Dendrimers Functionalized with Palladium Complexes of N-, N,N-, and N,N,N-Ligands

Pyridine, pyridine imine, and bipyridine imine ligands functionalized by a phenol have been synthesized and characterized, in many cases by X-ray diffraction. Several of these N-, N,N-, and N,N,N,-ligands have been grafted onto the surface of phosphorhydrazone dendrimers, from generation 1 to generation 3. The complexation ability of these monomers and dendrimers towards palladium(II) has been assayed. The corresponding complexes have been either isolated or prepared in situ. In both cases, the monomeric and dendritic complexes have been tested as catalysts in Heck couplings and in Sonogashira couplings. In some cases, a positive dendritic effect has been observed, that is, an increase of the catalytic efficiency proportional to the dendrimer generation.     

Theoretical study of dihydrogen bonds between (XH)2, X = Li, Na, BeH, and MgH, and weak hydrogen bond donors (HCN, HNC, and HCCH)

The dihydrogen-bonded (DHB) complexes formed by (XH)2, with X = Li, Na, BeH, and MgH, with one, two, and four protonic molecules (HCN, HNC, and HCCH) have been studied. These complexes have been compared to those of the XH monomers with the same hydrogen bond donor molecules. The energetic results have been rationalized based on the electrostatic potential of the isolated hydridic systems. The electron density properties have been analyzed within the AIM methodology, both at the bond critical points and the integrated values at the atomic basins. Exponential relationships between several properties calculated at the bond critical points (rho,nabla2rho, lambdai, G, and V) and variation of integrated properties (energy, charge, and volume) vs the DHB distance have been obtained.     

Study of geometry and electronic structure of molecules, cation-radicals, and anion-radicals of nitromethane, dimethylnitramine, and ethyl nitrate

The geometry of cation-radicals and anion-radicals of nitromethane, dimethylnitramine, and ethyl nitrate have been computed by means of modern quantum-chemical methods. Their electron affinities and ionization potentials have been determined. The validity of the results has been confirmed by comparison with the experiment.     

Isolation and stereostructures of citreoviral,citreodiol, and epicitreodiol

Three new metabolites (citreoviral, citreodiol, and epicitreodiol) have been isolated from the mycelium of $\text{Penicillium}$$\text{citreo-viride}$ B.(IFO 6050) and their stereostructures have been elucidated on the basis of their spectral data coupled with some chemical evidence. Furthermore, the absolute configurations of citreodiol and epicitreodiol have been determined by syntheses of the corresponding antipodes starting from L-rhamnose.     

Adsorption Behaviors of L-Histidine and DL-Tryptophan on Cholesterol, Silica, Alumina, and Graphite

The adsorption of L-histidine (L-His) and DL-tryptophan (DL-Trp) on cholesterol, silica, alumina, and graphite surfaces from aqueous solution at pH 9.2 has been studied in the temperature range of 25 to 50 degrees C. The data have been analyzed, wherever applicable, by Langmuir and Hill equations to obtain (1) the monolayer adsorption capacity (x(m)) and the equilibrium constant (k') for the adsorption and desorption processes and (2) the Hill coefficient (n) at different temperatures. The results of adsorption on different kinds of adsorbents have been compared. The energetic parameters for the adsorption process have also been evaluated and compared. Copyright 2001 Academic Press.     

Transition metal chelates: Synthesis,physicochemical, thermal,and biological studies

The transition metal complex of Mn(II), Co(II), Ni(II), Cu(II), Ti(III), Cr(III), Fe(III), Zr(IV), and UO₂(VI) ion with a Schiff’s base ligand derived from 2-hydroxy-[2-oxo-1,2-dihydro-3H-indol-3-ylidene]-benzohydrazide have been prepared. The complexes have been characterized by elemental analysis data, IR and electronic absorption spectra, magnetic moments, and thermogravimetric analysis data. The complexes of the 1: 1 metal-to-ligand stoichiometry have been formed. The physico-chemical data have suggested the octahedral geometry for all the complexes except for Cu(II); the Cu(II) complex has been square planar. Thermal analysis data of the ligand and its complexes have been analyzed, and the kinetic parameters have been determined using the Horowitz–Metzger method. According to the solid-state electrical conductivity measurements, the ligand and its complexes are semiconducting in nature. The antimicrobial activity of the ligand and the complexes towards E. coli, S. typhi, P. aeruginosa, and S. aureus has been tested by the disc diffusion method.     

