FTIR study of the mode of binding of the reactants on the Pd nanoparticle surface during the catalysis of the Suzuki reaction

In the Suzuki reaction between phenylboronic acid and iodobenzene catalyzed by palladium nanoparticles, our previous studies suggested that the phenylboronic acid adsorbs on the nanoparticle surface and then interacts with the iodobenzene that is present in solution. In the present study, FTIR is used to examine the change in the vibrational frequencies of phenylboronic acid in films with and without the addition of palladium nanoparticles. The large change in the B-O stretching frequency of phenylboronic acid from 1348 to 1376 cm(-1) in the presence of sodium acetate and palladium nanoparticles strongly suggests that the mode of binding of phenylboronic acid to the Pd nanoparticle surface involves a B-O-Pd type of bonding. Shifts in the B-C stretching mode and the out-of-plane phenyl C-C ring deformation bands associated with phenylboronic acid provide additional confirmations of the binding process. It is also shown that the phenylboronic acid needs to be in the deprotonated form in the presence of sodium acetate (phenylboronate anion) to bind to the palladium nanoparticle surface. No changes in the characteristic bands of iodobenzene were observed in films made in the presence of the palladium nanoparticles. The FTIR studies provide proof of the mode of binding that occurs in the nanoparticle surface for the first time and also confirms the mechanism of the Suzuki reaction that we proposed previously.     

Effect of the nature of the solvent and the temperature on the frequency and intensity of the stretching vibration of the Ge-H bond in the IR spectra of 1-hydrogermatranes

Conclusions The Ge-H stretching vibration in the IR spectra of 1-hydrogermatranes varies under the influence of the solvent and the temperature as a result of the presence of the transannular Ge N bond. The change in the length of this bond with variation in the polarity of the solvent and the temperature of the solutions is smaller in germatranes than for the Si N bond in the isostructural silatranes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1758–1761, August, 1985.     

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.     

Elements of the topology of the region of the existence of the metastable states of a two-component vapor

Entire regions of the metastable states for binary and single-component systems were constructed. It was established that the regions include temperature intervals from absolute zero to critical temperatures, and from vapor—condensate equilibrium to the conditions of spinodal decomposition of supersaturated vapor in the system. Algorithms for determining the regions of metastable states are presented. The data obtained on their basis are noted to coincide qualitatively with known results. Correlations found earlier are employed to calculate the critical pressures and temperatures for the binary systems in the study.     

Effects of the composition of the reaction mixture and the nature of the template on the structure of mesoporous aluminosilicates formed in the presence of lecithin

It has been established that supramolecular structures of lecithin can act as templates in the synthesis of mesoporous aluminosilicates. Mesoporous substances, with pore dimensions up to 100 Å and biporous materials can be obtained when various combinations of lecithin with cetyltrimethylammonium bromide or octadecylamine are used as template agents in the aluminosilicate system.     

A study of the lignin of the cotton plant of the subspeciesmexicanium

p-Hydroxybenzoic, vanillic, ferulic, and syringic acids, and also p-hydroxybenzalde-hyde and vanillin, have been found in an ethanol-benzene extract of the stems of cotton plants of the subspeciesmexicanium. The dioxane lignin (DLA) has been isolated by Pepper's method, the semiempirical formula of its phenylpropane structural unit and its molecular-mass distribution have been established, and its UV, IR, and PMR spectra have been recorded. The DLA has a comparatively low molecular mass and a lower degree of polydispersity than the dioxane lignin of the cotton plant of variety Tashkent-1, while the amounts of functional groups in them coincide, with the exception of a lower amount of carboxy groups in the DLA.     

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 pH of the medium on the chemical shifts in the PMR spectra and on the distribution of the π-electron density

The dependence of the chemical shifts of the ring protons on the pH of the medium for a number of 4-hydroxyquinoline derivatives was studied by means of PMR spectroscopy. The dipolar and uncharged hydroxy forms exist in equilibrium in aqueous solutions. The effect of intramolecular hydrogen bonding on the character of the dependence of the chemical shift on the pH of the medium in the case of 3-piperidinomethyl-4-hydroxyisoquinoline was investigated. The possibility of the separate protonation of the ring nitrogen and the side-chain nitrogen in 3-piperidinomethyl-4-hydroxyisoquinoline was established. The distribution of the -electron density in 4-hydroxyisoquinoline is in good agreement with its chemical behavior.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1546–1549, November, 1971     

Effect of the shape of human erythrocytes on the evaluation of the passive electrical properties of the cell membrane

The possible influence of the cell shape on the derivation of the passive electrical parameters of a biological cell membrane is discussed in light of two different models which describe the cell as a shelled ellipsoidal particle and as a biconcave disk obtained by the revolution of the Cassini oval, respectively. Whereas within the first model, the Laplace equation can be solved analytically, in the second one a numerical algorithm based on the boundary element method has been employed. We have compared the results obtained by these two different models in the case of normal human erythrocyte cell membrane, using radiowave dielectric spectroscopy measurements. Our findings show that, although in principle the cell shape might deeply affect the evaluation of the passive electrical parameters of the cell membrane, in the case of the erythrocyte shape modelled by the Cassini curve, only small deviations are evidenced in comparison to the values derived, as usually done in the dielectric spectroscopy of biological cell suspensions, from an ellipsoidal model analysis. This result gives further support to the reliability of the data reported in the literature based on an ellipsoidal shape erythrocyte model.     

