ELECTRONIC-STRUCTURES OF THE ALKALI-CONTAINING BUCKMINSTERFULLERENES (A-DELTA-C60) (A=LI,NA,K,RB,CS) AND THE HALOGEN-CONTAINING BUCKMINSTERFULLERENES (H-DELTA-C60) (H=F,CL,BR,I)

The geometrical parameters and electronic structures of C60, (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl, Br, I) have been calculated by the EHMO/ASED (atom superposition and electron delocalization) method. When putting a central atom into the C60 cage, the frontier and subfrontier orbitals of (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl) relative to those of C60 undergo little change and thus, from the viewpoint of charge transfer, A (A = Li, Na, K, Rb, Cs) and H (H = F, Cl) are simply electron donors and acceptors for the C60 cage resPeCtively. Br is an electron acceptor but it does influence the frontier and subfrontier MOs for the C60 cage, and although there is no charge transfer between I and the C60 cage, the frontier and subfrontier MOs for the C60 cage are obviously influenced by I. The stabilities DELTAE(X) (DELTAE(X) = (E(X) + E(C60)) - E(x partial derivative C60)) follow the sequence I < Br < None < Cl < F < Li < Na < K < Rb < Cs while the cage radii r follow the inverse sequence. The stability order and the cage radii order have been explained by means of the (exp-6-1) potential.

PROMOTER EFFECT OF HALOGEN ANIONS ON THE DIRECT ELECTROCHEMICAL REACTION OF CYTOCHROME-C AT GOLD ELECTRODES

The promoter effect of halogen anions for heterogeneous electron transfer between cytochrome c and a gold electrode was studied. It was found that the order of the promoter ability of halogen anions is I- > Br- > Cl- > F-. In addition, factors which can affect the promoter effect were discussed.

Quantitative structure-property relationship study on reductive dehalogenation of selected halogenated aliphatic hydrocarbons in sediment slurries

In this study, by the use of partial least squares (PLS) method and 26 quantum chemical descriptors computed by PM3 Hamiltonian, a quantitative structure-property relationship (QSPR) model was developed for reductive dehalogenation rate constants of 13 halogenated aliphatic compounds in sediment slurry under anaerobic conditions. The model can be used to explain the dehalogenation mechanism. Halogenated aliphatic compounds with great energy of the lowest unoccupied molecular orbital (E-lumo), total energy (TE), electronic energy (EE), the smallest bond order of the carbon-halogen bonds (BO) and the most positive net atomic charges on an atom of the molecule (q(+)) values tend to be reductively dehalogenated slow, whereas halogenated aliphatic compounds with high values of molecular weight (Mw), average molecular polarizability (a) and core-core repulsion energy (CCR) values tend to be reductively dehalogenated fastest. (C) 2001 Published by Elsevier Science Ltd.

辐射交联低烟无卤阻燃材料的研究

聚合物材料以其优异的电绝缘性能而广泛地用作电气绝缘材料。但聚合物材料易燃的缺点促使人们不断地对其进行阻燃性的研究，这种研究过程从添加卤素阻燃剂到非卤素化阻燃逐步完善。本文在阐述了聚合物材料燃烧特性及机理的基础上，介绍了几种常用的无卤阻燃剂的阻燃机理，并对氢氧化铝、氢氧化镁和红磷等应用于聚烯烃复合体系的阻燃性进行了实验研究。结果表明：氢氧化镁的阻燃性优于氢氧化铝，它们达到较好的阻燃效果时的添加量一般为120-150phr。氢氧化镁与红磷复配使用在添加量为90phr时，氧指数为40，阻燃性能十分优秀。材料具有良好的阻燃性能。但与此同时材料的机械性能、电性能及加工性能等都将受到一定程度的破坏。经过选用偶联剂及进行辐射交联改性， 材料的机械性能令人满意。交联度及电气性能的实验。最终得到符合九五科技攻关项目“辐射交联低烟无卤阻燃电线电缆的研究”的预期目标。

辐射交联无卤阻燃绝缘材料的研究

聚合物材料以其优异的电绝缘性能而广泛地用作电气绝缘材料。但聚合物材料易燃的缺点促使人们不断地对其进行阻燃性的研究，这种研究过程从添加卤素阻燃剂到非卤素化阻燃逐步完善。本文在阐述了聚合物材料燃烧特性及机理的基础上，介绍了几种常用的无卤阻燃剂的阻燃机理，并对氢氧化铝、氢氧化镁、红磷及膨胀型阻燃剂等应用于聚乙烯的阻燃进行了实验研究。结果表明：氢氧化铝和氢氧化镁在高添加量时（>150%）,材料具有良好的阻燃性能，但与此同时材料的机械性能、电性能及加工性能等都将受到一定程度的破坏；氢氧化铝和氢氧化镁混合使用时具有协同效应，红磷和氢氧化铝混合使用也具有很好的协同效果；膨胀型阻燃剂（IFR）以较少的添加量（约20%）可使聚乙烯（PE）/乙烯-醋酸乙烯酯（EVA）共混物获得较好的阻燃性能（OI为28），但由于IFR的颗粒太大导致材料的机械性能损失很大，另外材料燃烧时发烟量高及滴流现象还无法解决。 辐射交联技术广泛应用于聚合物材料的改性处理。本文阐述了聚合物辐射交联的一些规律，并研究了电子束辐照PE/EVA时辐照剂量对材料的机械性能、电学性能、凝胶含量及耐老化性能的影响，得出材料的最佳辐照剂量范围为80-120KGy。

