固定pH滴定法测定弱酸弱碱性药物

报道一种水溶液吕测定弱酸弱碱性药物的新型滴定分析方法－固定ｐＨ滴定法，其理论基础是弱酸弱碱在水溶液中各种存在形式的分布系数在ｐＨ值固定时为常数，对甲硝唑，盐酸美西律等离散常数在１０＾－８至１０＾－１１范围内的７种弱酸弱碱性药物进行测定。结果与药典法吻合，回收率在９９．４％～１００．６％，方法简便，快速，准确，制剂中的赋形剂及色物不影响测定。     

STUDY OF ACOUSTIC EMISSION DURING NON-ISOTHERMAL CRYSTALLIZATION OF POLYPROPYLENE

In this paper we have presented the results of acoustic emission (AE) during non-isothemal crystallization of polypropylene (PP) melt with mean cooling rate 4℃/min, and discussed the effects of molecular weight (MW) on AE activity. It is shown that the amount of AE ring-down counts during whole crystallization of PP depends on the MW strongly.The copious AE bursts have been observed at the late stage of PPcrystallization. AE bursts are caused by cracking, crazing and cavitation between spherulites and inside spherulites.     

邻苯二胺、邻氨基酚的电化学聚合及聚合的膜性质

邻苯二胺(ODB), 邻氨基酚(OAP)在酸性水溶液中易电聚合, 可形成致密的聚合膜。聚邻苯二胺(PODB)在PH<4时具有电活性, 其氧化还原反应与电变色效应对应。聚邻苯二胺,聚邻氨基酚(POAP)膜电极电位在pH=4～10范围对pH有Nernst响应, 电极系数分别为59mV/pH和57mV/pH。响应时间小于3分钟。PODB, POAP膜能与Ni~(2+), Co~(2+)过渡金属离子形成稳定的聚合络合膜。此膜在碱性介质中具有稳定的循环伏安行为, 膜中的金属离子可被H~+交换。PODB电极的—NH_2基可再修饰引入醌/氢醌功能团。     

Three Keggin-based complexes modified by an asymmetric ligand: structures,electrochemical, photocatalytic and fluorescence sensing properties

By using an asymmetric ligand with triazole and imidazole groups, three Keggin-based complexes were obtained, [Cu(HMET)₄(H₂O)₂](PMo₁₂O₄₀)₂·2H₂O (1), [Cu₃(HMET)₄Cl₂(H₂O)₂(XM₁₂O₄₀)₂]·4H₂O (X?=?Si, M?=?W 2, X?=?Ge, M?=?Mo 3) (MET?=?4-(2-imidazol-1-yl-ethyl)-4H-[1,3,4]triazole). Complex 1 contains discrete Keggin anions and mono-nuclear [Cu(MET)₄(H₂O)₂]²⁺ clusters. Complexes 2 and 3 are isostructural with tri-nuclear Cu clusters linked by Keggin anions to construct a 1D chain. The 1- to 3-CPEs show electrocatalytic properties and can also act as nitrite amperometric sensors. Complexes 1–3 exhibit photocatalytic activities for degradation of MB. Complexes 1–?3 own fluorescence sensing properties for detecting Hg²⁺ ions.

Graphical abstract

By using an asymmetric ligand three POM-based complexes were constructed. The 1– to 3–CPEs exhibit good electrocatalytic activities and can be used as nitrite amperometric sensors. The title complexes show good photocatalytic activities for degradation of MB. Moreover, complexes 1–3 can act as fluorescence sensors to selectively detect Hg²⁺.

     

Completely geometrically optimized DFT/ONIOM triple-helical collagen-like structures containing the ProProGly, ProProAla, ProProDAla, and ProProDSer triads

We report completely optimized ONIOM DFT/AM1 molecular orbital calculations on several collagen-like triple helices based upon the repeating triad, ProProGly. The requirement of Gly as every third amino acid in collagen can be attributed to its enantiomorphic nature, as it behaves as a Damino acid in collagen. We, therefore, explored related collagen-like triple helices with one of the central Gly's mutated to either L or DAla; l-Ala appreciably destabilizes, while d-Ala slightly stabilizes the triple helical structure. Mutation of the same Gly to DSer, which is simply DAla with an OH in place of one of the methyl H's, induces a much greater stabilization due to an additional H-bond formed between this OH and a C=O on an adjacent peptide strand. Energies are presented for the triple helices and their component strands (both optimized and distorted to their triple helical geometries) relative to the component amino acids. The variation of relative energies with the chosen reference is delineated.     

