Synthesis,structures and magnetic properties of two 2D → 3D entangled Cobalt(II) coordination polymers

Two Co(II) coordination polymers, namely Co(HBTC)(4-bpdb)·H₂O (1) and Co(HBTC)(3-bpdb)·H₂O (2) (H₃BTC = 1,3,5-benzenetricarboxylic acid, 4-bpdb = 1,4-bis-(4-pyridyl)-2,3-diaza-1,3-butadiene, 3-bpdb = 1,4-bis(3-pyridyl)-2,3-diaza-1,3- butadiene), have been hydrothermally synthesized and characterized both structurally and magnetically. Compound 1 exhibits a (2D → 3D) polythreaded architecture. It is assembled from HBTC^2? ligands to form a 2D puckered (4,4) layer plus 4-bpdb ligands which are orientated above and below each layer. The structure of compound 2 consists of a 2D (3,5) wavelike sheet constructed from HBTC^2? anions and 3-bpdb spacers. The uncoordinated carboxyl groups of the HBTC^2? ligands protrude from both sides of the wavelike sheet to form a 2D → 3D interdigitated motif. The magnetic properties of both compounds are also investigated, indicating antiferromagnetic interactions between the adjacent metal centers.     

溶剂热法CuInSe2粉体的形貌可控制备与表征

采用溶剂热法,通过改变反应温度和初始nCu/nIn比制备了一系列CuInSe2粉体。粉体的物相结构、形貌、光吸收性能分别用X射线衍射仪(XRD)、场发射扫描电镜(FESEM)、透射电镜(TEM)、紫外-可见分光光度计(UV-Vis)进行了表征。结果表明:180℃反应即可形成纯黄铜矿型CuInSe2粉体;随着反应温度的升高,粉体形貌有"片-片簇-球簇"的演变规律,其光吸收性能也随之增强,出现"红移"现象;初始nCu/nIn比能有效调控片簇的致密度。同时探讨了粉体不同形貌的形成机理。     

Synthesis,structures and magnetic properties of four 3D heterometallic cobalt(II)–barium(II) coordination polymers

Four heterometallic complexes, namely {[CoBa(2,5-pdc)₂(H₂O)₃]_n·2nH₂O} (1), [CoBa(2,5-pdc)₂(H₂O)₄]_n (2), [CoBa(2,5-pdc)₂(H₂O)₅]_n (3) and [CoBa₂(2,5-pdc)₃(μ₂-H₂O)₂(H₂O)₄]_n (4) (2,5-H₂pdc?=?pyridine-2,5-dicarboxylic acid), have been hydrothermally synthesized and characterized both structurally and magnetically. All four complexes exhibit 3D frameworks, in which the Co(II) centers are chelated by pyridine nitrogen and carboxyl oxygen atoms in a five-membered ring. The Ba(II) centers are chelated and bridged by carboxyl oxygen atoms to extend the structures into 3D frameworks. The networks of the complexes can be controlled via rationally choosing the appropriate ligand and tuning the ratio of the two types of metal centers. The magnetic properties of complexes 1, 2 and 4 have been investigated from 2 to 300 K.     

超分子2，2′-联咪唑镉(Ⅱ)配聚物的合成与结构表征

以硫氰酸根、叠氮基、二氰胺为桥联配体,分别与2,2′-联咪唑和硝酸镉反应,获得配聚物[Cd（SCN）2（H2biim）]n（1）,[Cd（N3）2（H2biim）]n（2）和[Cd2（NO3）（dca）3（H2biim）2.5]n（3）,3个化合物通过元素分析、IR、TGA等表征,并测定了它们的晶体结构。结果表明：化合物1和2分别是以μ1.3—SCN-和μ1.1-N3-双桥连接的一维链状结构,化合物3是以μ1.5-dca和μ3.3-H2biim交叉桥连的二维网状结构。对它们的荧光性质也进行了初步分析。     

镍螺旋化合物及其杂银配位聚合物的设计合成与结构

采用两个易扭转异构的双三齿有机配体，双吡啶二甲基-6,6′-二酰肼-2,2′-连吡啶(H₂L¹)和双吡啶二乙基-6,6′-二酰肼-2,2′-连吡啶(H₂L²)，和金属镍离子组装得到2个金属螺旋体(helicate)，Ni₂(HL¹)₂(PF₆)(BF₄)(CH₃OH)(H₂O)₂ (1)和Ni₂(HL²)(H₂L²)(ClO₄)₃(C₂H₅OH)(CH₃OH)H₂O)₃ (2),并测定了它们的晶体结构。同时由配体H₂L³出发,通过逐级组装的方法,得到一个镍-银杂金属的配位聚合物Ni₂Ag₂(HL³)₂(ClO₄)₂(CH₃CN)₃ (3)。单晶结构表明，配位聚合物3中配体H₂L³首先与镍离子组装成分子盒化合物(molecular box)，该结构单元进一步通过Ag离子与分子盒外围N原子配位，使分子盒互相串连成一维配位聚合物3，分子盒聚集体沿c方向伸展成一维链结构，链与链之间相互平行，进一步堆积成二维孔道结构。     

