覆银聚酰亚胺纳米棒阵列的制备及其SERS特性

通过在聚酰亚胺(PI)膜表面进行氧等离子体刻蚀得到纳米棒阵列,并溅射Ag膜形成了覆银聚酰亚胺纳米棒阵列。利用该方法能够简单快捷地制备出具有较强活性且结构可调的表面增强拉曼散射(SERS)衬底。通过改变氧等离子体刻蚀时间和溅射Ag膜厚度可以调节覆银PI纳米棒的间隙、密度和直径。通过对探针分子尼罗兰(NB)测试表征了覆银PI纳米棒衬底的SERS增强能力。通过改变氧等离子体刻蚀时间和Ag膜溅射厚度实现了衬底SERS增强能力的调节。在氧等离子体刻蚀时间为30 s和溅射Ag膜厚度为70 nm时,衬底的SERS增强能力达到最强,并且其拉曼信号展现出较好的一致性。     

银纳米粒子有序自组装体中偶联分子的表面增强拉曼光谱研究

采用自组装方法,分别以1,4-二巯基苯和对巯基苯胺为偶联分子,在光滑银基底表面上构筑了银纳米粒子的单层和双层有序结构.表面增强拉曼光谱研究表明,在有序银纳米粒子组装体中偶联分子的拉曼散射得到很大增强,其中1,4-对巯基苯的拉曼散射增强效应主要来自光滑银基底表面与单层银纳米粒子间的电磁耦合,而对巯基苯胺的拉曼散射增强效应则主要由两层银纳米粒子之间耦合作用所致.两种不同的耦合作用所产生的增强效应大致相近.     

金纳米棒:合成、修饰、自组装、SERS及生物医学应用

纳米颗粒作为信号感应单元在化学与生物传感应用中已引起广泛关注,这些功能和金属纳米结构与光相互作用时产生的表面等离子体共振密切相关.表面增强拉曼散射(SERS),是指吸附在粗糙的金属纳米结构表面的被分析物,在光照射下其拉曼光谱获得显著增强的异常表面光学现象,近年来.SERS技术已广泛用于物质检测和生物传感等研究,在生物医学领域表现出巨大的应用潜力并取得了令人瞩目的研究成果.本文阐述了金纳米棒的制备方法、表面修饰和共轭生物分子的方法.并从金纳米棒表面增强拉曼散射的角度系统阐述基于金纳米棒表面增强拉曼散射的1D,2D,3D自组装,并介绍了近期金纳米棒表面增强拉曼散射在生物医学检测与成像中最具有代表性的应用研究.     

纳米岛状银膜@金纳米针尖表面增强拉曼散射传感界面及多巴胺分子的传感分析

多巴胺缺乏是导致帕金森疾病临床症状的主要原因。为有效检测分析多巴胺分子,本文通过磁控溅射技术制备了一种具有纳米岛状结构的银薄膜,使用无机碱性双氧水作为清洁还原剂,还原制备了一种毛胆状多纳米针尖的金纳米结构,并将纳米岛状结构的银薄膜和毛胆状多纳米针尖的金纳米结构作为表面增强拉曼散射(SERS)基底。通过银膜承载多巴胺分子,并滴加覆盖毛胆状多针尖的金纳米结构,利用具有高粗糙度的银膜表面与金纳米针尖异质结构形成的界面"热点",有效增强多巴胺分子的拉曼散射信号,并在尿液样品中实现多巴胺分子的传感检测。本研究构建的银膜@金纳米针尖表面增强拉曼散射传感界面,对于生物标志物分子的检测具有灵敏度高和抗干扰能力强的优势。     

以Au/Cu纳米棒为基底的肺腺癌组织的特征表面增强拉曼光谱研究

通过金铜共混法制备了Au/Cu合金纳米棒,研究了铜掺杂对金纳米棒等离子体共振吸收和结构的影响,探究了Au/Cu合金纳米棒的等离子体共振拉曼增强效应.以Au/Cu合金纳米棒为基底对肺腺癌组织和癌旁正常组织进行了表面增强拉曼光谱检测.结果显示,癌变组织具有比癌旁正常组织更强的拉曼信号峰,位于1250,1344,1408,1568,1608和2560 cm~(-1)附近的拉曼峰分别与蛋白质的AmideⅡ氨基化合物、C—H弯曲振动、核酸中CH_3的对称变角振动、蛋白质色氨酸惰性环振动、蛋白质酰胺I谱带分子间反平行β-折叠的C—O健伸缩振动和蛋白质的巯基(S—H)伸缩振动有关,2936 cm~(-1)附近的拉曼峰为蛋白质CH_2的对称伸缩振动和CH_3的反对称伸缩振动共同作用产生.以铜掺杂的金纳米棒为基底的表面增强拉曼光谱法有望成为检测肺癌组织的有效手段.     

