四氯合镍酸三乙醇铵的固相合成及其热色性

可逆热变色材料作为感温防伪显示材料 ,它的应用已扩展到生产及日常生活的各个领域。例如 ,美国财政部已在新版的美元上使用了可逆热色性油墨[1 ] ;Nature公司生产了热色性釉料图案陶瓷杯 ,室温呈夜幕景色 ,倒入热水后显示白天景象 ,来显示水的冷热 ,给人以赏心悦目之感。在一些无法用常规仪器测温的场合 ,热色性示温涂料有着独特的优越性。本文通过固相反应合成了新化合物四氯合镍酸三乙醇铵 ,并借助光谱数据 ,探讨了该化合物的可逆热致变色机理。IFS 48FTIR傅立叶变换红外分光光度计 ,KBr压片 ;紫外 可见 近红外光谱采用UV 340 0分…     

席夫碱的合成及热色性研究Ⅲ——二取代苯甲醛-二-对-氨基苯甲烷类席夫碱

本文合成了二取代苯甲醛-二-对-二氨基苯基甲烧类席夫碱类的7个化合物,并应用物理方法进行了表征.通过加热显微观察,这些化合物都具热色性,而其中4种具有可逆热色性.此外应用差热分析阐述了这类席夫碱的吸热峰的ΔH(ΔS)与其结构的关系.     

四氯化碳在化学实验中的妙用

利用四氯化碳特殊的理化性质,改进了次氯酸的漂白实验、原电池装置、淀粉与碘的可逆热色性实验和防气体倒吸的实验装置,教学效果理想。     

化学防伪

化学防伪是最近刚刚出现的新型防伪技术。本文系统介绍了化学防伪的基本原理,对化学防伪对热色物质的基本要求等有关问题亦做了探讨。     

含席夫碱基的螺噁嗪类光致变色化合物的合成及性质

设计合成了一系列含席夫碱基的螺噁嗪双功能光致变色材料4a~4d. 通过¹H NMR, ¹³C NMR, IR和HRMS对其结构进行了表征. 新化合物在几种有机溶剂中均表现出了良好的光致变色性. 研究了化合物在几种高分子膜中的光致变色性. 比较了化合物4b的开环体在两种不同溶剂, 即甲醇和二甲亚砜, 以及3种高分子介质, 即聚甲基丙烯酸甲酯(PMMA)、聚乙烯醇缩丁醛(PVB)和聚乙烯醇(PVA)中的消色速率. 研究了化合物在甲醇、二甲亚砜、PMMA及PVB中的消色过程动力学, 根据化合物在溶液中和高分子介质中开环体消色过程的差别, 推测了存在两种动力学解释的原因. 研究结果显示, 化合物4d在PMMA膜中的耐疲劳度良好.     

高效液相色谱圆二色检测技术在手性化合物分析中的应用

对近年来高效液相色谱圆二色检测技术在手性化合物分析中的应用进展进行综述,简单介绍了高效液相色谱圆二色检测器的原理和特点,着重介绍了非手性色谱条件下圆二色检测技术在手性化合物对映体纯度测定、复杂基质中手性化合物分析以及在手性化合物绝对构型测定中的应用,并讨论了它的应用前景。     

新型含氮杂环螺吡喃化合物的合成及性能研究

为了改善螺吡喃的光致变色性能,提高这一系列化合物的耐疲劳度,在螺吡喃吲哚啉环的氮原子上通过短碳链引入含氮杂环基团,成功合成了1'-(3-N-杂环基丙基)-3',3'-二甲基-6-硝基螺[吲哚啉-2,2'(2H)苯并吡喃](4a～4f).这一系列新的化合物.用核磁共振氢谱、碳谱、红外光谱和元素分析对这些化合物进行结构表征.通过紫外吸收光谱研究化合物在不同溶液(乙醇、二氯甲烷和环己烷)中和不同高分子膜(PMMA和PVB)中的变色性质.进一步对化合物4a在不同溶液中的动力学性质,以及在PMMA膜和PVB膜中的热消色动力学性质进行了研究,拟合计算并比较了消色过程的动力学常数.最后,又将化合物4a和不含含氮杂环的螺吡喃母体进行比较,发现耐疲劳度有很大提高.     

水杨叉间溴缩苯胺的光发色和热消色反应过渡态

本文报道水杨叉间溴缩苯胺(1)的光致色变和热消色, 首次提出了它的光发色和热消色反应过渡态结构, 确认顺-反-反烯醇式水杨叉间溴缩苯胺(2)有光致色变性能, 而顺-顺-反式异构体则无此性能。选择1作为确定研究对象的另一个原因是由于激发态间位效应[9]的考虑, 1的氮原子将呈现更强的碱性, 降低热消色反应速率常数, 期望在较高的温度下观察到光致色变。     

新型双螺噁嗪分子的合成及性能

设计合成了3个双螺噁嗪化合物, 采用核磁共振谱、红外光谱和高分辨质谱对这些化合物进行了表征. 测试了光照前后化合物在不同溶剂中的紫外吸收光谱、荧光光谱以及在高分子薄膜中的消色动力学曲线. 结果表明, 目标化合物均具有良好的光致变色性能和耐疲劳度, 在材料、分子开光及生物探针领域有潜在的应用前景.     

