H-1 and C-13 NMR studies of TTHA complexes with diamagnetic rare earth ions

TTHA complexes with diamagnetic rare earth ions (La3+, Y3+ and LU(3+)) were studied by H-1 and C-13 NMR spectroscopy. A symmetric structural model was suggested for La(TTHA) complex and an asymmetric model for Y(TTHA) and Lu(TTHA) complexes. The complex formation was dependent on the pH value of the solution. The interactions of La(TTHA) with the additional metal ions (La3+, Y3+ and Ca2+) were relatively weak, but relatively strong for that of Lu(TTHA) with the additional Lu3+.

THE EFFECTS OF LANTHANIDE IONS AND THEIR COMPLEXES ON THE PHASE-TRANSITION PROPERTY OF DIPALMITOYLPHOSPHATIDYLETHANOLAMINE LIPOSOMES

The effects of metal ions and lanthanide complexes on the gel-to-liquid crystal phase transition temperature T-m of dipalmitoylphosphatidylethanolamine liposomes have been studied by differential scanning calorimetry (DSC) method. The results show that the addition of metal ions to the dipalmitoylphosphatidylethanolamine (DPPE) liposomes dispersions increases the main phase transition temperature T-m in the order of monovalent< divalent< trivalent cations. The enhancement of T-m is not large as increasing the lanthanide ions concentration. The enhancement of Pr3+ is larger than that of La3+. Remarkable differences were observed between La-citrate and La-lactate complexes at different pH solutions. At pH 7.0, La-citrate complex has no effect on the T-m, La-lactate complex, however, increases the T-m value, and the increase is larger than that of free lanthanide ions at the same concentration. The decrease of pH of complexes solutions lowers the phase transition temperature. We have preliminarily discussed the mechanism of the enhancements of lanthanide ions and the synergism of lanthanide ion and lactate ligand follow the ion induced dehydration of lipid and the potential effects of ion-lipid interaction.

Study of FT-Raman Spectroscopy on the Effects of Lanthanide Ions and Their Complexes on the Fluidity of Dipalmitoylphosphatidylethanolamine Bilayer

The effects of lanthanide ions and their complexes of citrate and DTPA ligands on the fluidity of dipalmitoylphosphatidylethanolamine (DPPE) bilayers have been studied by FT-Raman spectroscopy. the results show that lanthanide ions of lower concentrationn decrease the fluidity of acyl chains of DPPE bilayers and change the conformation of C C-C backbone from gauche to the trans lanthanide ions of higher concentration, however, increase the fluidity of acyl chains and increase the gauche population of C-C-C backbone. Lanthanide complex of citrate have no effect on the fluidity of acyl chains of DPPE bilayers in the region of experimental concentration, but La-DTPA complex increase slightly the fluidity of acyl chains. the results also indicated that lanthanide ion of lower concentration changed the lattice packing of hydrocarbon chains from hexagonal form to orthorhombic form, but it is still in hexagonal or distorted hexagonal lattice cell in the gel state in the presence of metal ions and lanthanide complexes of higher concentration

EFFECT OF LANTHANIDE IONS ON THE PHASE-BEHAVIOR OF DIPALMITOYLPHOSPHATIDYLCHOLINE MULTILAMELLAR LIPOSOMES

The effect of lanthanide ions (Ln(3+)) and their coordination compounds of diethylenetriamine pentaacetic acid (DTPA) on the phase behavior of dipalmitoylphosphatidycholine (DPPC) multilamellar liposomes has been studied by differential scanning calorimet

Interaction between single molecules of Mac-1 and ICAM-1 in living cells: An atomic force microscopy study

The interaction between integrin macrophage differentiation antigen associated with complement three receptor function (Mac-1) and intercellular adhesion molecule-1 (ICAM-1), which is controlled tightly by the ligand-binding activity of Mac-1, is central to the regulation of neutrophil adhesion in host defense. Several "inside-out" signals and extracellular metal ions or antibodies have been found to activate Mac-1, resulting in an increased adhesiveness of Mac-1 to its ligands. However, the molecular basis for Mac-1 activation is not well understood yet. In this work, we have carried out a single-molecule study of Mac-1/ICAM-1 interaction force in living cells by atomic force microscopy (AFM). Our results showed that the binding probability and adhesion force of Mac-1 with ICAM-1 increased upon Mac-1 activation. Moreover, by comparing the dynamic force spectra of different Mac-1 mutants, we expected that Mac-1 activation is governed by the downward movement of its alpha 7 helix. (c) 2007 Elsevier Inc. All rights reserved.

