四硫富瓦烯四硫纶桥联金属邻菲啰啉配合物的合成与性质

以2,3,6,7-四(2’-氰乙硫基)四硫富瓦烯为桥配体的前驱物, 合成了标题配合物μ-(ttftt)-[M(phen)]2 (M＝MnII, FeII, CoII, NiII, CuII, ZnII). 配合物的结构和性质经由元素分析、核磁共振波谱、红外光谱、紫外-可见光谱、荧光光谱、摩尔电导率和量子化学计算表征, 研究了电氧化还原和对Li/SOCl2电池的催化特性. 发现铁和钴配合物具有较高的催化活性且有利于电池的大电流和低温放电, 在25 ℃和电流密度25 mA/cm2条件下铁配合物使电池的电压和容量分别提高了133 mV和218 mAh.     

Acrylate ester-based monolithic columns for capillary electrochromatography separation of triacylglycerols in vegetable oils

A simple and reliable method for the evaluation of triacylglycerols (TAGs) in vegetable oils by capillary electrochromatography (CEC) with UV-Vis detection, using octadecyl acrylate (ODA) ester-based monolithic columns, has been developed. The percentages of the porogenic solvents in the polymerization mixture, and the mobile phase composition, were optimized. The optimum monolith was obtained at the following ratios: 40:60% (wt/wt) monomers/porogens, 60:40% (wt/wt) ODA/1,3-butanediol diacrylate and 23:77% (wt/wt) 1,4-butanediol/1-propanol (14 wt% 1,4-butanediol in the polymerization mixture). A satisfactory resolution between TAGs was achieved in less than 12 min with a 65:35 (v/v) acetonitrile/2-propanol mixture containing 5 mM ammonium acetate. The method was applied to the analysis of TAGs of vegetable oil samples. Using linear discriminant analysis of the CEC TAG profiles, the vegetable oils belonging to six different botanical origins (corn, extra virgin olive, hazelnut, peanut, soybean and sunflower) were correctly classified with an excellent resolution among all the categories.     

Effects of oxygen and carbon dioxide plasmas on the surface of poly(ethylene terephthalate)

Poly(ethylene terephthalate) was exposed to oxygen and carbon dioxide plasmas for different periods of time. The surface-modified samples were characterized by infrared spectroscopy, atomic force microscopy, and inverse gas-solid chromatography. The main difference between both types of plasma was connected to the time scale of degradation, which was much faster when using oxygen plasma. Aggregate globular features were produced by different treatments due to chain scission and further recombination of evolved products. Oxygenated functionalities were introduced in significant amounts after long exposure times to the oxygen plasma. As a consequence, the specific component of the surface free energy was clearly observed to increase after these long treatments.     

Synthesis and Crystal Structure of Ni(Ⅱ) Complex with N-Salicylaldehyde-N''''-phenoxyacetylhydrazine Ligand

1INTRODUCTIONHydrazoneshavebeenattractingmuchatten-tionfromchemistsinrecentyearsbecauseoftheirbiologicalactivities,chemicalandindustrialversa-tility,andstrongtendencytochelatetotransitionmetals[1,2],lanthanidemetals[3]andmaingroupmetals[4,5].Inthehydrazonecomplexes,thehydra-zoneligandcanactasaneutralormononegativebidentateligand,orevenasadianionictridentateliganddependingonthedonoratomsoftheligandsandthereactionconditions.Ontheotherhand,variouscompoundsderivedfromphenoxyaceticacidareveryus…     

Quantitative Correlation of Chromatographic Retention and Acute Toxicity for Alkyl（1- phenylsulfonyl） Cycloalkane Carboxylates and Their Structural Parameters by DFT

1 INTRODUCTION Quantitative structure-activity relationship (QSAR)is one of the necessary methods that could be emp- loyed to evaluate the hazards of organic chemicals. QSAR equation could be applied to predict the biological activity of unknown compounds, espe- cially for initial screening and evaluation of toxic compounds[1]. Moreover, the quantitative relation- ship between molecular structure and chromatogra- phic retention (capacity factor lgKW) could also bedeveloped to explain …     

Low-temperature heat capacities and standard molar enthalpy of formation of 4-（2-aminoethyl）-phenol （C8H11NO）