水杨叉间溴缩苯胺的光发色和热消色反应过渡态

亚稳态的可控转换是未来信息记录分子器件原理,因此,人们对光致色变化合物合成和光化学行为研究感到兴趣。水杨叉缩苯胺及其部份衍生物的固体、固相溶液和Lan-gmuir-Blodgett膜(LB膜)呈现光致色变性质。质子迁移是水杨叉缩苯胺的光致色变和热消色反应机理,反应按协同机理进行,反应     

“元素化学实验”中的热致变色现象(一)——部分Co(Ⅱ)化合物的热致变色现象及其变色机理探讨

以探讨Co²⁺鉴定实验过程中意外发现在适量CoCl₂溶液中加入适量NH₄SCN溶液的体系具有可逆热致变色现象为切入点,在分析和探讨其热致变色机理的基础上,顺势通过"先做后教、以做定教"实验教学的"翻转课堂"模式,即学生完成元素化学实验,具有亲身经历和切身体会后,以"问题"为导向,以生动直观的演示实验现象为基础,引导学生直观认识一些Co(Ⅱ)化合物的热致变色现象及其影响因素,启发学生应用化学原理与化学知识解释和探讨热致变色现象产生的本质,以加深学生对配合物的结构、性质以及分裂能概念的理解,培养学生的观察、分析、判断、归纳、推理、总结和探索规律的能力以及"批判性"思维能力。     

"元素化学实验"中的热致变色现象(二)——部分Cr(Ⅲ)化合物的热致变色现象及其变色机理探讨

在认识部分Co(Ⅱ)化合物的热致变色现象及变色机理的基础上,因势利导,创设问题“情境”,即再通过生动直观的演示实验,引导学生进一步认识一些Cr(Ⅲ)化合物的热致变色现象及其影响因素,引导和启发学生探讨和解释其热致变色的机理。进一步培养学生的观察、分析、判断、归纳、推理、总结和探索规律的能力以及“批判性”思维能力。     

Mechanochemical Synthesis and Temperature‐Dependent Optical Properties of Thermochromic (Ag1−xCux)2HgI4

Thermochromic materials are generally synthesized via high‐temperature melting reaction or solution‐based synthesis. Herein, all‐inorganic thermochromic compounds of (Ag_1?xCu_x)₂HgI₄ were synthesized by solvent‐free simple and scalable mechanochemical grinding at room temperature. Temperature‐dependent electronic absorption spectroscopy along with DSC analysis confirmed the thermochromic events within these materials, and the phase transition temperature varied with solid solution compositions. The photoluminescence (PL) spectra is red‐shifted with the increase in the Cu content in (Ag_1?xCu_x)₂HgI₄ (x=0–1).     

Migration of pseudoestrogen bisphenol A from various types of paper with thermochromic prints to artificial sweat solutions

Abstract

Thermochromic inks, materials that change color at a certain temperature, are increasingly used on papers and other materials in the areas of design, commercials, and security printing. Pseudo-estrogen bisphenol A (BPA) may be one of their main compounds present in mass fractions of up to several percent. In this work, the mass fractions of BPA in thermochromic prints on seven types of paper were determined. Migration of BPA from the surface of the thermochromic print to artificial sweat solutions was investigated as well. Total amount of BPA in papers with thermochromic prints was determined by an HPLC-UV method with ultrasonic-assisted extraction in methanol developed and validated in this work. Total amount of BPA, which ranged from 0.126 to 0.778?mg/g, was compared with the amounts extracted under the same conditions in two artificial human sweat solutions, which differed in chemical composition, ionic strength, and pH-value. Mass fractions of BPA extracted with artificial sweat solutions were from 0.047 to 0.175?mg/g with respect to the mass of the paper. On average, the mass fraction of BPA was four times less when extracted with artificial sweat solutions than the maximal amount extracted with methanol. The amounts of extracted BPA raise a concern of health risk through dermal exposure to BPA from thermochromic prints on paper.     

Zinc(II)–Organic Framework Films with Thermochromic and Solvatochromic Applications

Multiple-stimuli-responsive photoluminescence films based on a Zn^II–organic framework, {[Zn₂(Htpim)(3,4-pydc)₂] ⋅ 4 DMF ⋅ 4 H₂O}_n ( 1 , Htpim=2,4,5-tri(4-pyridyl)imidazole, 3,4-H₂pydc=3,4-pyridinedicarboxylic acid), were fabricated. This compound consisted of a 2D corrugated layer, {Zn(3,4-pydc)}_n, which was further pillared using a Y-shaped pillar N-donor ligand (Htpim) to form a 3D-pillared-layer framework with 1D open channels. The rectangular channels in the as-synthesized compound are fully occupied by guest DMF and H₂O molecules. The framework exhibits instant and reversible thermochromic properties corresponding to the removal of different H₂O and DMF guest molecules as temperature increases. The pale-yellow crystal undergoes significant redshifting to a greenish emission centered at 530 nm. Compound 1 also showed remarkable solvatochromic effects in the presence of various organic solvents without affecting its structural integrity. In addition, polycrystalline MOF films were grown on an α-Al₂O₃ support for switchable and fast-response thermochromic and solvatochromic sensors.     

