Studies on the Syntheses , Structures and Properties of Shiff Base and Their Palladium(II), Zinc(II) Complexes

发光金属配合物一直是无机光化学领域的研究热点之一，设计和合成发光颜色可调控的稳定的金属配合物具有重要的理论和现实意义。发光金属配合物在LEDs材料，生物分析荧光探针，气敏、光敏传感，光催化产氢和离子识别中有着很广泛的应用。席夫碱衍生物是一类由醛或酮和胺、肼、脲及其衍生物缩合而成的化合物，是一类含有多个配位点的配体。通过在醛或酮和胺、肼、脲引入不同的发光基团就可以得到不同发光性质的金属配合物。 四配位的钯配合物在有机催化和生物活性方面有独特的应用，本文设计合成了一类缩氨基硫脲席夫碱钯的配合物，并获得了其晶体结构。研究了此类配合物紫外可见吸收光谱和荧光发射光谱以及阴离子加入对其光谱性质的影响，并...Luminescence metal complexes are a fascinating class of molecules that have found applications in many areas of photochemistry, LED materials, bio-analysis, gas-sensitive or photo-sensitive sensor, photocatalytic and ion recognition. Therefore, the design and synthesis of light-emitting color adjustable and stable metal complexes has important theoretical and practical significance. Schiff base de...学位：理学硕士院系专业：化学化工学院化学系_无机化学学号：2052007115100

Assembly of silver(I) coordination polymers incorporating pyromellitic acid and N-heterocyclic ligands

通讯作者地址: Huang, RB (通讯作者), Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] mixed ligands coordination polymers [Ag-4(apym)(2)(pma)center dot(H2O)(2)](n) (1), {[Ag-4(dmapym)(4)(pma)center dot(H2O)(2)]center dot(H2O)(6)](n) (2), [Ag-2(apyz)(2)(H(2)pma)center dot(H2O)(4)](n) (3), {[Ag-4(apyz)(2)(pma)center dot(H2O)(2)]center dot(H2O)(2)}(n) (4) and {Ag-4(NH3)(8)(pma)center dot(H2O)(6)](n) (5) (apym = 2-aminopyrimidine, dmapym = 4, 6-dimethyl-2-aminopyrimidine, apyz = 2-aminopyrazine, H(4)pma = pyromellitic acid) were synthesized and characterized. For 1 and 2, as the substituents change from H to methyl, the dimensions of 1-2 decrease from three-dimension (3D) to one-dimension (ID) due to the steric effect of methyl groups. For 3 and 4, as the ratios of Ag2O/apyz/pma vary from 1:1:1 to 2:1:1. the structure of 3 is a 1D ladder structure built from Ag-apyz double chains and pma anions, while the structure of 4 is a two-dimension (2D) grid. As excess ammonia is added to above four reaction systems, the structure of 5 contains unprecedented {[Ag(NH3)(2)](+)}(n) chains and pma anions. The substituent on the pyrimidyl ring, ratios of reactants, solvent systems and ligand isomers intensively influence the coordination environments of metal ion and the coordination modes of the carboxyl group, and thus determine the structures of the coordination polymers. The photoluminescent properties of 1-5 were also investigated. (C) 2010 Elsevier Ltd. All rights reserved.National Natural Science Foundation of China 20721001 MSTC 2007CB81530

Self-assembly of silver(I) coordination polymers from aminopyrimidyl derivatives and malonate acid: From 1D chain to 2D layer

通讯作者地址: Huang, RB (通讯作者), Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] new silver(I) coordination polymers (CPs) of the formula [Ag-2(dmapym)(4)(mal)center dot H2O](n) (1) and [Ag-3(apym)(3)(mal)NO3](n) (2) (dmapym = 2-amino-4,6-dimethylprimidine, apym = 2-aminopyrimidine, H(2)mal = malonate) have been synthesized by reactions of AgNO3 and 2-aminopyrimidyl ligands with malonate under the ammoniacal condition. Both complexes have been characterized by element analysis, IR and single-crystal X-ray diffraction. The monodentate dmapym and tridentate mal ligands link Ag(I) ions to give complex 1 a one-dimensional (1D) H-shaped chain structure. The complex 2 is a two-dimensional (2D) double sheet structure constructed by (4,4) single sheet. Additionally, the hydrogen-bonding and C-H center dot center dot center dot pi interactions also direct the self-assembly of supramolecular architectures. The photoluminescence properties of the 1 and 2 were investigated in the solid state at room temperature. (C) 2010 Elsevier B.V. All rights reserved.National Natural Science Foundation of China 20721001 MSTC 2007CB81530