Chemisorption and reaction characteristics of methyl radicals on Cu(110)

Methyl radicals are generated by pyrolysis of azomethane, and the condition for achieving neat adsorption on Cu(110) is described for studying their chemisorption and reaction characteristics. The radical-surface system is examined by X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, temperature-programmed desorption, low-energy electron diffraction (LEED), and high-resolution electron energy loss spectroscopy under ultrahigh vacuum conditions. It is observed that a small fraction of impinging CH3 radicals decompose into methylene possibly on surface defect sites. This type of CH2 radical has no apparent effect on CH3(ads) surface chemistry initiated by dehydrogenation to form active CH2(ads) followed by chain reactions to yield high-mass alkyl products. All thermal desorption products, such as H-2, CH4, C2H4, C2H6, and C3H6, are detected with a single desorption peak near 475 K. The product yields increase with surface coverage until saturation corresponding to 0.50 monolayer of CH3(ads). The mass distribution is, however, invariant with initial CH3(ads) coverage, and all desorbed species exhibit first-order reaction kinetics. LEED measurement reveals a c(2 x 2) adsorbate structure independent of the amount of gaseous exposure. This strongly suggests that the radicals aggregate into close-packed two-dimensional islands at any exposure. The islanding behavior can be correlated with the reaction kinetics and is deemed to be essential for the chain propagation reactions. Some relevant aspects of the CH3/Cu(111) system are also presented. The new results are compared with those of prior studies employing methyl halides as radical sources. Major differences are found in the product distribution and desorption kinetics, and these are attributed to the influence of surface halogen atoms present in those earlier investigations.

Photochemistry of Halogens in the Marine Atmosphere

Diatomic halogen molecules diffusing into the marine atmosphere are photodissociated to atoms in daylight more rapidly than they undergo other fates. The geochemistry of ‘gaseous halogens’ is considered in terms of photolysis rates and the secondary reactions of the atoms produced. Diatomic halogens could be photolyzed predominantly by day and adsorbed on aerosol by night without yielding diurnal variations in currently measurable variables. Halogen atoms in the marine atmosphere react with ozone more rapidly than with other marine tropospheric constituents, this reaction yielding haloxy radicals that are also reactive.

(Z)-2-(2-chloro-3,3,3-trifluoroprop-1enyl)-6-methoxyphenyl acetate

The crystal structure of the title compound, C12H10ClF3O3, was determined in order to establish the configuration of the C double bond. The compound was found to be the Z isomer. The crystal structure is dominated by Cl center dot center dot center dot O halogen bonds [Cl center dot center dot center dot O = 3.111 (3) angstrom], as well as C-H center dot center dot center dot O and C-H center dot center dot center dot F hydrogen-bonding interactions, that connect neighboring molecules into a three-dimensional supramolecular network.

N-Acetyl-N-{2-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]phenyl}acetamide

The title compound, C13H11ClF3NO2, adopts a Z conformation. Halogen center dot center dot center dot oxygen interactions [Cl center dot center dot center dot O = 2.967 (3) angstrom] in the crystal packing lead to the formation of a dimer joined by two Cl center dot center dot center dot O bonds.

Promoting carbonization of polypropylene during combustion through synergistic catalysis of a trace of halogenated compounds and Ni2O3 for improving flame retardancy

The effect of combination between a trace of halogenated compounds (such as ferric chloride and ammonium bromide) and Ni2O3 particles on the carbonization of polypropylene (PP) was investigated during combustion. The results showed a synergistic catalysis of combined halogenated compounds with Ni2O3 in promoting the formation of the residual char during combustion. The investigation on the promotion mechanism showed that halide radical releasing from halogen-containing additives worked as a catalyst to accelerate dehydrogenation-aromatization of degradation products of PR which promote the degradation products to form the residual char catalyzed by nickel catalyst.

