A 3-D noninterpenetrating diamondoid network of a decanuclear copper(I) complex

The solvothermal reaction of CuCl(2).2H(2)O with pyridine-4-thiol and ethanol yielded a novel photoluminescent 3-D polymeric complex with an interesting decorated diamondoid network that is constructed of decanuclear copper(I) cluster units and mu(4)-Cl ligands. The in situ generation of CuSO(4).5H(2)O implies the spontaneous occurrence of desulfurization and redox reactions in the present system.     

Adsorption separation of terpene lactones from Ginkgo biloba L. extract using glass fiber membranes modified with octadecyltrichlorosilane

In this study porous glass fiber membranes were modified by reaction with octadecyl-trichlorosilane to form C18 hydrophobic membranes. The contact angle and the CH2 vibration bands at 2855 and 2920 cm(-1) found by FTIR measurements verified the successful immobilization of C18 groups on the glass fiber membranes. The resulting C18 hydrophobic membranes were used to adsorb terpene lactones from crude Ginkgo biloba L. extracts. In batch adsorption processes, the modified C18 membranes exhibited a better adsorption performance than commercial C18 solid phase extraction adsorbents. Different desorption solvents were tested and ethyl acetate was found to preferentially desorb terpene lactones from the modified C18 membranes. In flow adsorption experiments at 1 mL/min, terpene lactone contents higher than 6 wt% (the standardized content) could be achieved in the elution step using ethyl acetate.     

à 3E态CH3N自由基的稳定性

观察到了CH_3N自由基Ã ~3E←X~3A_2体系317-272 nm的荧光激发谱, 特别讨论了振动激发的Ã 态的稳定性. 报导了v_3~′=6态的色散荧光和荧光时间谱, 该态在240 Pa下的寿命大约是80 ns. 实验表明Ã ~3E 态CH_3N自由基是稳定的, 势能面至少距振动基态4800 cm~(-1)内是束缚的, 异构化或预离解作用并不重要.     

Folic acid analogs. III. N-(2-[2-(2,4-diarnino-6-quinazolinyl)ethyl]benzoyl)-l-glutamic acid

A trideaza analog of aminopterin, N-(4[2-(2,4-diamino-6-quinazolinyl)ethyl]benzoyl)-L-glutamic acid, was prepared by a Wittig condensation of 2,4-diaminoquinazoline-6-carboxaldehyde and [P-(N-[1,3-bis(ethoxycarbonyl)propan-1-yl]aminocarbonyl)phenylmethyl]triphenylphosphonium bromide followed by catalytic reduction and mild hydrolysis. This compound was found to have confirmed inhibitory activity against leukemia L1210 in mice.     

Curing and pyrolysis of epoxy resins containing 2-(6-oxido-6<Emphasis Type="Italic">H</Emphasis>-dibenz(<Emphasis Type="Italic">c</Emphasis>,<Emphasis Type="Italic">e</Emphasis>)(1,2)oxaphosphorin-6-yl)-1,4-naphthalenediol or bisphenol S

This work examines the curing kinetics, thermal properties, and decomposition kinetics of diglycidyl ether of bisphenol A (DGEBA) epoxies with three different curing agents, 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)-1,4-naphthalenediol (ODOPN), bisphenol A (BPA), and bisphenol S (BPS). The differential scanning calorimetry curing study reveals that the curing kinetics of the DGEBA/ODOPN epoxy is first order, independent of the scan rate. The ODOPN-containing epoxy, unlike the conventional BPA one, includes a phosphorus-containing bulky pendant aromatic group and results in an increase in the glass-transition temperature of 83 K, the char yield increases by a factor of 3, and the limiting oxygen index values increase from 23 to 27. For the BPS system, the glass-transition temperature increased slightly, and both the char yield and the limiting oxygen index value increased insignificantly when the test was conducted in air. Finally, the thermogravimetric analysis decomposition study in N₂ from Ozawa's analysis demonstrates that the DGEBA/BPS epoxy has the highest activation energy, followed by the regular DGEBA/BPA system, and lastly the DGEBA/ODOPN has the lowest activation energy. The low activation energy for the ODOPN system is attributed to the initial decomposition of the phosphorus compound in the formation of an insulating layer.     

