mixtures at pressures up to 1.25 kbar

Second order rate constants and activation parameters H, S, and V have been measured for the oxidation of [Co(en)2(SOCH2CO2)]+ by S2O82– and by IO4– in highly aqueous H2O – t-BuOH mixtures. The changes in solvation on going from the initial to the transition state are discussed on the basis of the transfer functions Gto, Hto and Sto. Whereas Gt changes smoothly as the proportion of t-BuOH increases, the plots of Ht and TSt exhibit mirror behaviour and pass through extrema located around x2(t- BuOH)=0.038. Information on the role of solvation is complemented by the determination of activation volumes. These are discussed in terms of intrinsic and solvational contributions. It is proposed that changes in hydrophobic hydration are of principal importance in determining the response of H, S, and V to changes in solvent composition in H2O – t-BuOH mixtures.     

Synthesis and constants of 6-nitro-2,3-dihydroquinolin-4(1h)-one

In the literature, there has appeared a communication [1] on the synthesis of 6-nitro-2, 3-dihydroquinolin-4(1H)-one (I) with mp 125–126C (2,4-dinitrophenylhydrazone, mp 269–270C) by the reaction of p-nitroaniline with acrylic acid. Quinolinone I with mp 232–234C (2,4-dinitrophenylhydrazone, mp 327–329C) was obtained by us by decarboxycyclization of N-(2-carboxy-4-nitrophenyl)--alanine in acetic anhydride in the presence of potassium acetate [2].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1390–1392, October, 1979.     

Swelling equilibrium and preferential sorption of crosslinked poly(methyl methacrylate) in the mixture acetonitrile + n-butanol

Measurements of preferential sorption,( ₃), determined by refractometry, and swelling equilibrium, ₃ ^–1, of PMMA networks have been carried out in the cosolvent mixture MeCN+BuOH at 25 and 49 C. With an intermediate mixture composition, ₃ ^–1 passes through a maximum at both temperatures. At 25 C MeCN is preferentially adsorbed by the network over most of the composition range, but a small inversion is detected. At 49 C MeCN is preferentially adsorbed over all the composition range.The behavior of the system crosslinked PMMA/MeCN + BuOH is compared with the results obtained for solutions of linear PMMA in mixtures formed by the same two solvents, MeCN and BuOH.     

The kinetics and mechanism of aquation and base hydrolysis of the cis-[Co(cyclen)Cl2]+ cation (cyclen=1,4,7,10-tetraazacyclododecane)

The aquation of cis-[Co(cyclen)Cl2]+ (cyclen=1,4,7,10-tetraazacyclododecane) has been studied over a range of temperatures with 0.1 mol dm–3 HNO3 as solvent. At 25°C, kaq=4.5×10–3 s–1 with H=78 kJ mol–1 and S298=–21 J K–1 mol–1. Base hydrolysis of cis-[Co(cyclen)Cl2]+ is extremely rapid with kOH=2.1×107 dm3 mol–1 s–1 at 25°C and I=0.1 mol dm–3. This is the largest rate constant so far reported for the base hydrolysis of a cis-dichloro-complex of a saturated macrocycle. The activation parameters, H=53 kJ mol–1 and S298=73 J K–1 mol–1 are consistent with a mechanism in which deprotonation of the substrate is rate-determining. This conclusion is confirmed by the observation of general base catalysis by formate ion. The Brønsted value for the reaction is ca. 0.72 and SN1(CB) and E2 mechanisms are considered to account for the kinetic results. Base hydrolysis of cis-[Co(cyclen)(OH)Cl]+ has also been studied in the pH range 6.5 to 8.7. The value of kOH=3.8×102 dm3 mol–1 s–1 at 25°C and I=0.1 mol dm–3 with H=110 kJ mol–1 and S298=171 J K–1 mol–1 are consistent with an SN1(CB) mechanism.     

