Synthesis and Spectra of a Kind of Novel Longer-Wavelength Benzoxazole Indole Styryl Cyanine Dye with a Carbazole-Bridged Chain

Based on cyanine dye probe oxazole yellow (YO) and Cy₃, a series of novel styryl cyanine dyes were designed and synthesized. Carbazole was inserted into the structures of YO and Cy₃ to act as a bridge to link the benzoxazole and indole group. This modification resulted in a novel kind of benzoxazole indole styryl cyanine dye with a carbazole-bridged chain. The dyes were characterized by ¹HNMR and MS. The spectra of the novel dyes were also performed and the results showed that the maximum emission wavelength of the carbazole styryl cyanine dye was shifted red, the Stokes shift increased and the fluorescence intensity enhanced compared with those of YO and Cy₃. These results indicated that the novel dye could be used as an excellent fluorescent probe in biological labeling.     

Study on Synthesis and Spectrum of Novel Styryl Cyanine Dyes with a Carbazole Bridged Chain

Based on the frequently-used cyanine dye probe thiazole orange (TO), a novel kind of cyanine dye was designed and synthesized. Carbazole was inserted into the methylidyne structure of TO as a bridge to afford a kind of novel styryl cyanine dye with carbazole bridged chain. The dyes were characterized by HNMR and MS. The spectra of the novel dyes were also studied and the results showed that the fluorescent wavelength of novel carbzole dye shifted red for 100 nm, stock shift increased by 70 nm and the fluorescent intensity enhanced by 70 times compared to that of TO. When the novel dye was labeled by BSA, its fluorescent wavelength changed little and the intensity enhanced. It is indicated that it can be used as an excellent fluorescent probe in biological labeling.     

Synthesis of Novel Carbazole based Styryl: Rational Approach for Photophysical Properties and TD-DFT

The synthesis and solvatochromic behavior of four novel carbazole based fluorescent styryl dyes were explained. In chlorinated solvents such as DCM and chloroform, these dyes show bathochromic shift in their absorption as well as emission. The styryl dyes 6b and 6c show solid state yellow fluorescence. DFT and TD-DFT computations were performed to study structural, molecular, electronic and photophysical properties of these dyes. The computed absorption and emission wavelength values are found to be in good agreement with the experimental results. The photophysical properties of these 1-styryl carbazole dyes are also compared with the recently reported 3-styrl carbazole dyes. The unique behavior of dye 6d is well explained by its optimized geometry found in the excited state. Ratio of ground to excited state dipole moment of the synthesized novel styryl compounds were calculated by Bakhshiev and Bilot-Kawski correlations.     

新型水溶性花菁双嵌染料荧光测定蛋白质的研究

基于蛋白质对双嵌花菁染料具有良好的荧光增强作用,以新型水溶性碳菁染1,1’-丙磺酸-3,3,3’,3’-四甲基吲哚三次甲基碳菁-5,5’-二磺酸钾为荧光探针,建立了一种新的蛋白质荧光检测体系。实验考察了探针的荧光特征、浓度、缓冲体系pH、盐浓度和乙醇有机试剂等参数对体系荧光的影响。当pH2.0,花菁染料最大荧光激发波长为548 nm,发射波长为562 nm,血清蛋白与探针作用随着探针浓度的增加而加强,荧光增强值逐渐上升;当探针浓度为1.00×10-6mol·L-1时,牛血清蛋白BSA和人血清蛋白HSA对花菁探针荧光增强作用最为明显,体系荧光强度与蛋白质浓度成良好的线性关系,BSA和HSA线性响应浓度范围分别为0.20～15.00μg·mL-1和0.20～12.00μg·mL-1, 检测限(3σ/K)为0.01μg·mL-1。测定了血清蛋白BSA的合成样品,当BSA浓度为4.00,6.00,8.00μg·mL-1时,回收率为94.5%～103.3%。     

一种新的磺酸吲哚菁染料的荧光光谱分析及其应用研究

研究了一种新型磺酸吲哚菁染料的荧光光谱并应用于蛋白质分析.结果表明,随着染料浓度增大,染料发生J聚合,荧光峰从564nm红移至605nm.当染料处于较低浓度时,离子强度影响不明显,而在较高浓度,J聚合增强,荧光增强变化明显;乙醇有机试剂显著增强染料荧光,并发生红移.应用于蛋白质分析,染料荧光强度随牛血清蛋白BSA或人血清蛋白HSA的增加而显著增强,在最优条件下,染料荧光强度与蛋白质浓度成良好线性关系,BSA线性范围为0.20-6.00μg/mL,检出限为0.08μg/mL;HSA线性范围为0.20-6.00μg/mL,检出限为0.1μg/mL.     