Preparation and characterization O-lauroyl chitosan/poly (L-lactic acid) blend membranes by solution-casting approach

O-Lauroyl chitosan/poly(L-lactide) (OCS/PLLA) blend membranes with different compositions were prepared by solution-casting approach using chloroform as common solvent. The experimental results of FT-IR, DSC and WAXD indicated that inter-association hydrogen-bond interactions existed between OCS and PLLA in the blend membranes. And SEM observation confirmed that the blend membranes with suitable compositions were compatible.     

12-钼磷酸—聚乙烯醇的光电子转移反应

12-钼磷酸—聚乙烯醇体系具有不可逆光致变色的特性。根据X射线光电子能谱、电子自旋共振谱、紫外及可见光谱的测试结果,笔者认为:在PMo_(12)-PVA的光电子转移反应中,PMo_(12)既是氧化剂也是光敏剂。PMo_(12)分子中氧可分成O_p、O_b和O_t三种情况.其中O_t可成为光化学的活性位置,它和PVA羟基上的氧均较易被紫外光激活。激活的0_t边使周围的一个电荷向金属原子(Mo~(Ⅵ))转移,边与PVA羟基上被激活的氧作用,电子就由此羟基上的氧向O_t转移,致使体系中部分PMo_(12)与PVA发生二电子或四电子氧化还原反应,形成Mo(Ⅵ、Ⅴ)配合物而变色,同时,PVA分子的部分羟基及该羟基位的碳上脱氢形成羰基而具有酮结构。此外,从Mo(V)的ESR特征信号随时间变化而减弱,但其吸收光谱的吸光度未变,于是推断该光化学反应过程中尚有Mo(Ⅳ)生成,已由XPS谱证实。     

Polyparametric modification equation for estimating thermodynamic properties of energetic nitro compounds

Calculation methods, based on hybrid density-functional theory with the basis sets of B3LYP/ 6-311+G (2d, p)//B3LYP/6-31G(d, p)and B3LYP/6-31+G(d)//B3LYP/6-31G(d, p), were applied to determine the thermodynamic characteristics of various energetic nitro compounds. A parametric modification equation and the least-squares approach were used to identify 21 of the energetic research compounds. The atomization energies of these 21 compounds have an average relative error of 0.21–0.25% of the experimental values. The enthalpy (H _f) and the Gibbs energy (G _f) of formation have mean absolute errors of 10.8–11.4 kJ/ mol (2.6–2.7 kcal/mol) and 10.0–10.3 kJ/mol (2.4 kcal/ mol), respectively. The enthalpy and the Gibbs energy of formation obtained exceed those in the literature obtained by semiempirical calculations. The calibrated least-squares parameters and parametric equations were used to predict H _f and G _f for the five newly developed energetic nitro compounds for further applications.Acknowledgements. The authors would like to thank the National Science Council of the Republic of China for financial support of this work under grant no. NSC-91-2113-M-014-003. The National Center for High-Performance Computing providing the computation facility is also acknowledged.     

Totally selective ring-opening of amino epoxides with ketones: a general entry to enantiopure (2R,3S)- and (2S,3S)-3-aminoalkano-1,2-diols

[Reaction: see text] Transformation of enantiopure diastereoisomers (2R,1'S)- and (2S,1'S)-2-(1-aminoalkyl)epoxides into the corresponding 4-(1-aminoalkyl)-1,3-dioxolanes is achieved by reaction with different ketones in the presence of BF3.Et2O. The conversion takes place in very high yields, total selectivity, and without epimerization. A mechanism to explain this transformation is proposed. The obtained 1,3-dioxolanes can be deprotected, and (2R,3S)- and (2S,3S)-3-aminoalkano-1,2-diols were isolated.     

Palladium-catalyzed tandem cyclization/Suzuki coupling of 1,6-enynes: reaction scope and mechanism

A palldium(0)-catalyzed tandem cyclization/Suzuki coupling reaction of various 1,6-enyne substrates was developed. This Pd-catalyzed enyne cyclization reaction represents a new process for the synthesis of stereodefined alpha-arylmethylene-gamma-butyrolactones, lactams, multifunctional tetrahydrofurans, pyrrolidines, and cyclopentanes. The mechanism of the reaction was studied by the employment of different enyne isomers and boronic acids; a pi-allyl palladium intermediate was suggested to explain the formation of the cyclic products. The stereochemistry of this reaction can be well explained by a chairlike transition state.