Investigation of the mechanism of the polarographic reduction of the sydnoneimmonium cation

The polarographic reduction of the sydnoneimmonium cation (I) was investigated in the case of 3--phenylisopropylsydnoneimine hydrochloride (sydnophen). The effect of the pH, alcohol concentration, ionic strength, and surface-active substances was studied, and the electrolysis was carried out at a controllable potential under various conditions. The cyclic voltampefograms were recorded. A mechanism for the reduction of I is proposed. Cleavage of the ring of I in the near-electrode space is observed in unbuffered media. The first direct proof of the existence of the unstable sydnoneimine base was obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1042–1048, August, 1975.     

Using of the Agglomeration-in-liquid for the Technology of the Fine Materials

The content of the fine and ultrafine particles in the raw material results in difficulty of the separation, the loss of the valuable components and ecological contamination. Secondary using of the fine particles is impossible without their granulation. This problem has been solved by the agglomeration-in-liquid method.An agglomeration-in-liquid method is a process to produce agglomerates in a liquid phase from solid particles suspended in the liquid. The surface of solid particles and the binding liquid must be of identical polarity, but the continuous phase must be of the opposite polarity. The water solutions of the surfactant are the binding liquids or the organic liquids.     

Role of the solvent in the dynamical transitions of proteins: the case of the lysozyme-water system

We study the dynamics of hydration water in the protein lysozyme in the temperature range 180 K相似文献   

The computation of the representation matrices of the generators of the unitary group

A method is presented for the efficient computation of the representation matrices of the unitary group, U(n) in the Gelfand—Tsetlin basis (corresponding to the usual spin-symmetry adapted basis for an N electron CI). The present scheme is conceptually and computationally attractive in that it is formulated directly in terms of Weyl tableaux and also that it permits simultaneous basis vector generation and matrix element evaluation. In addition the basis vectors are ordered so that subsequent restriction to the three dimensional rotation group is facilitated. An illustrative example is also presented.Taken in part from a thesis submitted to the University of London in partial fulfilment of the requirements for the degree of PhD.     

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

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 ΣA 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 γ position of the pyridine nucleus leads to a marked rise (almost twofold) in the value of ΣA;     

Structure of the products of the photoreaction of osthole

The results are given of a study of the photoreaction of osthole in chloroform and acetophenone. It has been shown that when it is irradiated in the latter solvent the cyclization characteristic for coumarins takes place at the double bonds both in the 3,4- position of the coumarin ring and in the side chain, leading to the formation of cyclobutane structures.Leningrad Sanitary-Hygienic Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 165–168, March–April, 1980.     

Investigation of the influence of the polarity of the solvent on the composition of the extractive substances and post-extraction residues of the bark ofAbies sibirica

The chemical compositions of the initial bark of the Siberian firAbies sibirica and of the solid residues after extraction with carbon dioxide, water, and alcohol have been studied. On successive extraction, the yield of extractive substances amounted to 25.05% of the absolutely dry bark. The carbon dioxide, aqueous, and alcoholic extracts obtained have been investigated. The carbon dioxide extract was found to contain 34.97% of essential oil, while only traces of it were detected in the aqueous and alcoholic extracts.Krasnoyarsk State Technological Academy. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 42–45, January–February, 1996. Original article submitted August 14, 1995.     

光亮剂对银电沉积行为的影响

用电势阶跃法和旋转圆盘电极法 (RDE)以及SEM和XRD测试手段 ,初步研究了光亮剂对氰化体系中银电沉积行为的影响 .研究表明 ,光亮剂的加入并未导致银电沉积成核机理的改变 ,但显著增强了镀液的微观平整效应 ,并且所得镀层的表观光滑程度明显改善 .XRD测试亦同时表明光亮剂的加入并未改变镀层的择优取向     

Effect of the pH of the medium on the chemical shifts in the PMR spectra and on the distribution of the π-electron density

The dependence of the chemical shift of the ring protons on the pH of the medium for a number of 3-hydroxyquinoline derivatives was studied by PMR spectroscopy. The regions of ionization of the molecules, which correspond to the ranges of acidic, neutral, and alkaline media, were found. In D₂O, 3-hydroxyquinoline is present only in the uncharged hydroxy form. The presence of intramolecular hydrogen bonding in 4-dimethylaminomethyl-3-hydroxyquinoline has a substantial effect on the character of the dependence of the chemical shift on the pH of the medium; the existence of separate protonation of the nitrogen atoms of the ring and the side chain of 4-dimethylaminomethyl-3-hydroxyquinoline was established. The distribution of the -electron density in the 3-hydroxyquinoline molecule is in good agreement with its chemical behavior during electrophilic substitution.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1540–1545, November, 1971.     

Investigation of the cardiotoxic peptides of the venom of the cobraNaja oxiana

Six populations of basic polypeptides have been found in the venom of the Central Asian cobraNaja oxiana Eichwald, and four of them — V″c-1, V″c-2, V″c-5, and V″c-6 — have been obtained in the electrophoretically homogeneous state. On a perfused frog heart preparation, all the basic polypeptides proved to be cardiotoxic. However, only some of them (V′c-2, V″c-3, and V″c-4) were characterized by arrhythmic activity as well as by the negative ino- and chronotropic effects, common for all of them. An enhancement of the specific cardiotoxic effect of each of the polypeptides by pure phospholipase A-2 has been shown.     

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-ε12,13-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.