Preparation,purification, and analysis of alkylated cyclodextrins

Methods of alkylation of α-, β- and γ-cyclodextrins have been optimized with regard to the parameters of reaction, degree of alkylation and yields. The analysis of the reaction mixtures and of the isolated single species has been performed by high temperature GC and HPLC. The phase systems of the preferably applied HPLC have been carefully adjusted by variation of both the stationary and mobile phases to the very different hydrophobicities of the various alkylated CD species which have been synthesized. Several partially or fully alkylated CD species were isolated from preparative scale HPLC separations in high purity.     

Synthesis and Antitubercular,Antimicrobial, and Hemolytic Activity of Methyl D-Glucopyranuronate and Its Simplest Derivatives

Methyl glucuronate and some of its simplest derivatives have been synthesized, and their antitubercular, antimicrobial, and hemolytic activities have been studied. The simplest derivatives of glucuronic acid have been shown for the first time to exhibit a high antitubercular activity which is comparable with the activity of isoniazid.     

Sterols of grapefruit,orange, and mandarin pulps

The composition and percentage distribution of the sterols in preparations of the free (I), glycosylated (II), and esterified (III) sterols in the pulp of citrus fruits have been studied. In the sterol preparations, cholesterol, campesterol, stigmasterol, and β-sitosterol have been identified and detected, and three other sterols have been detected but not identified. It has been established that the sequences of the relative amounts of sterols in preparations (I), (II), and (III) of the grapefruit and the orange are similar and differ from that of mandarin pulp.     

Solvatochromism and piezochromism of dicyano-, tricyano-, and tetracyano-diimine-iron(II) complexes

The solvatochromism of several dicyano-bis-diimine-iron(II) complexes in various binary aqueous solvent mixtures has been established, at 25 °C. A solvent sensitivity scale has been developed for these complexes. The solvatochromic properties of two tricyano-terdentate ligand iron(II) complexes in several solvents have also been determined, as have those of a series of tetracyano-diimine complexes in DMSO–water media. These results have been analysed and systematic but varied trends of solvation were demonstrated. Piezochromic parameters for two complexes have been obtained and are discussed in the context of a solvatochromism/piezochromism correlation.     

Water tetramer, pentamer, and hexamer in inert matrices

The infrared spectrum of water, isolated in inert matrices, has been studied in the interval from 60 to 4000 cm(-1). Experiments with partially deuterated water combined with DFT (density functional theory) calculations have been used to investigate the structure of matrix-isolated water tetramer. A few, strong intermolecular fundamentals of the water tetramer have been observed. Mid-infrared bands due to deuterated pentamers and hexamers have been observed and are used to discuss the assignments of these water clusters.     

Synthesis and characterization of monomers and polymers of acrylated phosphonate esters derived from glycerol,D-mannitol,D-sorbitol,pentaerythritol, and dipentaerythritol

Phosphonic acid ester derivatives of glycerol, D -mannitol, D -sorbitol, pentaerythritol, and dipentaerythritol have been synthesized by transacetalation reactions with diethyl 2,2-diethoxyethylphosphonate. These phosphonated derivatives of polyols and carbohydrates have been esterified to from the corresponding methacrylates. All these compounds have been characterized on the basis of their elemental analysis and spectroscopic (infrared including FT–IR, ¹H-, ¹³C-, ³¹P-NMR, and mass) methods. Transacetalation reactions with dialkyl 2,2-dialkoxyethylphosphonate lead to the synthesis of 1,3-dioxane derivatives in the case of D -mannitol, pentaerythritol, and dipentaerythritol, whereas a mixture of both 1,3-dioxane and 1,3-dioxolane derivatives is obtained with D -sorbitol and glycerol. The methacrylates of phosphonylated polyol derivatives show the capacity to dissolve and interact with metal salts such as bismuth bromide and uranyl nitrate. Some of the polymers obtained from these monomers have been characterized on the basis of their spectral and thermal (differential scanning calorimetry) properties.     

