Studies on the V－Cu－S Heterometallic Cluster Compounds（2）．Crystal Structure of［VS_4（CuPPh_3）_5Br_2］·0．5CH_2Cl_2

ＳｔｕｄｉｅｓｏｎｔｈｅＶ－Ｃｕ－ＳＨｅｔｅｒｏｍｅｔａｌｌｉｃＣｌｕｓｔｅｒＣｏｍｐｏｕｎｄｓ（２）．ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ［ＶＳ_４（ＣｕＰＰｈ_３）_５Ｂｒ_２］·０．５ＣＨ_２Ｃｌ_２ＺｈｅｎｇＦａ－Ｋｕｎ；ＹｕＸｉｕ－Ｆｅｎ（Ｓｔａ...     

Crystal Structure and Spectrum Properties of a Manganese Complex with Schiff Base Ligand，Mn（bzacen）（pyrimidine）（NCS）

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅａｎｄＳｐｅｃｔｒｕｍＰｒｏｐｅｒｔｉｅｓｏｆａＭａｎｇａｎｅｓｅＣｏｍｐｌｅｘｗｉｔｈＳｃｈｉｆｆＢａｓｅＬｉｇａｎｄ，Ｍｎ（ｂｚａｃｅｎ）（ｐｙｒｉｍｉｄｉｎｅ）（ＮＣＳ）￥ＦｅｎｇＹｕｎ－Ｌｏｎｇ；ＬｉｕＳｈｉ－...     

Flow－injection Chemiluminescence Sensor for the Determination of Free Chlorine in Tap Water

Ｆｌｏｗ－ｉｎｊｅｃｔｉｏｎＣｈｅｍｉｌｕｍｉｎｅｓｃｅｎｃｅＳｅｎｓｏｒｆｏｒｔｈｅＤｅｔｅｒｍｉｎａｔｉｏｎｏｆＦｒｅｅＣｈｌｏｒｉｎｅｉｎＴａｐＷａｔｅｒＳｈｕＮａＬＩＵ；ＷｅｉＱＩＮ；ＺｈｕＪｕｎＺＨＡＮＧ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉ...     

A New Advance in Preparation of Mo-S(O) Clusters

ＡＮｅｗＡｄｖａｎｃｅｉｎＰｒｅｐａｒａｔｉｏｎｏｆＭｏ－Ｓ（Ｏ）Ｃｌｕｓｔｅｒｓ￥ＹａｏＹｕａｎ－Ｇｅｎ；ＷｕＬｉｎｇ；ＺｈｕＹｏｎｇ－Ｂａｏ；ＬｕＳｈａｏ－Ｆａｎｇ；（ＦｕｊｔａｎＩｎｓｔｉｔｕｔｅｏｆＲｅｓｅａｒｃｈｏｎｔｈｅＳｔｒｕｃｔｕｒｅ...     

A Neutron Diffraction Study for the Crystal Structure of the Deuterium（hydrogen） L－Arginine Phosphate Monohydrate

ＡＮｅｕｔｒｏｎＤｉｆｆｒａｃｔｉｏｎＳｔｕｄｙｆｏｒｔｈｅＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆｔｈｅＤｅｕｔｅｒｉｕｍ（ｈｙｄｒｏｇｅｎ）Ｌ－ＡｒｇｉｎｉｎｅＰｈｏｓｐｈａｔｅＭｏｎｏｈｙｄｒａｔｅＣｈｅｎｇＺｈｉ－Ｘｕ；ＣｈｅｎｇＹｕＦｅｎ；Ｇｕ...     

Effects of Y(Ⅲ) Ions on the Fluorescence Properties of Ce(Ⅲ) Ion and the Organic Ligands in the Comp

ＥｆｆｅｃｔｓｏｆＹ（Ⅲ）ＩｏｎｓｏｎｔｈｅＦｌｕｏｒｅｓｃｅｎｃｅＰｒｏｐｅｒｔｉｅｓｏｆＣｅ（Ⅲ）ＩｏｎａｎｄｔｈｅＯｒｇａｎｉｃＬｉｇａｎｄｓｉｎｔｈｅＣｏｍｐｌｅｘＬＩＷｅｎ－ｌｉａｎ．（ＣｈａｎｇｃｈｕｎＩｎｓｔｉｔｕｔｅｏｆＰｈｙｓｉｃｓ...     