Davydov Splitting in Spectra of Cyanine Dye J-Aggregates, Formed on the Polynucleotides

It was found in our previous work (T. Y. Ogul'chansky et al. (2001) Spectrochimica Acta Part A 57, 2705–2715) that the carbocyanine dye Cyan iPr forms J-aggregates in the groove of poly(dA)-poly(dT). In the present paper we study in detail the spectral properties and energy levels structure of the Cyan iPr J-aggregates by means of absorption and fluorescence spectroscopy and polarization measurements. The energy structure of an aggregate consists of at least two exciton zones, and dipole moments of the absorption transitions to these zones are oriented at an angle of about 90° one to another. It was supposed that the transition moment of the lower zone is parallel to the polynucleotide axis and the moment of the upper zone is perpendicular. The fluorescent transitions are possible only from the lower exciton zone, while the excitations of higher zone undergo nonradiative transitions to the lower one.     

Spectroscopic Investigation on the Binding of a Cyanine Dye with Transferrin

Transferrin (Tf) can control the level of free iron as iron‐binding blood plasma glycoprotein in biological fluids. Tf has been exploited in the recent years on account of the potential function as a drug carrier targeting to tumor cells. Cyanine dyes have been widely studied as photosensitizers. The binding mechanism of Tf with 3, 3′‐di(3‐sulfopropyl)‐4, 5, 4′, 5′‐dibenzo‐9‐ethyl‐thiacarbocyanine triethylammonium salt (ETC) was characterized at varying pHs and temperatures by fluorescence, UV‐Vis absorption, circular dichroism (CD), and molecular modeling methods. The results showed that the static fluorescence quenching occurred between Tf and ETC. It was found that ETC bound strongly with Tf with an intrinsic binding constant (K_a), in the order of 10⁷ m ^?1. The thermodynamic parameters demonstrated that van der Waals force or hydrogen bonds were the major binding force. The binding of ETC‐Tf caused the secondary conformational change of Tf with increasing the α‐helix content in Tf, which was confirmed by the results of spectroscopic experiments. Molecular modeling revealed that ETC bound residues located in the N‐lobe of Tf by van der Waals force and induced local structural changes of Tf. This study may provide the theoretical foundations for ETC as a probe to label Tf, which is further beneficial to the Tf‐targeted drugs in vivo. Copyright © 2015 John Wiley & Sons, Ltd.     

Novel Thiazole Based Styryl Dyes with Benzimidazole Unit - Synthesis,Photophysical and TD-DFT Studies

Three new Y-shaped styryl dyes were designed and synthesized from thiazole carbaldehyde with different active methylene compounds as acceptor moieties. All the dyes were characterized by IR, ¹HNMR, MS/LCMS/HRMS. Spectroscopic properties and non-linear optical properties styryl derivatives were analyzed and the effect of change in solvent polarity on their absorption and emissive properties has been investigated. The dye with (1-phenylethylidene) propanedinitrile unit shows red shift absorption/emission profile among all the dyes. Density Functional Theory and Time Dependent-Density Functional Theory computations have been used for comparative study with the experimental data and also to understand the structural, molecular, electronic and photophysical parameters of the styryl dyes. The computational method was also employed to investigate the nonlinear optical properties of the styryl dyes in different organic solvent. The unsubstituted benzimidazolyl thiazole styryl dyes possess good non-linear optical properties.     