Synthesis,Spectral, and Coordination Properties of Halogen-Substituted Tetraarylporphyrins

2,3,7,8,12,13,17,18-Ocatbromo-5,10,15,20-tetra-(4-chloroprienyl)porphyrin and 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetra-(4-bromophenyl)porphyrin have been synthesized. The obtained compounds have been identified by electronic absorption and ¹H NMR spectroscopy as well as mass spectrometry. The complex-forming properties of the synthesized porphyrins in the zinc acetate (II)-acetonitrile system at 278–298 K have been studied. Kinetic parameters of the formation of the corresponding zinc complexes in acetonitrile have been determined.

     

Standard molar enthalpies,volumes, and heat capacities of adamantane in cyclohexane,n-hexane,and carbon tetrachloride. Interpretation using the scaled-particle theory

The volumes, heat capacities, and enthalpies of solution of adamantane in cycloxane,n-hexane, and carbon tetrachloride have been measured as a function of concentration at 25°C (15, 25, and 35°C for the volumes). The results extrapolated to infinite dilution have been resolved into cavity formation and interaction terms. The former have been calculated from the equations of the scaled-particle theory. To estimate the contribution from the latter, we have assumed some proportionality between adamantane-solvent and cyclohexane-solvent interactions. This assumption has been verified with the three different solvents for the three studied thermodynamic functions. The diameter of adamantane in solution has been determined to be 6.36 Å.     

Synthesis, FTIR, FT-Raman, UV-visible, ab initio and DFT studies on benzohydrazide

A systematic vibrational spectroscopic assignment and analysis of benzohydrazide (BH) has been carried out by using FTIR and FT-Raman spectral data. The vibrational analysis were aided by electronic structure calculations--ab initio (RHF) and hybrid density functional methods (B3LYP and B3PW91) performed with 6-31G(d,p) and 6-311++G(d,p) basis sets. Molecular equilibrium geometries, electronic energies, IR intensities, harmonic vibrational frequencies, depolarization ratios and Raman activities have been computed. Potential energy distribution (PED) and normal mode analysis have also been performed. The assignments proposed based on the experimental IR and Raman spectra have been reviewed and complete assignment of the observed spectra have been proposed. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO and LUMO energies and λ(max) were determined by time-dependent DFT (TD-DFT) method. The geometrical, thermodynamical parameters and absorption wavelengths were compared with the experimental data. The interactions of carbonyl and hydrazide groups on the benzene ring skeletal modes were investigated.     

Infrared, and Raman spectra, conformational stability, normal coordinate analysis, ab initio calculations, and vibrational assignment of 1-chlorosilacyclobutane

The infrared spectra (3500–40 cm⁻¹) of gaseous and solid and the Raman spectra (3500–30 cm⁻¹) of liquid and solid 1-chlorosilacyclobutane, c-C₃H₆SiClH, have been obtained. Both the axial and equatorial conformers with respect to the chlorine atom have been identified in the fluid phases. Variable temperature (−105 to −150°C) studies of the infrared spectra of the sample dissolved in liquid krypton have been carried out. From these data, the enthalpy difference has been determined to be 211±17 cm⁻¹ (2.53±0.21 kJ/mol), with the equatorial conformer being the more stable form and the only conformer remaining in the annealed solid. At ambient temperatures, approximately 26% of the axial conformers are present in the vapor phase. A complete vibrational assignment is proposed for the equatorial conformer, and many of the fundamentals of the axial conformers have also been identified. The vibrational assignments are supported by normal coordinate calculations utilizing ab initio force constants. Complete equilibrium geometries, conformational stabilities, harmonic force fields, infrared intensities, Raman activities, and depolarization ratios have been determined for both rotamers by ab initio calculations employing the 6-31G(d) basis set at the levels of restricted Hartree–Fock (RHF) and/or Moller–Plesset (MP) to second order. Structural parameters have also been obtained using MP2/6-311+G(d,p) ab initio calculations. The r₀ parameters for both conformers are obtained from a combination of the ab initio predicted values and the twelve previously reported microwave rotational constants. The results are discussed and compared to those obtained for some similar molecules.     

