Aggregate manganese Schiff base moieties by terephthalate or acetate: dinuclear manganese and trinuclear mixed metal Mn2/Na complexes

A reaction system consisting of terephthalic acid, NaOH, inorganic Mn(II) or Mn(III) salt, and salicylidene alkylimine resulted in dinuclear manganese complexes (salpn)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (1, salpn = N,N'-1,3-propylene-bis(salicylideneiminato); phth = terephthalate dianion), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (2, salen = N,N'-ethylene-bis(salicylideneiminato)), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(H(2)O) (3), and (salen)(2)Mn(2)(mu-phth) (4), while the absence of NaOH in the reaction led to a mononuclear Mn complex (salph)Mn(CH(3)OH)(NO(3)) (5, salph = N,N'-1,2-phenylene-bis(salicylideneiminato)). In addition, a trinuclear mixed metal complex H[Mn(2)Na(salpn)(2)(mu-OAc)(2)(H(2)O)(2)](OAc)(2) (6) was obtained from the reaction system by using maleic acid instead of terephthalic acid. Five-coordinate Mn ions were found in 4 giving rise to an intermolecular interaction and constructing a one-dimensional linear structure. Antiferromagnetic exchange interactions were observed for 1-3, and a total ferromagnetic exchange of 4 was considered to stem from intermolecular magnetic coupling. (1)H NMR signals of phenolate ring and alkylene (or phenylene) backbone of the diamine are similar to those reported in the literature, and the phth protons are at -2.3 to -10.1 ppm. Studies on structure, bond valence sum analysis, and magnetic properties indicate the oxidation states of the Mn ions in 6 to be +3, which are also indicated by ESR spectra in dual mode. Ferromagnetic exchange interaction between the Mn(III) sites was observed with J = 1.74 cm(-1). A quasireversible redox pair at -0.29V/-0.12V has been assigned to the redox of Mn(2)(III)/Mn(III)Mn(II), implying the intactness of the complex backbone in solution.     

TETRABUTYLAMMONIUM－TETRACYANOQUINODIMETHANE AS ELECTRON－TRANSFER MEDIATOR IN AMPEROMETRIC GLUCOSE SENSOR

ＴＥＴＲＡＢＵＴＹＬＡＭＭＯＮＩＵＭ－ＴＥＴＲＡＣＹＡＮＯＱＵＩＮＯＤＩＭＥＴＨＡＮＥＡＳＥＬＥＣＴＲＯＮ－ＴＲＡＮＳＦＥＲＭＥＤＩＡＴＯＲＩＮＡＭＰＥＲＯＭＥＴＲＩＣＧＬＵＣＯＳＥＳＥＮＳＯＲ￥ＣｈａｎｇＱｉｎｇＳＵＮ；ＷｅｎＢｅＳＯＮＧ；ＤｕｏＺ...     

全二维液相色谱（NPLC×RPLC）接口及其应用

用内径为0．53mm的填充毛细管正相液相色谱为第一维，用4．6mm（i．d．）×50mmRP-18e整体柱反相色谱为第二维，建立了定量环一阀切换接口的全二维液相色谱系统（NPLC×RPLC）．第一维色谱分离洗脱出的组分交替存储在十通阀上的两个定量环中，同时定量环中前一个组分被转移到第二维进行反相分离．因为第一维的流动相流量仅是第二维的1／500，自然解决了流动相兼容问题．采用芳香族化合物的混合物和中药丹参正己烷提取液对该全二维液相系统的分离能力进行了评价．     

含硫碳负离子的反应及其应用的研究 II: 固-液相转移催化共轭加成作用

亲核性的碳负离子与亲电性碳-碳重键的共轭加成反应是构成新碳-碳键的重要方法。某些α-亚磺酰基碳负离子虽然也能与α,β-不饱和酯进行共轭加成,但要有效地产生这类含硫碳负离子往往要用对潮气敏感的强碱性试剂,如氢化钠等。最近,我们报告了在固-液相转移催化条件下α-苯亚磺酰基乙酸甲酯(1)的碳负离子的     