两种新的时间分辨光谱技术

时间分辨光谱（Ｔｉｍｅ Ｒｅｓｏｌｖｅｄ Ｓｐｅｃｔｒｏｍｅｔｒｙ, ＴＲＳ）是研究物质光物理、光化学性质的基本手段。本文简要介绍了这一领域中较新的两种光谱技术：相调制法测定荧光寿命（Ｐｈａｓｅ－ｓｈｉｆｔ ａｎｄ 　Ｄｅｍｏｄｕｌａｔｉｏｎ Ｍｅａｓｕｒｅｍｅｎｔ ｏｆＦｌｕｏｒｅｓｃｅｎｃｅ　Ｌｉｆｅｔｉｍｅ）和利用步进扫描（Ｓｔｅｐ－Ｓｃａｎ）技术测量瞬态红外吸收光谱。     

Studies on the Stability of Four－membered Ring Chelates（Ⅳ）──Sulphur Coordinated Xanthate Complexes

ＳｔｕｄｉｅｓｏｎｔｈｅＳｔａｂｉｌｉｔｙｏｆＦｏｕｒ－ｍｅｍｂｅｒｅｄＲｉｎｇＣｈｅｌａｔｅｓ（Ⅳ）──ＳｕｌｐｈｕｒＣｏｏｒｄｉｎａｔｅｄＸａｎｔｈａｔｅＣｏｍｐｌｅｘｅｓＺＵＯＢｅｎ－ｃｈｅｎｇ；ＹＡＮＧＹｕｅ－ｈｕｉ；ＺＨＡＮＧＸｉａｏ－ｌｉ...     

Formation of Self-organization InAs Quantum Dots on (001) InP Substrate by As/P Exchange Reaction in MOCVD

ＦｏｒｍａｔｉｏｎｏｆＳｅｌｆ┐ｏｒｇａｎｉｚａｔｉｏｎＩｎＡｓＱｕａｎｔｕｍＤｏｔｓｏｎ（００１）ＩｎＰＳｕｂｓｔｒａｔｅｂｙＡｓ／ＰＥｘｃｈａｎｇｅＲｅａｃｔｉｏｎｉｎＭＯＣＶＤ＊ＷＡＮＧＢｅｎ－ｚｈｏｎｇ＊,ＺＨＡＯＦａｎｇ－ｈａｉ,ＰＥＮＧＹ...     

Neutron Diffraction Study on Structure of α－LiIO_3 Single Crystal under DC Voltage

ＮｅｕｔｒｏｎＤｉｆｆｒａｃｔｉｏｎＳｔｕｄｙｏｎＳｔｒｕｃｔｕｒｅｏｆα－ＬｉＩＯ_３ＳｉｎｇｌｅＣｒｙｓｔａｌｕｎｄｅｒＤＣＶｏｌｔａｇｅＣｈｅｎｇＹｕ－Ｆｅｎ；ＹａｎｇＺｈｅｎ；ＣｈｅｎｇＺｈｉ－Ｘｕ；ＧｕｏＬｉ－Ｐｉｎｇ（ＣｈｉｎａＩｎｓｔｉ?..     

新型含噻吩基8-羟基喹啉锌配合物的合成及光电性能简

设计合成了含噻吩基的新型配体(E)-2-[2-(3-噻吩基)乙烯基]-8-羟基喹啉(4)及相应的锌配合物5,产物结构经核磁共振、红外光谱和元素分析进行表征. 利用X射线单晶衍射仪测定了中间体(E)-2-[2-(3-噻吩基)乙烯基]-8-乙酰氧基喹啉(3)和配体4的单晶结构,结果表明中间体3晶体分子间并无明显的氢键作用,分子间呈交错堆叠;配体4分子之间由硫氢氧键弱作用相互排列形成网状结构. 通过核磁滴定及紫外和荧光滴定模拟了配体4在溶液中与金属锌的配位过程. 固体荧光寿命研究结果表明,配合物5的荧光寿命为18.8 ms. 通过电致发光器件研究发现,配合物5作为发光层具有良好的电致发光性能,同时具有较好的电子传输能力.     

新型含噻吩基8-羟基喹啉锌配合物的合成及光电性能

设计合成了含噻吩基的新型配体(E)-2-[2-(3-噻吩基)乙烯基]-8-羟基喹啉(4)及相应的锌配合物5, 产物结构经核磁共振、 红外光谱和元素分析进行表征. 利用X射线单晶衍射仪测定了中间体(E)-2-[2-(3-噻吩基)乙烯基]-8-乙酰氧基喹啉(3)和配体4的单晶结构, 结果表明中间体3晶体分子间并无明显的氢键作用, 分子间呈交错堆叠; 配体4分子之间由硫氢氧键弱作用相互排列形成网状结构. 通过核磁滴定及紫外和荧光滴定模拟了配体4在溶液中与金属锌的配位过程. 固体荧光寿命研究结果表明, 配合物5的荧光寿命为18.8 ms. 通过电致发光器件研究发现, 配合物5作为发光层具有良好的电致发光性能, 同时具有较好的电子传输能力.     

