FLUORESCENCE STUDIES ON SELF－ASSEMBLING BEHAVIOR OF AMPHIPHILES WITH NAPHALENE－1，5－DIOXY GROUP

ＦＬＵＯＲＥＳＣＥＮＣＥ　ＳＴＵＤＩＥＳ　ＯＮ　ＳＥＬＦ－ＡＳＳＥＭＢＬＩＮＧ　ＢＥＨＡＶＩＯＲ　ＯＦ　ＡＭＰＨＩＰＨＩＬＥＳ　ＷＩＴＨ　ＮＡＰＨＡＬＥＮＥ－１，５－ＤＩＯＸＹ　ＧＲＯＵＰＦＬＵＯＲＥＳＣＥＮＣＥＳＴＵＤＩＥＳＯＮＳＥＬＦ－ＡＳＳＥＭ...     

A NOVEL ARYL SHIFT IN THE OXIDATION OF ENOL SILYL ETHERS BY IODOSOBENZENE－BORON TRIFLUORIDE

Ａ　ＮＯＶＥＬ　ＡＲＹＬ　ＳＨＩＦＴ　ＩＮ　ＴＨＥ　ＯＸＩＤＡＴＩＯＮ　ＯＦ　ＥＮＯＬ　ＳＩＬＹＬ　ＥＴＨＥＲＳ　ＢＹ　ＩＯＤＯＳＯＢＥＮＺＥＮＥ－ＢＯＲＯＮ　ＴＲＩＦＬＵＯＲＩＤＥＡＮＯＶＥＬＡＲＹＬＳＨＩＦＴＩＮＴＨＥＯＸＩＤＡＴＩＯＮＯＦＥＮＯ...     

IMMOBILIZATION OF GLUCOSE OXIDASE AND CELLULASE BY ENTRAPMENT OF HYDROGEN－BOND COMPLEX

ＩＭＭＯＢＩＬＩＺＡＴＩＯＮ　ＯＦ　ＧＬＵＣＯＳＥ　ＯＸＩＤＡＳＥ　ＡＮＤ　ＣＥＬＬＵＬＡＳＥ　ＢＹ　ＥＮＴＲＡＰＭＥＮＴ　ＯＦ　ＨＹＤＲＯＧＥＮ－ＢＯＮＤ　ＣＯＭＰＬＥＸＩＭＭＯＢＩＬＩＺＡＴＩＯＮＯＦＧＬＵＣＯＳＥＯＸＩＤＡＳＥＡＮＤＣＥＬＬＵＬ...     

O－（1－BENZOTRIAZOLYL）－SULFATE AS ALEAVING GROUP IN SUBSTITUTION OF NUCLEOSIDE

Ｏ－（１－ＢＥＮＺＯＴＲＩＡＺＯＬＹＬ）－ＳＵＬＦＡＴＥＡＳＡＬＥＡＶＩＮＧＧＲＯＵＰＩＮＳＵＢＳＴＩＴＵＴＩＯＮＯＦＮＵＣＬＥＯＳＩＤＥ￥ＹａｏＳｈｕＺＨＡＮＧ，ＬａｉＸｉｎＷＡＮＧａｎｄＬｉＨｅＺＨＡＮＧ（ＳｃｈｏｏｌｏｆＰｈａｒｍａｃｅｕｔｉｃ...     

STUDIES ON THE SYNTHESIS OF TRACHYLOBAGIBBERELLINANALOGUE(Ⅱ)SYNTHESIS OF DIMETHYLESTER OF 3-HYDROXY-△1_10-12,16-CYCLOGIBBERELLIN 12

ＳＴＵＤＩＥＳ　ＯＮ　ＴＨＥ　ＳＹＮＴＨＥＳＩＳ　ＯＦ　ＴＲＡＣＨＹＬＯＢＡＧＩＢＢＥＲＥＬＬＩＮＡＮＡＬＯＧＵＥ（Ⅱ）ＳＹＮＴＨＥＳＩＳ　ＯＦ　ＤＩＭＥＴＨＹＬＥＳＴＥＲ　ＯＦ　３－ＨＹＤＲＯＸＹ－△１_１０－１２，１６－ＣＹＣＬＯＧＩＢＢＥＲＥＬ?..     

BIOTRANSFORMATION OF 2α，5α，10β，14β－TETRA－ACETOXY－4（20），11－TAXADIENE BY THE FUNGIJS CUNNINGHAMELLA ECHINULATA

ＢＩＯＴＲＡＮＳＦＯＲＭＡＴＩＯＮＯＦ２α，５α，１０β，１４β－ＴＥＴＲＡ－ＡＣＥＴＯＸＹ－４（２０），１１－ＴＡＸＡＤＩＥＮＥ　ＢＹ　ＴＨＥ　ＦＵＮＧＩＪＳ　ＣＵＮＮＩＮＧＨＡＭＥＬＬＡ　ＥＣＨＩＮＵＬＡＴＡＳｈａｎｇＨｕｔＨＵ；ＸｕＦａｎｇＴＩ...     