Synthesis of Novel Carbazole Fused Coumarin Derivatives and DFT Approach to Study Their Photophysical Properties

Novel coumarin derivatives have been synthesized by the classical Knoevenagel condensation of 4-hydroxy-9-methyl-9H-carbazole-3-carbaldehyde with active methylene compounds and characterized. Effect of solvent polarity on the photophysical properties, absorption and emission has been studied. The photophysical properties of the synthesized coumarins have been compared with some of the established analogous coumarin derivatives. Investigation of the structural parameters and understanding photophysical properties of the synthesized coumarin derivatives were carried out using Density Functional Theory (DFT) and Time Dependant Density Functional Theory (TDDFT) computations. The experimental values were correlated with the theoretical derived results. The ratio of the excited state and the ground state dipole moments was calculated by using solvatochromic and solvatofluoric data and compared with the values obtained from DFT and TDDFT computations.     

Synthesis and Characterization of a Fluorescent Water-Borne Polyurethane Based on a Novel Naphthalimide Dye

A waterborne-polyurethane (WPU) dye, based on the fluorescent dye 4-diamino propane-N-allyl-1,8- naphthalimide (WPU-DAN), was synthesized by attaching 4-diamino propane-N-allyl-1,8- naphthalimide (DAN) onto both ends of the polyurethane (PU) chains according to a prepolymer?ionomer process. The synthetic process was confirmed by Fourier transform infrared spectroscopy (FTIR) and UV-visible absorption. The glass transition temperature, molecular weight and average particle sizes were measured. The glass transition temperatures of WPU and WPU-DAN were 46.6 and 49.8°C, respectively. In addition, the particle size distributions of WPU-DAN and WPU were 140 and 134 nm, respectively. The thermal behaviour of WPU-DAN showed improvement compared to WPU. The fluorescence intensity of WPU-DAN was enhanced more than DAN due to the naphthalimide groups attached to the chains, and the fluorescence intensity of WPU-DAN and DAN were increased by increasing temperature. Moreover, the fluorescence intensity of WPU-DAN emulsion was stable during 30 days and no loss of fluorescence intensity occurred for these days.     

新型β-氨基醇类高碳糖的合成及波谱研究

用C10高碳糖合成了具有潜在生物活性的C10高碳糖氨基醇类化合物及其中间体,并对所合成化合物的IR、ESI-MS/MS、1H NMR和13C NMR图谱进行归属,确证了化合物的结构.     

Studies on the Spectral-Luminescent Properties of the Novel Homodimer Styryl Dyes in Complexes with DNA

Series of homodimer styryls containing on (p-dimethylaminostyryl) pyridinium residues that are connected with aliphatic linkage group was synthesized. Spectral luminescent properties of obtained dyes in free state and in nucleic acids presence were studied. It was shown that DNA binding affinity of the novel homodimers exceeds that of parent monomer (p-dimethylaminostyryl)pyridine iodide. For homodimers with the linkage 4–10 carbon atoms preference in binding to DNA than to RNA was observed. It could be concluded that parent monomer has different mechanisms of binding to nucleic acids than corresponding homodimer dye.     

新型聚合物氮杂假冠醚的合成与红外光谱研究

以苯酚为起始剂 ,用先聚合后功能基化和钠离子模板的方法 ,合成了具有交联酚醛型分子骨架 ,以氮杂冠醚环为功能基的新型聚合物。用FTIR光谱跟踪监控的方法 ,获得了各合成反应的较佳实验条件和一系列聚合物的红外光谱资料 ;根据FTIR光谱和元素分析信息及其它辅助手段 ,确认了聚合物及其中间体的结构。研究了聚合物与金属离子配合物的红外光谱。结果表明 ,聚合物与Na 和Ca2 的配合物中 ,除—CH2 OCH2 — ,CH2 NCH2 和PhOCH2 —参予了配位外 ,—CH2 OH亦不同程度地参与了配位。     

The Influence of the Molecular Structure of Cyanine Dye on the Component Composition of Molecular Layers

The formation of the component composition of symmetric cationic cyanine dyes on glass is studied. The absorption spectra of layers of three homologous series of dyes with end heterocyclic groups of different spatial and chemical compositions are measured, and the absorption spectra of monomer components and aggregates are separated. The component compositions of layers of different thicknesses are compared. It is shown that the widening of the absorption spectra of molecular layers against the spectra of ethanol solutions of these compounds is caused mainly by the formation of various monomer stereoisomers and molecular aggregates and their interaction with the substrate surface and the neighborhood. The number of isomer forms and their relative concentrations depend on the layer thickness, the electron donor ability and spatial structure of end groups, and the cation conjugation chain length. The influence of the anion manifests itself only in the concentration ratio of the formed monomers and a small shift of the maxima of their absorption bands. The increase in the number of monomer forms produced in the layer corresponds to the increase in the conjugation chain length. Spatial obstacles created by heterocyclic groups inhibit the formation of definite stereoisomers, which reduces the number of components of the layer.     

