Complex conductivity of water-saturated packs of glass beads

The low-frequency conductivity response of water-saturated packs of glass beads reflects a combination of two processes. One process corresponds to the polarization of the mineral/water interface coating the surface of the grains. The other process corresponds to the Maxwell-Wagner polarization associated with accumulation of the electrical charges in the pore space of the composite medium. A model of low-frequency conductivity dispersion is proposed. This model is connected to a triple-layer model of electrochemical processes occurring at the surface of silica. This model accounts for the partition of the counterions between the Stern and the diffuse layers. The polarization of the mineral/water interface is modeled by the electrochemical polarization model of Schurr for a spherical grain. We take into account also the DC surface conductivity contribution of protons of the sorbed water and the contribution of the diffuse layer. At the scale of a macroscopic representative elementary volume of the porous material, the electrochemical polarization of a single grain is convoluted with the grain size distribution of the porous material. Finally, the Maxwell-Wagner polarization is modeled using the complex conductivity of a granular porous medium obtained from the differential effective medium theory. The predictions of this model agree well with experimental data of spectral induced polarization. Two peaks are observed at low frequencies in the spectrum of the phase. The first peak corresponds to the distribution of the size of the beads and the second peak is due to the roughness of the grains.     

Lipids of the oils of the fruit and leaves ofHoppopha? rhamnoides

The analysis of some lipids of four forms of the common sea buckthorn has shown that they all differ with respect to the composition of the fatty acids of the triacylglycerols of the leaves. One of the forms is characterized by an infringement of the specificity of the composition of the fatty acids in positions 2 of the triacylglycerols of the oils of the seeds and the leaves.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. V. L. Komarov Institute of Botany, Academy of Sciences of the Azerbaidzhan SSR, Baku. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 710–715, November–December, 1981.     

Surface tension of the Widom-Rowlinson model

We consider the computation of the surface tension of the fluid-fluid interface for the Widom-Rowlinson [J. Chem. Phys. 52, 1670 (1970)] binary mixture from direct simulation of the inhomogeneous system. We make use of the standard mechanical route, in which the surface tension follows from the computation of the normal and tangential components of the pressure tensor of the system. In addition to the usual approach, which involves simulations of the inhomogeneous system in the canonical ensemble, we also consider the computation of the surface tension in an ensemble where the pressure perpendicular (normal) to the planar interface is kept fixed. Both approaches are seen to provide consistent values of the interfacial tension. The issue of the system-size dependence of the surface tension is addressed. In addition, simulations of the fluid-fluid coexistence properties of the mixture are performed in the semigrand canonical ensemble. Our results are compared with existing data of the Widom-Rowlinson mixture and are also examined in the light of the vapor-liquid equilibrium of the thermodynamically equivalent one-component penetrable sphere model.     

Cathode of a hydrogen-oxygen fuel cell with a solid polymer electrolyte: The effect of the flooding of pores by water on the characteristics of the active layer

A computer model of the active layer of the cathode of a hydrogen-oxygen fuel cell with a solid polymer electrolyte is studied. The active mass of the electrode consists of equidimensional grains of the substrate (agglomerates of carbon particles with platinum particles embedded in them) and a solid polymer electrolyte (Nafion). The flooding by water can be experienced by both the pores in the substrate grains, which facilitate the oxygen penetration into the active layer of the electrode, and the voids between the grains. All possible versions of the flooding of these pores by water are considered. A calculation of the optimum, at a given polarization of the electrode, value of electrochemical activity, the thickness of the active layer, and the weight of platinum is performed. The major parameters of the system are the concentrations of grains of the substrate and solid polymer electrolyte, the size of these grains, the platinum concentration in the substrate grains, the average diameter of pores in the substrate grains, and the polarization of electrodes. The ultimate aim of the work is to estimate how the flooding of pores of the active layer of the cathode by water affects the magnitude of the optimum current, the effective thickness of the active layer, and the weight of platinum.Translated from Elektrokhimiya, Vol. 41, No. 1, 2005, pp. 35–47.Original Russian Text Copyright © 2005 by Chirkov, Rostokin.     

Calculations of the distribution of trace impurities in cylindrical pores

The equilibrium distribution of a trace impurity and the self-diffusion coefficients of molecules of the base component and the trace impurity in narrow cylindrical pores were calculated using the lattice-gas model. Two types of lattice structures with six and eight closest neighbors were considered. The sizes of the base component and impurity molecules were taken to be identical. Lateral interactions were taken into account in the quasi-chemical approximation. The equilibrium distributions of the trace impurity across a pore section in the gas and liquid phases of the base component and at the interface for the case of capillary condensation were considered. The probability of existence of isolated dimeric clusters was estimated and the self-diffusion coefficients of the base component and trace impurity for a single-phase distribution of the base component were calculated. The effects of the energy of interaction of impurities with the pore walls and the concentration of the base component on the diffusion mobility of the impurities were analyzed. The concentration dependences of the partition coefficient for the trace impurity between the pore center and the pore wall and the concentration dependences of the self-diffusion coefficients for the trace impurity molecules become nonmonotonic with an increase in the base component concentration. These effects are due to the displacement of the impurity from the near-surface area to the bulk of a pore following an increase in the pore coverage by the base component and to higher mobility of the impurity in the free bulk of the pore. Further filling of the pore bulk reduces the mobility of all molecules. The energetics of intermolecular interactions also plays a certain role. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 605–615, April, 2000.     

