微接触印刷术制备强发光有机荧光材料阵列

许多共轭的有机发光体在溶液中具有很高的发光性，但是当把它们制备成薄膜时发光就会变弱，但是利用微接触印刷术将有机荧光分子印刷到硅基片上形成有序微米阵列，得到的阵列的荧光强度非常强，是薄膜强度的几倍，同时研究了阵列尺寸与荧光强度之间的关系。     

有机酸中电解制备荧光碳点的性能及应用研究

在小分子有机酸电解液中,以高纯石墨棒为工作电极,通过一步电解刻蚀法剥落制备荧光性碳纳米颗粒(carbon dots,CDs)。通过分析不同电解底液制得碳点溶液的光谱性质,探究碳点可能的发光机理。实验结果表明,相同条件下电解得到的碳点的发光性能受有机酸底液类型影响明显,不同底液制得的碳点可能具有不同表面结构基团,从而推测此方法制备碳点的发光机理为表面态发光。半胱氨酸碳点(cysteine carbon dots,CECDs)具有较高的荧光量子产率和较好的光稳定性,并且呈现出不同于有机荧光染料分子的光谱依赖性。基于银离子对碳点荧光信号的猝灭作用,可将其作为荧光探针检测银离子的含量。荧光猝灭率(F0/F)与银离子浓度在1. 00×10-8～2. 30×10-7mol/L范围内呈现良好的线性关系,相关系数为0. 990 9。     

Eu3+掺杂TiO2荧光探针的制备及对氯氰菊酯的检测应用

以钛酸四丁酯为前体,采用液相法制备了水溶态纳米Eu3+掺杂TiO2荧光探针,并对其发光性质进行了研究。通过紫外吸收和荧光光谱研究了它和氯氰菊酯之间的相互作用,结果发现,氯氰菊酯对Eu3+掺杂TiO2的荧光具有猝灭作用,根据Stern-Volmer猝灭方程,计算出其猝灭常数为1.017×1011 L/(mol.s),并讨论了猝灭机理。依据氯氰菊酯浓度和Eu3+掺杂TiO2的荧光强度成正比,建立了一种快速检测农药的新方法。其检测范围为2.5×10-10～2.5×10-7mol/L,检出限为2.5×10-11mol/L,回收率在89.25%～93.55%之间。     

阳离子荧光敏感器的器件化问题研究

通过对石英玻片表面修饰，制作了联有多氨基链萘基的超薄膜荧光敏感器件，研究了它在镍、铜等金属离子水溶液及有机溶剂中的荧光猝灭现象。发现其荧光光谱无论在水或其他有机溶剂中都存在着单体和激基缔合物（excimer)的发射峰，当处于镍离子水溶液中时，其单体峰随离子浓度的增大出现了先增强后减弱的现象，而激基缔合物的发光峰则仅略有减弱但变化不大。在铜离子水溶液中其荧光的变化情况和镍离子有所不同，对单体荧光只能观察到强度减弱的趋势，而激基缔合物则变化不大。比较了未联结的敏感器化合物分子在有机溶剂中荧光被铜离子猝灭的行为，发现与其在器件表面时有很大的差别，表明其分子结构和构象也有很大的不同。     