Self-assembly, thermal stability and photoluminescence of two mixed-ligand silver(I) networks via 2D -> 2D and 2D -> 3D parallel interpenetration of (4,4) nets

通讯作者地址: Huang, RB (通讯作者), Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 2. Xiamen Univ, State key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] mixed-ligand silver(I) coordination polymers (CPs) [Ag-2(dmapym)(2)(suc)center dot H2O](n) (1) and [Ag-2(dmapym)(2)(bdc)center dot 2H(2)O](n) (2), (dmapym = 2-amino-4,6-dimethylpyrimidine, H(2)suc = succinic acid, H(2)bdc = 1,3-benzenedicarboxylic acid), were synthesized and characterized. The structure of 1 presents an argentophilic interaction enhanced 2-crossing [2]-catenane motif formed between pairs of parallel interpenetrating 2D 4(4)-sql nets. For 2, as the dicarboxylate changes from flexible H(2)suc to rigid V-shaped H(2)bdc, each highly undulated 2D 4(4)-sql net was penetrated in parallel by the two nearest neighbouring ones and thus the overall 2D -> 3D network is formed. The geometries and flexibility of dicarboxylates influence the coordination environments of metal ions and arrangement of ligands and thus determine the structures of the CPs. The photoluminescent and thermal properties of 1 and 2 have also been investigated.National Natural Science Foundation of China 20721001 MSTC 2007CB81530

Influence of symmetric benzene-polycarboxylate acids on the structures of silver-aminopyrimidyl derivative system

通讯作者地址: Huang, RB (通讯作者), Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 2. Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] novel coordination polymers, [Ag(BTC)(1/3)(ADMP)](n) (1), [Ag(BDC)(1/2)(ADMP)](n) (2) (2-amino-4,6-dimethylpyrimidine = ADMP; H3BTC = 1,3,5-benzenetricarboxylic acid; H2BDC = 1,4-benzenedicarboxylic acid), have been synthesized under the ammoniacal conditions and structurally characterized. In complex 1, H3BTC ligand showing a new coordination mode links silver atoms to generate a two-dimensional (2-D) honeycomb-like structure, which is further linked through ADMP ligands to produce a complicated three-dimensional (3-D) framework. Complex 2 features a 2-D infinite layer framework consisting of binuclear silver clusters, which is further stacked via intermolecular C-methyl-H center dot center dot center dot pi it short contacts and Van der Waals interactions to form a 3-D supramolecular architecture. (C) 2009 Elsevier B.V. All rights reserved.National Natural Science Foundation of China 20721001 MSTC 2007CB81530

Degradation of Rice Straw by Aspergillus glaucus Mutant and integration with Biohydrogen Production

对灰绿曲霉(Aspergillus glaucus)突变株EU7-22进行单因子和正交实验,确定菌株利用稻草产纤维素酶的液态发酵优化组合条件为:稻草粉3%、蛋白胨0.5%、温度35℃、起始pH 5。在优化条件下培养4~5 d可达到产酶高峰。利用优化培养后的酶液水解稻草粉产糖,在最适条件下,稻草粉酶解反应24 h后,糖化率可达49%。利用稻草粉做底物,EU7-22和产氢克雷伯氏菌HP1联合发酵,1 g稻草粉可产氢23.7 mL。The optimal conditions for cellulase production of Aspergillus glaucus mutant strain EU7-22 was achieved as follows: rice straw powder quantity 3%,peptone quantity 0.5%,original pH 5,and temperature 35℃,by orthogonal experiments.The strain reached its maximum cellulose activity after 4~5 days fermentation.When the cellulase was applied for saccharification of rice straw,a saccharification rate of 49% was obtained after 24h hydrolysis.The saccharification liquid was subsequently used for hydrogen production.A yield of 23.7 mL H2/g rice powder was acquired when using Klebsiella oxytoca HP1 as the hydrogen producer.国家“863”计划项目(2001AA515040);; 福建省重点科技项目(2005I016);; 厦门市科技项目(3502Z20041070