Theoretical conformational analysis of the methylamide of N-acetyl-L-alanyl-L-prolyl-L-alanine. II

Summary 1. Spatial forms of Ac-L-Ala-L-Pro-L-Ala-NHMe with trans peptide bonds are the most preferred. Elongation of the peptide chain promotes the stabilization of the trans configuration of the tertiary amide group.2. In the structure of the compound investigated, the dominating role is played by the interaction of the neighboring residues.3. Of the six types of conformations of X-Pro-Y observed in proteins, the first four belong to the preferred forms of the Ac-L-Ala-L-Pro-L-Ala-NHMe molecule.M. M. Shemyakin Institute of Bioorganic Chemistry, Academy of Science of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 626–630, September–October, 1975.     

脉冲激光溅射下固液界面生长的碳纳米管及其机理初探

以脉冲激光束直接溅射浸在水中的单质碳样品，发现在固液界而也能产生碳纳米管．实验还发现碳纳米管的形成与样品的结构有密切的关联：石墨的层状结构越完整，碳纳米管的形成越容易，而且石墨层而相对于激光束的取向也会显著地影响碳纳米管的生成．通过对实验结果的分析，探讨了激光液相溅射产生碳纳米管的机理，认为激光溅射产生的碳蒸气被水束缚在固液的界而内，而完整的晶而使碳蒸气在界而内的分布具有准二维的性质，为碳纳米管的生长提供了较为理想的环境．     

The role of the phase quasiequilibrium in the reaction system chlorotriorganosilane—water—acetone

On the basis of analysis of product composition in the hydrolytic polycondensation (HPC) of chlorotriorganosilanes, the parameters of the kinetic and the diffusion field, the zone of the reaction, and the region of the conodes of the phase diagrams are determined. It is suggested that the conodes correspond to a phase quasiequilibrium, which defines the composition of the reaction products. The results of this investigation confirm the previously discovered features of HPC of dichloromethylphenylsilanes: the formation of the siloxane bond during the hydrolysis of chloroorganosilanes by water mainly occurs in the organic phase of the system and proceeds as the heterofunctional polycondensation of the reaction products with the starting chloroorganosilanes. The role of the phase quasiequilibrium consists of the creation of a field of reagent concentration, based on which one can control the composition of the reaction products.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1222–1226, July, 1994.     

A study of the conformational states of cyclopeptide systems

Summary 1. An empirical method for the quantitative determination of the number of NH groups of different types in peptides based on measurements of the integral intensity of the amide A bands in the IR spectra has been developed.2. The IR spectra of the diastereomeric cyclohexaalanyls in CHCl₃ solutions have been studied; they indicate the participation of an average of four NH groups in IMBHs.3. On the basis of a theoretical conformational analysis and of dipole-moment measurements, the system of IMHBs and the type of dominant conformation of the cyclohexapeptides in nonpolar solvents have been established.M. M. Shemyakin Institute of the Chemistry of Natural Compounds of the Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 347–357, May–June, 1971.     

Äquidensitometrie: Eine Methode zur Beurteilung der Struktur von Plasmen—Qualitative Beurteilung des Lanthan-Gleichstrombogens durch Äquidensitometrie von monochromatischen Bogenphotographien

A new method has been developed for the experimental characterization of d.c. arc plasmas. The method consists of the combination of the spectral photography of d.c. arc plasmas with a slitless, stigmatic plane-grating spectrograph and the characterization of the photographs with the aid of photographic equidensitometry. The principles of the method are described. The method is used for the investigation of a lanthanum d.c. arc plasma. The qualitative results of the measurements of the axial distributions of the light emission and lanthanum and calcium particle concentrations in the arc are discussed. The limitations and shortcomings of the method are pointed out.     

Phospholipids of seeds of kenaf of the variety "Uzbekskii-1503"

Summary The qualitative and quantitative compositions of the combined phospholipids of the seeds of kenaf of the variety "Uzbekskii-1503" have been determined for the first time.The fatty-acid composition of the combined phospholipids and triglycerides and also of the main and two minor components of the phospholipids have been studied. On the basis of the results of acid hydrolysis and of IR spectroscopy, the glycerophospholipid structures of the main and minor components of the total material have been confirmed. The enzymatic hydrolysis of the main fractions of the total material has been performed: the position distribution of the fatty acids has been determined and from this the possible molecular compositions of the phosphatidylcholines, phosphatidy lethanolamines, and phosphatidy linositols have been calculated. Kenaf seeds can serve as a source of the medicinal preparation phytin.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 485–487, July–August, 1977.     

