Synthesis and Spectral Properties of Novel Water-soluble Indocyanine Dyes as Fluorescent Dyes for Proteins Detection

Two novel water‐soluble indocyanine dyes were synthesized. Their chemical structures were confirmed by ¹H NMR, IR, MS and UV‐vis techniques. The absorptions of the prepared dyes in different solvents were measured. Two dyes exhibited negative solvatochromism, with a blue shift of the absorption and an emission maximum in (bovine serum albumin) protonic solvent relative to non protonic solvent. The fluorescence properties of the dyes in both free state and BSA were investigated. Significant enhancement of the fluorescence intensity for the Dye2 was observed in the presence of BSA. Dye2 could be proposed as fluorescent dyes for BSA detection in aqueous solution.     

新型水溶性荧光标示剂吲哚方酸菁染料的合成及光谱性能

用方酸与不同的N烷基取代吲哚啉季铵盐缩合制备了一系列对称的水溶性方酸菁染料. 通过核磁共振氢谱和质谱对合成的染料结构进行了表征, 研究了它们在不同溶剂中的吸收和发射光谱. 结果表明, 随着溶剂极性的增大, 染料的吸收光谱发生蓝移, 表现为负向溶剂化效应, 在极性溶剂中的荧光量子产率比在水中的大. 考察了N位取代基对染料水溶液光稳定性的影响, 结果表明在吲哚环N原子上引入较大的苄基有助于提高光稳定性, 且随着苄基上取代基吸电子能力的增强, 染料的光稳定性增强.     

Aza-BODIPY荧光染料的合成、表征及性能研究

aza-BODIPY荧光染料是近10年发展起来并受到广泛关注的一类新型荧光化合物,它极有可能发展成可应用于光动力学治疗的光敏剂.本工作合成了5个aza-BODIPY 1a～1e,用IR,NMR,MS和元素分析对它们进行了表征.研究了它们的紫外吸收光谱与荧光发射光谱,结果表明1a～1e具有较高的摩尔吸光系数,在aza-BODIPY母环的3,5位或1,7位的苯环4位有供电子取代基时能使化合物的最大紫外吸收波长和荧光发射波长红移.测试了1a～1d的循环伏安曲线,根据各化合物的氧化还原电位讨论了它们的结构稳定性.     

Synthesis and Spectral Characterization of Novel Sulfhydryl-reactive Benzimidazole Fluorescent Probes

Three sulfhydryl-reactive fluorescent probes, which contain 2-(1H-benzoimidazol-2-yl)-phenol and maleimide group, were synthesized and their structures were characterized by IR and 1H NMR. Their photo-physical properties and the specificity to sulfhydryl group in the 2-mercapto-ethanol as well as the L-cysteine adducts were indicated by fluorescence intensity. Preliminary tests revealed that the probes could react selectively with the cysteine molecules, suggesting that these probes might be generally useful in biomedical researches.     

Illuminating Protein Phase Separation: Reviewing Aggregation-Induced Emission,Fluorescent Molecular Rotor and Solvatochromic Fluorophore Based Probes

Protein phase separation process involving protein unfolding, misfolding, condensation and aggregation etc. has been associated with numerous human degenerative diseases. The complexity in protein conformational transitions results in multi-step and multi-species biochemical pathways upon protein phase separation. Recent progresses in designing novel fluorescent probes have unraveled the enriched details of phase separated proteins and provided mechanistic insights towards disease pathology. In this review, we summarized the design and characterizations of fluorescent probes that selectively illuminated proteins at different phase separated states with a focus on aggregation-induced emission probes, fluorescent molecular rotors, and solvatochromic fluorophores. Inspired by these pioneering works, a design blueprint was proposed to further develop fluorescent probes that can potentially shed light on the unresolved protein phase separated states in the future.     

