Determination of the mechanism of the oxidation of the trichloromethyl radical by the photolysis of chloral in the presence of oxygen

The photooxidation of chloral was studied by infrared spectroscopy under steady-state conditions with irradiation of a blackblue fluorescent lamp (300 nm < λ < 400 nm, λ_max = 360 nm) at 296 ± 2 K. The products were hydrogen chloride, carbon monoxide, carbon dioxide, and phosgen. The kinetic results reveal that the reaction proceeds via chain reaction of the Cl atom: The results lead to the conclusion that mechanism (B) is confirmed to be more likely than mechanism (A), which was favored at one time by Heicklen for the mechanism of the oxidation of trichloromethyl radicals by oxygen molecules: The ratio of the initial rates of CO and CO₂ formation gave k₇/k₆ = 4.23M^?1, and the lower limit of reaction (5) was found to be 3.7 × 10⁸M^?1 sec^?1.     

Characteristics of the cholinesterase of the venom of the central Asian cobra

Summary 1. By rechromatography on sulfoethyl-Sephadex C-50, an electrophoretically homogeneous preparation of cholinesterase has been obtained from the venom ofNaja oxiana Eichwald.2. The activity of the cholinesterase isolated depends on the concentration of the enzyme and the time and temperature of incubation, and also on the pH. The following must be considered the optimum conditions: time of incubation of the enzyme with the substrate 20–30 min, pH 8.0–8.5, temperature 37–38°C.3. Diisopropyl phosphorofluoridate (DIPF) in a concentration of 2 µM completely suppresses the activity of the cobra venom cholinesterase.4. The venom cholinesterase hydrolyzes acetylcholine chloride and acetylthiocholine bromide but has no effect on butyrylthiocholine bromide, in which respect it resembles the true cholinesterases.5. Preparations of cobra venom cholinesterase do not possess a lethal action and do not potentiate the activity of the neurotoxins of the same venom.Institute of Biochemistry, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 783–789, November–December, 1972.     

Quantum-chemical investigation of the influence of the vacant orbitals of the heteroatom on the shaping of the electronically excited states and luminescence-spectroscopic properties of triphenylgallium

The electronic structure of the triphenylgallium molecule in the ground and electronically excited states has been calculated in the framework of the CNDO/S-CI method in sp and spd bases. The electron density in the AO's and atoms, the first ionization potential the energies and matrices of the changes in the electron density of the S_n and T_n states, the matrix elements of the spin-orbit coupling operator $$ " align="middle" border="0"> and $$ " align="middle" border="0"> , the intensities and directions of polarization of the S_n S_o and T₂ T_n transitions, and the phosphorescence lifetimes have been calculated. The following spectroscopic parametrization has been proposed for the Ga atom in the sp and spd bases: 1/2(I_s + a_s) = 10.075 eV, 1/2(I_p + A_p) = 4.265 eV, 1/2(I_d + A_d)=0, _Ga ^p =5 eV, _Ga ^d =O, _Ga ^sp =–7 eV, _Ga ^spd =–10 eV, and _s,p,d=1.433. The influence of the d AO's on the shaping of the orbital nature of the S₁ and T₂ states has been analyzed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 584–590, September–October, 1985.     

On the nature of the anhydride of the lactam of guanidinoglutaric acid

When glutamic acid is amidinated, guanidinoglutaric acid is formed. This is readily converted by boiling in water to its lactam [2-imino-4-oxo-5-(3′-propane acid) imidazolidine; GGAL]. In the present study GGAL is dehydrated to form a second lactam, anhydro-GGAL (AGGAL), with trifluoroacetic anhydride. The molecular weight of this compound was ascertained gravimetrically by precipitation with flavianic acid and by mass spectrography to be 153.14. UV and infrared spectra and hydrogen and ¹³C NMR studies determined its structure as an imidazolidine ring fused to a pyrrol ring, 2-imino-4-oxo-imidazolidine-1,5-pyrrolidone-8. On paper electrophoresis, GGAL traveled to the anode, while AGGAL traveled to the cathode. On TLC plates (butanol 60, H₂O 25, acetic 15), the R_f value of GGAL was 0.42 and that of AGGAL was 0.38, confirming that AGGAL was more basic than GGAL. The preparation of 1,3-di-(phenylcarbamoyl)-GGAL is also described.     

