Sugar conjugates of fulvestrant (ICI 182,780): efficient general procedures for glycosylation of the fulvestrant core

We have prepared glucose and cellobiose conjugates at the phenolic 3- and hydroxylic 17-positions of the pure anti-estrogenic compound fulvestrant (ICI 182,780), which has recently been approved in the USA for the treatment of advanced postmenopausal breast cancer. Glycosylation at the 17-position was achieved most effectively using pivaloyl protection of the sugar imidates employed, which we found suppressed the competing transacylation reaction and led to improved yields of the product glycosides.     

A density functional theory computational study of the role of ligand on the stability of CuI and CuII species associated with ATRP and SET‐LRP

Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with Cu^I and trigonal bipyramidal with axial halide complexes with [Cu^IIX]⁺ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [Cu^IIX]⁺ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [Cu^IIX]⁺ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007     

锰(Ⅱ)-高碘酸钾-灿烂绿体系测定水中痕量锰

在 HAc- Na Ac环境中 ,锰 ( )对于高碘酸钾氧化灿烂绿的反应具有很强的催化作用。据此 ,建立了催化动力学光度法测定痕量锰 ( )的新方法。该方法的检出限为 2 .2 2× 10 -11g/ m L ,测定线性范围为0 .1— 12 ng/ m L。直接用于环境水样中锰的测定 ,获得满意的结果     

关于均值KIRCHHOFF板非线性边界镇定问题的几点注记

对于均值K IRCHHOFF板非线性边界镇定问题给出几点注记.首先应用G reen公式对具有非线性边界反馈控制的均值K IRCHHOFF板所决定的非线性系统的能量衰减速度进行了重新推导,从而修正了前人的结果.然后应用极大单调函数的定义和分部积分技巧,对均值K IRCHHOFF板非线性边界镇定问题所决定的非线性算子A的极大单调性给出了重新证明,进而更正了已有文献中相应证明的欠妥之处.     

新型稀土芳香羧酸类配合物的合成及其光致和电致发光性质

合成了新型可溶性稀土芳香羧酸类配合物，测定了有机配体的三重态能级，并考察了其光致发光相对强度、荧光寿命，发现该系列稀土配合物具有很高的光致发光效率。利用其优良的溶解性，采用高聚物掺杂、旋涂技术将其制成薄膜应用于电致发光研究中，成功地制备出具有高色纯度的稀土有机电致发光器件。对于ITO／PVK／PVK：Tb(AS)3Phen：PBD／PBD／Al电致发光器件，其最大亮度为32cd．m^-2。     

硅酸盐中桥联键的机制及其性质的CNDO/2法研究

法计算模型,分析了桥联键的成键机制,解释了硅酸盐的通常性质。以体系总能量随桥角变化关系,解释了硅酸盐矿物及沸石分子筛中桥角Si-O-T出现的范围和几率。 由计算结果还发现,桥氧上具有较高的非键p-电子电荷Q_o~n,并随桥氧的第三配原子性质和距离R(M-O~(br))而变化,使桥氧具有授受电子的双重性质。在此基础上,探讨了沸石分子筛的碳离子催化活性机理,提出了锁与匙匹配原子对的催化活性中心的新观点。     

Development and critical comparison of greener flow procedures for nitrite determination in natural waters

Two greener procedures for flow-injection spectrophotometric determination of nitrite in natural waters were developed and critically compared. Replacement of toxic reagents, waste minimization and treatment were exploited to attend the standards of clean chemistry. The flow system was designed with solenoid micro-pumps in order to minimize reagent consumption and waste generation. The first procedure is based on the Griess diazo-coupling reaction with sulfanilamide and N-(1-naphthyl)ethylenediamine (NED) yielding an azo dye, followed by photodegradation of the low amount of waste generated based on the photo-Fenton reaction. The second procedure is based on the formation of iodine from nitrite and iodide in acid medium in order to avoid the use of toxic reagents. For Griess method, linear response was achieved up to 1.0 mg L^− 1, described by the equation A = − 0.007 + 0.460C (mg L^− 1), r = 0.999. The detection limit was estimated as 8 μg L^− 1 at the 99.7% confidence level and the coefficient of variation was 0.8% (n = 20). The sampling rate was estimated as 108 determinations per hour. The consumption of the most toxic reagent (NED) is reduced 55-fold and 20-fold in comparison to batch method and flow injection with continuous reagent addition, respectively. A colorless residue was obtained by in-line photodegradation with reduction of 87% of the total organic carbon content. The results obtained for natural water samples were in agreement with those achieved by the reference method at the 95% confidence level. For the nitrite–iodide method, linear response was observed up to 2.0 mg L^− 1, described by the equation A = − 0.024 + 0.148C (mg L^− 1), r = 0.999. The detection limit was estimated as 25 μg L^− 1 at the 99.7% confidence level and the coefficient of variation was 0.6% (n = 20). The sampling rate was estimated as 44 determinations per hour. Despite avoiding the use of toxic reagents, the nitrite–iodide method presented worst performance in terms of selectivity and sensitivity.