Pyrophosphate-selective fluorescent chemosensor based on 1,8-naphthalimide-DPA-Zn(II) complex and its application for cell imaging

A new zinc(II) complex with a two-dipicolylamine-substituted 1,8-naphthalimide for recognition of pyrophosphate with ratiometrical fluorescence changes in aqueous solution has been synthesized and characterized. Its biological application to monitor the intracellular pyrophosphate (PPi) was successfully demonstrated by the observation that the fluorescence of 1 was enhanced by the presence of the Zn(2+) ion and was quenched by addition of PPi.     

Dendrimers as ligands: an investigation into the stability and kinetics of Zn2+ complexation by dendrimers with 1,4,8,11-tetraazacyclotetradecane (cyclam) cores

We have investigated the complexation of Zn(2+) with 1,4,8,11-tetrakis(naphthylmethyl) cyclam (1; cyclam=1,4,8,11-tetraazacyclotetradecane) and with two dendrimers consisting of a cyclam core with four dimethoxybenzene and eight naphthyl appendages (2), and twelve dimethoxybenzene and sixteen naphthyl appendages (3). An important, common feature of model compound 1 and dendrimers 2 and 3 is that their potentially fluorescent naphthyl units are quenched by exciplex formation with the cyclam nitrogen atoms. Complexation with Zn(2+), however, prevents exciplex formation and results in the appearance of an intense naphthyl fluorescence signal that can be used for monitoring the complexation process. Luminescence titration, together with competition experiments and (1)H NMR titration, have shown that 1:1 and 1:2 (metal/ligand) complexes are formed in the cases of 2 and 3, whereas model compound 1 gives only a 1:1 complex. We have also investigated the 1:1 complexation kinetics by the stopped-flow technique. In the case of 1, a second-order process (k(1)=44x10(5) M(-1) s(-1)) is followed by two consecutive first-order steps (k(2)=0.53 s(-1) and k(3)=0.10 s(-1)). For 2, a slower second-order process (k(1)=4.9x10(5) M(-1) s(-1)) is followed by a slow first-order step (k(2)=0.40 s(-1)). In the case of 3, only a very slow second-order process was observed (k(1)=1.2x10(5) M(-1) s(-1)). The different metal-ion incorporation rates for model compound 1 and dendrimers 2 and 3 have been discussed in terms of conformational changes of the dendron subunits affecting the chelating properties of the cyclam core. This work reports the first kinetic study on metal-ion coordination by dendrimers with a well-defined coordination site.     

Tetrakis(2-quinolinylmethyl)ethylenediamine (TQEN) as a new fluorescent sensor for zinc

A new fluorescent sensor for zinc that binds 1 equivalent of zinc ion, N,N,N',N'-tetrakis(2-quinolylmethyl)ethylenediamine (TQEN), has been prepared and characterized. Zinc-bound TQEN exhibits fluorescence around 383 nm upon excitation at 317 nm, while free TQEN emits very weak fluorescence. UV-Vis and 1H NMR spectral changes also detected the binding of TQEN with zinc ion. The crystal structure of zinc complex with TQEN was determined by X-ray crystallography and compared with that of the TPEN-Zn complex (TPEN =N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine). The binding affinity of TQEN with zinc ion is very high (Kd < 1 microM in aqueous dmf solution). Competition experiments reveal that the zinc-binding affinity of TQEN is lower than the parent, strong metal ion chelator TPEN, and comparable to EGTA (EGTA = ethylene glycol-bis(2-aminomethyl)-N,N,N',N'-tetraacetic acid).     

1-乙酰基-3-(2-羟基-4,6-二甲氧基苯基)-5-苯基-2-吡唑啉的合成及锌离子探针的研究

设计合成了1-乙酰基-3-(2-羟基-4,6-二甲氧基苯基)-5-苯基-2-吡唑啉(4), 测试了其紫外光谱和荧光光谱, 研究了其对锌离子的选择性识别作用. 结果表明, 化合物4作为锌离子荧光探针, 受常见离子的干扰较小, 对于锌离子有着较高的选择性和较低的检出限.     