2-噻吩甲酰基-2-咔唑-N-丁基三氟丙酮化合物的合成与光谱研究

在苯和 5 0 %NaOH介质中 ,温度在 70～ 80℃时 ,1 ,4 二溴丁烷与咔唑 (CZ)反应 ,生成N 溴丁基咔唑 (BCZ)。在丙酮和K2 CO3 介质中 ,温度在 5 0℃时 ,N 溴丁基咔唑与噻吩甲酰三氟丙酮 (TTA)反应 ,生成 2 噻吩甲酰基 2 咔唑 N 丁基三氟丙酮 (TCBTA)。TCBTA为浅褐色针状结晶 ,熔点 2 1 1～ 2 1 4℃。详细研究了CZ ,BCZ ,TTA和TCBTA的紫外光谱和红外光谱 ,以及TCBTA的色谱 /质谱 ,证实了TCBTA合成产物的真实性。在氯仿中TCBTA的最大吸收波长为 2 4 1 ,2 6 5和 2 95nm ,摩尔吸光系数依次为 1 88× 1 0 5,1 2 5× 1 0 5和 1 0 8×1 0 5L·mol-1 ·cm-1 。TCBTA用于Fe(Ⅲ )和Nd(Ⅲ )的萃取 ,萃取率比TTA分别高 3倍和 1 6倍 ,与Nd(Ⅲ )形成络合物的荧光强度 ,TCBTA是TTA的 6倍 ,表明TCBTA具有优良的光敏特性。     

Comparative Study of Novel Fluorescent Cyanine Nucleotides: Hybridization Analysis of Labeled PCR Products Using a Biochip

This study investigated the synthesis and substrate properties of Cy5-labeled dUTP derivatives with different substituents, linkers between the dye unit and pyrimidine heterocycle and fluorophore charges. Fluorescently labeled nucleoside triphosphates were studied as substrates using multiplex PCR with Taq and Vent (exo-) DNA polymerases, the typical representatives of the A and B polymerase families. The efficiency of nucleotide incorporation during PCR was assessed with a multi-parameter hybridization analysis using a diagnostic DNA microarray. The hybridization analysis indirectly estimates the incorporation efficiency of dye-labeled nucleotides in multiplex PCR. Our results demonstrated higher efficiencies of substrates with electrically neutral dyes than electropositive and electronegative Cy5 residues.     

Identification of Absorption Bands of Monomers and Aggregates in a Layer of Cyanine Dye and Determination of the Orientation of Molecules

Optics and Spectroscopy - The problem of allocating bands of individual monomers or aggregates of the absorption spectrum of a multicomponent structure arises in the study of molecular layers or...     

掺杂功能磺酸的导电聚苯胺的合成及其红外光谱研究

合成了参杂对甲苯磺酸（ＴＳＡ）,十二烷基苯磺酸（ＤＢＳＡ）,樟脑磺酸（ＣＳＡ）和磺基水杨酸（ＳＳＡ）的导电聚苯胺要品：Ｄｐａｎ／ＴＳ,Ｄｐａｎ／ＤＢＳＡ,Ｄｐａｎ／ＣＳＡ,Ｄｐａｎ／ＳＳＡ,并对这些样品进行了表征,研究了它们的红外光谱特性。     

一种新的双偶氮染料掺杂聚合物薄膜的光致双折射及偏振全息的研究

作为一种有可能作为永久信息存储的材料,合成出一种新的双偶氮材料(BA1)。当样品被波长为532nm的光激发时,几乎大部分BA1分子从反-反态转化到顺-顺态,产生了光致双折射。因此,研究了BA1分子掺杂的PMMA薄膜的光致双折射和透过信号与入射光强度的关系。实验结果表明:透过信号强度随着泵浦光的增强而增强。通过偏振态互相平行(SS)和垂直(SP)的两束偏振光用来研究偏振全息存储,结果表明SP光栅形成的衍射信号要比SS光栅的衍射信号强很多。