LiCl急冷过程中结构变化研究的一种几何学方法

计算了900 K、698 K、498 K和298 K温度下共4800个Voronoi多面体并对它们进行了统计分析. 计算表明: 在玻璃态转变温度区间, Voronoi多面体的统计分布有明显的变化。在以阳离子为中心的Voronoi多面体中, 在298 K时,四面体、五面体和六面体占总数的80%以上。     

用交流阻抗法研究某些离子选择电极的响应特性

用交流阻抗法研究了两种液膜胆R汁酸电极和两种聚氯乙烯(PVC)膜钙离子选择电极. 从体电阻R_b和电荷传递电阻R_(ct)得到膜内离子迁移活化能E_a, 及电极的表观标准交换电流密度i°_0等信息. 结果表明: E_a比R_b更能反映离子在膜内迁移的情况, 离子在PVC膜中的迁移比在液膜中困难得多; i°_0能在一定程度上反映电极性能的优劣等。     

容量法测定氧化钒中的各种价态钒

用NaOH溶液处理样品，分离V（V）然后以Fe(Ⅱ）滴定测定之。定量加入过量的V（V）到上述残渣中并用H2SO4溶解，用Fe(Ⅱ）滴定，计算出V（Ⅱ），V（Ⅲ）的含量。V（Ⅳ）的测定是通过从总钒量中扣除V（Ⅱ）、V（Ⅲ）、V（Ⅴ）的含量得到。V（Ⅱ）、V（Ⅲ）和V（Ⅴ）的回收率均大于96％，其8次测定结果的相对标准偏差分别为：9．8％、0．4％、1．2％；本法快速、简便，在实际应用中效果良好。     

On the low temperature magnetic properties of some sulfites of divalent iron

Zero field Mössbauer spectra and powder susceptibility measurements show that the condensed, hydrogen bonded network compound FeSO₃ 3H₂O orders antiferromagnetically (T_Néel 9.5 K). The related anhydrous material FeSO₃ also shows antiferromagnetic exchange but no evidence of long range three-dimenstional magnetic order to as low as 1.4 K.Supported by the U.S. National Science Foundation Division of Materials Research—Solid State Chemistry Program Grant No. DMR 8313710.     

A Kinetic Evidence for the Nitroxyl Radicals Recycling Mechanism in the Photostabilizing Process of HALS

The photoinduced bulk polymerization of a reactive-hindered amine fight stabilizers(r-HALS), 4-acryloyl-2, 2, 6, 6-tetramethylpiperidinyl (ATMP), was performed at 80℃ by using a DPC technique. An unique periodic exponential attenuation-type oscillating curve was found when the polymerization was carried out in air, but this phenomenon was not found in nitrogen.It is supposed that this unique kinetic performance may be attributed to nitroxyl radicals that are produced in situ from the oxidation of ATMP. ATMP polymer with narrow polydispersity (d =1.03) can be obtained by photoinduced solution polymerization of ATMP. The signal detected in ESR may be assigned to the nitroxyl radicals in the matrix of ATMP polymer. Since this kind of recycling of nitroxyl radicals is well documented for the photostabilizing mechanism of HALS, the present results may serve as a kinetic evidence for this mechanism.     

ATOMIC FORCE MICROSCOPY STUDIES OF POLYCAPROLACTONE RINGED SPHERULITES*

The surface morphology of free-surface PCL ringed spherulites was investigated by using atomic forcemicroscopy. The spherulites were obtained by crystallization of PCL/PVC blends of different compositions. It was found thatthe ringed spherulite exhibited regularly fluctuating rings on its surface. Compared with the bright-dark ring pattern of thespherulite under a polarizing microscope, it was proved that the optical characteristics of the ringed spherulite underpolarizing microscope coincided with its surface characteristics. The bright rings in polarizing micrographs of the spherulite coincided with the convex rings on its surface, while the dark rings coincided with the concave rings.     

A novel trilinear decomposition algorithm： Three-dimension non-negative matrix factorization

Non-negative matrix factorization(NMF)is a technique for dimensionality reduction by placing non-negativity constraints onthe matrix.Based on the PARAFAC model,NMF was extended for three-dimension data decomposition.The three-dimension non-negative matrix factorization(NMF3)algorithm,which was concise and easy to implement,was given in this paper.The NMF3algorithm implementation was based on elements but not on vectors.It could decompose a data array directly without unfolding,which was not similar to that the traditional algorithms do.It has been applied to the simulated data array decomposition andobtained reasonable results.It showed that NMF3 could be introduced for curve resolution in chemometrics.     

Prediction of retention indexes. I. Structure-retention index relationship on apolar columns

A simple method is reported for predicting the retention index (RI) of a chemical compound from the number of carbon and carbon equivalent atoms in the molecule, the RI increment for atom addition and the group retention factors (GRFs) for substituents and functional groups. Atoms other than carbon such as oxygen, nitrogen, sulfur, chlorine, bromine and iodine are assigned carbon atom equivalency of approximately 1, 1, 2, 2, 3 and 4, respectively and are counted for their contribution towards RI prediction. The GRFs of substituents and functional groups are derived from the RIs of reference compounds and series of homologues. Ring structures, ring fusion, ring connection, iso- and neo-carbons, chain branching and unsaturation are also assigned GRFs. The predicted RIs of a number of alicyclic, aliphatic and aromatic hydrocarbons, primary, secondary and tertiary alcohols, phenols, aliphatic amines, aromatic amines, heterocyclics, carboxylic acids, acid esters, aldehydes, ketones, and halogenated compounds, are found to be within +/- 3% of the observed values. The structure-retention index relationship thus developed is extremely useful in the tentative identification of radioactive side products formed in tritium labeling by radiation-induced methods.     

Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second‐order Møller–Plesset (MP2)/6‐31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero‐point energy (ZPE) and CCSD(T)/6‐31G* single‐point calculations. From the PES obtained with the CCSD(T)//MP2/6‐31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four‐membered ring intermediate, INT2, which is a barrier‐free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four‐membered product P_2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier‐free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier‐free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P₃ via a transition state TS3 with an energy barrier of 25.8 kJ/mol. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007