Efficient and mild benzoin condensation reaction catalyzed by simple 1-N-alkyl-3-methylimidazolium salts

The benzoin reaction, catalyzed by simple 1-N-alkyl-3-methylimidazolium salt-based ionic liquid via carbene intermediate, to give the α-hydroxyl ketone proceeds in CH₂Cl₂ under mild conditions.     

Spiro(benzoxasilole) catalyzed polymerization of oxetane derivatives

A spiro(benzoxasilole) catalyst, 3,3,3′,3′-tetrakis(trifluoromethyl)-1,1′-(3H,3H′)-spirobis(1,2-benzoxasilole) was used to polymerize 3,3-R,R′-oxetanes: BEMO (R, R′ = ethoxymethyl), AMMO (R = azidomethyl, R′ = methyl), NMMO (R = nitratomethyl, R′ = methyl), BAMO (R, R′ = azidomethyl), and BCMO (R, R′ = chloromethyl) with descending rates in this order. ³¹P-NMR of polymerization mixtures quenched using Bu₃P are consistent with an oxonium ion propagating species. Water is not a cocatalyst because it increases the induction period which is not eliminated by the proton trap 2,6-di-t-bu-tylpyridine. The propagating chains were terminated by transfer with the ether oxygen of the polymer either intermolecularly or intramolecularly. The index of propagation to chain transfer, Kk_ik_p/k_tr, varies over more than three orders of magnitude for BEMO > AMMO > NMMO > BAMO. However, k_p/k_tr for the four monomers differ by less than a factor of five indicating the same factors are affecting propagation and chain transfer. Addition of benzyl alcohol and propandiol produced poly(BEMO) having one and two hydroxyl termini, respectively. These telechelic polymers can be used to synthesize linear triblock or multiblock copolymers of oxetane derivatives. © 1992 John Wiley & Sons, Inc.     

The Synthesis and Structure of Silica-Sodalite from Nonaqueous Systems

A silica polymorph, silica-sodalite was synthesized from a nonaqueous system NaOH-SiO2-C2H4(OH)2 and its chemical compositionwas determined to be Si12 O24,2C2H4(OH)2 by the X-fluorescence,thermogravimetric and organic elemental analyses. The single crystal X-ray diffraction structure determination of the silica-sodaliteshowed that the silica-sodalite is cubic, spacing group I23 and unitcell parameter a= 8.8354A. The IF and solid state high resolution Siand 13 C NMR spectra of the silica-sodalite were measured and discussed .     

甲基丙烯酸三丁基锡和甲墓丙烯酸异戊酯共聚合参数的测定

有机锡聚合物兼具杀菌防腐的生物活性功能和一般高分子材料的结构功能，有着潜在的应用前景［１］。本工作应用Ｘ射线萤光光谱测定甲基丙烯酸三丁基锡（ＴＢＴＭ）和甲基丙烯酸异戊酯（ＩＰＭＡ）共聚物中锡的含量。方便，迅速地获得了该共聚物的组成，计算了ＴＢＴＭ和ＩＰＭＡ在四氢呋喃中，５５℃下共聚合的竞聚率，其结果分别为０．２９和０．２４。     

H_3PO→H_2POH异构化反应的LMO研究

1引言最近二、三十年来，定域化分子轨道（LM阿理论在化学的各领域内都得到了广泛的应用［‘－‘］．本文试图采用LMO方法的计算来研究化学反应．期望对反应过程中电子在各原子间的转移和重新排布，以及键的断裂和生成有一个具体的了解．对于HaPO、H。POH异构化反应（见图1）来说，可看成是H’原子绕P原子向0原子方向移动的结果，而角度zH‘PO的大小可看成是反应过程的一个标度或“反应坐标”．本文中氢原子的编号H‘护p‘仅是为计算和分析的方便而加以标识的．每给定一个ZH‘PO角度，我｛rl都采用GAUSSIAN80程序在3－21G基组…