STUOIES ON TRANSITION METAL COMPLEXES OF SCHIFF BASE—OXYGEN—CARRYING PROPERTIES OF THREE COBALT（Ⅱ） COMPLEXES OF N－SALICYLIDENEAMINO ACIDS

ＳＴＵＯＩＥＳＯＮＴＲＡＮＳＩＴＩＯＮＭＥＴＡＬＣＯＭＰＬＥＸＥＳＯＦＳＣＨＩＦＦＢＡＳＥ—ＯＸＹＧＥＮ—ＣＡＲＲＹＩＮＧＰＲＯＰＥＲＴＩＥＳＯＦＴＨＲＥＥＣＯＢＡＬＴ（Ⅱ）ＣＯＭＰＬＥＸＥＳＯＦＮ－ＳＡＬＩＣＹＬＩＤＥＮＥＡＭＩＮＯＡＣＩＤＳＸｉａ...     

RESOLUTION OF DL－α－AMINO ACIDS ON A L－HYDROXY PROLINE CHIRAL PHASE BY LIGAND－EXCHANGE CHROMATOGRAPHY

ＲＥＳＯＬＵＴＩＯＮＯＦＤＬ－α－ＡＭＩＮＯＡＣＩＤＳＯＮＡＬ－ＨＹＤＲＯＸＹＰＲＯＬＩＮＥＣＨＩＲＡＬＰＨＡＳＥＢＹＬＩＧＡＮＤ－ＥＸＣＨＡＮＧＥＣＨＲＯＭＡＴＯＧＲＡＰＨＹ￥ＴａｏＣＨＥＮ；ＴｉａｎＢａｏＨＵＡＮＧ（ＣｈｅｎｇｄｕＩｎｓｔｉｔｕｔ...     

ELECTRON TRANSFER AGENT DEPENDENCY OF MONOOXYGENATION OF CYCLOHEXANE CATALYZED BY SILICA IMMOBILIZED N，N＇－BIS［2－（BENZIMIDAZOLYLMETHYL）］AMINO FERROUS ACETATE COMPLEX

ＥＬＥＣＴＲＯＮＴＲＡＮＳＦＥＲＡＧＥＮＴＤＥＰＥＮＤＥＮＣＹＯＦＭＯＮＯＯＸＹＧＥＮＡＴＩＯＮＯＦＣＹＣＬＯＨＥＸＡＮＥＣＡＴＡＬＹＺＥＤＢＹＳＩＬＩＣＡＩＭＭＯＢＩＬＩＺＥＤＮ，Ｎ＇－ＢＩＳ［２－（ＢＥＮＺＩＭＩＤＡＺＯＬＹＬＭＥＴＨＹＬ）］ＡＭ...     

THE EXCITED STATES AND VIBRATIONAL FREQUENCIES OF Bli_2~e（e＝0，＋1，－1）CLUSTERS

ＴＨＥＥＸＣＩＴＥＤＳＴＡＴＥＳＡＮＤＶＩＢＲＡＴＩＯＮＡＬＦＲＥＱＵＥＮＣＩＥＳＯＦＢｌｉ：（ｅ＝０，＋１，－１）ＣＬＵＳＴＥＲＳＴＨＥＥＸＣＩＴＥＤＳＴＡＴＥＳＡＮＤＶＩＢＲＡＴＩＯＮＡＬＦＲＥＱＵＥＮＣＩＥＳＯＦＢｌｉ：（ｅ＝０，＋１，－１）Ｃ...     

Gels from a semifluorinated n-alkane in fluorinated solvents as a probe for intermolecular interactions

Diblock semifluorinated n-alkanes can form aggregates and gels in fluorinated solvents. We have investigated the thermal behavior of binary mixtures comprising F(CF₂)₈(CH₂)₁₆H and fluorinated solvents. The solvents were perfluorohexane, perfluoroheptane, perfluorooctane, perfluorooctyl bromide, perfluorodecalin, and perfluorotributylamine. The phase diagrams were used to calculate the activity coefficients of the two components and the main excess thermodynamic functions. The solubility and self-assembly behavior of F₈H₁₆ in the fluorinated solvents are related to the different solute–solvent dispersion interactions that depend on the polarizabilities and ionization potentials of the interacting species, and on the structural properties of the solvent.     