含氟香豆素荧光探针的合成及其荧光性能研究

以7-羟基-4-三氟甲基香豆素和1,4,7,10-四氮杂环十二烷(Cyclen)为原料,合成了具有多荧光侧臂的新型香豆素类荧光探针化合物,该合成方法经济简单,且环境友好。关键中间体及目标物经1HNMR、13CNMR和LC-MS分析表征,根据其荧光发射强度的不同讨论了探针化合物在乙腈中的荧光性能。     

新型水溶性不对称五甲川吲哚菁染料的合成、荧光性能及荧光标记

合成了枝状聚乙二醇醚链取代的新型不对称五甲川吲哚菁荧光染料,利用1H NMR、HRMS等技术手段表征了化合物的结构,并测定了染料的荧光性能、光稳定性,标示了牛血清白蛋白。结果表明,该染料的最大吸收波长为657 nm,最大荧光发射波长为671 nm,荧光量子产率为0.24,经过8 h的光照反应,染料有4.4%产生光降解,溶于水,n(染料)∶n(牛血清白蛋白)=2∶1时,标记蛋白质的染料/蛋白质(D/P)值达1.57。     

BODIPY-吡咯类荧光染料的合成及光谱识别性能

采用Knoevenagel反应以氟化硼配位二吡咯甲川类荧光染料BODIPY(4,4-difluoro-4-bora-3a,4adiaza-s-indacene)为母体,经吡咯甲醛或杯吡咯甲醛合成了四个BODIPY荧光染料1a~1d,用MS,NMR和元素分析进行结构确证。考察了它们的紫外吸收光谱与荧光发射光谱,结果表明1a~1d具有较高的摩尔吸光系数,在BODIPY母环的3,5位双取代物(1c和1d)相对于单取代物(1a和1b)其最大吸收波长和发射波长分别红移了约90nm和80nm,说明BODIPY-吡咯衍生物中共轭程度增强,光谱出现红移。阴离子识别研究表明,1b和1d能够与Cl-形成多重氢键,导致吸收光谱红移和荧光猝灭。     

Synthesis of 5-Alkyl- and 5-Phenylamino-Substituted Azothiazole Dyes with Solvatochromic and DNA-Binding Properties

A series of new 5-mono- and 5,5′-bisamino-substituted azothiazole derivatives was synthesized from the readily available diethyl azothiazole-4,4′-dicarboxylate. This reaction most likely comprises an initial Michael-type addition by the respective primary alkyl and aromatic amines at the carbon atom C5 of the substrate. Subsequently, the resulting intermediates are readily oxidized by molecular oxygen to afford the amino-substituted azothiazole derivatives. The latter exhibit remarkably red-shifted absorption bands (λ_abs=507–661 nm) with high molar extinction coefficients and show a strong positive solvatochromism. As revealed by spectrometric titrations and circular and linear dichroism studies, the water-soluble, bis-(dimethylaminopropylamino)-substituted azo dye associates with duplex DNA by formation of aggregates along the phosphate backbone at high ligand–DNA ratios (LDR) and by intercalation at low LDR, which also leads to a significant increase of the otherwise low emission intensity at 671 nm.     

Synthesis,Photophysical Properties and TD-DFT Calculation of Fluorescent Dyes Based on Pyrenylthiazoles

Pyrene is one of significant fluorescent material and its fluorescence properties are excellent.It has been widely used for such as OLEDs,DSCs,LMOGs and so on[1-5].What＇s more,pyrene has been successfully applied to signaling the presence of metal ions,nucleic acids,proteins and so on[6-9].Thus,the development of the fluorescent dyes based on pyrene has been a research focus[10-12].However,the synthesis of many pyrene derivatives needed the high-cost coupling reaction such as Heck reaction and Suzuki reaction[1-3,10-12].     

新型香豆素荧光探针的合成及其对三聚氰胺的识别性能研究

合成了一系列基于香豆素的新荧光探针化合物,荧光性质测定表明1,4,7,10-四氮杂环十二烷的香豆素荧光探针对三聚氰胺具有识别作用,检测限为5.0×10-11mol/L.     

