化合物颜色成因简介

从过渡金属离子d-d电子跃迁和电荷转移及其影响因素出发,讨论了化合物呈色的本质,对影响化合物呈色的主要因素进行了论述,重点阐明了化合物颜色与其分子结构的关系,并列举了部分常见化合物的颜色及变化规律.通过分析,说明了化合物的颜色与其结构、环境因素和人的视觉等有着密切的关系.     

微量元素对绿色翡翠的影响

应用电子探针对绿色翡翠样品进行了分析。结果表明,翡翠中的微量元素Cr和Fe是绿色翡翠致色的关键,当这些金属离子以类质同象进入硬玉晶格时,就会使硬玉呈现他色(由非主要化学成分引起的颜色);Ca、Mg等元素则对翡翠的质地有着重要的影响。     

温和条件下元素对M~(2+)/Fe~(2+)/Fe~(3+)-LDHs转化成尖晶石铁氧体过程的影响(英文)

研究了二价金属离子在温和条件下(低于100℃,暴露于空气中)从水滑石M2+/Fe2+/Fe3+-LDHs(M=Co,Ni,Mn,Zn)转化成尖晶石铁氧体的过程中所起的作用。结果表明,该转化过程不仅与晶化温度有关,还与M2+在元素周期表中所处的位置有关。当这些二价金属离子处于同一周期并且相邻较近时,M2+的半径越大,水滑石微晶向尖晶石铁氧体的转化就越容易。此外,Fe2+在转化过程中起着至关重要的作用,如果没有Fe2+的参与,在此条件下的转化将无法进行。     

基于可识别不同价态铁离子的多控荧光开关及分子逻辑门的构建

本文研究了5-磺基水杨酸(SSA)与多种金属离子的相互作用的荧光光谱,发现Fe3+可以选择性猝灭SSA的荧光,而其他金属离子如Ca2+、K+、Cr3+、Ni 2+Mn2+、Pb2+、Cu2+、Zn2+、Co2+以及Fe2+均不能猝灭SSA的荧光。同时发现,加入EDTA竞争Fe3+或加入盐酸羟胺还原Fe3+均可以使SSA的荧光恢复。可以通过质子(H+/OH-)、配位(Fe3+/EDTA)和化学氧化还原(盐酸羟胺/K2S2O8)三种方式对其荧光进行可逆调控。在此基础上,分别以SSA和SSA-Fe3+体系作为起始状态,构建了两化学输入的NOR、OR和INHIBIT分子逻辑门。     

超重力场中水溶液的电化学反应特性

以Fe3+/Fe2+电对体系和铁氰酸根离子为研究对象, 分别采用循环伏安法、线性扫描伏安法和计时电流法等考察了在超重力条件下Fe3+/Fe2+电对体系和铁氰化钾离子的电化学行为, 为认识和发展超重力场中电化学反应过程的研究提供了一定的理论及实验依据.     

Li+掺杂对TeO2:Tm3+/Er3+/Yb3+纳米材料上转换发光的增强作用

采用水热法制备了发白光的Li+掺杂α-TeO2∶Tm3+/Er3+/Yb3+和β-TeO2∶Tm3+/Er3+/Yb3+纳米上转换发光材料。采用X射线衍射、透射电镜和上转换发光光谱对制备的TeO2∶Tm3+/Er3+/Yb3+/Li+纳米材料进行表征,结果显示:Li+的掺入基本不改变纳米材料的晶型和结构;在980 nm近红外光的激发下,纳米材料发射出中心波长476 nm的蓝光,525 nm及545 nm的绿光和659 nm及675nm的红光,分别对应于Tm3+的1G4→3H6能级跃迁,Er3+的2H11/2→4I15/2和4S3/2→4I15/2能级跃迁,Er3+的4F9/2→4I15/2能级跃迁和Tm3+的3F2→3H6能级跃迁;Li+的掺入能够增大白光体系的发光强度,基本不改变纳米材料的白光颜色。此外,探讨了纳米材料的上转换发光机理。     