荧光染料的进展

本文综述了荧光染料的进展，介绍了荧光染料的主要品种：香豆素类、萘酐类、花类、罗丹明类、吡咯并吡咯类、杂环离子型以及超分子化合物。     

类人胶原蛋白与Ca(Ⅱ)相互作用的荧光光谱研究

为了制备具有实际应用价值并能应用于人体的类人胶原蛋白-钙螯合物,采用荧光猝灭光谱法和紫外-可见吸收光谱法研究不同温度下类人胶原蛋白(HLC)分子与无机金属Ca(Ⅱ)离子间的相互作用,其中Ca(Ⅱ)离子的浓度为1.0×10-5—1.0×10-4mol/L。实验结果表明:无机Ca(Ⅱ)离子能够猝灭类人胶原蛋白分子的内源荧光,并形成HLC-Ca(Ⅱ)复合物;依据Stern-Volmer方程可知在类人胶原蛋白与Ca(Ⅱ)的结合过程中,动态猝灭和静态猝灭这2种猝灭机制同时存在;类人胶原蛋白分子与Ca(Ⅱ)离子以摩尔比1∶1形成蛋白-金属螯合物;根据273 K和298 K时Ca(Ⅱ)与HLC分子之间的结合常数以及相应的热力学参数可确定二者间的结合是自发反应过程,其中疏水作用力占据主导地位。因此,本研究为类人胶原蛋白-Ca(Ⅱ)复合物的大规模制备和进一步应用研究提供了理论依据和实验指导。     

离子聚合物对罗丹明B荧光发光行为的影响

传统荧光分子由于具有聚集诱导猝灭效应,其在高浓度或固态状态下荧光消失,限制了其实际应用。为克服这一缺陷,研究合成基于丙烯酸树脂的离子聚合物并将罗丹明 B荧光分子原位掺杂于聚合物体系中。利用聚合物链段上的离子与荧光分子之间的电荷作用抑制荧光分子在体系中的聚集,设计合成了不同罗丹明 B掺杂量和不同玻璃化温度下的荧光树脂,探讨了罗丹明 B掺杂量、玻璃化温度、聚合物质量百分浓度、不同溶剂以及环境温度对荧光树脂性能的影响。结果表明,通过电荷的吸引作用,利用聚合物链段的吸附和阻隔,可促进荧光分子的有效分散,从而实现固化涂膜的有效发光。     

含银纳米晶TiO2有序多孔膜层的制备及其光学性能

以单分散聚苯乙烯(PS)微球为原料,水为稀释溶剂,利用垂直沉降法制备出多层PS球有序阵列模板.采用溶胶-凝胶法制备TiO2溶胶,并用胶晶模板法制备出锐钛矿型TiO2有序多孔薄膜.然后将金属银纳米晶掺入多孔膜骨架中制备出含银纳米晶的TiO2有序多孔发光薄膜.分析了掺银的TiO2有序多孔膜的形貌与结构,并研究了掺银的TiO2有序多孔膜吸附罗丹明B及量子点CdSe荧光物质的荧光增强性能.结果表明:掺银的TiO2薄膜基本呈现多孔结构并保留有一定的有序性.有序多孔骨架中银纳米晶的表面荧光增强作用可大幅度提升荧光物质的荧光性能,从而扩展了TiO2有序多孔薄膜在生物信息探测、光信息处理领域的应用.     

层层自组装技术制备类水滑石基新型薄膜材料的研究进展

类水滑石（layered double hydroxides,LDHs）具有各向异性的结构特征、特殊的理化特性及多功能性,在材料科学领域得到广泛应用。本文围绕近年来LDHs基薄膜材料的研究进展,系统概括了层层自组装技术（layer-by-layer self-assembly,LBL技术）制备的LDHs基新型薄膜材料的基础作用力（如静电吸附作用、氢键作用等）,阐述了LDHs与无机分子（如蒙脱石、二氧化锰、石墨烯等）、有机分子（如聚乙烯醇、荧光染料、聚苯乙烯磺酸盐等）等组装制备的特性薄膜材料,并总结了其在光、电、催化、生物无机材料等方面的应用。指出伴随着制备方法、化学组成及成膜作用力等方面基础研究的深入以及对LBL技术的功能化、实用化研究的日臻成熟,以LBL技术构筑的LDHs基薄膜材料必将对材料、化学、生物等科技领域产生深远的影响。     

纳米碲化镉/石墨烯水溶液的制备及荧光性能研究

以石墨为原料,通过热还原法制备了还原性氧化石墨烯(rGO),然后采用水热法将CdTe量子点与r GO以非共价键的方式复合在一起,制备出了纳米CdTe/rGO水溶液。通过X射线衍射仪、紫外-可见分光光度计、透射电子显微镜和荧光分光光度计对样品进行了表征。结果表明,160℃下水热30 min制备的CdTe/rGO荧光性能最好。CdTe量子点均匀地负载在rGO表面;CdTe量子点的团聚体尺寸由复合前的220 nm减小到60~120 nm;并在527 nm处产生荧光猝灭,说明rGO与CdTe量子点之间存在着光诱导电子转移,从而为制备性能可靠的光伏器件提供可能。     