Dendrimers as ligands. Formation of a 2:1 luminescent complex between a dendrimer with a 1,4,8,11-tetraazacyclotetradecane (cyclam) core and Zn2+

We have investigated the formation of metal complexes between Zn2+ and two derivatives, 1 and 2, of the well-known 1,4,8,11-tetraazacyclotetradecane (cyclam) ligand. Compound 1 is 1,4,8,11-tetrakis(naphthylmethyl) cyclam, and compound 2 is a dendrimer consisting of a cyclam core with appended 12 dimethoxybenzene and 16 naphthyl units. Compound 1 exhibits an emission band with a maximum around 480 nm, assigned to the formation of exciplexes between amine and excited naphthyl units. Dendrimer 2 exhibits three types of weak emission bands, assigned to naphthyl localized excited states (lambdamax = 337 nm), naphthyl excimers (lambdamax ca. 390 nm), and naphthyl-amine exciplexes (lambdamax = 480 nm). In CH3CN-CH2Cl2 1:1 v/v, titration of ligand 1 with Zn2+ causes the disappearance of the exciplex emission and the appearance of a strong naphthyl localized fluorescence; the titration plot is linear and reaches a plateau for a 1:1 stoichiometry, showing that a highly stable [Zn(1)]2+ complex is formed. In the case of 2, titration with Zn2+ causes the disappearance of the exciplex band, with a concomitant increase in the excimer and naphthyl localized emissions; the titration plot is again linear, but in this case it reaches a plateau for a 2:1 stoichiometric ratio, showing the unexpected formation of a [Zn(2)2]2+ complex. Such an unexpected stoichiometry for the complex of the dendritic ligand has been fully confirmed by 1H NMR titrations. The results obtained show that the dendrimer branches not only do not hinder, but in fact favor coordination of cyclam to Zn2+.     

基于N-(9-蒽甲基)-L-组氨酸的NOR荧光逻辑门

合成了一个新的组氨酸衍生物, N-(9-蒽甲基)-L-组氨酸(1), 并对其进行了元素分析、电喷雾电离质谱(ESI-MS)、核磁共振氢谱(1H-NMR)和碳谱(13C-NMR)等波谱表征. 考查了pH值及15种不同金属离子对其荧光强度的影响. 实验结果表明, 中性水溶液条件下, Zn2+和Cd2+能使体系荧光增强, 而Pb2+、Co2+、Hg2+、Ni2+和Cu2+等则使体系荧光有不同程度的猝灭.其中, Cu2+和Ni2+猝灭能力最强, 它们与化合物1均形成了物质的量比为1:2的配合物, 络合常数分别为2.88×10⁶和1.12×10⁶ L2·mol-2. Cu2+和Ni2+对化合物1的荧光猝灭为静态猝灭过程. 在此基础上, 以Cu2+和Ni2+作为两个输入信号, 以蒽的特征荧光发射作为输出信号, 构建了一个NOR荧光分子逻辑门.     

Stepwise Synthesis and Spectral Characteristics of meso-trans-Diphenyldi(1-naphthyl)tetrabenzoporphin and Its Zinc Complex

A reaction of phthalimide with phenylacetic acid in the presence of zinc oxide furnished 3-oxoisoindolenyl-3'-oxoisoindolinylidene-1,1'-benzylidine which at heating with 1-naphthylacetic acid in the presence of zinc oxide provided zinc meso-trans-diphenyldi(1-naphthyl)tetrabenzoporphin complex. Proceeding from this compound a meso-trans-diphenyldi(1-naphthyl)tetrabenzoporphin was prepared. The spectral characteristics of compounds obtained were studied.     

Water-soluble distyrylbenzenes: one core with two sensory responses--turn-on and ratiometric

The synthesis of four water-soluble distyrylbenzenes (compounds 1-4) is reported. Their acidochromicity in aqueous media was investigated. Blue shifts and increases in the quantum yields were observed as a general response. The pH-dependent photophysics of 1b-3b in water reveal unexpected protonation sequences upon titration: compound 1b is green-yellow fluorescent at high pH (10) but becomes very weakly fluorescent between pH 5 and pH 3, whereas below pH 2 strong blue fluorescence is observed. This behavior can be explained in terms of the interplay in the protonation of aniline and of the carboxylate groups. In compound 4, a higher basicity of the amino group is observed and ratiometric fluorescence change takes place upon protonation or on reaction with zinc salts in water. Compound 4 can therefore act as a weak ratiometric zinc ligand in water, even though it has only a dimethylamino unit as a binding motif.