Preparation of Thermochromic Films from Latexes Made by Miniemulsion Polymerization

Thermosensitive‐thermochromic pigments are classified as smart materials capable of detecting and/or responding to environmental stimuli, and specifically in this study, changes in temperature that induce a change in the color of the material. This study aims to obtain nanoparticles of poly(styrene‐co‐butyl acrylate) and poly(styrene‐co‐methyl methacrylate), containing thermosensitive‐thermochromic pigments that are incorporated into the monomer droplets in miniemulsion polymerization. Miniemulsion polymerization has the advantage that the pigment particles can be dispersed directly in the monomer droplets and are encapsulated when the miniemulsion droplets are polymerized. Using controlled/living radical polymerization (or Reversible Deactivation Radical Polymerization), it is possible to produce polymers with better control of microstructure and narrower molecular weight distributions. Nitroxide‐mediated polymerization (NMP) is conducted using the BlocBuilder initiator, as well as a conventional free radical polymerization (FRP) using potassium persulfate (KPS) and 2,2‐azobis(2‐methylpropionitrile) (AIBN). Stable latexes containing the thermosensitive‐thermochromic pigments are obtained by both NMP and FRP. Films are made from the latexes and shown to exhibit thermochromic behavior.     

Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4‐Hydroxythiophenol

Solvothermal reactions between copper(I) halides and 4‐mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu₃X(HT)₂]_n (X=Cl, 1 ; Br, 2 ; and I, 3 ). The structures of these coordination polymers have been determined by X‐ray diffraction at both room‐ and low temperature (110 K), showing a general shortening in Cu?S, Cu?X and Cu?Cu bond lengths at low temperatures. 1 and 2 are isostructural, consisting of layers in which the halogen ligands act as μ₃‐bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as μ₄‐mode but the layers are quasi‐isostructural with 1 or 2 . These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2 , but weaker for 3 at room temperature, whereas upon cooling at 77 K 1 and 2 show stronger yellow emission, and 3 displays stronger green emission. DFT calculations have been used to rationalize these observations. These results suggest a high potential for this novel and promising stimuli‐responsive materials.     

The novel thermochromic and energy-storage microcapsules with significant extension of color change range to different tones

In order to solve the problem of narrow color change range for common thermochromic material, the novel thermochromic and energy-storage microcapsules (TCEMs) was designed and synthesized by in-situ polymerization. The TCEMs contained optimizational thermochromic components and phase change materials, and exhibited the dual functional performances of thermochromic and energy-storage. Then, the TCEMs were applied to polyester/cotton blend fabric with waterborne polyurethane by coating process. The growing process, exterior morphology, color change effect, temperature-regulable behavior and thermal activity of the TCEMs and the treated fabrics were investigated. The results demonstrated that both TCEMs and modified fabrics had good energy-storage effect and remarkable thermochromic property. Especially, while surrounding temperature changed from 15?°C to 45?°C, the colors of TCEMs and treated fabrics could change from cool-tone (blue) to warm-tone (red), which significantly improved the color change range of the thermochromic material and made the color vary between different tones instead of changing in the region of similar color. The TCEMs exhibited great potentiality in the applying fields of decoration, anti-counterfeiting, architecture and intelligent textile, etc.     

Influence of Temperature and Time on the Stability of Silver in Silica Sol-Gel Glasses

The darkening of silica sol-gel glasses doped with 0.05 mol% silver was studied. Six sols were prepared from TEOS and silver nitrate. Different additives were used, to influence the chemical and physical states of silver: oxidizing or reducing agents (H₂O₂, As₂O₅), colloid stabilizer (sodium citrate) and network modifiers (Li₂O, CaO). Sols were gelified at 60°C and densified at 600°C. The samples without additives and those prepared with H₂O₂ at room temperature even if they were protected from light. With increased temperature, the darkening became samples were heated above, 400°C, reversible bleaching took place. This darkening-bleaching is of thermal nature (“thermochromic effect”) and seems to be determined by a reversible aggregation-disaggregation of tiny silver particles. The presence of sodium citrate, as an additive delayed the darkening effect and the presence of CaO delayed it even further. Lithium oxide inhibited it totally.     

Thermochromic Organoaminomodified Silica Composite Films Containing Phosphomolybdic Acid

A novel thermochromic sol-gel film has been prepared for the first time through entrapping phosphomolybdic acid into a kind of inorganic-organic matrix co-hydrolyzed from tetraethylorthosilicate and 3-aminopropyltriethoxysilane. The thus-obtained amorphous nanocomposite film was characterized by IR spectra, UV-vis absorption spectra, XRD, TG-DTA, and ESR. Results show that phosphomolybdate polyanions interact with R-NH⁺₃ cations strongly and disperse homogeneously in the sol-gel matrix. The sol-gel film exhibits thermochromic properties. Annealed from 120 to 180°C, the transparent film changes from pale-yellow to blue. A possible charge-transfer process has been suggested to explain the thermochromism.