Functionalized Fluorescent Organic Nanoparticles Based AIE Enabling Effectively Targeting Cancer Cell Imaging

We report a fluorescent dye TM by incorporating the tetraphenylethylene (TPE) and cholesterol components into perylene bisimides (PBI) derivative. Fluorescence emission spectrum shows that the dye has stable red emission and aggregation-induced emission (AIE) characteristics. The incorporation of cholesterol components triggers TM to show induced chirality through supramolecular self-assembly. The cRGD-functionalized nanoparticles were prepared by encapsulating fluorescent dyes with amphiphilic polymer matrix. The functionalized fluorescent organic nanoparticles exhibit excellent biocompatibility, large Stokes’ shift and good photostability, which make them effective fluorescent probes for targeting cancer cells with high fluorescence contrast.     

A study of some intermolecular interactions between organic dye molecules in aqueous solution by fluorescence quenching and difference absorption spectrophotoinetry

Intermolecular interactions between the fluorescent organic dyes Fluorescein, Fluorescein Diiodide, Eosin, Rose Bengal, Erythrosin, Phloxine, Phloxine B, Rhodamine 6G, Lissamine Rhodamine B200 and the non fluorescent Crystal Violet and Malachite Green in aqueous solution have been studied by fluorescence quenching and difference absorption spectrophotometry. Equilibrium constants for the interactions have been determined by the two techniques mentioned and are compared. Absorption and fluorescence spectra and rates of photolysis of solutions obtained by extracting aqueous solutions of the mixed dyes into organic solvents are described.     

Fabrication of nanosheets of a fluorescent metal–organic framework [Zn(BDC)(H2O)]n (BDC = 1,4-benzenedicarboxylate): Ultrasonic synthesis and sensing of ethylamine

A supramolecular metal–organic framework (MOF) constructed by two-dimensional (2D) infinite coordination polymers, [Zn(BDC)(H₂O)]_n (1, BDC = 1,4-benzenedicarboxylate), was synthesized by the reaction of zinc acetate with H₂BDC in dimethylformamide (DMF) under ultrasonic irradiation at ambient temperature and atmospheric pressure. Yield of 1 varied from 43.4% to 53.2% for the reaction time of 10–90 min. Samples with different morphologies, i.e. nanobelts, nanosheets, and microcrystals, were obtained under ultrasound irradiation for different reaction times. Fluorescence emission of nanosheets of [Zn(BDC)(H₂O)]_n was found to be highly sensitive to ethylamine, and solid state fluorescence intensity decreased with increasing contents of ethylamine in acetonitrile solution due to weak fluorescence quenching effect.     

Plasmonic molecular nanohybrids-spectral dependence of fluorescence quenching

We demonstrate strong spectral dependence of the efficiency of fluorescence quenching in molecular systems composed of organic dyes and gold nanoparticles. In order to probe the coupling with metallic nanoparticles we use dyes with varied spectral overlap between the plasmon resonance and their absorption. Hybrid molecular structures were obtained via conjugation of metallic nanoparticles with the dyes using biotin-streptavidin linkage. For dyes featuring absorption above the plasmon excitation in gold nanoparticles, laser excitation induces minute changes in the fluorescence intensity and its lifetime for both conjugated and non-conjugated mixtures, which are the reference. In contrast, when the absorption of the dye overlaps with the plasmon resonance, the effect is quite dramatic, reaching 85% and 95% fluorescence quenching for non-conjugated and conjugated mixtures, respectively. The degree of fluorescence quenching strongly depends upon the concentration of metallic nanoparticles. Importantly, the origin of the fluorescence quenching is different in the case of the conjugated mixture, as evidenced by time-resolved fluorescence. For conjugated mixtures of dyes resonant with plasmon, excitation features two-exponential decay. This is in contrast to the single exponential decay measured for the off-resonant configuration. The results provide valuable insight into spectral dependence of the fluorescence quenching in molecular assemblies involving organic dyes and metallic nanoparticles.     