双亲性光敏感遥爪聚合物C-PNIPAAm的合成与性能

以7-羟基-4-甲基香豆素为原料,依次与环氧氯丙烷、二硫化钠反应得一含香豆素基元的二硫化物(C-S-S-C),并以其与三丁基膦复合体系为链转移剂,偶氮二异丁腈(AIBN)为引发剂,N-异丙基丙烯酰胺(NIPAAm)为单体制备了末端为香豆素光响应基元的双亲性遥爪聚合物(C-PNIPAAm).用傅里叶变换红外(FT-IR)光谱、凝胶渗透色谱(GPC)、氢核磁共振(1H-NMR)等对该聚合物进行了结构表征.研究显示该双亲性遥爪聚合物可在水中直接形成胶束,并以荧光素为疏水性客体考察了聚合物胶束的光控释放行为.在波长大于310 nm的紫外光照射下,聚合物链末端的香豆素单元可进行光二聚,胶束结构随之改变,因而所负载的荧光素可得到逐步有效释放.动态激光光散射(DLS)检测显示,光二聚反应使聚合物胶束平均粒径从56.6 nm增大至101.0 nm.     

单细胞激光拉曼光谱检测重组大肠杆菌细胞表达甲酸脱氢酶

甲酸脱氢酶(FDH,EC1.2.1.2)在工业生产中有重要的应用价值,工业上应用的FDH可以通过构建高水平表达重组FDH蛋白的基因工程菌生产,用分子生物学的方法检测重组蛋白的高效表达和积累操作繁杂,耗时耗力且需要破碎细胞。为了寻找一种简单快速,不需破碎细胞,且能实时检测FDH重组蛋白在基因工程菌中表达情况的方法,本研究应用单细胞激光拉曼光谱分析技术(LTRS),研究IPTG诱导不同时间后甲酸脱氢酶重组蛋白(FDH)在大肠杆菌细胞中的表达水平。结果表明,FDH的特征峰1004,1355,1455和1667cm-1随着IPTG诱导时间的延长而增强,说明在诱导培养过程中FDH重组蛋白在重组大肠杆菌细胞中表达并积累,这4个峰强的增加值所反映的FDH表达量与SDS-PAGE电泳分析结果一致。实验结果证明,LTRS是快速有效检测单个大肠杆菌活细胞体内重组FDH实时表达的一种非入侵方法。     

超高效液相色谱-串联四极杆质谱法检测小型家电外壳中的六溴环十二烷

建立了加热回流萃取-超高效液相色谱-串联四极杆质谱检测小型家用电器中六溴环十二烷( Hexabromocyclododecane,HBCD)的方法.实验优化了电子电器类产品的前处理方法,以甲苯-甲醇(10∶1,V/V)为萃取剂,加热回流4h.萃取出的溶液经N2吹干,初始流动相复溶,涡旋、离心、过膜,经ACQUITYTMUPLC BEH C18色谱柱分离;以甲醇-乙腈(4∶1,V/V)-10 mmol/L醋酸铵为流动相,质谱的多反应监测模式(MRM)进行检测,HBCD的3种同分异构体在3 min内完全分开.该物质的检山限为0.014 mg/L:定量限为0.068 mg/L;标准曲线的线性范围为1.6～ 32.4 mg/L,线性相关系数大于0.996,萃取回收率为68.0％～75.2％.通过外标法定量,并将本方法应用于实际样品(电视机外壳、电子相框、电磁炉外壳等)的检测.     

Structure and Luminescence Property of a Hexanuclear Thiosemicarbazone Silver（I） Cluster

A new hexanuclear silver(I) compound containing thiosemicarbazones with groups of 1-naphthalene was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spectrum.The title compound crystallizes in monoclinic,space group P2 1 /c with a=16.101(4),b=24.855(7),c=14.492(4),β=109.730(5)°,V=5459(3)3,C 90 H 102 Ag 6 N 24 O 6 S 6,M r=2455.54,D c=1.494 g/cm 3,μ(MoKα)=1.228 mm-1,F(000)=2472,Z=2,the final R=0.0761 and wR=0.1507 for 5258 observed reflections (I > 2σ(I)).In the structure,the S atom of ligand L serves as a triply bridged chelator to connect the six silver atoms into a Ag 6 L 6 cluster.Luminescence investigation reveals that the compound exhibits two ligand-independent cluster-centered electron transfer bands and one ligand-dependent charge transfer band.     

非线性弹性杆振动方程的全局吸引子及正则性

证明了非线性弹性杆振动方程全局吸引子的正则性,并进一步获得了(H_0~1(Ω)×H_0~1(Ω),(H~2(Ω)∩H_0~1(Ω))×(H~2(Ω)∩H_0~1(Ω)))-全局吸引子的存在性.