Upconversion and fluorescence spectral studies of Er3+/Yb3+-codoped Bi(2)Q(3)-GeO2-Ga(2)Q(3)-Na2O glasses

The absorption spectra and upconversion fluorescence spectra of Er3+/-Yb3+-codoped natrium-gallium-germanium-bismuth glasses are measured and investigated. The intense green (533 and 549 nm) and red (672 nm) emission bands were simultaneously observed at room temperature. The quadratic dependence of the green and red emission on excitation power indicates that the two-photon absorption processes occur. The influence of Ga2C3 on upconversion intensity is investigated. The intensity of green emissions increases slowly with increasing Ga2O3 content, while the intensity of red emission increases significantly. The possible upconversion mechanisms for these glasses have also been discussed. The maximum phonon energy of the glasses determined based on the infrared (IR) spectral analysis is as low as 740 cm(-1). The studies indicate that Bi2O3-GeO2-Ga2O3-Na2O glasses may be potential materials for developing upconversion optical devices (c) 2006 Published by Elsevier B.V.

Synthesis and applications of 3-[6-(hydroxymethyl)pyridin-2-yl]-1,1 '-bi-2-naphthols or 3,3 '-bis[6-(hydroxymethyl)pyridin-2-yl]-1,1 '-bi-2-naphthols

A series of new 1,1'-bi-2-naphthol (BINOL) derived ligands, 3-[6-(hydroxymethyl)pyridin-2-yl]-BINOLs or 3,3'-bis[6(hydroxymethyl)pyridin-2-yl]-BINOLs, bearing one or two chiral pyridinylmetlianols attached to a binaphthyl skeleton, have been synthesized using the Suzuki cross-coupling reaction. The resulting compounds have been used as ligands in the enantioselective addition of diethylzinc to aldehydes; the products were obtained with up to 96% ee.

Synthesis and properties of optically active aromatic polyimides derived from optically pure 1,1'-bi-2-naphthol

A series of new optically active aromatic polyimides containing axially dissymmetric 1,1'-binaphthalene-2,2-diyl units were prepared from optically pure (R)-(+)-or (S)-(-)-2,2'-bis(3,4-dicarboxyphenoxy)-1,1'-binaphthalene dianhydrides and various aromatic diamines via a conventional two-step procedure that included ring-opening polycondensation and chemical cyclodehydration. The optically pure isomer of dianhydride was prepared by a nucleophilic substitution of optically pure (R)-(+)or (S)-(-)1,1'-bi-2-naphthol with 4-nitrophthalonitrile in aprotic polar solvent and subsequent hydrolysis of the resultant tetranitrile derivatives, followed by the dehydration of the corresponding tetracarboxylic acids to obtain the dianhydrides. These polymers were readily soluble in common organic solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and m-cresol, etc., and have glass transition temperatures of 251-296 degrees C, and 5% weight loss occurs not lower than 480 degrees C. The specific rotations of the optically active polyimides ranged from +196 degrees to +263 degrees, and the optical stability and chiroptical properties of them were also studied. (C) 1997 John Wiley & Sons, Inc.

The synthesis of a 1,1'-bi-2-naphthol-based bis(ether anhydride) and aromatic polyimides derived therefrom

2,2'-Bis(3,4-dicarboxyphenoxy)-1,1'-binaphthyl dianhydride was used as a new monomer with various aromatic diamines to obtain polyimides by the usual two-step method. The bis(ether anhydride) was prepared by a nucleophilic substitution of I,1'-bi-2-naphthol with N-phenyl-4-chlorophthalimide, N-methyl-4-nitrophthalimide or 4-nitrophthalonitrile in aprotic polar solvent, and subsequent hydrolysis of the resulting bis(ether imide)s or bis(ether dinitrile), and then dehydration of the corresponding tetracarboxylic acid to afford the dianhydride. Most of the obtained polyimides were soluble in chloroform, pyridine, DMF, etc. The polyimide prepared from p-phenylene diamine was partial crystalline, whereas the others showed amorphous patterns in a WAXD study. These polymers have glass transition temperatures between 255-294 degrees C and 5% weight loss temperatures in the range of 502-541 degrees C in nitrogen and 473-537 degrees C in air. (C) 1997 Elsevier Science Ltd.

Synthesis of new bis-BINOLs linked by a 2,2 '-bipyridine bridge

A series of new G-symmetric chiral ligands 8, 9, 11 and 12, consisting of two binaphthyl units linked by a 2,2'-bipyridine bridge, has been synthesized via Suzuki cross-coupling reactions.

