近红外漫反射光谱法对固态样品的无损分析

本文应用目标因子分析研究了固态样品的近红外漫反射光谱，用目标因子分析成功地确定了固态样品的物种数、物种种类和各物种的含量。     

Ab initio study of the complexes of halogen-containing molecules RX (X=Cl, Br, and I) and NH3: towards understanding the nature of halogen bonding and the electron-accepting propensities of covalently bonded halogen atoms

Ab initio calculations have been performed on a series of complexes formed between halogen-containing molecules and ammonia to gain a deeper insight into the nature of halogen bonding. It appears that the dihalogen molecules form the strongest halogen-bonded complexes with ammonia, followed by HOX; the charge-transfer-type contribution has been demonstrated to dominate the halogen bonding in these complexes. For the complexes involving carbon-bound halogen molecules, our calculations clearly indicate that electrostatic interactions are mainly responsible for their binding energies. Whereas the halogen-bond strength is significantly enhanced by progressive fluorine substitution, the substitution of a hydrogen atom by a methyl group in the CH(3)X...NH(3) complex weakened the halogen bonding. Moreover, remote substituent effects have also been noted in the complexes of halobenzenes with different para substituents. The influence of the hybridization state of the carbon atom bonded to the halogen atom has also been examined and the results reveal that halogen-bond strengths decrease in the order HC triple bond CX > H(2)C=CHX approximately O=CHX approximately C(6)H(5)X > CH(3)X. In addition, several excellent linear correlations have been established between the interaction energies and both the amount of charge transfer and the electrostatic potentials corresponding to an electron density of 0.002 au along the R-X axis; these correlations provide good models with which to evaluate the electron-accepting abilities of the covalently bonded halogen atoms. Finally, some positively charged halogen-bonded systems have been investigated and the effect of the charge has been discussed.     

Oxidative coupling of methane over Na-Mn-W/SiO2 catalyst at higher pressure

Na-Mn-W/SiO₂ catalysts were prepared and their catalytic performance for oxidative coupling of methane (OCM) was evaluated in a stainless-steel microreactor at elevated pressure. The results show that a CH₄ conversion of 15.1% with a C₂₊ selectivity of 71.8% was obtained under 750^oC, 1.0×10⁵h^-1 GHSV, CH₄/O₂ ratio of 8 and 1.0 MPa. Moreover, 17.3% CH₄ conversion with 51.6% C₂ selectivity and 23.6% C₃-C₄ selectivity was obtained under 750^oC, 2.0×10⁵h^-1 GHSV, CH₄/O₂ ratio of 8 and 1.0 MPa.     

Sm2Fe17合金的氢化-歧化过程演化

通过X射线衍射(XRD)、扫描电镜(SEM)和能谱分析(EDX)等手段重点研究了Sm2Fe17合金在氢化-歧化过程中的相组成、相的变化以及微观结构的演化规律。研究表明：在0．1MPa的H2气氛下，Sm2Fe17合金首先吸氢；400℃时合金出现部分脱氢现象；在T≥500℃逐渐开始歧化为SmHx和α—Fe，同时生成了大量的微晶或非晶组织；随着温度的升高，合金中的微晶非晶逐渐晶化，750℃时晶化完全，晶粒长大至20～100nm。通过对Sm2Fe17合金的氢化一歧化过程研究，建立了该过程的微观结构变化规律的物理模型。     

Uncoupled metabolism stimulated by chemical uncoupler and oxic-settling-anaerobic combined process to reduce excess sludge production

The effects of three uncoupled metabolic systems (conventional activated sludge process with the addition of 3,3′,4′,5-tetrachlorosalicylanilide [TCS], oxic-settling-anaerobic [OSA] process modified by insertion of a sludge-holding tank in the sludge return line, and TCS and OSA combined process) on reducing excess sludge production were studied. Compared with the control conventional activated sludge process, the most effective system was the combined process, which could reduce excess sludge production by 46.90%. The 180-d operation results confirmed that TCS is an effective chemical uncoupler in reducing the sludge yield but that it had an adverse effect on substrate removal capability, effluent nitrogen concentration, and sludge settleability. The OSA process decreased excess sludge production by only 26% but had less adverse effect on effluent quality and could improve sludge settleability. The effluent total phosphorous concentration of the three systems was slightly lower than of the control unit. Microbial populations were monitored by both microscopic and molecular biologic analysis method (polymerase chain reaction [PCR]-denaturing gradient gel electrophoresis [DGGE]). The presence of TCS caused metazoans to disappear and decreased the number and activity of protozoa. PCR amplification of 16S rRNA and sequent DGGE analysis found a shift in the diversity of the predominant species. The results imply that OSA combined with the chemical uncoupler process may effectively reduce excess sludge yield and not affect process performance significantly.     

Facile synthesis of 9-（N-amino-4-fluoromethyl-3-pyrrolidinyl）-2- fluoro-6-aminopurine from trans-4-hydroxy-L-proline

A novel and simple procedure for synthesis of azanucleoside by Mitsunobu reaction between N-(p-nitrobenzyloxycarbonyl)- trans-4-hydroxy-D-proline methyl ester obtained from trans-4-hydroxy-L-proline after six-step reaction and 2-fluoro-6-azidopurine is described,and azanucleoside is fluorinated by new fluridizer 2,2-difluoro-1,3-dimethylimidazolidine (DFI).All reactions could be carded out under mild condition.     

轻希土硫氰酸盐与2,3,11,12,-四苯基-1,4,7,10,13,16-六氧-2,11-十八环二烯配合物的合成及XPS研究

合成了六种轻希土硫氰酸盐与标题不饱和冠醚的新固体配合物,进行了元素分析,摩尔电导率、DTA、UV、IR和XPS等表征。对Ln(NCS)_3·L和Ln(NCS)_3的XPS研究中,得到它们组成原子芯能级电子(Ln3d_(5/2),Ols,Nls,S2p)的结合能信息;观察到除Y3d_(5/2)外Ln3d_(5/2)(Ln=La、Ce、Pr、Nd、和Sm)的伴峰结构,Ln3d_(5/2)结合能与原子序数呈线性关系,并推断类似化合物Pm3d_(5/2)结合能在1035eV附近.     

从头计算方法比较TiSi_2的C54相和C49相

采用平面波超软赝势描述多电子体系,利用密度泛函理论和广义梯度近似,计算出C54相和C49相TiSi2的晶格常数、体弹性模量、形成能、电子态密度(DOS)和Mulliken电荷布居等性质.通过比较这两种物质的性质,发现尽管两者形成能很相近,但C49相结构对称性差、体弹性模量小、熔点低,Ti原子d轨道的反键强、离子性弱.这些性质上的差异和C49相TiSi2在固相反应中优先形成有关.