荧光染料用于涤纶织物染色的荧光性能研究

在实验条件下，染色织物的荧光反射率随荧光染料的浓度增加而增加，超过一定浓度后，有下降趋势；在pH=5左右，荧光反射率最高；荧光增白剂会提高染色织物的荧光反射率，在荧光黄2GFL中，当荧光增白剂的浓度由0.1％增加到5％时，荧光反射率由8．43增加至18．59，而对非荧光染料只有增艳的作用，不产生荧光。荧光染料染色织物的荧光反射率随着加入非荧光染料量的增加而减弱。     

一种基于氧杂蒽结构的“Turn-Off”型荧光探针研究及对磷酸酯类物质检测

设计了一种基于氧杂蒽结构的"Turn-Off"型荧光探针(P3),在生理pH条件下对磷酸根(Pi)较好的荧光淬灭性能,在与其它竞争性含氧阴离子(硫酸根、硝酸根、碳酸氢根)以及其它常见阴离子(氟离子、氯离子、溴离子等)对该识别的竞争性影响考察中,亦显示了较好的特异性。从荧光滴定法得到荧光探针(P3)与磷酸根(Pi)形成超分子复合物的摩尔比为1∶1,复合物稳定常数K为5.28*103。通过量子化学计算表明磷酸根与!共轭体系产生了较强的相互作用,并导致P3分子平面上翘,在一定程度上破坏了原先的共面型,磷酸根上氧部位的孤对电子与!共轭体系存在着轨道交叠,即p-!共轭作用。可将此探针应用于磷酸酯类物质的检测。     

蛭石功能材料研究进展

蛭石是中国优势非金属矿产之一,具有二维(2D)层状结构和独特的高膨胀性能等优点,可应用于构建新型功能材料,但其存在结构稳定性差和纳米尺度控制难等问题。该文阐述了天然层状蛭石的结构与性质,回顾了近年来国内外关于蛭石复合功能材料的相关报道,重点分析了蛭石的剥离与改性及其在吸附、催化剂载体、有机-无机复合材料、储能、药物载体等方面的研究进展。最后针对蛭石研究存在的主要问题,提出今后研究的重点在蛭石剥离,多级结构复合功能材料和有机-无机复合功能材料的构建,以及相关机理的探索。     

The Effects of Fluorescent Substances on the Photofading of Colours

The addition of fluorescent brightening agents of the pyrazoline-type accelerates the photofading of triphenylmethane dyes, while the dyes quench the photoreactions of the fluorescent brightening agents. The accelerations were most marked when irradiation was carried out in the maximum fluorescence excitation region of the fluorescent brightening agents. Stern-Volmer quenching studies and chromatographic analyses of the photoproducts revealed that the accelerated photofading reactions involved triplet sensitizations of the dyes by the fluorescent brightening agents.     

Stacked Thiazole Orange Dyes in DNA Capable of Switching Emissive Behavior in Response to Structural Transitions

Functional nucleic acids with the capability of generating fluorescence in response to hybridization events, microenvironment or structural changes are valuable as structural probes and chemical sensors. We now demonstrate the enzyme-assisted preparation of nucleic acids possessing multiple thiazole orange (TO) dyes and their fluorescent behavior, that show a spectral change from the typical monomer emission to the excimer-type red-shifted emission. We found that the fluorescent response and emission wavelength of the TO dyes were dependent on both the state of the DNA structure (single- or double-stranded DNA) and the arrangement of the TO dyes. We showed that the fluorescent behavior of the TO dyes can be applied for the detection of RNA molecules, suggesting that our approach for preparing the fluorescent nucleic acids functionalized with multiple TO dyes could be useful to design a fluorescence bioimaging and detection technique of biomolecules.