Synthesis and structures of new compounds based on tetrahedral rhenium chalcocyanide cluster anions [Re4Q4(CN)12]4− (Q = S or Se) and [Cu(bipy)2]2+ cations

The reactions of the rhenium chalcocyanide cluster salts K₄[Re₄Q₄(CN)₁₂]·6H₂O (Q = S or Se) with Cu²⁺ cations coordinated by the bidentate ligand 2,2′-bipyridyl (bipy) produced two new cluster compounds, [Cu(NH₃)(bipy)₂]₂[Re₄S₄(CN)₁₂]·bipy·3.25H₂O (1) and [{Cu(bipy)₂}₂Re₄Se₄(CN)₁₂]·bipy·8.5H₂O (2). The structures of these complexes were solved by X-ray diffraction. Compound 1 is ionic. Compound 2 is molecular. In the structures of both compounds, there are staking interactions between the {Cu(bipy)₂}²⁺ cationic moieties and the solvate 2,2′-bipyridyl molecules. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1875–1878, November, 2006.     

Chloride substitution of [CpRu(dppf)Cl] with sulfur-containing ligands

The reactions of CpRu(dppf)Cl (1) with the sulfur-containing ligands, thiophenol HSPh, 2-mercaptopyridine C₅H₄N(SH), thiourea SC(NH₂)₂, vinylene trithiocarbonate SCS(CH)₂S and ethylene trithiocarbonate SCS(CH₂)₂S, yielded chloro-substituted derivatives, viz. the mono-ruthenium(II) complexes CpRu(dppf)(SPh) (2), [CpRu(dppf)(SC₅H₄NH)]BPh₄ (3)BPh₄, [CpRu(dppf)(SC(NH₂)₂]PF₆ (4)PF₆, [CpRu(dppf)(SCS(CH)₂S)]Cl (5)Cl and [CpRu(dppf)(SCS(CH₂)₂S)]Cl (6)Cl, respectively. Treatment of 1 with AuCl(SMe₂) in the presence of NH₄PF₆ gave [(CpRu(dppf)(SMe₂)]PF₆ (7)PF₆. The reaction of 1 or 6 with SnCl₂ resulted in cleavage of chloro and dithiocarbonate ligands, respectively, to give CpRu(dppf)SnCl₃ (8). All complexes were spectroscopically characterized and the structures of 2 and cationic complexes 4-7 were determined by single-crystal diffraction analyses.     

Fully aromatic liquid crystalline homopolyesters and copolyesters of 1,1′-binaphthyl-4,4′-diol

A series of fully aromatic, thermotropic polyesters based on 1,1′-binaphthyl-4,4′-diol, BND, was prepared by the melt polycondensation method and characterized for their thermotropic behavior by a variety of experimental techniques. The homopolymer of BND with terephthalic acid formed a nematic melt at 353°C. In contrast, the polyester from BND and 2,6-naphthalenedicarboxylic acid had a melting transition, T_m, above 400°C, so it was not possible with the equipment available to determine whether it formed a nematic melt. All of the copolymers of BND formed nematic melts at much lower T_m values than those of its respective homopolymers, as expected, because of the copolymerization effect of the added monomer. Moreover, all of the copolymers had higher glass transition temperatures, T_g, than those of other liquid crystalline polyesters and higher thermal stabilities. © 1994 John Wiley & Sons, Inc.     

Synthesis of 1,1-dihydroperfluorooxaalkan-1-ols and their interaction with terephthaloyl chloride

A series of 1,1-dihydroperfluorooxaalkan-1-ols and ,,,-tetrahydroperfluorooxaalkanediols has been synthesized. Some tercphthalates were synthesized by the reaction of these alcohols and diols with terephthaloyl chloride.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1573–1576, June, 1996.     

Antioxidant activity and Neurite outgrowth-enhancing activity of scorbamic acid and a red pigment derived from ascorbic acid

Abstract

L-Ascorbic acid (AA), known as vitamin C, can form browning products by a non-enzymatic process during storage and the browning products cause deterioration of agricultural products. In the browning reaction, a red pigment, 2,2´-nitrilodi-2(2´)-deoxy-L-ascorbic acid ammonium salt (NDA), is generated from AA via L-scorbamic acid (SCA) as an intermediate. However, the biological activities of SCA and NDA have not yet been clarified. In this study, we assayed the antioxidant activities of SCA and NDA using ABTS radical cation and their neurite outgrowth-enhancing activities in PC12 cells. SCA showed stronger radical-scavenging activity than that of AA, while NDA hardly showed any activity. SCA and NDA enhanced the neurite outgrowth induced by dibutyryl cyclic AMP after their incorporation into cells in the same manner as that of AA. The results indicated that SCA has antioxidant activity and that SCA and NDA have neurite outgrowth-enhancing activity.     

