Two Novel Oxamidato-bridged Tetranuclear Complexes M[Cu(PMoxd)]3(ClO4)2 (M=Mn, Ni, Cu(PMoxd)=N,N′-bis(pyridyl-methyl)-oxamidatocopper(II)): Syntheses, Spectra, Magnetic and Electrochemical Properties

Two novel oxamidato-bridged Mn[Cu(PMoxd)]₃(ClO₄)₂ (1) Ni[Cu(PMoxd)]₃(ClO₄)₂ (2) tetranuclear complexes were prepared and characterized by i.r., e.p.r., electronic spectra, cyclic voltammograms, and magnetic properties. The magnetic analysis was carried out by means of the theoretical expression of the magnetic susceptibility deduced from the spin Hamiltonian H=−2JS_M(S_Cu1+ S_Cu2 + S_Cu3) (M=Mn, Ni), leading to J=−20.4 cm⁻¹; −121.1 cm⁻¹ for complexes (1) and (2) respectively. Magnetic measurements indicate that the overall magnetic behavior of the tetranuclear species are antiferromagnetic.     

β-环糊精交联聚合物树脂相分光光度法测定水中痕量汞

以β-环糊精和环氧氯丙烷为原料合成了环糊精聚合树脂,将其作为显色剂2-[5-溴-(2-吡啶偶氮)]-5-二乙氨基苯酚的载体,采用β-环糊精-2-[5-溴-(2-吡啶偶氮)]-5-二乙氨基苯酚树脂相分光光度法测定微量汞.配合物的最大吸收波长为585nm,表观摩尔吸光系数为8.17×105L/mol·cm,汞含量在0～10μg/25mL范围内服从比尔定律,线性回归方程:y=0.0013 0.0163x,相关系数r=0.9994,加标回收率为98.5%～101.0%,与双硫腙法相比无显著性差异.该方法已用于工业废水中痕量汞的测定,结果令人满意.     

单向应力条件下松弛时间率相关的非线性粘弹性本构模型

基于单向拉伸实验研究和内变量理论 ,提出了一种新的简单的一维非线性粘弹性本构关系 .对两种粘弹性材料 ,即高密度聚乙烯和聚丙烯进行了不同加载速率作用下的拉伸实验研究 ,实验结果表明 ,两种材料的应力应变关系与加载速率相关 ;对材料的应力应变实验数据进行拟合发现 ,材料的松弛时间具有很强的应变率相关性 ,当应变率发生数量级变化时 ,材料的松弛时间也发生数量级的变化 .采用内变量理论 ,导出了在单轴应力条件下松弛时间率相关的非线性粘弹性本构关系的迭代形式 ,并给出其收敛条件 .当采取一次迭代形式时 ,本构关系退化为松弛时间率相关的Maxwell模型 .数值拟合的结果表明 ,一次迭代形式的本构关系就可以很好地拟合和预测实验结果 .     

具有超疏水性质的图案化Ag膜

以重氮树脂(DR)/聚丙烯酸(PAA)自组装膜的微图案作为模板, 通过DNA和聚二甲基二烯丙基氯化铵(PDDA)在模板上的层层沉积制备了图案化的DNA膜. 再在其中进行Ag的化学沉积得到图案化的Ag膜. 最后利用低表面能的十二烷基硫醇对Ag膜进行表面修饰, 制备了具有超疏水性质的图案化Ag膜. 其静态接触角达到约168°.     

Photophysics properties of 4-formacyl-triphenylamine and 4,4''''-bisformacyl-triphenylamine

The photophysical processes of 4-formacyl-triphenylamine (FTA) and 4,4'-bisformacyl-triphenyl-amine (BTA) have been studied. The fluorescences of FTA and BTA with donor (triamine) and acceptor (formacyl) moieties show the twisted intramolecular charge transfer (TICT) emission in polar solvents and photoinduced charge transfer (ICT) emission in nonpolar solvents. These could be supported by the solvent effect, temperature effect and the quenching process by strong electron-deficient compounds.     