碳酸钙微粒稳定的橄榄油/水乳液及其缓释性能

1907年,Pickering发现超细固体颗粒对乳液具有一定的稳定作用~([1]).此后,由固体颗粒单独稳定的乳状液也被称为Pickering乳液.Pickering乳液在新材料合成、生物活性分子保护、食品和医药等领域具有重要的应用价值~([2-7]).     

Assignment of the ferriheme resonances of the low-spin complexes of nitrophorins 1 and 4 by (1)H and (13)C NMR spectroscopy: comparison to structural data obtained from X-ray crystallography

In this work we report the assignment of the majority of the ferriheme resonances of low-spin nitrophorins (NP) 1 and 4 and compare them to those of NP2, published previously. It is found that the structure of the ferriheme complexes of NP1 and NP4, in terms of the orientation of the ligand(s), can be determined with good accuracy by NMR techniques in the low-spin forms and that angle plots proposed previously (Shokhirev, N. V.; Walker, F. A. J. Biol. Inorg. Chem. 1998, 3, 581-594) describe the angle of the effective nodal plane of the axial ligands in solution. The effective nodal plane of low-spin NP1, NP4, and NP2 complexes is in all cases of imidazole and histamine complexes quite similar to the average of the His-59 or -57 and the exogenous ligand angles seen in the X-ray crystal structures. For the cyanide complexes of the nitrophorins, however, the effective nodal plane of the axial ligand does not coincide with the actual histidine-imidazole plane orientation. This appears to be a result of the contribution of an additional source of asymmetry, the orientation of one of the zero-ruffling lines of the heme. Probably this effect exists for the imidazole and histamine complexes as well, but because the effect of asymmetry that occurs from planar exogenous axial ligands is much larger than the effect of heme ruffling the effect of the zero-ruffling line can only be detected for the cyanide complexes, where the only ligand plane is that of the proximal histidine. The three-dimensional structures of the three NP-CN complexes, including that of NP2-CN reported herein, confirm the high degree of ruffling of these complexes. There is an equilibrium between the two heme orientations (A and B) that depends on the heme cavity shape and changes somewhat with exogenous axial ligand. The A:B ratio can be much more accurately measured by NMR spectroscopy than by X-ray crystallography.     

Change in the lipid composition of lichens in the spring period

The dynamics of the amount of total lipids, the ratio of the main classes of lipids, the amount of fatty acids, and the ratio of individual phospholipids in three epiphytic species of lichens from the Zhigulevsk reserve have been followed. It has been shown that all the classes of lipids of the lichens change to some degree or other in this period. The dynamics of the fatty acids has also confirmed a known rule: an increase in the amount of saturated and a decrease in the number of unsaturated fatty acids of the membranes with a rise in the temperature of the environment. This is the first time that the dynamics of the hydroxy acids have been followed.Institute of the Ecology of the Volga Basin, Tol'yatti. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 660–664, September–October, 1993.     

Wang-Landau algorithm: a theoretical analysis of the saturation of the error

In this work we present a theoretical analysis of the convergence of the Wang-Landau algorithm [Phys. Rev. Lett. 86, 2050 (2001)] which was introduced years ago to calculate the density of states in statistical models. We study the dynamical behavior of the error in the calculation of the density of states. We conclude that the source of the saturation of the error is due to the decreasing variations of the refinement parameter. To overcome this limitation, we present an analytical treatment in which the refinement parameter is scaled down as a power law instead of exponentially. An extension of the analysis to the N-fold way variation of the method is also discussed.     

Regio- and sterochemistry of the [2+2]-cycloaddition reaction between enones and alkenes. A DFT study

