C(2×2)S/Fe(001)吸附体系的SCF-Xa-MS研究

采用SCF-X_α-MS方法, 对于C(2×2)S/Fe(001)吸附体系, 选择Fe_5S和Fe_9S两种原子簇模型, 研究了该吸附体系的电子结构、吸附成键特征及其相互作用图象。结果表明, S吸附于Fe(001)单晶表面具有较强的定域性质, S原子与底物Fe原子之间的吸附相互作用主要表现为S(3p)-Fe(4s,3d)之间的轨道相互作用。通过对表面吸附键长的优化, 其结果与X.S.Zhang等的ARPEFS的实验结果一致。     

Poly(methyl methacrylate)/silica/titania ternary nanocomposites with greatly improved thermal and ultraviolet-shielding properties

Poly(methyl methacrylate) (PMMA)/silica/titania ternary nanocomposites with covalent bonding interaction between polymer and inorganic phases have been prepared using a novel non-hydrolytic sol-gel method. Transmission electron microscope (TEM) image of silica/titania binary inorganic component indicates a core-shell-like structure. Scanning electron microscope (SEM) images suggest that the well dispersed silica/titania particles in the hybrid are on the nanometer-scale. The transparencies of nanocomposites are maintained in visible region while the absorption band in ultraviolet (UV) region is red shifted with increasing inorganic content. The thermogravimetric analysis (TGA) results show that the thermal stability of PMMA copolymer increases dramatically with the addition of silica/titania moieties both in nitrogen and in air.     

Effect of the Secondary Reduction on the Enantioselectivity and Function of Additives in the Chiral Oxazaborolidine‐Catalyzed Asymmetric Borane Reduction of Ketones

The secondary reduction in the direct and oxazaborolidine‐catalyzed asymmetric borane reduction of ketones was investigated by the use of GC/MS tracing titration and control experiments. The results indicate that the secondary reduction affects the enantioselectivity only in noncoordinated solvents at low temperature and not under the usual catalytic reduction conditions because the intermediate alkoxyborane is unstable and quickly converts to borane and dialkoxyborane. The function of an alcohol additive in the asymmetric borane reduction of ketones is to consume excess borane in the reduction system thus inhibiting noncatalytic reduction, which leads to increased enantioselectivity in the catalytic reduction.     

On-surface isostructural transformation from a hydrogen-bonded network to a coordination network for tuning the pore size and guest recognition

Rational manipulation of supramolecular structures on surfaces is of great importance and challenging. We show that imidazole-based hydrogen-bonded networks on a metal surface can transform into an isostructural coordination network for facile tuning of the pore size and guest recognition behaviours. Deposition of triangular-shaped benzotrisimidazole (H₃btim) molecules on Au(111)/Ag(111) surfaces gives honeycomb networks linked by double N–H⋯N hydrogen bonds. While the H₃btim hydrogen-bonded networks on Au(111) evaporate above 453 K, those on Ag(111) transform into isostructural [Ag₃(btim)] coordination networks based on double N–Ag–N bonds at 423 K, by virtue of the unconventional metal–acid replacement reaction (Ag reduces H⁺). The transformation expands the pore diameter of the honeycomb networks from 3.8 Å to 6.9 Å, giving remarkably different host–guest recognition behaviours for fullerene and ferrocene molecules based on the size compatibility mechanism.

A hydrogen-bonded network on a Ag(111) surface can transform into an isostructural Ag(i) coordination network, giving drastically different host–guest recognition behaviours.     