Screening of High-yield Cellulase Mutants of Aspergillus glaucus

以一株具有较高纤维素酶活性的野生菌株-灰绿曲霉XC9为出发菌株,经过紫外线、氯化锂、甲基磺酸乙酯(EMS)等物理化学诱变剂多重诱变处理,获得了抗葡萄糖阻遏的突变株E2-26、E5-65、U6-31和EU7-22,其CMC酶活与出发菌株相比分别提高至1.7、1.4、1.3、2.0倍.突变株经PDA斜面接种传代5次后产酶性能仍然保持稳定.变株的菌丝、孢子颜色也发生了较大的改变.对突变株EU7-22的形态结构进行了观察,并与出发菌株XC9作了发酵性状的比较,发现其产酶性能有了明显提高.Cellulase producing strain,Aspergillus glaucus XC9,was selected as the initial strain for mutation.Four mutant strains(E2-26,E5-65,U6-31,EU7-22)were obtained after it was treated multiplicatively with UV-ray,ethyl methane sulphonate(EMS)and LiCl.The CMC activity of mutants increased to 1.7,1.4,1.3 and 2.0 times comparing with the initial strain respectively.The spore colours of mutants also varied.The morphological and fermentative properties of mutant strain EU7-22 were studied in this paper.The producing capability of cellulase of mutant strain was remarkably enhanced.国家“863”计划项目(2001AA515040);; 福建省重点科技项目(2005I016);; 福建省青年科技人才创新项目(2005J003);; 厦门市科技项目(3502Z20041070)资

N-(对二甲氨基苯基)水杨醛亚胺选择性识别氟离子研究

以具有激发态分子内质子转移荧光的水杨醛亚胺衍生物N-(对二甲氨基苯基)水杨醛亚胺(1)为阴离子识别受体,研究了乙腈中受体1荧光对多种阴离子的响应,发现1对氟离子表现出高的响应选择性.乙腈中1的质子转移荧光位于545 nm,加入氟离子后,于479 nm处出现1的阴离子荧光.氟离子经由布朗斯特酸碱作用影响受体1的激发态质子转移荧光,实现了双重荧光比率法对氟离子的高选择性识别响应

Bis(1-(4-(dimethylamino)benzylidene)-4-phenylthiose micarbaznato)palladium(Ⅱ):Synthesis,Crystal Structure and Its Dual Fluorescence Property

The title compound bis(1-(4-(dimethylamino)benzylidene)-4-phenylthiosemicar-bazato)-palladium(Ⅱ)(PdL2) was obtained by reacting 1-(4-(dimethylamino)benzylidene)-4-phenyl-thiosemicarbazide with dichlorobis(benzonitrile)palladium(Ⅱ) in methanol,and its structure was characterized by single-crystal X-ray diffraction.The crystal of PdL2 was obtained in dimethyl-formamide(DMF) solvent with solvent molecules involved in the cell and crystallizes in the monoclinic system,space group C2 with a = 18.485(15),b = 7.090(5),c = 17.595(11) ,β = 121.21(3)o,V = 1972(2) 3,Z = 2,Mr = 847.40,Dc = 1.427 g/cm3,μ = 0.624 mm-1,F(000) = 880,R = 0.0607 and wR = 0.1358.The Pd atom adopts a distorted square planar coordination geometry with two Pd-N and two Pd-S bonds.The ligand loses a proton from its tautomeric thiol form and coordinates to the Pd atom via mercapto sulfur and the imine nitrogen atom,which binds to palladium as bidentate N,S-donors forming five-membered chelate rings.The complex formed hydrogen bonding interaction w..