Synthesis and characterization of optically active aromatic polyimides derived from 2,2 '-bis(2-trifluoro-4-aminophenoxy)-1,1 '-binaphthyl and aromatic tetracarboxylic dianhydrides

Optically active 2,2'-bis(2-trifluoro-4-aminophenoxy)-1,1'-binaphthyl and its corresponding racemate were prepared by a nucleophilic substitution reaction of 1,1'-bi-2-naphthol with 2-chloro-5-nitrotrifluorotoluene and subsequently by the reduction of the resulting dinitro compounds. a series of optically active and optically inactive aromatic polyimides also were prepared therefrom, These polymers readily were soluble in common organic solvents such as pyridine, N,N'-dimethylacetamide, and m-cresol and had glass-transition temperatures of 256 similar to 278 degrees C. The specific rotations of the chiral polymers ranged from 167 similar to 258 degrees, and their chiroptical properties also were studied. (C) 1999 John Wiley & Sons Inc.

New optically active aromatic polyimides II: Synthesis and properties of optically active aromatic polyimide based on (R)-(+)-2,2 '-bis(2-trifluoro-4-aminophenoxy)-1,1 '-binaphthyl

Optically active (R)-(+)-2, 2'-bis(2-trifluoro-4-aminophenoxy)-1, 1'-binaphthyl was prepared from 1, 1'-bi-2-naphthol. The optically active aromatic polyimide was also successfully synthesized. This new polymer has good solubility, thermal stability etc. Its specific rotation was found to be +174 degrees, and its chiroptical property was also studied.

(+/-)-7,7,9,9-Tetramethyl-2,3 : 4,5-dinaphthol,6,8-trioxa-7,9-disilacyclonona-2,4-diene

The title compound, C24H24O3Si2, is a twofold symmetric silicocrown ether with the two dimethylsilyl groups attached to the O atoms of 1,1'-bi-2-naphthol, and bridged by another O atom.

超宽带光纤放大器用的新型掺铋发光材料

最近，一种新型的掺铋发光材料引起了人们的关注。这种发光材料有长的荧光寿命（τ＞200μs），在800nm激光激发下发射波长在1200～1600nm区间的超宽带荧光（荧光半高宽FWHM＞200nm），其发光性质与以往文献中报道的Bi^3＋或Bi^2＋掺杂的发光材料的性质截然不同；光发射截面（σem）是光掺铒光纤放大器玻璃（EDFAG）的2～3倍，其σem×FWHM值是EDFAG的10倍左右，σem×τ值是掺Ti^3＋蓝宝石的3倍左右。

Synthesis, characterization and catalytic properties of chiral BINOL functionalized mesoporous silicas for enantioselective Morita-Baylis-Hillman reaction

Several Chiral BINOL functionalized mesoporous silicas were prepared by post grafting of organosilane derivatives of (S)-BINOL (1,1'-bi-2-naphthol) on SBA-15 and characterized by C-13 CP/MAS NMR, FT-IR, UV-visible absorption spectra, elemental analysis, powder XRD, nitrogen adsorption-desorption isotherms and TEM techniques. Their catalytic properties were demonstrated in enantioselective Morita-Baylis-Hillman reaction of 3-phenylpropanal and cyclohexenone.

Asymmetric Michael addition of aldehydes to nitroolefins catalyzed by L-prolinamide derivatives using phenols as co-catalysts

The asymmetric Michael addition of aldehydes to nitroolefins was investigated using L-prolinamide derivatives of 2-(2'-piperidinyl)pyridine as catalyst and a variety of phenols as co-catalyst. Extensive screening toward the effect of prolinamides, phenols, and solvents on this transformation revealed that a combination of (S)-2-(2'-piperidinyl)pyridine-derived trans-4-hydroxy-L-prolinamide 2c, (S)-1,1'-bi-2-naphthol, and dichloromethane was a promising system. This system was shown to be amenable to a rich variety of aldehydes and nitroolefins and afforded the nitroaldehyde products with excellent yield, enantiomeric excess (up to 99%) and diastereoselectivity ratio (up to 99/1), even in the case of 1 mol % catalyst loading and 1.5 equiv of aldehydes.

