新型有机锗倍半氧化物及硫化物的合成

已先后合成的倍半氧化物类及倍半硫化物类化合物的前体,即有机锗三氯化物中只含1个锗原子。为了考查从含2个锗原子的前体合成的有机锗倍半氧化物及硫化物的药物活性,我们合成了1类化合物及相应的倍半氧化物(2类)及倍半硫化物(3类),并合成了酰基苯胺化合物1_e、2_e及3_e。结果见表1。     

Synthesis of Calix[4]arene Derivatives with NLO Properties

The new chromophore compounds with NLO properties were prepared by Knoevenagel condensation from forrnyl or diformyl calix[4/arene and isophorone derivatives in the presence of piperidine and acetic acid, respectively. In these chromophore calix[4]arenes, the ring locked trienes were employed as the conjugation bridge and electron acceptor in D-π-A units. The NMR spectra demonstrated that they existed in a cone conformation and consequently non-conjugated D-π-A units could be oriented at nearly the same direction.     

A facile synthesis of 2-substituted-2,3-dihydro-4(1H)-quinazolinones in 2,2,2-trifluoroethanol

2-Substituted-2,3-dihydro-4(1H)-quinazolinones were obtained in high yields by condensation of anthranilamide with aryl, alkyl or heteroaryl aldehydes or ketones in the refluxing 2,2,2-trifluoroethanol without any catalyst.     

Reduced Overlap Population Analysis for Triosmium Clusters

The use of reduced overlap population (ROP) analysis from EHMO calculations as a means to gauge the presence of metal–metal bonds in triosmium clusters is examined. A number of triosmium clusters containing bridging ligands have been used as test cases, including the bis-ethoxy bridged cluster Os₃(μ-OEt)₂(CO)₁₀, 1b, and some of its group 15 derivatives Os₃(μ-OEt)₂(CO)₉(EPh₃), 2. These latter clusters are newly synthesized and have been characterized completely, including by single-crystal X-ray crystallographic studies. In honour of Professor Dieter Fenske on his 65th birthday.     

Hydrogen–hydrogen bonding in biphenyl revisited

The evidence for the stabilizing nature of the H–H bonding in planar biphenyl is succinctly reviewed. The stabilizing nature of the H–H bonding is revealed through a comparison of the atomic energy of every atom in planar biphenyl with the same atom in the twisted equilibrium structure. It is shown that the barrier to rotation via the planar transition state is the net resultant of a stabilisation of the four ortho-hydrogen atoms (by 8 kcal/mol each), a stabilisation of the two para-carbon atoms (by 3 kcal/mol each) and by the dominant destabilisation of the two carbon atoms joining the two rings—the two junction carbon atoms—(by 22 kcal/mol each). The energetic stabilisation of the four ortho-hydrogen atoms is further shown to be in large proportion due to the formation of the hydrogen–hydrogen interatomic surface. Furthermore, neither the “bond order” between the two junction carbon atoms nor the total electron delocalisation between the two rings exhibit a significant change in going from the planar to the twisted equilibrium geometry. These findings are in contrast with the classical view of a balance between “steric non-bonded repulsion” and better electron delocalisation as a function of the twist dihedral angle. Similar conclusions have been recently reached by Pacios and Gómez through a study of the electrostatic potential at the position of the hydrogen nuclei. We dedicate this article to Professor TM Krygowski on the occasion of his 70th birthday wishing him a long and productive life.     

硼离子对铕掺杂SiO2干凝胶发光性能的影响

采用溶胶-凝胶法制备了Al单掺和B，Al共掺的Eu掺杂SiO2干凝胶。利用荧光光谱、IR，XRD，DSC，TG／DTG等技术研究了硼离子、退火温度对样品发光性质的影响。经500℃以上退火处理用248nm激发的样品，产生Eu^3＋离子^5D0→^7FJ的特征发射，^5D0→^7F1的跃迁分裂为两个峰。比较615nm处的发光强度，掺硼酸样品的发光强度是不加硼酸发光强度的3．3倍。这是因为B离子的加入，在材料中形成了Si—O—B键，破坏了网络的对称性，加强了Eu^3＋的红光发射。当退火温度上升到850℃用350nm激发时，样品有很强的Eu^2＋蓝光发射。Al单掺的发射中心在437nm处，发射半峰宽约为70nm，而B，Al共掺样品的发光中心蓝移到425nm处，单掺样品的蓝光强度几乎是共掺样品强度的2倍。这是由于硼酸的加入改变了基质的网络结构，从而导致单掺和共掺样品发射峰位和强度的改变。     

CRYSTALLIZATION AND MELTING OF POLY（ETHYLENE OXIDE） CONFINED IN NANOSTRUCTURED PARTICLES WITH CROSS-LINKED SHELLS OF POLYBUTADIENE