Rare earth doped beta-diketone complexes as promising high-density optical recording materials for blue optoelectronics

Some kinds of rare earth beta-diketone complexes with blue-violet light absorption edge were synthesized using the ligands of thenoyltrifluoroacctone (HTTA), 2, 2'-dipyridyl (BIPY) and different metal ions (Gd3+, Sm3+ and La3+). Their contents, structures and optoelectronic parameters were monitored by elemental analysis, MS, IR and UV spectra. The solubility of rare earth beta-diketone complexes in 2, 2, 3, 3-tetrafluoro-1-propanol (TFP) and absorption properties of their films in the region 300-800 nm were measured. The influence on the difference of absorption maximum from rare earth beta-diketone complexes to beta-diketone ligand by different metal ions was studied. In addition, the thermal stability of rare earth beta-diketone complexes was also reported. (C) 2005 Elsevier B.V. All rights reserved.

Effects of sensing temperature on the NO2-sensing properties of octa-iso-pentyloxymetallonaphthalocyanine spin-coated films

A kind of 1,6,10,15,19,24,28,33-octa-iso-pentyloxy-2,3-metallonaphthalocyanines complexes MNc(iso-PeO)(8) (M = Co, Cu, Pd) are used as spincoating film-forming materials. The surface morphologies of the films prepared were studied first. These films were then used for the experiments of NO2 sensing. The effects of sensing temperature as well as the NO concentration on the sensing properties were studied. The experimental results showed that the three MNc(iso-PeO)(8) films were uniform, smooth and dense. Due to the different metal ions (M) on the center of naphthalocyanine, the CoNc(iso-PeO)(8) film had a higher film resistance and response-recovery rate in the NO2 sensing experiments. On the contrary, the response to NO2 of the PdNc(iso-PeO)(8) and CuNc(iso-PeO)(8) films were superior to that of CoNc(iso-PeO)(8). By varying the sensing temperature, it was found that the elevation of sensing temperature could improve the sensing response, recovery ratio, and sensitivity of the sensing films. At high concentrations of NO2, the response time became shorter. (c) 2007 Elsevier B.V. All rights reserved.

新型多氮杂环金属配合物的合成及其光谱研究

采用溶液析出法,合成了以2-（2′-羟基-5′-甲基苯基）苯并三唑（HMPB）为配体的多氮杂环金属配合物M（HMPB）2（M=Co,Ni）,利用元素分析、激光解析飞行时间质谱等进行了表征,并研究了新配合物的红外特征光谱和紫外-可见电子吸收光谱。结果表明：HMPB配体通过N和O原子与中心金属以二齿形式配位,中心金属的配位数为4;配合物红外特征吸收谱带位于400～2 500 cm^-1,形成金属配合物后,2-（2′-羟基-5′-甲基苯基）苯并三唑的羟基的伸缩振动吸收、CN振动峰和C─O特征吸收有明显改变,同时确定了配位键M─N和M─O的特征峰位置;配合物在紫外区有强吸收,其最大吸收峰位于335～345 nm。

Effect of Fe impurity on the optical loss of Nd-doped phosphate laser glass

The optical loss coefficient at 1053-nm wavelength, influenced by Fe ions in N31-type Nd-doped phosphate laser glass, was determined precisely and analyzed in detail. It is found that the optical loss coefficient per unit of Fe concentration (cm^(-1)/ppmw) increases with Fe concentration in the range of 0---300 ppmw, but it approaches a constant as the Fe concentration is larger than 300 ppmw. Such a concentration effect is due to a shift in the redox equilibrium between Fe3+ and Fe2+ ions in the glass. The effect of oxygen pressure, temperature, and variable valence states of other metal ions in glass samples on the optical loss is also discussed.