含氟香豆素基哌嗪荧光探针的合成及其性能研究

以7-羟基-4-三氟甲基香豆素和哌嗪为原料,首次合成了具有双荧光侧臂的新型香豆素类荧光探针化合物,研究发现其中间隔基较少的化合物对Cu2+具有较高的选择性,并且对Cu2+的识别不受其它金属离子的干扰.Cu2+在2.0×10-6～1.0×10-4mol/L范围内,探针的荧光强度与其浓度有较好的线性关系.     

两亲性双硫键双菁染料的合成及谷胱甘肽响应荧光性质研究

菁染料具有优秀的光学性质,常用于肿瘤组织的实时可视化荧光成像。但普通菁染料成像背景较高,对肿瘤组织的靶向能力差。将菁染料自组装成纳米粒子可使染料形成聚集并实现荧光淬灭（聚集淬灭效应）,降低其在普通组织的成像背景;同时,纳米粒子的高渗透长滞留效应（EPR效应）可提高染料对肿瘤组织的靶向能力。本文设计合成了一种双硫键双菁染料（SO₃Cy7-ss-Cy7.5）,该染料由于两亲性的特性易在水溶液中自组装成纳米粒子,荧光淬灭高达92%;当纳米粒子与谷胱甘肽（GSH）响应后,淬灭的荧光逐渐恢复,最终实现16倍的荧光强度增强。因此,该双菁染料具有良好的肿瘤组织高分辨成像潜力。      

Synthesis and Spectral Properties of Novel Water-soluble Near-infrared Fluorescent Indocyanines

Two fluorescent pentamethine and a squarylium indocyanines containing at least one p-carboxybenzyl group on N atoms in the heterocyclic rings were synthesized. They had good water solubility and photostability. Their maximum absorption and maximum emission were 600-700 nm in water. When it was anchored onto nanostructured TiO2 electrode, compared with in water, the squaraine showed double absorption peaks (one blue shifted and another red shifted) and absorption intensity of the red shift peak increased with the increase of the time of irradiation. The intensity of the blue one decreased simultaneously. We proposed that the presence of two electronic charge forms of squaraine anchored on the TiO2 film might be the reason.     

Synthesis,Characterization of Novel Bisheteroaryl Bisazo Dyes,and Their Dyeing and Solvatochromic Behavior

4‐Phenyl‐2‐aminothaizole was diazotized and coupled with N‐(alkyl)‐2‐oxo‐3‐cyano‐4‐methyl‐6‐hydroxypyridine (2‐pyridone). The resultant dyes were named as N‐(alkyl)‐6‐hydroxy‐4‐methyl‐2‐oxo‐5‐((4‐phenylthiazole‐2‐yl)diazenyl)‐1,2‐dihydro pyridine‐3‐carbonitrite and duly characterized. The diazotized aryl amines were then coupled to a moiety of above‐mentioned dyes at 5‐position of thiazole. The obtained bisheteroaryl azo dyes were characterized by elemental analysis and spectral studies. Solvent effects on the visible absorption spectra of the dyes were evaluated. The color of the dyes is discussed with respect to the nature of the heterocyclic ring, aromatic amines, and substituents present therein. All these dyes were applied as disperse dyes on to polyester fabrics, and their fastness properties were evaluated. © 2013 Wiley Periodicals, Inc. Heteroatom Chem 24:208–220, 2013; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21085     

新型不对称五甲川菁染料的合成及光稳定性能研究

合成并表征了5种不对称五甲川菁染料,染料在甲醇中的最大吸收和荧光光谱在646—666nm之间.光降解实验证明两端取代基结构呈不对称的染料,其光稳定性明显高于两端取代基结构对称的染料.染料荧光光谱和pH值的关系表明,染料中引入苯环取代基可以增强染料在酸性或碱性溶液中的稳定性.