光导薄膜表面静电荷积累过程的动力学特征

本文对电照相用高分子光导材料薄膜涂层的表面电性能进行了研究,确定了表面充电过程宏观动力学的表征方法、动力学方程以及影响电荷沉积速度的因素。     

HCF(~1A'''')+SO_2反应的动力学研究

用激光光解-激光诱导荧光方法研究了室温下(T=293K)HCF(X%A′)自由基与SO2分子的反应动力学.实验中1HCF(X%A′)自由基是由213nm激光光解HCFBr2产生的,用激光诱导荧光(LIF)检测HCF(X%A′)自由基的相对浓度随着11反应时间的变化,得到此反应的二级反应速率常数为:k=(1.81±0.15)×10-12cm3?molecule-1?s-1,体系总压为1862Pa.高精度理论计算表明,HCF(X%A′)和SO2分子反应的机理是典型的加成-消除反应.我们运用RRKM-TST理论计算了1此二级反应速率常数的温度效应和压力效应,计算结果和室温下测定的二级反应速率常数符合得较好.     

A copper- and amine-free sonogashira reaction employing aminophosphines as ligands

An efficient Pd-catalyzed Sonogashira coupling reaction was achieved in the absence of a copper salt or amine with an inorganic base and easily prepared, air-stable aminophosphine ligands in commonly used organic solvents; good to excellent yields were obtained. Under optimized reaction conditions, the Sonogashira coupling reaction occurred selectively when an enyne substrate was employed and no Heck reaction product was detected; acetone-masked acetylene and trimethylsilylacetylene can also be efficiently coupled, providing a method to make terminal alkynes.     

钕的氢氧化物和氧化物纳米线的制备及表征

以金属钕为起始原料，采用简单的碱性溶液下水热法制备出氢氧化钕纳米线。所得到的水热产物采用X-射线衍射、扫描电镜和透射电镜等进行了结构与形态表征。研究发现，水热处理的温度、碱液浓度和碱的种类等对水热产物的形貌、长径比和结晶状态有较大影响，提高水热温度和增加碱液浓度有利于氢氧化钕纳米线的生长。在相同水热反应温度(180 ℃)、水热时间(45 h)和碱浓度下，5 mol·L^-1 NaOH溶液体系制备的氢氧化钕纳米线具有较高纯度和较长的长径比，其直径为20～40 nm，长度为2～10 μm。该氢氧化钕纳米线在空气气氛下500 ℃烧结后形成具有体心立方结构的C型Nd₂O₃，该Nd₂O₃仍具有一维纳米线形貌。升高焙烧温度时产物的形貌和相结构都发生了明显变化。     

取代基效应与乙烯-α-烯烃共聚物的序列结构——5.乙烯-乙烯醇共聚物

本文应用取代基效应(SCS)方法研究了乙烯-乙烯醇(EVA)共聚物,得到了羟基(-OH)在两种不同溶剂中的SCS参数:在苯酚+重水(80/20W/W)中参数为S_1=42.77±0.08ppm,S_2=7.155±0.06ppm,S_3(s)=-4.08±0.02ppm,S_3(t)=-3.09±0.02ppm,S_4=0.48±0.03ppm,S_5=0.26±0.05ppm,在以邻二氯苯为溶剂时参数为S_1=44.97±0.61ppm,S_2=7.40±0.00ppm,S_3(s)=-4.51±0.17ppm,S_3(t)=-3.13±0.00ppm,S_4=0.63±0.04ppm,S_5=0.36±0.00ppm,同时利用所得到的SCS参数对该共聚物的~(13)C NMR谱进行了归属。     

双酚-S-双(3-甲基丙烯酰氧基-2-羟丙基)醚的聚合及其应用

以MMA为起始原料经转变为GMA,再与双酚-S反应合成了一种新的含有砜基的交联剂BisS-GMA。这种双酚-S型交联剂与MMA可以顺利地用紫外光或BPO-胺体系引发聚合。新的双酚-S型交联剂BisS-GMA与双酚-A型交联剂Bis-GMA相比,具有活性高与粘结强度高两个显著优点。它还可以和二氧化硅填料混合组成复合树脂,经光引发或BPO-DHET体系引发聚合,得到的复合树脂其物性已达到国外同类产品的水平。DHET作为促进剂要比DMT性能好,前者配制的交联剂液体组份贮存稳定性好,经半年后而不“失活”,后者配制的液体组份则在较短的时间内“失活”。