高硅氧发光玻璃的制备及其荧光性能

abstract {Silica glass is an attractive host matrix for the emission ions of rare earth and transition metal ions because it has small thermal expansion coefficient, strong thermal resistance, large fracture strength and good chemical durability and so on. However, a major obstacle to using it as the host matrix is a phenomenon of concentration quenching. In this paper, we introduces a novel method to restrain the concentration quenching by using a porous glass with SiO₂ content > 95% (in mass) and prepare intense fluorescence high-SiO₂ glasses and high-SiO₂ laser glass. The porous glass with high-SiO₂ content was impregnated with rare-earth and transition metal ions, and consequently sintered into a compact non-porous glass in reduction or oxidization atmospheres. Various intense fluorescence glasses with high emission yields, a vacuum ultraviolet-excited intensely luminescent glass, high silica glass containing high concentration of Er³⁺ ion, ultrabroad infrared luminescent Bi-doped high silica glass and Nd³⁺-doped silica microchip laser glass were obtained by this method. The porous glass is also favorable for co-impregnating multi-active-ions. It can bring effective energy transferring between various active ions in the glass and increases luminescent intensity and extend range of excitation spectrum. The luminescent active ions-doped high-SiO₂ glasses are potential host materials for high power solid-state lasers and new transparent fluorescence materials.}

铕离子掺杂和铕铝共掺高硅氧玻璃的光谱性能

Eu-doped and Eu/Al-codoped high silica glass to investigate the properties of europium ions in high silica glasses were obtained. The porous glasses were immersed into europium nitrate solution or mixed solution of europium nitrate and aluminum nitrate. After dried, the doped porous glasses were sintered at 1200°C to obtain Eu-doped and Eu/Al-codoped high silica glasses. The reduction of Eu³⁺&rarrEu²⁺ was observed in Eu/Al-codoped high silica glass. The ratio of trivalent and bivalent europium ions was adjusted by the addition of aluminum ions and then the luminescent color of the glasses was controlled. A detailed mechanism was given to explain this reduction process.

温梯法蓝宝石（Al2O3）晶体的脱碳去色退火研究

温度梯度法（TGT）生长的Al2O3晶体因石墨发热体在高温时的挥发和原料中过渡性金属离子的存在，晶体在不同部位呈现不同颜色，一般上部为浅红色，尾部为浅黄绿色，将TGT法生长的Al2O3晶体（Ф110×80mm^3）依次经过高温氧化气氛、高温还原气氛脱碳、去色退火实验，即“两步法”退火实验，晶体变成无色、透明，经测试，Al2O3晶体的完整性、光学透过率和光学均匀性均有显著提高。

An anionic antimicrobial peptide from toad Bombina maxima

Amphibian skin is a rich resource of antimicrobial peptides like maximins and maximins H from toad Bombina maxima. A novel cDNA clone encoding a precursor protein that comprises maximin 3 and a novel peptide. named maximin H5. was isolated from a skin cDNA library of B. maxima. The predicted primary structure of maximin H5 is ILGPVLGLVSDTLDDVLGIL-NH2,. Containing three aspartate residues and no basic amino acid residues. maximin H5 is characterized by an anionic property. Different from cationic maximin H peptides. only Gram-positive strain Staphylococcus aureus was sensitive to maximin H5. while the other bacteria] and fungal strains tested ere resistant to it. The presence of metal ions. like Zn2+ and Mg2+, did not increase its antimicrobial potency. Maximin H5 represents the first example of potential anionic antimicrobial peptides from amphibians, The results provide the first evidence that. together kith cationic antimicrobial peptides. anionic antimicrobial peptides may also exist naturally as part of the innate defense system. (C), 2002 Elsevier Science (USA). All rights reserved.