Small fixed aggregates of a poly(ethylene oxide)-block-polybutadiene diblock copolymer(PEO-b-PB)in THFsolution were obtained by adding a selective solvent for PB blocks,followed by cross-linking the PB shells.Themorphologies of the nanostructured particles with a cross-linked shell were investigated by atomic force microscopy andtransmission electron microscopy.The average behaviors of the PEO crystallization and melting confined within thenanostructured particles were studied by using differential scanning calorimetry experiments.For the deeply cross-linkedsample(SCL-1),the crystallization of the PEO blocks was fully confined.The individual nanoparticles only crystallized atvery low crystallization temperatures(T_cs),wherein the homogenous primary nucleation determined the overallcrystallization rate.For the lightly cross-linked sample(SCL-2),the confinement effect was T_c dependent.At T_c(?)42℃,thecrystallization and melting behaviors of SCL-2 were similar to those of the pure PEO-b-PB diblock copolymer.At T_c>42℃,SCL-2 could form PEO lamellae thicker than those of the pure PEO-b-PB crystallized at the same T_c.     

Living free-radical copolymerization of allyl glycidyl ether with methyl acrylate

An investigation of the copolymerization of allyl glycidyl ether (AGE) with methyl acrylate (MA) was performed in the presence of benzyl imidazole-1-carbodithioate (BICDT) on the thermal initiation condition. Results showed that the process has good characteristics of living free radical polymerization, i.e. the molecular weight of the obtained polymer increases linearly with monomer conversion, molecular weight distribution is very narrow, and a linear relationship between ln([M]₀/[M]) and polymerization time is found. The copolymer structure containing epoxy groups was demonstrated from the ¹H nuclear magnetic resonance (1H NMR) spectrum. It was found that the content of AGE in the copolymer increases with the increase in monomer conversion and molar faction of the AGE in the monomer feed. However, the polymerization could slow down when the fraction of AGE increases in the monomer feed. Taking advantage of living polymerization character, functional block copolymers PSt-b-P (MA-co-AGE) were prepared in the presence of PSt RAFT agent. __________ Translated from Journal of Anhui University of Science and Technology, 2006, 26(3): 56–61 [译自: 安徽理工大学学报]     

Electrochemical investigation of hymecromone at a multi-wall carbon nano-tube/cetyl pyridine bromine composite film electrode

A multi-wall carbon nanotube (MWNT)/cetyl pyridine bromine (CPB) composite film modified glassy carbon electrode (GCE) was developed for the electrochemical determination of hymecromone in phosphonate buffer. Electrochemical behaviour of hymecromone at the composite film electrode was investigated with voltammetry. Compared with an irreversible oxidation of hymecromone at the bare GCE, the oxidation peak current was enhanced greatly at the film electrode. Some parameters such as pH, scan rate, accumulation potential and accumulation time were optimized. Under optimal conditions, an oxidation peak at 0.82 V was employed to determine hymecromone electrochemically. A linearity between the oxidation peak current and the hymecromone concentration was obtained in the range of 3.0 × 10⁻⁷ − 2.0 × 10⁻⁵ mol 1⁻¹ with a detection limit of 8.0 × 10⁻⁸ mol 1⁻¹. The proposed procedure was successfully applied to assay hymecromone in pharmaceutical formulation with satisfactory results. The text was submitted by the authors in English.     

Synthesis and mechanism research of an ethylene glycol-based sol-gel method for preparing PZT nanopowders

Lead zirconate titanate nanopowders Pb(Zr_0.52Ti_0.48)O₃ (PZT) were prepared by modified sol-gel process in ethylene glycol system with zirconium nitrate as the zirconium source. The research showed that it was critical to add lead acetate after the reaction of zirconium nitrate and tetrabutyl titanate in ethylene glycol system for preparing PZT of exact titanium content. The reaction mechanisms of the sol synthesis, preparation of xerogel and agglutinating process were characterized through using FT-IR, NMR, TG-FTIR, and GC-MS. The experiment proved that ethylene glycol system did not rely on hydrolysis and condensation reactions in the process of the sol formation, but on the formation of chain or network large molecules from complexation of ethylene glycol and all Ti and minor Pd, Zr. In the preparation of xerogel, the complexation reaction was so completed that it formed large molecules network composed of metal and dioxyethyl. Bulk weight loss happened before 350°C in the process of sintering xerogel to prepare PZT nanopowders. Volatile matters and vapor phase decomposition resultants were primarily oxy-compounds including ethylene glycol, aldehyde-ketone compounds, carbon dioxide and nitrate radical conversion matters. After 350°C, primary vapor phase decomposition resultants were carbon dioxide and minor carbonyl compound.