Relation of the decay of free radicals in irradiated polyethylene to the molecular motion of the polymer and the configurations of the free radicals

Decay reactions of the free radicals produced in irradiated polyethylene (high-density and low-density materials) were examined in connection with the molecular motion of the matrix polymer. Three temperature regions, in which the free radicals decay very rapidly, at around 120, 200, and 250°K, were designated T_A, T_L, and T_B, respectively. The decay of the free radicals at these temperatures had activation energies in high-density polyethylene of 0.4 kcal/mole for T_A, 9.4 kcal/mole for T_L, and 18.4 kcal/mole for T_B. In low-density polyethylene these quantities were 0.7 kcal/mole for T_A, 23.1 kcal/mole for T_L, and 24.8 kcal/mole for T_B. Comparison of time constants for the decay reactions and for molecular motion of the matrix polymer indicate that the decay in T_A and T_B is closely related to molecular motion in the amorphous regions of the polymer. The decay of the free radicals at T_L in high-density polyethylene is due to molecular motion associated with local mode relaxation at lamellar surfaces, while that of low-density polyethylene is due to local mode relaxation in the completely amorphous region. Steric configurations of the free radicals which decay in the respective temperature regions were also investigated.     

Theoretical analysis of the dependence of the vibration spectra of a monosaccharide on the conformation of the hexapyranose ring

Using the molecular mechanics method, we calculated the vibration spectra of methyl-2,6-di-O-acetyl-3,4-anhydro-α-DL-(6,6-²H₂) derivatives of galactopyranoside (G) and talopyranoside (T) molecules, the former in three conformations of the hexapyranose ring (half-chair¹H₀ and⁰H_1dis and also distorted boat^2.5B_dis), and the latter in the E₀+¹H₀ conformation. The sensitivity of vibration frequencies to variations of the hexapyranose ring conformation and to the configuration of the C(2) substituent is analyzed within spectral domains containing specific vibrations. Institute of Physics, Byelorussian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 35, No. 6, pp. 35–45, November–December, 1994. Translated by A. Arbuznikov     

Composition of the triacylglycerols of the seeds of some representatives of the family labiatae

The fatty acid compositions of five species and the compositions of the triacylglycerols of 22 species of the family labiatae have been studied for the first time. Octadeca-12,13-dienoic acid has been detected in five species. The typical compositions of the triacylglycerols differs from those of known plant oils with a similar set of fatty acids by the absence of triacylglycerols of the S₃ type and the presence of the S₂U type (0.1–1.6%). The main types are SU₂ (5–24%) and U₃ (74–95%). In a comparison of the position-species composition of the oils studied it was found that the oils of the plants of this family are distinguished by a greater diversity of species of triacylglycerols and also by the nature of the distribution of the unsaturated acyl residues between the 1,3- and 2-positions. In the majority of oils studied, the 2- position is enriched with the 18:1 acid, while the 18:2 acid is distributed predominantly in the 1,3- positions, and the nature of the distribution of the 18:3 acid is determined by its proportion in the total.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 618–625, September–October, 1979.     

Dependence of the composition of the lipids of the seeds ofPlectranthus glaucocalyx on the conditions of growth

A change in the geographical growth zone and in the density of the soil has a substantial influence on the amount of lipids in the seeds ofPlectranthus glaucocalyx Maxim. and their degree of unsaturation, and also on the structure of the triacylglycerols.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 30–35, January–February, 1984.     

Integral intensities of the absorption bands of the skeletal vibrations of the heteroaromatic ring in the IR spectra of the furanoquinoline alkaloids

Summary 1. The integral intensities of the bands of the skeletal vibrations of the heteroaromatic ring in the 1480–1630-cm^–1 region of eight furanoquinoline alkaloids have been measured.2. A connection has been found between the values of A and the structures of the furanoquinoline alkaloids and their derivatives which enables such a series of heteroaromatic compounds to be identified: It has been shown that the introduction of an -OCH₃ group into the position of the pyridine nucleus leads to a marked rise (almost twofold) in the value of A;In derivatives of dictamnine (VII-XII), the value of A depends on the position of the methoxy group and on the nature of the substituent in position 7 of the benzene ring;With an increase in the delocalization of the unshared pair of electrons of the oxygen atom of the furan ring, the value of A of the series of alkaloids investigated (VI-XIV) decreases; andCompounds (V-XIV) have the very high values of A of 5.0–7.0 practical units and they exceed the value of the intensities of the carbonyl bandsv(C=0).Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 223–227, March–April, 1976.     

Correlation of the reactivity of organometallic chlorides in the oxidation of magnesium with the electronic structure of the organic moiety

From the linear correlation of the chemical shift (¹⁹F) in compounds R-C≡C-C₆H₄-F-p (reference PhF, solvent to-luene) with the Hammett σ _p constants of substituents R, the σ _p constants of organometallic substituents R [Cp(CO)₃Mo, Cp(CO)₃W, Cp(CO)₂Fe, Cp(PPh₃)Ni, Ph₂Bi, Ph₂Sb, Ph₃Sn] were calculated. The logarithm of the rate constant of magnesium oxidation with compounds RCl linearly correlates with the σ _p constants of the organometallic groups R.     