对称性降低的SiO2/Ag核壳结构纳米粒子的制备及表面增强拉曼活性研究

采用湿化学还原法在自组装的单层阵列二氧化硅纳米粒子表面沉积银膜制备了SiO2核/Ag帽复合纳米结构。通过透射电镜(TEM)、扫描电镜(SEM)、X射线衍射(XRD)和紫外-可见分光光度计(UV/Vis)研究和表征了该复合纳米结构的表面形貌、结构及光学性质。所制备的复合纳米粒子表面粗糙,其表面呈现无数纳米级谷粒状结构,SiO2内核粒径为350nm的银纳米帽的表面等离子共振吸收的2个共振峰分别位于382和689nm处。以亚甲基蓝作为探测分子研究了SiO2粒径为350和450nm的SiO2/Ag帽状复合纳米粒子的表面增强拉曼散射(SERS)活性,增强因子分别为3.6×109和3.9×109。结果表明,湿化学还原法制备的SiO2核/Ag帽复合纳米结构是很好的拉曼活性基底。     

银纳米粒子簇的设计、 制备和表面增强拉曼光谱

通过匹配激光光斑直径与胶体微球的尺寸, 设计制备了银纳米粒子的表面增强拉曼散射(SERS)基底, 并将其用于研究单个银纳米粒子簇的表面增强拉曼光谱. 在制备纳米粒子的过程中, 考察了等离子体刻蚀时间与银沉积厚度对“单”银纳米粒子结构与形貌的影响. 将吡啶、 巯基苯和罗丹明R6G作为SERS探针分子, 研究了其SERS效应, 通过荧光共振能量转移(FRET)机理, 实现了染料分子在单银纳米粒子簇上的SERS效应. SERS光谱测试与相关计算结果表明, 单个银纳米粒子簇的拉曼增强因子能够达到约10⁶.     

帽状银纳米粒子的制备及表面增强拉曼活性研究

采用真空热蒸发法在自组装的单层阵列二氧化硅纳米粒子表面沉积银膜制备了帽状银纳米粒子。通过透射电镜(TEM)、扫描电镜(SEM)和紫外-可见-近红外分光光度计 (UV-Vis-NIR)对其表面形貌及光学性质进行了表征。以吡啶-(2-偶氮-4)间苯二酚作为探针分子，研究了该复合纳米粒子的表面增强拉曼散射 (SERS) 活性，增强因子高达2.88×10⁶。结果表明在二氧化硅纳米粒子表面制备的帽状银纳米粒子是很好的表面增强拉曼散射活性基底。     

蜂窝状Ag纳米颗粒膜制备及应用于表面增强拉曼散射基底

通过静态呼吸图法制备了具有高度有序微结构的聚苯乙烯-嵌段-聚4-乙烯吡啶共聚物(PS-b-P4VP)膜。以该嵌段共聚物膜为模板,可制得金属纳米粒子阵列。借助光化学还原途径制得了具有蜂窝状微结构的Ag纳米颗粒膜。以罗丹明6G(R6G)为探针分子,考察了蜂窝状Ag纳米颗粒膜用作表面增强拉曼散射(SERS)基底的性能。蜂窝状Ag纳米颗粒膜对R6G分子的表面拉曼散射增强因子高达1.31×10~9。另外,该SERS基底还显示了较低的检测限,检测限低至10~(-10)mol·L~(-1)。拉曼信号面扫显示了基底很好的信号均匀性。在此SERS基底上30μm×30μm范围内随机收集的120个拉曼信号强度的相对标准偏差仅为～12%。     

Cu2O/Ag纳米复合物的表面增强拉曼光谱

用一种简单的化学还原方法制备了银纳米粒子包覆的氧化亚铜（Cu2O）纳米复合物。扫描电子显微镜显示Cu2O 为八面体型的纳米粒子,表面光滑,结构对称。包覆的Ag部分占据Cu2O粒子表面。通过比较Ag/Cu2O纳米复合物、Ag溶胶及Cu纳米粒子表面吸附的4-巯基吡啶（4-Mpy）分子表面增强拉曼光谱（SERS）发现,利用此方法得到了Cu2O粒子表面吸附分子的拉曼光谱。银纳米粒子所产生的电磁场增强又增强了吸附在Cu2O上的4-Mpy拉曼信号。这种方法为初步研究Cu2O表面吸附分子性质提供了依据,扩宽了SERS的使用范围,使SERS应用在纳米半导体材料上成为可能。     

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

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性;均苯四甲酸二酐;联苯四羧酸二酐;二羟基联苯胺;聚酰亚胺;聚苯并噁唑;耐热性     

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.     

柴油加氢精制催化剂制备技术

柴油加氢精制催化剂制备技术的发展大致经历了3个阶段,由此形成了三代柴油加氢催化剂:单层分散的负载型金属硫化物催化剂,多层分散的负载型金属硫化物催化剂和非负载型金属硫化物催化剂。本文对金属硫化钼基柴油加氢精制催化剂的应用背景、制备思想及催化剂研究开发现状进行了系统的总结,对柴油加氢催化剂的发展方向进行了展望。