This paper reports that low-temperature heat capacities of 4-（2-aminoethyl）-phenol （C8H11NO） are measured by a precision automated adiabatic calorimeter over the temperature range from 78 to 400 K. A polynomial equation of heat capacities as a function of the temperature was fitted by the least square method. Based on the fitted polynomial, the smoothed heat capacities and thermodynamic functions of the compound relative to the standard reference temperature 298.15K were calculated and tabulated at the interval of 5K. The energy equivalent, εcalor, of the oxygen-bomb combustion calorimeter has been determined from 0.68g of NIST 39i benzoic acid to be εcalor=（14674.69±17.49）J·K^-1. The constant-volume energy of combustion of the compound at T=298.15 K was measured by a precision oxygen-bomb combustion calorimeter to be ΔcU=-（32374.25±12.93）J·g^-1. The standard molar enthalpy of combustion for the compound was calculated to be ΔcHm = -（4445.47 ± 1.77） kJ·mol^-1 according to the definition of enthalpy of combustion and other thermodynamic principles. Finally, the standard molar enthalpy of formation of the compound was derived to be ΔfHm（C8H11NO, s）=-（274.68 ±2.06） kJ·mol^-1, in accordance with Hess law.     

Excited states of boron isoelectronic series from explicitly correlated wave functions

The ground state and some low-lying excited states arising from the 1s2 2s2p2 configuration of the boron isoelectronic series are studied starting from explicitly correlated multideterminant wave functions. One- and two-body densities in position space have been calculated and different expectation values such as , , , , , and , where r, r12, and R stand for the electron-nucleus, interelectronic, and two electron center of mass coordinates, respectively, have been obtained. The energetic ordering of the excited states and the fulfillment of the Hund's rules is analyzed systematically along the isoelectronic series in terms of the electron-electron and electron-nucleus potential energies. The effects of electronic correlations have been systematically studied by comparing the correlated results with the corresponding noncorrelated ones. All the calculations have been done by using the variational Monte Carlo method.     

Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Deltag)]-mediated photoreactions

Thyronine derivatives are essential indicators of thyroid gland diseases in clinical diagnosis and are currently used as standards for developing ordinary biochemical assays. Photooxidation of gland hormones of the thyronine (TN) family and structurally related compounds (TN, 3,5-diiodothyronine,3,3',5-triiodothyronine and 3,3',5,5'-tetraiodothyronine or thyroxine) was studied using rose bengal, eosin and perinaphthenone (PN) as dye sensitizers. Tyrosine (Tyr) and two iodinated derivatives (3-iodotyrosine and 3,5-diiodotyrosine) were also included in the study for comparative purposes. Irradiation of aqueous solutions of substrates containing xanthene dyes with visible light triggers a complex series of competitive interactions, which include the triplet excited state of the dye (3Xdye*) and singlet molecular oxygen [O2(1Deltag)]-mediated and superoxide ion-mediated reactions. Rate constants for interaction with the 3Xdye*, attributed to an electron transfer process, are in the order of 10(8)-10(9) M-1 s-1 depending on the dye and the particular substrate. The photosensitization using PN follows a pure Type-II (O2(1Deltag) mediated) mechanism. The presence of the phenolic group in Tyr, TN and iodinated derivatives dominates the kinetics of photooxidation of these compounds. The reactive rate constants, k(r), and the quotient between reactive and overall rate constants (k(r)/k(t) values, in the range of 0.7-0.06) behave in an opposite fashion compared with the overall rate constants and oxidation potentials. This apparent inconsistency was interpreted on the basis of an internal heavy atom effect, favoring the intersystem-crossing deactivation route within the encounter complex with the concomitant reduction of effective photooxidation.     

1H and 13C spectral assignment of symmetrical bis[(4-aminosubstituted)quinolinium] derivatives

1H and 13C NMR spectroscopic data of both the quinolinium ring and the spacers for 32 symmetrical bisquinolinium compounds were assigned by a combination of one- and two-dimensional experiments (DEPT, HMBC, HMQC). The compounds have electron-releasing groups at position 4 of the quinolinium ring, with several arylalkyl linkers such as the 3,3'-, 4,4'-bis(methylene)biphenyl and 4,4'-bis(methylene)bibenzyl moieties.     

Diversity oriented synthesis of hispanane-like terpene derivatives from (R)-(+)-sclareolide

(R)-(+)-Sclareolide 1 has been used as a starting material to develop a diversity oriented methodology to access hispanane 28 a, and hispanane-like derivatives 27 b-27 e. This methodology is based on the intramolecular Friedel-Crafts acylation of the corresponding 12-desoxylabdanoic-like acids 27, for the construction of the cycloheptane ring which is characteristic of the hispananes. Acids 27 are obtained from alcohols 20, available by addition of the lithium or magnesium reagents to amide 12 (followed by Luche reduction), or to aldehyde 21. This sequence has resulted in the preparation of hispanane framework 27 a. The versatility of this methodology therefore allows a structural diversity oriented synthesis, since it allows the access to a wide variety of hispanane-like derivatives.