Isomer conversions in perfluoro-1-ethylindane under the action of antimony pentafluoride

Perfluoro-1-ethylindane on heating with SbF₅ is isomerized to perfluoro-1,1-dimethylindane, perfluoro-,-o-trimethylstyrene, and perfluoro-1,2-dimethylindane. In the presence of SbF₅, the latter two products are converted one into the other. In addition, in SbF₅ perfluoro-1,2-dimethylindane is defluorinated to perfluoro-2,3-dimethylindene and fluorinated to perfluoro-2,3-dimethyl-4,5,6,7-tetrahydroindene which is further fluorinated to perfluoro-1,2-dimethyl-4,5,6,7-tetrahydroindane and is converted at 200C to perfluoro-1,7-dimethylindane. The latter is also formed on heating perfluoro-,-o-trimethylstyrene with SbF₅ at 200C.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 645–652, March, 1990.     

Surface tension as a function of temperature for some molten metals

Results are given for Sn, In, and Ge from the melting points up to 1700 C, for Pb up to 1400 C, for Tl up to 1100 C, for Bi up to 1300 C, and for Cd up to 600 C. In every case the surface tension is a linear function of temperature. Estimates are made of the critical temperatures of Cd and Ge. It is shown that deductions on the structure of the melts can be drawn from surface-tension data.     

Reaction of diazoalkanes with unsaturated compounds. 10. 1,3-Dipolar cycloaddition of diazocyclopropane to strained cycloalkenes

The reaction of diazocyclopropane, generated in situ by alkaline hydrolysis of N-nitroso-N-cyclopropylurea at –20 to –40C, with the double bond of norbornene hydrocarbons or 3,3-dimethylcyclopropene is a 1,3-dipolar cycloaddition and affords 45–70% yields of thermally stable 1-pyrazolines possessing a spiro-joined cyclopropane fragment. Methylenecyclopropane under the same conditions is a less effective and selective interceptor of diazocyclopropane, forming in 10% yields not only isomeric 1-pyrazolines but the corresponding product of cyclopropylization, dispiro[2.0.2.1]heptane.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1057–1062, May, 1991.     

The viscoelasticity and structure of fibrous proteins

Summary DynamicYoung's moduli of wool fibres in water have been measured over a range of two decades in rate of extension and at temperatures from 0 to 90 C. Small displacements were used, corresponding to extensions of 0.1%. These were imposed upon mean extensions of (a) 1%, (b) 15% and (c) 40%, representative of the three main extension regions of-keratin. The results obtained show great differences from the slopes of the corresponding regions of the force-extension curve carried out at the same temperature and rate of extension.Comparison of the small-strain dynamic moduli in the three regions (a), (b) and (c) indicate that there is a component of the modulus in (a) amounting to 1.3×10¹⁰ dynes/cm² which is associated with intact-helical filaments, and which is substantially constant up to at least 70 C.Approximate superposition of the dynamic moduli at different rates was achieved using theWilliams-Landel-Ferry (WFL) equation with a reference temperature of 35 C. It is thereby concluded that under the present conditions-keratin has an effective glasstransition in the vicinity of –15 C. Above 60–70 C the WLF relation was not obeyed, indicating the presence of a relaxing process with a different temperature-dependence from that of the normal viscoelastic mechanisms; it is suggested that this process may consist in the fission and re-formation of cystine groups.

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Zusammenfassung Die dynamischenYoung-Moduln von Wollfasern in Wasser wurden über einen Bereich von zwei Dekaden der Streckgeschwindigkeit und Temperaturen zwischen 0 und 90 gemessen. Die maximal verwendeten Auslenkungen entsprechen einer Ausdehnung von 0,1%. Diese wurden den mittleren Dehnungen von (a) 1%, (b) 15% und (c) 40% überlagert entsprechend den drei Hauptbereichen der Dehnung von-Keratin. Die erhaltenen Ergebnisse zeigen gro\e Differenzen für die Steigungen der entsprechenden Bereiche Kraft-Dehnungs-Diagramm für gleiche Temperaturen und gleiche Dehnungsgeschwindigkeit.Ein Vergleich der Dehn-Moduln für kleine Dehnungen in den drei Bereichen (a), (b) und (c) zeigen, da\ in (a) eine Komponente des Moduls von etwa 1,3×10¹⁰dyn/ cm² enthalten ist, verbunden mit den intakten-Helices der Moleküle. Und diese bleiben im wesentlichen unverändert bis zu Temperaturen von wenigstens 70 C.Näherungsweise Superposition der dynamischen Moduln bei verschiedenen Dehngeschwindigkeiten konnte mit Hilfe derWilliams-Landel-Ferry (WLF)-Gleichung hinsichtlich einer Referenz-Temperatur von 35 C erreicht werden. Hieraus folgt, da\ unter den angewandten Bedingungen das-Keratin eine effektive Glasübergangstemperatur in der Nachbarschaft von –15C besitzt. Oberhalb von 60 bis 70 C wird die WLP-Gleichung nicht befolgt. Das zeigt die Mitwirkung von Relaxations-Prozessen mit einer unterschiedlichen Temperatur-Abhängigkeit von der der normalen viscoelastischen Mechanismen an. Es ist zu vermuten, da\ dieser Proze\ auf der Aufspaltung und Wiederbildung von Cystin-Gruppen beruht.