Role of the supramolecular structure of the reactants in the kinetics of the liquid-phase synthesis and decomposition of explosives

Formulas relating the observed rate constant of the initial reaction step (k _ef) to the rate constants of the elementary steps (k _i ), to the monomer-association species equilibrium constants (K _i ), and to the concentrations of the reactants (A _i ) and solvent have been obtained for a number of simple kinetic models of liquid-phase explosive material synthesis and decomposition reactions involving associating reactants. The k _ef = F(k _i , K _i , and A _i ) relationship is independent of the rate law of the reaction and is governed by the association species type (autoassociation or heteroassociation species) and by the number of association species kinds. In the case of parallel reactions involving association species, as distinct from the same reactions involving unassociated reactants, concentration variations have an effect on the ratio of the rates of the parallel steps and on the product yield ratio. By varying the reaction temperature, it is possible to make the rates of the parallel steps to vary in opposite ways. When monomers, dimers, and tetramers are present in the reaction mixture, the temperature dependence of lnk _ef may have an extremum. These deduced regularities are in qualitative agreement with experimental data.     

Research on the rupture of the covalent bond of the dichlorine molecule

Abstract  

Photoinduced reaction of gas-phase dichlorine molecules on the short wavelength side of the A-band gives a negative value for the asymmetry parameter of Cl (² P _1/2) fragments, which conflicts with the intrinsic electronic transition mechanism. In this paper, the dissociation process of the dichlorine molecule has been investigated at numerous excitation wavelengths in the range 310–470 nm using the numerical method and the frontier molecular orbital maps are drawn to obtain insight into the character of the relevant molecular orbitals. The possibilities of radial nonadiabatic transition from the C¹Π_u to the third Ω = 1_u (σ _u* ← σ _g) electronic state are also examined, and found to cause large variations for the angular distribution functions. The wavelength dependence of the beta parameter β ₂(Cl*), which is computed from the partial cross-section with the RZD transition mechanism, agrees with the experimental behavior and further justifies the conclusion that the decrease of beta in the Cl + Cl* channel is because of the radial nonadiabatic interaction between the C and 1_u(III) excited states and this interaction is a key mechanism decreasing the beta parameter value. At last, the kinetic energy distributions of fragments are obtained in the asymptotic region.     

Role of the conformations of tetraoxides in the mechanism of the recombination of peroxide radicals

The MINDO/3 method was used to calculate the equilibrium three-dimensional structure of the simplest representatives of the series of tetraoxides (TO) — H₂O₄ and CH₃O₄H. In the harmonic approximation their force field, and the frequencies and forms of the normal vibrations were calculated. Satisfactory agreement between the theoretically calculated and experimentally measured frequencies was obtained for a peroxide condensate. It was shown that the recombination of tertiary peroxide radicals proceeds through a transoid configuration of the TO, while recombination of primary and secondary peroxide radicals is associated with the formation of a cisoid configuration.Translated from Teoreticheskaya i ksperimental'naya Khimiya, Vol. 22, No. 3, pp. 363–366, May–June, 1986.     

Investigation of the toxins of the venom of the spiderLinothele sp.

Two low-molecular-mass toxins — Lsl and Ls2 — have ben isolated from the venom of a spiderLinothele sp. (fam. Dipluridae) with the aid of gel filtration and reversed phase high-performance liquid chromatography (HPLC). It hs been shown that they are highly toxic on cerebroventricular injection into white mice: the LD-50 values of toxins Lsl and Ls2 are 24 and 19 g/kg, respectively, which are 25 and 31 time greater than the toxicity, of the whole venon, the LD-50 of which is 0.6 mg/kg. According to mass spectrometry the molecular masses of toxins Ls1 and Ls2 are 337 and 505 Da, while their yields were, respectively, 0.21 and 0.43 % of the weight of the whole venom.Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 229–233, March–April, 1996. Original article submitted October 6, 1995.     

Kinetics of the reaction of the sulfate radical with the oxalate anion

The kinetics of the reaction of the sulfate radical, SO₄⁻, with the oxalate anion C₂O₄²⁻ was studied in aqueous solution and second-order rate constants, corrected for the effects of ionic strength, derived. Measurements were carried out over the temperature range 24–60°C resulting in the expression k₀ = 2.10 ± 0.96 × 10⁸ exp(−1080 ± 140/T) L mol⁻¹ s⁻¹. © 1996 John Wiley & Sons, Inc.     