Major,trace, and natural radioactive elements in bituminous coal from Australia,Romania, Russia,South Africa and Ukraine: A comparative study

Summary Five samples of bituminous coal collected from different basins (Australia, Romania, Russia, South Africa and Ukraine) have been investigated by using different analytical techniques. Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Mo, Sn, In, Sb, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Lu, Hf, Ta, W, Hg, Th and U have been determined by neutron activation analysis, ⁴⁰K, ²³⁸U, ²³⁵U and ²³² Th have been measured radiometricaly, H, C, O, N, and S have been dosed by dynamic flash combustion, while gravimetric methods have been used to measure moisture and ash content together with calorific power. Major mineralogical fractions have been investigated by means of X-ray diffraction. The results have shown significant positive correlations between radiometric and activation analysis results, between calorific power and carbon, nitrogen and hydrogen concentrations and negative significant correlations between calorific power and ash content. According to the Romanian Regulations, only Cr and Ni for Romanian coal exceeded the minimum threshold to be considered unpolluting elements. The distribution of rare earth elements, La to Th ratio, as well as of Sc, La and Th together with Co, Hf and Th have confirmed that, irrespective of sample sources, the mineral part of coal has a composition close to that of the upper continental crust.     

Alkaloids ofNitraria komarovii. X. Structures of tetrahydronitramarine,tetrahydrokomarovinine, dihydroisokomarovine,and tetrahydroisokomarovine

The alkaloid nitraraine and four new bases have been isolated for the first time from the epigeal part ofNitraria komarovii. Their structures have been established with the aid of chemical transformations and spectral characteristics: tetrahydronitramarine, tetrahydrokomarovinine, dihydroisokomarovine, and tetrahydroisokomarovine. Passages have been effected to nitramarine, komarovinine, isokomarovinine, and komarovidinine. Tetrahydroisokomarovine is a new alkaloid, while this is the first time that tetrahydronitroamarine, tetrahydrokomarovinine, and dihydroisokomarovine have been found in nature. Nitrarine, isonitrarine, and schoberidine have been isolated from the seeds with fruit.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 61–67, January–February, 1990.     

磷烯的制备、结构、性质及器件应用

磷烯是继石墨烯之后一种新型的二维材料,具有优异的物理、化学和机械性能,在各类器件中具有大的应用潜力。目前对磷烯的最新制备方法、特性调控和应用的系统总结较少。本文对磷烯的制备、结构、性质、改性方法及其器件应用进行了系统的综述。首先概括了磷烯"自上而下"和"自下而上"的制备方法,对其结构和性质进行了总结,同时讨论了磷烯的修饰改性方法,最后对磷烯的器件应用进行了较详细的介绍,并在此基础上对磷烯的研究方向和前景进行了展望。     

Heavy oil as an emulsion: Composition,structure, and rheological properties

Recent works devoted to studying the structure and rheological properties of water/oil disperse systems have been reviewed. Contemporary understandings of crude heavy oil as a water-in-oil emulsion have been discussed. Data on the mechanism of the stabilizing effect of natural lipophilic surfactants and ultradispersed particles of different natures contained in oil have been presented. Methods that are used to improve the transport characteristics of heavy oil—in particular, the formation of low-viscosity oil-in-water emulsions—have been listed. Colloidal and rheological properties of heavy oil-in-water emulsions, which are increasingly applied for pipeline transportation of oil, have been considered.