     

Kinetics and mechanism of the oxidation of acetaldehyde by chromic acid in perchloric acid

Summary The oxidation of MeCHO by chromium(VI) has been studied in HClO₄ medium over a wide range of experimental conditions and has been found to obey the rate law;v=k[MeCHO][HCrO ₄ ^– ][H⁺]. The calculated H and-S values for the reaction are 30±2kJ mol^–1 and 171±7J mol^–1deg^–1, respectively. The mechanism is discussed in terms of carbon-hydrogen bond cleavage.     

Thermal study of synthesis of cryptohalite

The present work represents a thermal study of synthesis of cryptohalite (Ammonium silicon hexafluoride) by sintering of quartz with ammonium fluoride using a derivatograph. The reaction products were identified microscopically and by using a Siemens Crystalloflex diffractometer. The DTA curves indicate that the intensive formation of cryptohalite takes place at 125–155C by an endothermic reaction. Cryptohalite is unstable and dissociates at 320–335C as represented by the sharp and large endothermic peaks at these temperatures.The resulted cryptohalite is colorless in thin sections and crystallizes in cubic system, in the form of octahedral crystals with perfect (111) cleavage. The dimorph bararite is not detected in all runs.

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Zusammenfassung Mittels eines Derivatographen wurde die Synthese von Kryptohalit (Ammoniumsiliziumhexafluorid) durch Sintern von Quarz mit Ammoniumfluorid thermisch untersucht. Die Reaktionsprodukte wurden mikroskopisch und mit Hilfe eines Siemens-Crystalloflex Diffraktometers identifiziert. Die DTA-Kurven zeigen, da\ die intensive Bildung von Kryptohalit in einer endothermen Reaktion bei 125–155C abläuft. Wie durch die scharfen und intensiven endothermen Peaks bei 320–335C gezeigt wird, ist Kryptohalit bei dieser Temperatur instabil und dissoziiert.Das erhaltene Kryptohalit ist in dünnen Schnitten farblos und kristallisiert im kubischen System in der Form von oktaedrischen Kristallen mit perfekter (111) Spaltbarkeit. Das dimorphe Bararit konnte in keinem der Versuche beobachtet werden.

     

Measurement of specific heat and energetic characterization of materials up to high temperatures

A new DSC system has been developed which not only allows quantitative results in the temperature of –160C to 700C, but also allows the quantitative determination of a variety of material properties up to 1500C. For example, the specific heat of materials can be measured to at least 1400C, while enthalpies, etc. can be measured to 1500C.

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Zusammenfassung Ein neuartiges DSC Messystem (Netzsch DSC 404) wurde entwickelt, das sich durch hohe Reproduzierbarkeit der Basislinie, grosse Empfindlichkeit und breiten Temperaturanwendungsbereich (–160C bis 700C resp. bis 1500C) auszeichnet. Die Messanordnung ermöglicht die Verwendung von unterschiedlichen GasatmosphÄren als auch Messungen im Vakuum. Es werden Beispiele der Bestimmung von SchmelzvorgÄngen, der Glasumwandlungstemperatur, der KristallinitÄt und der spezifischen WÄrme, sowohl für Polymere als auch für anorganische Materialien dargestellt und diskutiert.