Influence of the Support on the Catalytic Characteristics of the Deposited Palladium in the Liquid-Phase Hydrogenation of Diphenylacetylene

Palladium catalysts on various types of supports were studied in the liquid-phase hydrogenation of diphenylacetylene. Samples of Pd/SiO₂–Al₂O₃, Pd/MgAl₂O₄, Pd/Al₂O₃, and Pd/TiO₂ were characterized by the chemisorption of the CO and IR spectroscopy of adsorbed CO. The use of n-hexane as the solvent increases the reaction rate, which can be explained by the better solubility of hydrogen in the liquid phase. It is established that the acid–base properties of the support do not affect the activity and selectivity of the catalysts in the reaction under study. However, they alter the electronic state of palladium. According to the catalytic tests, Pd/TiO₂ has the highest activity (turnover frequency) and selectivity to alkene. The comparison of the obtained catalytic data and the results of IR spectroscopy made it possible to conclude that this is due to the electron density redistribution between the palladium and TiO _x particles, which is caused by the strong metal–support interaction.     

Investigation of the lability of the conformations of some alkaloids of the quinolizidine series

Summary The IR and NMR spectra of lupinine, epilupinine, and a series of other alkaloids of the quinolizidine series have been studied.It has been shown that the inhibition of the inversion processes in the molecules of the alkaloids in the solid phase is revealed in a change in the nature of the absorption in the 500–1200 cm^2–1 region.V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 49–54, January, 1971.     

Effect of the oxidation state of manganese in the manganese oxides used in the synthesis of Mn-substituted cordierite on the properties of the product

Catalysts based on Mn-substituted cordierite 2MnO · 2Al₂O₃ · 5SiO₂ have been synthesized using different manganese oxides (MnO, Mn₂O₃, and MnO₂) at a calcination temperature of 1100°C. The catalysts differ in their physicochemical properties, namely, phase composition (cordierite content and crystallinity), manganese oxide distribution and dispersion, texture, and activity in high-temperature ammonia oxidation. The synthesis involving MnO yields Mn-substituted cordierite with a defective structure, because greater part of the manganese cations is not incorporated in this structure and is encapsulated and the surface contains a small amount of manganese oxides. This catalyst shows the lowest ammonia oxidation activity. The catalysts prepared using Mn₂O₃ or MnO₂ are well-crystallized Mn-substituted cordierite whose surface contains different amounts of manganese oxides differing in their particle size. They ensure a high nitrogen oxides yield in a wide temperature range. The product yield increases with an increasing surface concentration of Mn³⁺ cations. The highest NO_x yield (about 76% at 800–850°C) is observed for the MnO₂-based catalyst, whose surface contains the largest amount of manganese oxides.     

On the Effect of the Aglycon Structure of Three Aryl β-D-Galactosides on the Yield and the Regioselectivity of the Transglycolytic Synthesis of N-Acetyllactosamine

ABSTRACT

We examined the effect as donors of three aryl β-D-galactosides (i.e. p-nitrophenyl β-D-galactopyranoside, o-nitrophenyl β-D-galactopyranoside and phenyl β-D-galacto-pyranoside) on the regioselectivity and the yield of the synthesis of N-acetyllactosamine obtained from the transglycosylation reaction catalyzed by a crude preparation of β-D-galactosidase from Bacillus circulans at 25 °C, 37 °C and 55 °C, respectively. Using p-nitrophenyl β-D-galactopyranoside the reaction results were fully regiospecific at all the temperatures considered: the maximum molar yield (74%) was obtained at an incubation temperature of 55 °C. Using o-nitrophenyl β-D-galactopyranoside as the donor the reaction was still highly regioselective and the maximum molar yield (50%) was achieved at an incubation temperature also of 55 °C. Using phenyl β-D-galactopyranoside transglycolytic products appear only at an incubation temperature of 55 °C but at very low molar yield (about 14%) and lower regioselectivity.     

Effects of the working conditions on the values of the kinetic parameters of the thermal decompositions of some complexes

The kinetic parametersn, A andE (the order of the decomposition reaction, the pre-exponential factor and the activation energy of the thermal decompositions) of some complexes of general formula [MCl₂(GTD)₂]Cl, where GTD=Girard T-diacetylmonoxime cation andM=central metal ion=Mn(II), Fe(III) and Co(II), were calculated through their TG curves. The effects of working conditions such as the sample weight and the rate of heating on the evaluated kinetic parameters are discussed.