Electronic structures and chemical bonding in 4d transition metal monohalides

Bond distances, vibrational frequencies, dipole moments, dissociation energies, electron affinities, and ionization potentials of NIX (XM = Y-Cd, X = F, Cl, Br, I) molecules in neutral, positively, and negatively charged ions were studied by density functional method, B3LYP. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides ionic component, covalent bonds are formed between the 4d transition metal s, d orbitals, and the p orbital of halogen. For both neutral and charged molecules, the fluorides have the shortest bond distance, iodides the longest. Although the opposite situation is observed for vibrational frequency, that is, fluorides have the largest value, iodides the smallest. For neutral and anionic species, the dissociation energy tends to decrease with the increasing atomic number from Y to Cd, suggesting the decreasing or weakening of the bond strength. For cationic species, the trend is observed from Y to Ag.

Interactions of thiamine monophosphate (TMP) with one- and two-dimensional polymeric halogenomercurate anions. Crystal structures of (TMP)(Hg2Br5)center dot 0.5H(2)O and (TMP)(2)(Hg3I8)

An investigation into the interactions between thiamine monophosphate (TMP) and anions has resulted in the preparation and X-ray characterization of the compounds (TMP)(Hg2Br5).0.5H(2)O (1) and (TMP)(2)(Hg3I8) (2). In each compound the TMP molecule exists as a monovalent cation in the usual F conformation. The halogenomercurate anions occur in two-dimensional (2-D) network in 1 or one-dimensional (1-D) chain in 2. In both 1 and 2, the structures consist of alternating cationic sheets of the hydrogen-bonded TMP molecules and anionic sheets of the polymeric halogenomercurate anions. The TMP molecule binds to the polymeric anions through the characteristic 'anion bridge I', C(2)-H..X...pyrimidinium (X = Br in 1 and 1 in 2), and electrostatic interactions between electropositive S(1) and halogen atoms. The 'anion bridge II' of the type N(4'1)-H...X...thiazolium (X = phosphate group) plays a role in stabilizing the molecular conformation. The biological implication of the host-guest-like complexation between TMP and polymeric anions is discussed.

A mechanistic study of electrochemical oxidation processes of (OEP)Mg(II) in the presence of anions

In the presence of F-, OH-, Cl-, electrochemical redox of (OEP)Mg(II) [2,3, 7,8,12,13,17,18 octaethyl-21H, 23H-porphine magnesium (II)] are investigated in DCE/0.1 mol/L solution by cyclic voltammetry and spectroelectrochemistry, In the presence of anions, anions are axially coordinated to (OEP)Mg(II) generate (OEP)Mg(II)Y, the E-1/2 of (OEP)MS(II)Y oxidation are negatively shifted. A chemical reaction following the second oxidation step is observed, the E-1/2 of the reaction product is obtained. Mechanism of (OEP)Mg(II) in the halogen and OH- anions titration process has been proposed.

ANALYSIS OF ANGULAR OVERLAP PARAMETERS FOR THE LAOXEU3+ (X = CL, BR, I) SERIES

The Angular Overlap Model (AOM) is applied to the LaOX:Eu3+(X = Cl, Br, I) series involving sigma, pi, delta and phi effects based on the experimental energy levels. The calculations are made in two cases. (1) Consider oxygen and halogen having the same bond-length. (2) Consider the real structure. In both cases, the results show that for sigma-bonding parameters, the values of e(sigma) decrease with increasing charge number of halogen, i.e. Cl- > Br- > I-, this indicates that the bonding ability also decreases with this order. The absolute values of each parameter are much larger than zero-therefore they all must be included in a practical analysis. In the second case, the values of the e(pi) parameter are negative, which means a ''back-bonding'' is formed, and this is profitable for the formation of sigma-bonding, usually referred to as ''synergic effect''.

Liquid phase oxidation of toluene to benzaldehyde with molecular oxygen over copper-based heterogeneous catalysts

We conducted the liquid phase oxidation of toluene with molecular oxygen over heterogeneous catalysts of copper-based binary metal oxides. Among the copper-based binary metal oxides, iron-copper binary oxide (Fe/Cu = 0.3 atomic ratio) was found to be the best catalyst. In the presence of pyridine, overoxidation of benzaldehyde to benzoic acid was partially prevented. As a result, highly selective formation of benzaldehyde (86% selectivity) was observed after 2 h of reaction (7% conversion of toluene) at 463 K and 1.0 MPa of oxygen atmosphere in the presence of pyridine. These catalytic performances were similar or better than those in the gas phase oxidation of toluene at reaction temperatures higher than 473 K and under 0.5-2.5 MPa. It was suggested from competitive adsorption measurements that pyridine could reduce the adsorption of benzaldehyde. At a long reaction time of 4 It, the conversion increased to 25% and benzoic acid became the predominant reaction product (72% selectivity) in the absence of pyridine. The yield of benzoic acid was higher than that in the Snia-Viscosa process, which requires corrosive halogen ions and acidic solvents in the homogeneous reaction media. The catalyst was easily recycled by simple filtration and reusable after washing and drying.