     

Kinetics and mechanism of osmium(VIII) mediated cerium(IV) oxidation of dimethylsulfoxide in aqueous sulfuric acid

Under the experimental conditions [DMSO]T [CeIV]T [Os]T the kinetics of oxidation of dimethylsulfoxide (DMSO) to dimethylsulfone (DMSO2) have been followed at different temperatures (40–55°C) in 1.0 mol dm–3 sulfuric acid media. The rate of disappearance of [CeIV] shows a first-order dependence on both [Os]T and [DMSO]T and zeroth-order kinetics with respect to [CeIV]. The suggested mechanism involves oxidation of DMSO by OsVIII in a rate-determining step through an outer-sphere mechanism, followed by rapid regeneration of OsVIII by CeIV from OsVI. The rate law conforms to: –d[CeIV]/dt=k0=k[Os]T[DMSO]T. The values of k and the activation parameters are: 102k=(4.9 ± 0.10) mol–1 dm3 s–1 at 40°C, [H2SO4] =1.0 mol dm–3;H=58±3kJmol–1, S= –88 ±5JK–1mol–1.     

Kinetics and mechanism of the oxidation of thiosulphate by hexachloroplatinate(IV)

Summary Rate constants for the oxidation of thiosulphate by hexachloroplatinate(IV) have been measured. The kinetics of the oxidation of thiosulphate follow a second-order rate law, first order with respect to thiosulphate and first order with respect to platinum(IV). The influence of pH is small. The rates are found to depend on the nature and concentration of the cations and follow the order: Cs⁺>Rb⁺>K⁺>Na⁺>Li⁺. The activation parameters calculated from the temperature studies are: H=42.9 k J mol^–1 and S=–102 JK^–1 mol^–1. A mechanism of the reaction in terms of intermediate formation of free radicals followed by the formation of tetrathionate is postulated to explain the kinetic behaviour.     

Kinetics of aquation of trans-dichlorobis(N,N′-dimethylethylenediamine)cobalt(III) ion in water–methanol in water–propan-2-ol media

The complex trans-[Co(dmen)2Cl2]Cl (dmen=N,N-dimethylethylenediamine) has been prepared and characterized by elemental analysis, u.v.-vis. and i.r. spectra. The kinetics of the primary aquation of trans-[Co(dmen)2Cl2] in H2O, H2O–MeOH and H2O–i-PrOH have been examined over a wide range of solvent compositions and temperatures (40–55°C). Plots of rate constants (log k) versus the reciprocal of the dielectric constant of the medium (Ds–1) and Grunwald–Winstein values of the solvent (Y) were found to be non-linear. The variation of enthalpies (H) and entropies (S) of activation with solvent composition has been determined. Plots of H or S versus the mole fraction of each solvent exhibit extrema at x2=ca. 0.16 and 0.27 for MeOH and at x2=ca. 0.03 and 0.14 for i-PrOH. Furthermore, the cycle relating the free energy of activation in H2O to that in H2O–co-solvent shows that the stabilizing influence of the changes in the solvent structure is greater on the emergent five-coordinate cation in the transition state than that on the complex ion in the initial state, with the difference becoming greater as the mole fraction of the co-solvent increases.     

Extended Hückel MO calculations of the conformation of several amino acids

The conformation of the amino acid residues, glycine, alanine, proline, and phenylalanine have been predicted from molecular orbital calculations of appropriate model compounds. Using the current main chain rotation convention (, ) the principle conformations were found to be glycine (0, 0), alanine (240, 240), proline (120, 330) and phenylalanine (30, 330). Several secondary conformations were also found for glycine. A comparison of the predicted conformations is in good agreement with experimental data on comparable residues or model compounds.Supported by National Institutes of Health Grants No. FR 5409-07 and GM 16312-01.Recipient of a Public Health Service Research Career Development Award AM 1159-01.     

Analytische Dichtegradienten-Zentrifugation bei Temperaturen zwischen +4?C und +40?C

Zusammenfassung Es wird gezeigt, da\ die bei der analytischen Dichtegradienten-Zentrifugation benötigten Parameter, die von Hearst u. Mitarb. tabelliert wurden, auch für andere Temperaturen als 25C gültig sind. Das ist von gro\er Wichtigkeit, da hochempfindliche Enzyme nur bei Temperaturen um + 4C lÄnger als 24 h nativ bleiben. Man ist deshalb auf eine Zentrifugation bei dieser Temperatur angewiesen. Weil man oft nur sehr wenig Substanz isolieren kann, bleibt nur die Dichtegradienten-Zentrifugation als Methode der Wahl. Ein Vergleich der gemessenen Molekulargewichte bei 6C und 25C zeigt keine Abweichungen, die über die Me\genauigkeit hinausgehen.