基于香豆素骨架的重金属和过渡金属离子荧光探针的研究进展

按照对不同金属离子的识别归类总结了近五年来以香豆素为荧光基团的重金属和过渡金属离子(Cr3+,Cd2+,Pb2+和Hg2+;Fe3+,Co2+,Ni2+,Cu2+,Zn2+和Ag+)荧光探针的研究进展,并简要介绍了该类探针的设计、作用机理及应用,展望了该领域的发展趋势。     

由Mg-Fe(Ⅱ)-Fe(Ⅲ) LDH层状前体制备MgFe_2O_4尖晶石的研究

提出了一种由层状前体合成单一晶相镁铁尖晶石的新方法,首先对Mg Fe(Ⅱ) Fe(Ⅲ)水滑石的制备进行了系统研究,成功合成了Mg2 +/Fe2 +/Fe3+摩尔比分别为 1/2/1,4/5/3,2/1/1的系列水滑石层状前体,结果表明在以上三种投料比下均可制备出晶型较好的水滑石层状前体,并探讨了合成条件对晶体结构的影响规律.在此基础上,利用X射线衍射、振动样品磁强计和穆斯堡尔谱等手段研究了层状前体焙烧产物的结构、组成、磁性及微观信息,研究表明当Mg2 +/Fe2 +/Fe3+投料摩尔比为 2/1/1时,焙烧层状前体可得到晶相单一的尖晶石型铁氧体     

Fe3+/Ba2+/Co2+/Zn2+/Cu2+在NH4HCO3-NH3·H2O和NaOH-Na2CO3体系中的热力学分析

通过对Fe3+/Ba2+/Co2+/Zn2+/Cu2+在NH4HCO3-NH3·H2O和NaOH-Na2CO3体系中的热力学分析,得到各金属离子总浓度(cMe)与pH值的关系,确定了2种体系中5种离子完全共沉淀的pH值范围.结果表明:在NH4HCO3-NH3·H2O体系中,Co2+、Zn2+、Cu2+3种离子和氨的配位能力很强,其中Cu2+与氨的配位能力最强,在相同的pH值条件下,Cu2+沉淀困难,5种金属离子的完全共沉淀区域由Cu2+决定.在NaOH-Na2CO3体系中,随总碳浓度(cc)的增加,Ba、Co、Zn、Cu的溶解度都随之减小,当cc=1.0 mol·L-1时,各金属离子完全共沉淀的pH值范围为7.5～11.在两种体系中,Fe的溶解度都是随pH值的增大而减小,最终达到平衡.以NaOH-Na2CO3 为沉淀剂.在pH=10.0的条件下,采用化学共沉淀法合成出了晶粒细小、粒度均匀的Y型纯相结构的平面六角铁氧体微粉.     

硫酸溶液中电化学改性石墨电极对Fe3+/Fe2+的电催化性能与准电容特性

通过循环伏安(CV)、恒电流充放电和电化学阻抗谱(EIS)等测试方法,研究了电化学改性石墨电极对硫酸溶液中Fe3+/Fe2+的电催化性能与准电容特性.结果表明:由于电化学改性石墨电极表面存在大量的含氧活性官能团,使其对Fe3+/Fe2+的氧化还原反应具有极高的电催化性能,并具有可逆反应过程特征.在含有0.5mo·lL-1Fe3++0.5mo·lL-1Fe2+的2.0mo·lL-1H2SO4溶液中,其表观面积比电容是不含铁离子硫酸溶液的1.808倍,达到2.157F·cm-2;同时,铁离子浓度的增大也能够进一步提高其电容量.Fe3+/Fe2+电对的加入增加了充放电时间,有效提高了电化学电容器(EC)的电容存储容量和高功率特性.电化学阻抗谱测试同样证实体系具有明显的电容特性.因此,可以利用电化学改性石墨电极表面的含氧活性官能团和溶液中Fe3+/Fe2+的氧化还原特性来共同储存和释放能量.     