含轴手性磺酸配体的镉配合物(英)

The crystal structure of [Cd(BDA)(phen)₂(H₂O)](H₂O)₂ (1) (BDA=6,6′-dibromo-2,2′-dimethoxy-1,1′-binaphthylene-4,4′-disulfonate, phen=1,10-phenanthroline)consists of a cadmium center whose coordination environment can be best described as a slightly distorted octahedron defined four nitrogen atoms from two phen ligands and two oxygen atoms differently from BDA ligand and water. There are strong hydrogen-bonding interactions between water and sulfonate group of BDA ligands to construct the 3D network. CCDC: 277921.     

Investigation on the thermal degradation of acrylic polymers with fluorinated side-chains

The thermal degradation of poly-2,2′,3,3′,4,4′,5,5′,6,6′,7,7′,7″-tridecafluoroheptylacrylate and poly-2,2′,3,3′,4,4′,5,5′,6,6′,7,7′-dodecafluoroheptylmethacrylate has been studied in isothermal conditions at 450-750 °C using pyrolysis-gas chromatography. The type and composition of the pyrolysis products give useful information about mechanism of thermal degradation. It was shown that the main thermal degradation process for both polymers is random main-chain scission. The major degradation products for fluorinated polyacrylate are monomer, dimer, saturated diester, trimer, and corresponding methacrylate. The fluorinated polymethacrylate gives monomer as the main product of thermal destruction. As a result of side-chain reaction, the thermal degradation of the fluorinated polyacrylate also produces remarkable amounts of alcohol. On the other hand, the respective alcohol is only a minor component among the pyrolysis products of the fluorinated polymethacrylate. For both polymers, the main nontrivial degradation product coming from the alkyl ester decomposition is the corresponding fluorinated cyclohexane. The formation of the fluorinated cyclohexanes may be accounted for a nucleophilic bimolecular substitution pathway.     

Rearrangement ofO-perfluoroisobutenylacetone oxime. The structure of 2,2-bis(trifluoromethyl)-5-methyl-gD4-pyrrolin-3-one

Dehydrofluorination ofO-(-hydroperfluoroisobutyl)acetone oxime affords 2,2-bis(tri-fluoromethyl)-5-methyl-⁴-pyrrolin-3-one; the molecular structure of the latter was unambiguously established by X-ray diffraction method.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 951–953, May, 1994.     

Influence of extractions on physicochemical characterization and bioactivity of Piper nigrum oils: Study on the non-isothermal decomposition kinetic

Black pepper oils have been investigated frequently in the recent years. However, there is a significant variation in physicochemical properties and bioactivity of oils depended on extraction techniques. In this study, the systemic investigation of four various extraction methods was performed to evaluate the physicochemical characterizations, antioxidant and antibacterial activity. The investigation of ¹H NMR, FTIR and UV–Vis spectra confirmed presence of non-volatile components in oils extracted through supercritical CO₂ and hexane-soaking extractions which induced their typical thermal properties. The isothermal behaviour of extracted oils related to evaporation was within range of 3.2–7.3% (w/w) at 27 °C. The SEM images of the black pepper confirmed different operation manners of mechanism between extractions using the solvents and heating process. The lowest MIC for both essential oils from conventional hidrodistillation and microwave-assisted hidrodistillation against two bacteria including E. coli and B. subtilis were found to be 137 µg mL⁻¹. The non-isothermal decomposition kinetics were investigated on the essential oil of microwave-assisted hydrodistillation extraction. The activation energies and pre-exponent factors of non-isothermal decomposition were found to be in range of 36.5–73.7 KJ mol⁻¹ and 4.98 × 10³–1.97 × 10⁸ s⁻¹, respectively, dependent on conversional fractions of the oil. The results revealed that chemical components, physicochemical properties and bioactivity of black pepper essential oils depended on the extraction techniques.