Influence of the Position of the Connecting Spacer of the Chromophore on the Nonlinear Optical Response

A new chromophore, C1 , based on a similar DπA‐structure as in the FTC ‐chromophore but with a hydroxyalkyl spacer perpendicular to the direction of the dipole moment was synthesized. Both chromophores and the CLD ‐chromophore were used to prepare high T_g nonlinear optical vinyl polymers. The influence of the position of the spacer on the DπA‐system on the NLO response of the resulting polymers was investigated.

     

An improvement of the resolution of the identity approximation for the formation of the Coulomb matrix

A straightforward modification of the resolution of the identity (RI) approximation to the Coulomb interaction is described. In the limit of basis sets that are dominated by high angular momentum functions the observed speedups in realistic test systems reach a factor of 2 compared to the standard RI algorithm, and a factor of up to 300 compared to the standard algorithm to form the Coulomb matrix. More moderate savings on the order of 0-20% are obtained for the more commonly used smaller basis sets. A series of test calculations is reported to illustrate the efficiency of the algorithm.     

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     

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.     

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.     

Study of the influence of the graphite powder particle size on the structure of the Sonogel-Carbon materials

In this paper, the influence of carbon particles size on structure and on electrochemical and physical properties of the Sonogel-Carbon electrodes, with respect to Sonogel materials without graphite, have been studied. The materials have been characterized electrochemical and structurally; several Sonogel-Carbon materials were synthesized using different types of graphite powder as massive modifiers, adding in some cases other modifiers, such as octadecyl (C18) and polyethyleneglycol (PEG). Differential pulse voltammetry and cyclic voltammetry were the voltammetric techniques employed to evaluate the electrochemical behaviour; Scanning Electron Microscopy, Energy Dispersive Spectroscopy and Infrared Spectroscopy were the techniques employed to realize the superficial/structural characterization of the materials. The results obtained in both studies were very useful to explain the structure of the Sonogel-Carbon materials. Furthermore, they allowed to conclude that electrodes based on RW-B and UF graphites show very similar electrochemical behaviours and internal structures.     

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.     

Synthesis of the Stereoisomers of the Sex Pheromones of the Southern Corn Rootworm

ＩｎｔｒｏｄｕｃｔｉｏｎＣｈｉｒａｌｉｔｙｄｕｅｔｏｍｅｔｈｙｌｂｒａｎｃｈｉｎｇｉｓａｂｕｎｄａｎｔａｍｏｎｇｓｅｖｅｒａｌｎａｔｕｒａｌｌｙｏｃｃｕｒｉｎｇｓｅｃｏｎｄａｒｙｍｅｔａｂｏｌｉｔｅｓ.Ｔｈｉｓｓｔｒｕｃｔｕｒａｌｆｅａｔｕｒｅｉｓｐａｒｔｉｃｕｌａｒｌｙｐｒｅｄｏｍｉｎａｎｔａｍｏｎｇｉｎｓｅｃｔｐｈｅｒｏｍｏｎｅｓ[1] ,ｍａｎｙｏｆｗｈｉｃｈａｒｅｏｆｅｃｏｎｏｍｉｃｓｉｇｎｉｆｉｃａｎｃｅ .Ａｓａｃｏｎｓｅｑｕｅｎｃｅ ,ａｃｏｎｓｉｄｅｒａｂｌｅｅｆｆｏｒｔｈａｓｂｅｅｎｍａ…     

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.     

Contributions to the Chemistry of the Binary Compounds of the Transition Elements

Phase and structural relationships of the sulfur, selenium, and tellurium compounds of the 4d and 5d transition elements of groups IV to VII of the periodic system are discussed. Homologous elements behave very similarly with respect to the chalcogens, and this is particularly the case for niobium and tantalum, and for molybdenum and tungsten. However, zirconium, niobium, and molybdenum have a greater tendency towards formation of chalcogen-poor phases than their homologues hafnium, tantalum, and tungsten. Subchalcogenides are known only for zirconium and niobium. The number of phases and the tendency towards formation of solid solutions are considerably smaller among the tellurides than among the sulfides and selenides. The crystal structures of the telluride phases also differ from those of the sulfide and selenide phases of analogous composition. In addition, a review of the phase and structural relationships of the arsenic and antimony compounds of the 4d and 5d transition elements of groups V to VII is given.     

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.     