Analysis of Fissure-Filled Emeralds and Rubies by Diffuse Reflectance Fourier Transform Infrared Spectroscopy

ABSTRACT

Although diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is mainly used for powdered solid samples, it was found to be highly effective for the analysis of certain gemstones. Small amounts of oils and resins used to fill cracks and fissures in substandard (included) emeralds and rubies could be detected. Because of their very low levels, these organic adulterants can be difficult to detect by measurement of the infrared transmittance spectrum. Rubies have a significantly larger “window-of-detection” for organic clarifying agents than do emeralds. In some cases the spectral information was sufficient to identify the oil or polymer resin. Emeralds that were treated over 20 years ago are still easily identified. The position of the emerald or ruby in the sample holder can affect the intensity of C-H and O-H stretching frequencies as well as those brands characteristic to the gemstones.     

邻氯酚红-Fenton体系对金属离子的光化学传感研究

利用具有高度选择性的光化学传感器来识别和检测金属离子是近年来的一个热点研究领域~([1]),因为被测物引起的体系颜色变化直观可见且灵敏,这方面已有许多成功的报道~([1-5]).邻氯酚红(CPR)是一种氯取代的三苯甲烷类酸性染料,除了纤维染色之外已被用于蛋白质和药物测定~([6]).     

基于三联吡啶衍生物的Fe~(2+)/Fe~(3+)化学比色敏感器

合成和表征了一种新的化合物(E)-4-′(4-(2-(2-萘)乙烯基)苯基)-2,2′:6′,2″-三联吡啶L.用Fe2+或Fe3+来滴定时,L的溶液(三氯甲烷和乙醇的体积比为1∶20)颜色分别从无色变成洋红色和橙红色,相应的紫外可见吸收光谱都在374和574 nm出现特征吸收峰.此外,即使存在其它过量金属阳离子时,L对Fe2+或Fe3+离子仍然表现出很强的敏感性和选择性.另外,还研究了L对Fe2+或Fe3+离子及两者共同存在时的线性检测浓度范围和最低检测极限(LOD).     

Preparation and Characterization of Polyesterurethane Metallopolymers Containing Transition Metal Ions

Several series of metallopolymers (MP) were synthesized from a MDI-based polyesterurethane and various transition metal ion species, namely, copper(II), manganese(II), cobalt(II), iron(III) and chromium(III). Each series of MP were prepared by using different initial molar ratios urethane groups/metal ions (U/M). MP were characterized in comparison with the parent polyurethane (PU) by atomic absorption spectrometry (AAS), UV-vis absorption spectroscopy, FT-IR spectroscopy, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA) and tensile testing. The transition metal ions form coordination complexes with polyurethane functional groups, the intermolecular complexation resulting in the crosslinking of polymer chains. As a consequence, modifications take place in the original structure of PU, e.g. hydrogen bonding and crystallinity of the hard-segment domains. MP compared with PU present differences in viscoelastic and mechanical behaviors, which generally indicate the reinforcing effect of metal ions on the polyurethane matrix, as well in thermal stability. It was revealed that each transition metal ion has specific effects on the structure and properties of PU. The implications and mechanisms behind these observations are discussed.     

XAS study on copper red in ancient glass beads from Thailand

Glass has been used in ornaments and decorations in Thailand for thousands of years, being discovered in several archeological sites and preserved in museums throughout the country. To date only a few of them have been examined by conventional methods for their compositions and colorations. In this work we report for the first time an advanced structural analysis of Thai ancient glass beads using synchrotron X-ray absorption spectroscopy (XAS) and energy-dispersive X-ray (EDX) spectrometry. Four samples of ancient glass beads were selected from four different archeological sites in three southern provinces (Ranong, Krabi and Pang-nga) of Thailand. Archaeological dating indicated that they were made more than 1,300 years ago. A historically known method for obtaining a red color is to add compounds containing transition elements such as gold, copper, and chromium. For our samples, EDX spectrometry data revealed existing fractions of iron, copper, zinc, and chromium in ascending order. Thus, copper was selectively studied by XAS as being potentially responsible for the red color in the glass beads. K-shell X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) of copper were recorded in fluorescence mode using an advanced 13-element germanium detector. Comparisons with XANES spectra of reference compounds identified two major forms of copper, monovalent copper and a metallic cluster, dispersed in the glass matrix. The cluster dimension was approximated on the basis of structural modeling and a theoretical XANES calculation. As a complement, EXAFS spectra were analyzed to determine the first-shell coordination around copper. XAS was proven to be an outstanding, advanced technique that can be applied to study nondestructively archaeological objects to understand their characteristics and how they were produced in ancient times.     