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Analytical density gradient centrifugation at temperatures between +4C and +40 C

It is shown that all the parameters needed for analytical density gradient centrifugation tabulated by Hearst et al. for 25C are valid for other temperatures, too. This will be important in the investigation of highly sensitive enzymes which are only stable at temperatures near +4C over a period of 24 h. Comparison of molecular weights determined at 6C und 25C shows no difference greater than 2%, which will be within the experimental error.

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Das Bundesministerium für Bildung und Wissenschaft hat diese Arbeiten gro\zügig unterstützt.     

Kinetics and mechanism of decarboxylation of cis-carbonato- and bicarbonato(3,3′,3′′-triaminotripropylamine)cobalt(III) ions

The acid-catalysed hydrolysis of [Co(trpn)(CO3)]+ and [Co(trpn)(HCO3)]2+ ions (trpn = 3,3,3-triaminotripropylamine) have been studied spectrophotometrically in aqueous 1.0m HClO4/NaClO4. For the carbonato complex, [HClO4] = 0.02–0.25m and T = 20–35°C; for the bicarbonato complex, [HClO4] = 0.025–0.30m and T = 25°C. Both complexes hydrolyse to form the same cis-diaqua species. The rate law for the hydrolysis is d(ln[CoIII])/dt = k0+k1[H3O+]. The values of the rate constants (25°C), H (kJmol–1) and S (Jmol–1K–1)are:[Co(trpn)(CO3)]+,k0 = (1.7±0.6)× 10–4s–1, H 0 = 57±21, S 0 = –126±75; k1 = (1.0 ±0.1)×10–2m–1s–1, HDagger;1 = 62±8, S1 = –75 ±21, and for [Co(trpn)(HCO3)]2+, k0 = (2.9±0.7)× 10–4s–1, and k1 = (7.8±1.0)×10–2m–1s–1. The carbonato complex exhibits a deuterium isotope effect with k1D/k1H = 1.9, consistent with a rapid pre-equilibrium protonation, followed by rate-controlling ring-opening. The rate constants k0 and k1 (25°C and = 1.0m) for the ring-opening decarboxylation of the two systems studied lie within the experimental error. The results are compared with o ther related systems and the factors which influence the ring-opening decarboxylation (steric hindrance, ring strain, electron-donor ability of the amines) are discussed. The k1 path is interpreted in terms of concerted ring-opening and bond-making in the highly unstable aquabicarbonato intermediate.     

Effect of the reduction temperature on the formation and activity of bimetallic Ni-Tc catalysts

The effect of the temperature on the formation, surface state, and catalytic activity in the reactions of dehydrogenation of cyclohexane and dehydrocyclization of n-hexane by Ni-Tc/-Al₂O₃ mono- and bimetallic catalysts was investigated. TcO₂, NiCl₂, and metal phases, and at a high temperature (500–700C), NiAl₂O₄ spinel and Ni-Tc clusters, were found on the surface of all of the catalysts. It was shown that the maximum activity is observed in reduction of monometallic catalysts at 500C and bimetallic catalysts at 700–800C. Synergism appeared in the bimetallic catalysts due to the formation of Ni-Tc clusters.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2486–2490, November, 1990.     

Untersuchungen über das dielektrische Verhalten von Polypropylen

Zusammenfassung Das Verhalten von Polypropylen im elektrischen Wechselfeld wurde im Frequenzbereich von 0,15 kHz bis 300 kHz und im Temperaturbereich von –75 C bis +140 C untersucht. Es konnte sowohl ein Tieftemperaturdispersionsgebiet —-Absorption — als auch ein Hochtemperaturdispersionsgebiet —-Absorption — beobachtet werden. Die Untersuchungsergebnisse wurden, um die Breite des Dispersionsgebietes und die zugehörigen -Stufen zu bestimmen, nach demCole-Cole-Kreisbogengesetz analysiert. Aus dem Anstieg der Geraden: logf _max 1/T _K wurden sowohl für die- als auch fur die-Absorption die experimentellen Aktivierungsenergien berechnet. Eine Deutung der Ergebnisse wurde versucht.