On the mechanism of the formation of ozonides of the alkali metals

Conclusions A mechanism of the formation of ozonides of alkali metals was proposed on the basis of data obtained in an investigation of the reaction of oxygen-labeled KOH with ozone, the reaction of KOH with atomic oxygen, and the reaction of KOH with ozone; this mechanism is based upon: the catalytic decomposition of ozone on the surface of the solid alkalies into molecular and atomic oxygen, the interaction of the latter with the hydroxide, forming a superperoxide, and an interaction of the superperoxide with ozone, forming the ozonide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1183–1187, June, 1967.     

Synthesis of the amide of the C-terminal tetrapeptide of the sequence of oxytocin

The synthesis has been effected of the amide of the tetrapeptide forming the sequence 6–9 of oxytocin with the use of benzyl protection of the thiol function of cysteine by two main schemes 1+3 and 2+2. The advantageousness of performing the synthesis by the 2+2 scheme has been shown. The overall yield of tetrapeptide using the method of condensation with the formation of mixed anhydrides amounted to 51% by the scheme proposed.All-Union Scientific-Research Institute of the Technology of Blood Substitutes and Hormone Preparations, Moscow. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 393–400, May–August, 1992.     

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.     

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.     

The dynamics of the accumulation of the alkaloids of the genus Ungernia

Summary A study ofU. victoris, U. tadshicorum, andU. trisphaera with respect to the vegetation periods and growth sites has shown that the maximum accumulation of alkaloids takes place in the early vegetation period and that naturally dried leaves do not contain alkaloids. The alkaloid content also depends on the growth site.In the period of the vigorous development of the epigeal part, some alkaloids are possibly converted into one another (hippeastrine into lycorine, galanthamine into narwedine, and narwedine into galanthamine).Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 60–64, January, 1971.     

Importance of the catalytic effect of the substrate in the functionality of lubricant additives: the case of molybdenum dithiocarbamates

Molybdenum dithiocarbamates (MoDTCs) are lubricant additives very efficient in reducing the friction of steel, and they are used in a number of industrial applications. The functionality of these additives is ruled by the chemical interactions occurring at the buried sliding interface, which are of key importance for the improvement of the lubrication performance. Yet, these tribochemical processes are very difficult to monitor in real time. Ab initio molecular dynamics simulations are the ideal tool to shed light on such a complicated reactivity. In this work, we perform ab initio simulations, both in static and tribological conditions, to understand the effect of surface oxidation on the tribochemical reactivity of MoDTC, and we find that when the surfaces are covered by oxygen, the first dissociative steps of the additives are significantly hindered. Our preliminary tribological tests on oxidized steel discs support these results. Bare metallic surfaces are necessary for a stable adsorption of the additives, their quick decomposition, and the formation of a durable MoS₂ tribolayer. This work demonstrates the importance of the catalytic role of the substrate and confirms the full capability of the computational protocol in the pursuit of materials and compounds more efficient in reducing friction.     

Ecotoxicity of the Adipate Plasticizers: Influence of the Structure of the Alcohol Substituent

A significant increase in the production of plastic materials and the expansion of their areas of application contributed to the accumulation of a large amount of waste of polymeric materials. Most of the polymer composition is made up of plasticizers. Phthalate plasticizers have been recognized as potentially hazardous to humans and the environment due to the long period of their biodegradation and the formation of persistent toxic metabolites. It is known that the industrial plasticizer dioctyl adipate is characterized by reduced toxicity and a short biodegradation period. The paper describes the synthesis of a number of new asymmetric esters based on adipic acid and ethoxylated butanol by azeotropic esterification. The receipt of the products was confirmed by IR spectra. The physicochemical properties of the synthesized compounds were investigated. The glass transition temperatures of PVC composites plasticized with alkyl butoxyethyl adipates were determined using DSC analysis. The ecological safety of esters was assessed by the phytotesting method. Samples of adipates were tested for fungal resistance, and the process of their biodegradation in soil was also studied. It is shown that the synthesized esters have good plasticizing properties and are environmentally safe. When utilized under natural conditions, they can serve as a potential source of carbon for soil microorganisms and do not form stable toxic metabolites; therefore, they are not able to accumulate in nature; when the plasticizers under study are disposed of in the soil, toxic substances do not enter.     

Composition of the complex of biopolymers of the cell walls of the grape

The complex of high-molecular-weight substances of the cell walls of the grape has been studied. It has been shown that the complex contains polysaccharides, proteins, and phenolic substances presumably linked through O-glycosidic bonds."Magarach" Scientific-Research Institute of Wine-Making and Wine-Growing, Yalta, M. V. Frunze Simferopol' State University, Khimiya Prirodnykh Soedinenii, No. 5, pp. 564–567, September–October, 1984.