Speciation studies by capillary electrophoresis- Simultaneous determination of chromium(III) and chromium(VI)

A method for the simultaneous determination of chromium(III) and chromium(VI) by capillary electrophoresis (CE) has been developed. The chromium(III) has been chelated with 1,2-cyclohexanediaminetetraacetic acid (CDTA) in order to impart a negative charge and similar mobility to both the chromium(III) and the chromium(VI) species. The effects of the amount of the reagent, pH and heating time required to complete the complexation have been studied. Factors affecting the CE behaviour such as the polarity of electrodes and the pH of electrophoretic buffer have been investigated. The separated species have been monitored by direct UV measurements at 214 nm. The detection limits achieved are 10 microg/l for Cr(VI) and 5 microg/l for Cr(III) and linear detector response is observed up to 100 mg/l. The procedure has been applied to the determination of both chromium species in industrial electroplating samples and its accuracy was checked by comparing the results (as total chromium) with those of atomic absorption spectrometry. No interference occurred from transition metal impurities under optimized separation conditions. The method is also shown to be feasible for determining Cr(III) as well as other metal ions capable to form complexes with CDTA (like iron(III), copper(II), zinc(II) and manganese(II)) in pharmaceutical preparations of essential trace elements.     

MASS SPECTRAL FRAGMENTATION STUDIES ON THIOPHENOTROPONE AND THIOPHENOTROPILIDENE DERIVATIVES AND THEIR METAL TRICARBONYL COMPLEXS

Abstract

The mass spectral fragmentation of thiophenotropone, thiophenotropilidene derivatives and their iron and chromium tricarbonyl complexes are fully reported and discussed. The fragmentation patterns of the complexes are characterised by successive loss of three carbonyl groups. In general, the resulting ions after elimination of the metal behave in the same manner as the organic ligand. The iron complexes behave differently from their corresponding chromium complexes. The thiopheno[b]tropilidene iron tricarbonyl complex and its isomer thiopheno[c]tropilidene iron tricarbonyl complex could not be differentiated by mass spectrometry, such differentiation was achieved by proton magnetic resonance.     

过渡金属乙烯齐聚与聚合催化剂研究进展

综述了近年来过渡金属配合物催化乙烯齐聚与聚合的最新进展;介绍了乙烯齐聚或聚合的反应时间、反应温度、乙烯压力、助催化剂用量等反应条件及配体上不同取代基对前过渡金属(铬,锆,钛,钒)和后过渡金属(铁,钴,镍,铜)配合物的催化活性和齐聚或聚合产物的影响;分别以钛和镍配合物催化剂为例,介绍了前过渡金属和后过渡金属催化乙烯齐聚或聚合的机理。     

不同水煤浆分散剂与煤之间的相互作用规律研究 Ⅴ. 煤在分散剂水溶液中的溶出离子及其对CWS性质的影响

通过原子吸收和等离子体原子发射光谱法，研究了6种不同分散剂对14种煤溶出Ca2+、Mg2+、Fe3+(Fe2+)、Al3+、SiO32－离子的影响。结果表明，煤中溶出高价离子的数量，主要取决于分散剂与高价离子间的相互作用特征，以及矿物质的种类和数量。煤在不同分散剂水溶液中溶出高价离子的多少，并不单纯与水煤浆（CWS）的流变性或煤的成浆性具有相关性。煤中矿物质对CWS性质的影响，是多种因素综合作用的结果，溶出离子的种类和数量只是其中的重要因素之一。