Recent developments in polymeric charge transfer complexes

The recent literature on polymeric charge transfer complexes is reviewed with emphasis on the author's own work. After a definition of the area and a survey of investigations on the spatial arrangement of donor and acceptor sites in the solid state, a variety of applications of these complexes is presented. Electrically conductive polymers are excluded. These applications are: compatibilization of polymer blends, liquid crystalline supramolecular organization, new developments in photo-conductivity, electroluminescence, nonlinear optical properties, photorefractivity and reversible optical storage.     

Flaked capillary columns with crown ether complexes for gas-liquid chromatography

Flaked capillary columns with an OV-101/CE-Na{in3}PO{in4} hydrophobic-hydrophilic sorbent have been suggested. This sorbent provides for the analysis of polar and nonpolar substances, including amines and aminoalcohols, in aqueous and organic solvents. The efficiency of new columns was demonstrated for the analysis of 25 organic substances of various classes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2169–2173, December, 1994.The work was financially supported by the Russian Foundation for Basic Research, Project No. 93-03-4969.     

Thermal decomposition of hexamminecobalt(III) chloride

The results of comparative thermal analysis (TG-DTG-DTA-DSC) of the thermal decomposition of hexamminecobalt(III) chloride in air atmosphere are reported. The kinetics and mechanism of the thermal decomposition, the process enthalpy and the variation in specific thermal capacity of the solid product reaction with temperature were determined.     

Metal–Nitrosyl complexes as a source of new vasodilators: Strategies derived from systematic chemistry and nitrosyl ligand reactivity

A series of nitrosyl complexes of empirical formula K_n[M(CN)₅NO], where M = V, Cr, Mn and Co and n = 3, or M = Mo and n = 4, have been prepared which are notional analogues of the widely used vasodilator sodium nitroprusside. Their reactivity towards common nucleophiles (OH^?, NH₂R, NHR₂, HS^? and RS^?), acid and photolysis has been investigated to elucidate the desired properties required of new metal nitrosyls which may have some potential as new non-cyanide-based vasodilators.     

Modeling of drug molecule orientation within a receptor cavity in the BiS algorithm framework

The BiS algorithm is suggested for modeling the drug molecule orientation within a receptor cavity. It is based on the assumption of complementarity of the field created by biologically active compounds and the field of the responsive receptor. The comparison of predicted orientations of various biologically active compounds on the relevant receptors with the data of X-ray structural studies (Protein Data Bank) reveals that the results obtained with this approach surpasses those reported in the literature. The suggested technique made it possible to elucidate the details of the action mechanism of DNA antimetabolites, dihydrofolate reductase inhibitors. The dependence of the activity on the structural parameters of “ligand-receptor” complexes is determined.     

Initiation process of L‐lactide polymerization carried out with zirconium(IV) acetylacetonate

Lactide polymerization using zirconium(IV) acetylacetonate [Zr(acac)₄] as an initiator was investigated. In the reaction between Zr(acac)₄ and the monomer molecule, lactide deprotonation and the release of acetylacetone occurred. The structures of the obtained complexes were analyzed with high‐resolution NMR spectroscopy. A computational method was used to calculate the hypothetical structures. The role of the obtained complexes in the initiation of polymerization and the reaction of chain growth was proposed. The influence of the reaction temperature on the structures of the complexes was investigated. Polylactide chain growth proceeded by an insertion‐coordination mechanism. The polymer chain grew on one ligand, which was formed in advance from a deprotonated lactide. The molecular masses of the obtained polymers were the same as the theoretical masses and were directly proportional to the reaction conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1886–1900, 2004     

meso-四(4-乙酰氧基苯)卟啉-铜(Ⅱ)-乳化剂OP体系荧光熄灭法测定微量铜(Ⅱ)的研究

本文研究了高灵敏的meso-四(4-乙酰氧基苯)卟啉[T(4-AOP)P]-铜(Ⅱ-乳化剂OP体系。在酸度为pH5.0～5.6范围内形成的三元络合物可引起T(4-AOP)P-OP荧光强度的定量熄灭,其Ex=413nm,EM=656.9nm,Cu(Ⅱ)浓度在0～0.150μg/ml范围内有良好的线性关系,回归方程F=25.51-8.45m,试验了14种离子的干扰影响,并用此法测定了小球藻中Cu的含量,回收率达96～104％。     

Manganese(II) complexes with diethylamine in aqueous solutions

Interaction between MnCl₂ and diethylamine (DEA) in aqueous solutions has been studied by UV, IR, and EPR spectroscopy as part of the design and research program on models of natural photosystems. The composition of the precipitate for comparable concentrations of reagents and solute oxygen has been investigated. Mn(II) was found to be oxidized with oxygen to give MnO₂·H₂O as a precipitate. In the solution over the precipitate, Mn(III) complexes with DEA are formed; the complex molecule has four and six amine molecules in the coordination sphere.     

An observation of electron phase transition in SmB6 at low temperatures

In order to reveal the nature of the ground state of archetypal intermediate-valence compound SmB₆, a comprehensive study of its transport and magnetic properties was carried out on high-quality single crystals at temperatures of 1.8-300 K in magnetic fields up to 7 T. A drastic enhancement of negative magnetoresistance was observed below 14 K, with the maximum absolute value of Δρ/ρB²∼2.2×10⁻³ T⁻² at T≈5.2 K. This effect seems to be attributable to anomalous magnetic scattering of many-body (exciton-polaronic) complexes induced by fast valence fluctuations on Sm sites. The observed anomalies of magnetotransport, thermoelectric and magnetic characteristics are discussed in terms of electron phase transition to the coherent state of interacting many-body complexes occurring at T^*∼5 K.     

Chemical Reactivity of Tetrasulfur Tetranitride: Synthesis,Physical Properties,and Structural Characterization of the Amorphous Phase Cu7S4N4

Tetrasulfur tetranitride, S₄N₄, reacts with elemental Cu within inert solvents to a black‐blue material of approximate composition Cu₇S₄N₄ which is totally amorphous to X‐rays and which cannot be made crystalline by either thermal treatment or electron radiation. Cu₇S₄N₄ explodes if heated above 234 °C or when subjected to mechanical shock to eventually yield copper(I) sulfide; this together with the characteristic infrared spectrum of Cu₇S₄N₄ indicates the presence of molecular S₄N₄ units inside the amorphous phase. The metastable nature of Cu₇S₄N₄ is also mirrored by electron microscopy which furthermore allows the structural characterization of its degradation products. Based on experimental EXAFS data offering characteristic Cu—N and Cu—S distances, a theoretical crystalline approximant of Cu₇S₄N₄ was suggested and structurally optimized by density‐functional total‐energy calculations including periodic boundary conditions. This model incorporates a central S₄N₄ unit bonded to three shells of Cu atoms of different functionalities; in addition, a partial rupture of the S₄N₄ unit is likely to allow for a lowering of the total energy of the metastable phase. The latter observation supports the impossibility to make Cu₇S₄N₄ crystallize using ₄N₄ crystallize using whatever kind of measures.