De novo RNA synthesis and homology modeling of the classical swine fever virus RNA polymerase

Classical swine fever virus (CSFV) non-structural protein 5B (NS5B) encodes an RNA-dependent RNA polymerase (RdRp), a key enzyme which initiates RNA replication by a de novo mechanism without a primer and is a potential target for anti-virus therapy. We expressed the NS5B protein in Escherichia coli. The rGTP can stimulate de novo initiation of RNA synthesis and mutation of the GDD motif to Gly-Asp-Asp (GAA) abolishes the RNA synthesis. To better understand the mechanism of viral RNA synthesis in CSFV, a three-dimensional model was built by homology modeling based on the alignment with several virus RdRps. The model contains 605 residues folded in the characteristic fingers, palm and thumb domains. The fingers domain contains an N-terminal region that plays an important role in conformational change. We propose that the experimentally observed promotion of polymerase efficiency by rGTP is probably due to the conformational changes of the polymerase caused by binding the rGTP. Mutation of the GDD to GAA interferes with the interaction between the residues at the polymerase active site and metal ions, and thus renders the polymerase inactive. (c) 2005 Elsevier B.V. All rights reserved.

微悬臂传感器研究生物相关分子与金属离子相互作用

利用微悬臂传感器研究了生物相关分子与金属离子的相互作用过程及检测。本论文取得的主要成果如下： （1）利用微悬臂传感器在流动体系中研究了多巴胺在金表面的吸附过程及其与铁离子的相互作用与检测。结果表明，多巴胺在金表面多层吸附，通过分子间氢键和表面电荷转移效应诱导悬臂向镀金面偏转。多巴胺与铁离子的作用过程可以分为两个阶段：第一阶段，铁离子与外层多巴胺络合，并脱离悬臂表面；第二阶段，铁离子与靠近金表面层多巴胺形成化合物，并且可能先以不稳定的单齿络合，而后生成稳定的双齿螯合。利用电化学和XPS手段对上述过程进行了表征，并设计实验对推理进行了验证。多巴胺修饰的悬臂还是一个很好的铁离子传感器，具有较高的灵敏度和选择性，检测限能达到510-10 mol/L。 （2）利用微悬臂传感器在流动体系中研究了组氨酸在金表面的吸附过程及其与铁离子的相互作用与检测。考察了不同pH值和Cl-浓度对组氨酸吸附及其与铁离子作用的影响。结果表明，随着pH值的增加，组氨酸的吸附构象会发生变化，并且导致组氨酸的吸附稳定性、吸附量和分子间静电斥力增大。在碱性溶液中咪唑环较羧基基团优先在金表面发生吸附。组氨酸修饰悬臂与铁离子作用的结果表明，在中性和碱性溶液中组氨酸能与铁离子在悬臂表面形成稳定的化合物。两者的作用过程分为两个阶段：第一阶段组氨酸中咪唑环上远离金表面的N3原子与铁离子形成单齿配合物，此时化合物之间通过静电斥力使得悬臂向下偏转；第二阶段，组氨酸上靠近金表面的N1原子开始与铁离子作用，通过分子构象的改变最终与邻近的单齿配合物形成双齿配合物，并开始逐渐覆盖悬臂表面，形成网络结构使得悬臂表面形成一种收缩的应力，而使悬臂向镀金面偏转。第二阶段不但与作用时间有关，而且同氯离子的浓度紧密关联。只有当氯离子浓度大于或等于50mmol/L时，才会出现悬臂向镀金面偏转的现象。组氨酸修饰的悬臂还是一个很好的铁离子传感器，检测限能达到510-9 mol/L级。 （3）将肽（Gly-Gly-His）共价键合到MPA修饰的悬臂表面，首先研究肽与Cu2+ 的相互作用过程。研究发现作用过程与Cu2+ 的浓度有关，高浓度时Cu2+ 与肽快速吸附，并通过与不同肽链上的羧基和咪唑环配位诱导悬臂向镀金面偏转；而后肽链上的氮原子与Cu2+配位，同时构象发生变化，由直链转变成折叠状，进而增加链间的作用力使悬臂向反向偏转；而铜离子浓度低时不能实现悬臂表面快速的形成向内的拉力，所以不会产生向镀金面偏转，而直接在构象变化推动悬臂反向偏转。考察了检测过程中溶液pH、离子强度和干扰离子对检测的影响。结果表明该传感器对铜离子有较宽响应范围，最低响应浓度为210-10 mol/L。