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性

用廉价的均苯四甲酸二酐(PMDA)代替部分或全部3,3,′4,4′-联苯四羧酸二酐(BPDA),与3,3′-二羟基联苯胺(HAB)进行缩聚,然后脱水酰亚胺化,制备了5种聚酰亚胺(PI)。TGA分析显示,这些PI的DTG曲线为2个峰,可分为生成聚苯并唑(PBO)再发生PBO分解的2个阶段。PI膜在500℃通N2气1 h,所得聚合物膜的DTG曲线仅为1个峰,表明这些PI可充分转变成PBO。用FTIR表征了PI和PBO膜的结构。PBO的耐热性(用失重5%时的温度Td表示)比PI高100~170℃。PMDA-HAB PBO的耐热性高于BPDA-HABPBO。HAB-BPDA-PMDA PBO的耐热性优于二元PBO。当PMDA在二酐单体中所占的摩尔分数为75%时,PBO的Td高达643℃。     

HCOO在Cu(110)、Ag(110)和Au(110)表面的吸附

采用密度泛函理论(DFT)以及广义梯度近似方法(GGA)计算了甲酸根(HCOO)在Cu(110)、Ag(110)和Au(110)表面的吸附. 计算结果表明, 短桥位是最稳定的吸附位置, 计算的几何参数与以前的实验和计算结果吻合. 吸附热顺序为Cu(110)(-116 kJ·mol-1)>Ag(110)(-57 kJ·mol-1)>Au(110)(-27 kJ·mol-1), 与实验上甲酸根的分解温度相一致. 电子态密度分析表明, 吸附热顺序可以用吸附分子与金属d-带之间的Pauli 排斥来关联, 即排斥作用越大, 吸附越弱. 另外还从计算的吸附热数据以及实验上HCOO的分解温度估算了反应CO2+1/2H2→HCOO的活化能, 其大小顺序为Au(110)>Ag(110)>Cu(110).     

Transition metal complexes of the tripodal ligand 4-(2′-pyridylmethyl)-4-azaheptane-1,7-diamine. Crystal structures of [CuLCl]ClO4 and [NiL(MeCN)2](ClO4)2

The tripodal ligand 4-(2′-pyridylmthyl)-4-azaheptane-1,7-diamine has been prepared by reaction of 2-aminemethyl pyridine with acrylonitrile, followed by the reduction of the nitrile groups. Copper(II), nickel(II), zinc(II), cobalt(III) and chromium(III) complexes of the ligand have been prepared and characterized and the crystal structures of the complexes [CuLCl]ClO₄ and [NiL(MeCN)₂](ClO₄)₂ determined. The copper complex is five coordinate with approximate square pyramidal stereochemistry with the apical position occupied by a primary amine donor. The nickel complex is octahedral with the pyridine nitrogen donor lying trans to an acetonitrile ligand.     

SYNTHESIS AND CHARACTERIZATION OF METAL COMPLEXES WITH AMPICILLIN

Abstract

The reaction, in water, of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions with sodium ampicillinate at room temperature has allowed isolation of dimers with the following general formula [M(amp)Cl]₂ × nH₂O (n = 1.5?3.2). The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibilities and spectroscopic methods (IR, Raman, EPR and UV-Visible). A dinuclear structure based on octahedrally coordinated metal ions is proposed.     

Magnetism of metal-nitroxide compounds involving bis-chelating imidazole and benzimidazole substituted nitronyl nitroxide free radicals

Coordination compounds based on imidazole and benzimidazole substituted nitronyl nitroxide radicals with transition metal ions and trivalent lanthanide ions are described from the perspective of their magnetic properties.For the transition metal compounds the crystal structures show various metal-nitroxide dimensionalities including mononuclear (0D), one-dimensional (1D) and two-dimensional (2D) complexes. The mononuclear complexes were isolated with most metal ions of the first transition series. One copper(II) complex shows a copper(II)-radical ferromagnetic coupling (J = +75 cm⁻¹) while for the other mononuclear compounds, mainly with manganese(II), the metal-radical interactions are antiferromagnetic. The one-dimensional and two-dimensional complexes are manganese(II) compounds which show canting effects leading to weak ferromagnetism.For the trivalent lanthanide ions [La(III), Gd(III) and Eu(III)], three series of mononuclear complexes were obtained in which the metal center is bound to four, two or one nitroxide radicals depending on the counter ions and ancillary ligands. Unexpectedly, in most gadolinium(III) complexes, the Gd(III)-radical interactions were found to be antiferromagnetic in contradiction with other foundings and previous theoretical models. In support to the magnetic studies, the optical properties of the lantanide complexes have also been investigated and are briefly described.     