阴离子导向组装：两个具有不同阳离子的多维Ag(I)配合物的晶体结构

Assembly of [Ag（CN）2]^- units with M（Ⅱ）-diamine complex cations [Cu（LN-N）2]^2＋, where LN-N represents L2-diaminopropane （pn） and ethylenediamine （en）, afforded two complexes, [Cu（pn）2][Ag2（CN）4] （1） and [Cu（en）2][Ag3（CN）5] （2）, which were characterized by elemental analysis, IR, UV-Vis and ESR spectra. Single crystal X-ray analyses show that these complexes have 2D and 3D architectures through silver-silver interactions and other weak interactions. The luminescence behaviors of the two complexes were also studied by means of emission spectra.     

Synthesis, structure and properties of two bimetallic compounds [Co(bpy)2 (NiL)] (ClO4)2 and {[Co(phen)3](NiL)}(ClO4)2 containing a macrocyclic oxamide ligand

Two compounds, [Co(bpy)₂(NiL)](ClO₄)₂ (1)and {[Co(phen)₃](NiL)}(ClO₄)₂ (2), have been synthesized: (H₂L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacylotetradeca-7,12-diene, bpy=2,2-bypyridine and phen = 1,10-phenanthroline). Compound (1) contains a discrete binuclear [Co(bpy)₂(NiL)]²⁺ cation, while compound (2) is composed of [Co(phen)₃]²⁺ cations and NiL neutral fragments. The magnetic properties of compound (1) have been dealt with by isotropic one-ion approximation of the Co^II ion with a spin--orbit coupling in an O_h symmetry environment. The electronic spectra of these two compounds have also been discussed.     

Effect of ligand structure of stationary phase of high performance hydrophobic interaction chromatography on renaturation efficiency of GuHCl-denaturedα-chymotrypsin

The renaturation of the denaturedα-chymotrypsin (α-Chy) with 1.7 mol·L-1 gua-nidine hydrochloride (GuHCI) by three kinds of stationary phase of high performance hydropho-bic interaction chromatography (STHIC) with a comparable hydrophobicity but different ligand structures was investigated. The obtained result indicates that the ligand structures of the three STHIC contribute to the renaturation efficiency ofα-Chy in the order of the end ligands PEG-600< phenyl group < tetrahydrofurfuryl alcohol (THFA).     

New Ni(II)Cu(II)Ni(II) trinuclear complexes with an 5=3/2 high-spin ground

Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)₂]₂[Cu(opba)]}(ClO₄)₂, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-l,10-phenanthroline(NO₂-phen) (2), 2,2′-bipyridyl(bpy) (S) and 4,4′-dimethyl-2,2′-bipyridyl(Me₂bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)₂]₂[Cu(opba)]}(ClO₄)₂3H₂O has been studied in the 4–300 K range, giving the exchange integral J—109 cm^?1. The HMT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure.     

Synthesis, Structure and Characterization of [Cu(2,2'-bpy)2][{Cu(2,2'-bpy)2}2W12O40(H2)]·4H2O

An organic-inorganic compound [Cu(2,2'-bpy)2][{Cu(2,2'-bpy)2}2W12O4o(H2)]·4H2O (Mr = 4048.00) was prepared from the hydrothermal reaction of Na2WO4·2H2O, CuCl2·2H2O,2,2'-bipyridine (2,2'-bpy) and H2O at 160 ℃ for 4 days. The compound crystallizes in the monoclinic system, space group P21/n with a = 18.9196(8), b = 20.4212(8), c = 21.8129(9)(A), β=96.992(3)°, V= 8365.0(6) (A)3, Dc= 3.214 g/cm3, Z = 4,μ(MoKα) = 17.269 mm-1 and F(000) = 7324.Of the 119837 total reflections, 17315 were unique (Rint = 0.0489). The final R = 0.0385 and wR =0.0770 for 11142 observed reflections with I ＞ 2σ(I). Single-crystal X-ray diffraction reveals that the structure is composed of [{Cu(2,2'-bpy)2}2W12O40(H2)]2- anions, discrete [Cu(2,2'-bpy)2]2 cations and lattice water molecules, and the anion is made up of a {W12O40(H2)}6- α-Keggin core decorated with two {Cu(2,2'-bpy)2}2 groups through bridging oxygen atoms.