云南澜沧老厂大型银多金属矿床成矿年代及地球化学

老厂矿床位于三江成矿带南段昌宁—孟连裂谷的次级澜沧断陷盆地中，昌宁—孟连裂谷是三江成矿带南段的重要成矿段之一，其大地构造位于保山―掸邦微陆块东缘，兰坪—思茅盆地、临沧地块西缘，属东特提斯构造域，是冈瓦纳古陆与欧亚大陆巨型缝合带的组成部分。 矿床开采历史悠久，始于明朝永乐二年（1404年），至今已605年。古时炼银弃铅，最高年产白银30万两。解放后主要开采古人废弃的高铅炉渣，并对深部原生矿体进行了初步勘探，90年代至今对深部银铅矿体进行了详细勘查，深部矿体是矿床主要的开采对象。它以独特的成矿地质特征、富银（铅锌矿石中平均含量为629×10-6，方铅矿中平均2069×10-6）、伴生元素多（In、Se、Te、Ga、Cd、Bi）、规模大（In、Se、Te、Cd已达大型规模）、含Sn等特征而受到广大地质工作者的关注。它是“三江”成矿带南段最具代表性的铅银矿床类型之一，也是昌宁—孟连裂谷内目前探明的唯一大型银铅锌多金属矿床，具有十分重要的研究价值。 虽然前人已从矿床地质、成矿条件、控矿因素等方面对老厂大型银铅锌多金属矿床进行过研究，但研究工作较为零散，在成矿物质与成矿流体来源、矿床成因、花岗斑岩与成矿等方面还存在较大争议。本文在深入细致的野外地质工作基础上，利用多种现代分析测试技术，对矿床进行了较为系统的矿物学、岩石学、年代学和矿床地球化学研究，进而查明了矿床成矿物质与成矿流体来源、揭示了成矿地球动力学背景、探讨了矿床的成因、初步建立了矿床成因模式。论文取得的主要成果如下： 1．查明了硫化物的物质组分及形成阶段。闪锌矿以高铁（早期平均11.51%，晚期平均8.41%）为基本特征，并伴生多种特征的微量元素，早期闪锌矿是Fe、In的主要载体，Cu、Cd、Mn则主要富集在晚阶段闪锌矿中；方铅矿是Ag的主要载体，其早期富Ag、Te、Bi，含Se、Cu，中期主要富Ag，晚期以含As、Bi为特征；其它硫化物成分较单一。 2．揭示了伴生元素赋存状态和富集规律。矿床伴生元素含量高，闪锌矿中Cd平均4293.19×10-6，In平均555.37×10-6，方铅矿中Te平均143.81×10-6，As、Se、Bi、Ga含量也很高。初步估算金属储（万吨）量分别为： Ga 0.097，Cd1.84， In0.13，Se0.06 ，Te0.15，Bi1.28，As4.31。闪锌矿是Ga、In、Cd主要载体，Te、Bi主要赋存在方铅矿中，Se则主要在铅锌、黄铁矿石中富集。 3．首次获得了精确的成矿年代学数据。单颗粒闪锌矿—黄铁矿Rb-Sr法获得矿床成矿年龄t=（45±3.6）Ma，（87Sr/86Sr）i=0.70977±0.00034。证实了矿床成矿与隐伏花岗斑岩关系密切，矿床形成是三江成矿带南段对喜马拉雅碰撞造山成矿运动的响应。 4．首次系统研究了花岗斑岩的地质、地球化学特征。矿床花岗斑岩具高硅、超钾、富碱、贫钠和低镁、钙、铁、磷的特征，岩石为过铝质岩石；其轻稀土富集、Eu为弱负异常、基本无Ce异常、岩石富集大离子亲石元素，具有较高的锶初始值和较低εNd及高的Nd模式年龄，与三江地区富碱斑岩具有相似的地球化学特征。岩浆主要来源于加厚下地壳重熔，成岩过程中有地幔物质的加入，为同碰撞构造环境下形成。 5．首次探讨了容矿沉积建造及矿石、矿物的地球化学特征。矿床碳酸盐岩轻稀土富集、Eu正异常及Ce异常和其微量元素特征与热水沉积岩石相似，表明了碳酸盐岩的热水沉积成因，同时矿石及其硫化物微量和稀土元素特征也指示了在早石炭世矿区发生了广泛的火山喷流热水沉积成矿作用。 6．查明了成矿物质及成矿流体来源。成矿元素研究显示矿床成矿物质具有多来源的特征，Pb同位素研究表明矿床Pb可能来自不同地层岩石的淋滤， S同位素组成显示其可能主要来源于海水对下伏火山岩地层的淋滤与海水硫酸盐的还原，花岗斑岩岩浆也可能提供了部分S。C-O、H-O同位素和矿石及其硫化物稀土元素反映矿床早期成矿流体主要源于深部岩浆，晚期主要来源于喜山期花岗斑岩岩浆热液。 7．初步建立了成矿模式。老厂矿床是长期以来多种地质作用下的综合产物，具有成矿物质多来源，成矿阶段多期次特点。经历了早石炭世火山喷流热水沉积成矿和喜山期花岗斑岩岩浆热液叠加改造成矿作用，热水成矿作用下形成了以黄铁矿为主的块状硫化物矿床，喜山期富碱花岗斑岩岩浆热液流体携带了大量的Cu、Mo、Ag、Pb等成矿元素，在它的叠加改造作用下形成了老厂银多金属矿床。总之矿床为火山喷流沉积—岩浆热液叠加改造成因。

Hydrothermal synthesis and structure of [{Mo8V4O36(VO4)(VO)(2)}(n)](7n-) bi-capped alpha-Keggin fragments linked to a chain

The title compound, (H(2)en)(3)H3O {MO8V4O36 (VO4) (VO)(2)} . 4H(2)O, was hydrothermally synthesized and structurally characterized by means of IR, ESR spectrum and single crystal X-ray diffraction. It crystallized in a monoclinic system with space group P2(1)/c, a=1. 980 4(4) nm, b=2. 063 4(4) nm, c=1. 192 0(2) nm, (beta =94. 76(3)degrees and deep black colour. The compound contains V-centered bi-capped alpha -Keggin fragments {Mo8V7O42} that are linked together by edge-shared units (VO5)-O-N via V-O-V bonds, forming a chain.