Morphology control of soap-free seeded P(St-EA-AA) latex particles

Soap-free poly(styrene-ethyl acrylate-acrylic acid) latex particles with narrow size distribution and with surface carboxyl groups were synthesized by semicontinuous emulsion polymerization, and the particles with homogeneous multihollow structure were obtained after alkali posttreatment. Effects of treatment conditions and crosslinking agents on particle morphology were investigated. Results showed that the multihollow structure can be formed inside the uncrosslinked particles only when the treatment temperature exceeded 50 °C, the pH was higher than 10.0, the amount of 2-butanone was more than 3.0 ml and the treatment time was longer than 30 min. Furthermore, the volume expansion of the particles increased with the temperature increased to 90 °C, the pH to 12.5 or the amount of 2-butanone to 7.0 ml, and this value increased first and then decreased with the treatment time prolonged. Fine pores can be generated in the shell of particles crosslinked by 0.2 g of ethyl glycol dimethylacrylate (EGDMA), while no hollow structure formed inside particles when 0.4 g of EGDMA or 0.2 g of divinyl benzene was used.     

DMF-甲醇体系粘度与核磁共振化学位移的同时关联

提出了一个基于局部组成概念上的核磁共振模型. 利用该模型和以前别人提出的局部组成型粘度方程, 成功地同时关联属于传递性质的粘度数据和属于波谱性质的核磁共振化学位移数据，关联所得到化学位移的平均绝对偏差小于0.0072，粘度的平均绝对偏差小于0.0006 mPa•s，结果表明提出的局部组成模型是合理的.     

Spectral regions selection to improve prediction ability of PLS models by changeable size moving window partial least squares and searching combination moving window partial least squares

Changeable size moving window partial least squares (CSMWPLS) and searching combination moving window partial least squares (SCMWPLS) are proposed to search for an optimized spectral interval and an optimized combination of spectral regions from informative regions obtained by a previously proposed spectral interval selection method, moving window partial least squares (MWPLSR) [Anal. Chem. 74 (2002) 3555]. The utilization of informative regions aims to construct better PLS models than those based on the whole spectral points. The purpose of CSMWPLS and SCMWPLS is to optimize the informative regions and their combination to further improve the prediction ability of the PLS models. The results of their application to an open-path (OP)/FT-IR spectra data set show that the proposed methods, especially SCMWPLS can find out an optimized combination, with which one can improve, often significantly, the performance of the corresponding PLS model, in terms of low prediction error, root mean square error of prediction (RMSEP) with the reasonable latent variable (LVs) number, comparing with the results obtained using whole spectra or direct combination of informative regions for a compound. Regions consisting of the combinations obtained can easily be explained by the existence of IR absorption bands in those spectral regions.     

Flow injection chemiluminescence determination of polyhydroxy phenols using luminol-ferricyanide/ferrocyanide system

It was found that the weak chemiluminescence produced from the reaction of polyhydroxy phenols with luminol in alkaline solution could be strongly enhanced by ferricyanide and ferrocyanide. Based on this found, a new flow injection chemiluminescence method is proposed for the determination of four polyhydroxy phenols: pyrogallol, phlorglucinol, quinol and resorcinol. The detection limits of the method are 0.03 μg ml⁻¹ pyrogallol, 0.03 μg ml⁻¹ phlorglucinol, 0.04 μg ml⁻¹ quinol, and 0.02 μg ml⁻¹ resorcinol. The possible mechanism of CL reactions is also discussed briefly.     

Dynamic study of photosensitized one-electron oxidation of polyG by menadione

Quinones including menadione are ubiquitous in nature. They play important roles in aerobic respira- tion and photosynthesis[1,2]. In addition, exogenous quinones are used as antibiotics and anticancer drugs. Their function is closely related to their red…     

Sorption and desorption of radiostrontium on calcareous soil and its solid components

The effect of different solid components of calcareous soil on the retention of Sr was investigated by using batch technique and selective extraction method. The sorption and desorption isotherms of Sr on the untreated calcareous soil and the three treated soils were determined at 20°C, pH 7.8±0.2 and in the presence of 0.001 M CaCl₂. It was found that all isotherms are linear and that the sorption of Sr on the calcareous soil can be described by a reversible sorption process and the sorption mechanism is mainly ion exchange.