具有聚集诱导发光性质的近红外荧光染料

聚集诱导发光(AIE)现象的发现为解决传统有机荧光分子在高浓度和聚集形态下存在的荧光猝灭问题提供了最佳方案,并实现了在光电器件、化学传感、生物成像和靶向治疗等众多领域的广泛应用。随着对AIE发光机理研究的不断深入,AIE分子体系得到了极大的扩展。其中,一类具有给体-受体结构的AIE分子能够显著降低分子能隙,使发光分子波长从可见光区(400~700 nm)延伸到近红外(NIR)区(700~1700 nm)。由于NIR发光分子在生物医学领域中的独特优势,其已成为目前AIE研究的热点。随着对NIR分子设计及应用的不断探索,附加不同功能且发光波长更长的AIE分子也被开发出来了,并实现了对生物体特定组织的NIR荧光成像、光声成像、光动力治疗和光热治疗等。本文总结了近年来具有AIE性能的NIR荧光分子的结构及其在生物医学领域的相关应用。     

Simple,Selective, and Sensitive Spectrophotometric Method for Determination of Trace Amounts of Nickel（Ⅱ）, Copper （Ⅱ）, Cobalt （Ⅱ）, and Iron （Ⅲ） with a Novel Reagent 2-Pyridine Carboxaldehyde Isonicotinyl Hydrazone

A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.     

New Complexes of Ditopic Ligands with “d” and/or “s” Metal Ions

Abstract

The asymmetric compartmental macrocycles containing one N₂O₂ or N₃O₂ Schiff base and one O₂O₃ or O₂O₄ crown-ether like chamber, have been obtained by condensation reaction of the formyl precursors 3,3′-(3-oxapentane-1, 5-diyldioxy) bis (2-hydroxybenzaldehyde) or 3,3′-(3,6-dioxaoctane-1,8-diyldioxy)-bis(2-hydroxybenzaldehyde) with ethyl ethylenediamine (H₂L_A, H₂L_C), 1,5-diamino-3-azamethylpentane(H₂L_B, H₂L_D), also in the presence of metal ions as templating agents. These ditopic ligands, with dissimilar coordination sites, have been designed and used for the selective complexation of “d” and/or “s” metal ions, respectively into the Schiff base and the crown ether chamber. The selectivity of these processes strongly depends on the size and on the donor atom sets of the sites. The possibility to obtain mononuclear M(L)·nH₂O (M = Ni²⁺, Cu²⁺, Co²⁺), Mn(L)(CH₃COO)·nH₂O or Na(L) and hetero-dinuclear MNa(L)(CH₃COO) (M = Ni²⁺, Cu²⁺, Co²⁺) and MnNa(L)(CH₃COO)₂·nH₂O complexes has been successfully tested. The ligands and complexes have been characterized by ir, nmr, mass spectrometry and magnetic susceptibility measurements.

Two of the ligands used for the preparation of the solid samples, i.e., to H₂L_A and H₂L_B, have been employed to study complexation reactions of Co(II) and Na(I) in solution. In order to obtain information on the ligand preorganization effect toward the complex stabilities, a simpler open chain parent compound of H₂L_B (H₂L_E) has been also prepared and studied. FT-IR spectra show that H₂L_A is unable to complex Na⁺ in DMSO while the complexation reactions of Na⁺ by H₂L_B and of Co²⁺ by H₂L_A take place with slow kinetics. Therefore, thermodynamic data have been obtained only for the systems Co²⁺/H₂L_B and Co²⁺/H₂L_E. The thermodynamic parameters obtained for the complexation reactions show that the pre-organization of the donor atoms in H₂L_B does not add a significant contribution to the stabilities of the complexes. Both H₂L_B and H₂L_E form in DMSO 1:1, 1:2 and 1:3 = M:L complexes with very similar stabilities and almost equal enthalpies of formation. Physico-chemical studies suggest besides that the slow reaction of Na⁺ with H₂L_B is probably due to the formation of a 1:1 complex where the metal cation, initially occupying the O₃ cage of the ligand, slowly binds also the oxygens of the phenolic moieties. Spectral and calorimetric data on solutions containing H₂L_B and different Co²⁺: Na⁺ ratios evidence that in DMSO no stable heterodinuclear complexes form when the neutral ligand is considered.     

Synthesis of Some Novel Class of Bis(isoxazoline) and Bis(aziridine) Derivatives

Synthesis of some new bis(isoxazoline) derivatives has been described from terepthaldehyde derived bis(nitrones) using microwave irradiation via 1,3‐dipolar cycloaddition reaction. Bis(isoxazoline) derivatives in turn successfully converted into new bis(aziridine) derivatives via Baldwin rearrangement. Simple reaction methodology, non involvement of catalysts, and good to excellent yields are the important features noticed in this synthesis.