Calculations at DFT/B3LYP/6-31G+(d,p) level of theory have been performed on the photochemical interaction between enones and alkenes. The photochemical reaction of cyclopentenone with ethyl vinyl ether can be explained assuming the reaction occurs through the triplet excited state of the enone. The interaction between the LSOMO of triplet cyclopentenone and the HOMO of ethyl vinyl ether accounts for the observed stereochemistry. The same behaviour has been observed in the reaction of 3-methylcyclohexenone with 1,1-dimethoxyethene, vinyl acetate, and allene. In the reaction of 3,5,5-trimethylcyclohexenone with methyl cyclobutene-1-carboxylate, the observed regiochemistry can be explained assuming a sensitized reaction able to populate the triplet state of methyl cyclobutene-1-carboxylate. The coupling of the HSOMO of this species with the LUMO of the cyclohexenone derivative account for the observed regiochemistry. Furthermore, the coupling of the radical carbon atoms on the biradical intermediate accounts for the observed stereochemistry. In the reaction of 3-methylcyclohexenone with methyl cyclohexene-1-carboxylate the coupling between the LSOMO of triplet state of 3-methylcyclohexenone and the HOMO of the alkene gave two possible biradical intermediates. The most stable one accounts for the observed regiochemistry. The coupling of the radical carbon atom on the HSOMO and LSOMO of the biradical intermediate accounts for the observed stereochemistry. The coupling between the LSOMO of the triplet state of 3-phenylcyclohexenone and the HOMO of cyclopentene accounts for the observed regiochemistry. The stereochemistry can be explained considering the coupling of the LSOMO and HSOMO in the biradical intermediate.     

Clustering chemical databases using adaptable projection cells and MCS similarity values

In this paper we propose a new method based on measurements of the structural similarity for the clustering of chemical databases. The proposed method allows the dynamic adjustment of the size and number of cells or clusters in which the database is classified. Classification is carried out using measurements of structural similarity obtained from the matching of molecular graphs. The classification process is open to the use of different similarity indexes and different measurements of matching. This process consists of the projection of the obtained measures of similarity among the elements of the database in a new space of similarity. The possibility of the dynamic readjustment of the dimension and characteristic of the projection space to adapt to the most favorable conditions of the problem under study and the simplicity and computational efficiency make the proposed method appropriate for its use with medium and large databases. The clustering method increases the performance of the screening processes in chemical databases, facilitating the recovery of chemical compounds that share all or subsets of common substructures to a given pattern. For the realization of the work a database of 498 natural compounds with wide molecular diversity extracted from SPECS and BIOSPECS B.V. free database has been used.     

Hydrohysteretic Phenomena of “Extremely Diluted Solutions” Induced by Mechanical Treatments: A Calorimetric and Conductometric Study at 25 <Superscript>∘</Superscript>C

The purpose of this study was to obtain information about the influence of successive dilutions and succussions (violent shaking) on the structure of water. “Extremely diluted solutions” (EDS) are solutions obtained through the iteration of two processes: 1:100 dilution and succussion. Those two processes are repeated until extreme dilutions are reached, so that the chemical composition of the end solution is identical to that of the solvent. We measured the heats of mixing and the electrical conductivity of basic solutions of such EDS, and compared these results with the analogous heats of mixing and electrical conductivity of the untreated solvent. The measurements were carried out as a function of the age of the samples. We found some relevant exothermic excess heat of mixing, and higher electrical conductivity than those of the untreated solvent, also in function of time. The measurements show a good linear correlation between the two independent physico-chemical quantities, implying a single cause for this behavior of the extremely diluted solutions. The slopes of the linear correlation depend on the age of the EDS. Such a phenomenon could result from a variation of the shape of molecular aggregates that characterize the two different supramolecular structures of the water of different ages. This behavior could provide important support for understanding the nature of the phenomena described herein. A really intriguing phenomenon is the evolution of some physico-chemical properties with time. This hints at a “trigger” effect on the formation of molecular aggregates that result from the succussion procedure. We show that successive dilutions and succussions can permanently alter the physico-chemical properties of the aqueous solvent, the extent of which depends on the age of the samples.     

Torsion potential works in rhodopsin

We investigate the role of protein environment of rhodopsin and the intramolecular interaction of the chromophore in the cis-trans photoisomerization of rhodopsin by means of a newly developed theoretical method. We theoretically produce modified rhodopsins in which a force field of arbitrarily chosen part of the chromophore or the binding pocket of rhodopsin is altered. We compare the equilibrium conformation of the chromophore and the energy stored in the chromophore of modified rhodopsins with those of native rhodopsins. This method is called site-specific force field switch (SFS). We show that this method is most successfully applied to the torsion potential of rhodopsin. Namely, by reducing the twisting force constant of the C11=C12 of 11-cis retinal chromophore of rhodopsin to zero, we found that the equilibrium value of the twisting angle of the C11=C12 bond is twisted in the negative direction down to about -80 degrees. The relaxation energy obtained by this change amounts to an order of 10 kcal/mol. In the case that the twisting force constant of the other double bond is reduced to zero, no such large twisting of the bond happens. From these results we conclude that a certain torsion potential is applied specifically to the C11=C12 bond of the chromophore in the ground state of rhodopsin. This torsion potential facilitates the bond-specific cis-trans photoisomerization of rhodopsin. This kind of the mechanism is consistent with our torsion model proposed by us more than a quarter of century ago. The origin of the torsion potential is analyzed in detail on the basis of the chromophore structure and protein conformation, by applying the SFS method extensively.