氟硼荧(BODIPY)染料的研究进展

氟硼荧(BODIPY)染料是一种新型荧光化合物,因其突出的优点而得到广泛的应用.详细评述了短波长BODIPY及长波长BODIPY染料结构的研究进展,总结当前研究的方向,展望BODIPY类荧光染料的发展.     

溴代呋喃杂环取代BODIPY染料的合成及光谱性能研究

通过吡咯和2-呋喃甲醛经一步法合成了新型含呋喃环的BODIPY荧光染料,并进一步溴化合成了一溴和二溴五元杂环类BODIPY染科,所有合成的染料分子均通过质谱、核磁等手段进行了结构表征.并测试了这些荧光染料的吸收光谱和发射光谱,研究了不同极性的溶剂对染料光谱性能的溶剂化效应以及Br原子对染料光谱的重原子效应.结果表明:随...     

红光区双效发光材料BODIPY的制备及其光谱性质

通过吲哚衍生物与1,8-萘内酰亚胺缩合及氟硼化反应，得到meso位无取代和甲基取代的两种配体（Ⅰ、Ⅲ）及两种氟硼二吡咯（BODIPY）染料（Ⅱ、Ⅳ）。其结构和光学性能经NMR、HRMS、单晶、UV-Vis吸收光谱、荧光发射光谱和固体荧光光谱进行了表征。结果表明，meso位引入甲基后配体Ⅲ较配体Ⅰ的固体荧光发射峰红移了34 nm。BODIPY染料具有较强的双效荧光（溶液和固体荧光），其中BODIPY染料Ⅳ的溶液和固体荧光量子产率分别高达65.8%和76.3%，其固体荧光量子产率较meso位无取代BODIPY染料Ⅱ（14.6%）提高了4.2倍。BODIPY染料Ⅳ较强的双效发光可归因于其固体堆积方式中无C—H…π作用以及层与层之间存在的“头-尾”π-π堆积。不同于其他提高固态荧光的策略，在母体meso位引入小位阻甲基的策略使BODIPY具有双效红光发射性能，也丰富了双效有机发光材料的种类。     

BODIPY类液晶化合物的研究进展

氟硼二吡咯(BODIPY)荧光染料具有荧光量子产率高、摩尔消光系数大、易于进行化学改性及光物理化学稳定性好等优点,一直以来成为有机化学工作者的研究热点。将BODIPY荧光团改性成为液晶化合物是一个新兴的研究方向。综述了BODIPY液晶化合物的研究进展,包括这类化合物的结构特点、液晶性能及应用前景等方面。     

水溶性二氟化硼-二吡咯甲烷(BODIPY)类荧光染料研究进展

简要介绍了二氟化硼-二吡咯甲烷(BODIPY)荧光染料的基本结构、优异的光物理和光化学性能以及自身存在的溶解性差等缺陷,重点综述了近年来各种水溶性BODIPY类荧光染料衍生物的合成及其在水环境中作为荧光探针的应用研究成果,并提出通过对BODIPY母体染料结构进行化学修饰,开发研制出许多具有不同性能的BODIPY衍生物并研究其应用将成为国内外十分活跃的研究课题。     

五元杂环取代BODIPY染料的合成及光谱性能研究

以吡咯和2-呋喃甲醛、2-噻吩甲醛为原料,经缩合、氧化、环化反应合成了含新型五元杂环的BODIPY荧光染料,进一步溴化分别得到两种一溴代染料,所有合成的染料分子均通过质谱、核磁等手段进行了结构表征,并测试了这些染料的吸收光谱和发射光谱.结果表明:所有染料随着溶剂极性的增大表现出一定的溶剂化效应,吸收和发射波长变化不大(...     

新型溴代长波长BODIPY类荧光染料的合成及表征

通过吡咯和乙酰氯经一步法合成了含吡咯取代基的长波长BODIPY染料,溴化后得到一溴和二溴染料,染料通过质谱、二维核磁等手段进行了结构表征.测试了这些染料的吸收光谱和发射光谱,研究了不同极性的溶剂对染料光谱性能的溶剂化效应以及Br原子对染料光谱的重原子效应.结果表明:随着溶剂极性的增大所合成的染料吸收波长均发生了蓝移,发射波长变化不大,摩尔消光系数逐渐增大,荧光量子产率逐渐减小,表现出明显的溶剂化效应;在同一溶剂中,随着染料结构中Br原子取代基数目的增加,发射波长发生红移,吸收波长变化不大,摩尔消光系数逐渐增大,荧光量子产率逐渐减小,表现出明显的重原子效应.     

基于氟硼二吡咯亚甲基荧光探针的研究进展

氟硼二吡咯亚甲基(BODIPY)荧光染料具有易于修饰、高摩尔消光系数、高荧光量子产率、优异的光稳定性、对溶剂的极性和pH敏感性低等许多突出特性,被广泛用于有机小分子荧光探针的构建.综述了2019年以来BODIPY荧光探针在金属阳离子、阴离子、活性氧和生物硫醇等检测方面的研究进展,梳理了这些探针的设计思路,对比了它们的检...     

荧光小分子pH探针的最新研究进展

细胞内的H+在生理及病理过程中发挥着至关重要的作用。因此,研究细胞内的H+具有重要的理论和实践意义。荧光法由于其非破坏性,高的灵敏度和选择性,以及广泛可用的荧光染料在测定pH时比其他方法更具优越性。文章以不同的荧光团分类:香豆素、荧光素、罗丹明、BODIPY、花菁、双光子染料等,按pKa从小到大的顺序排列,综述了近十年来,荧光小分子pH探针的研究进展。     

新型氟硼二吡咯纳米粒子荧光探针的合成与性能

为了解决氟硼荧类染料(BODIPY)在肿瘤诊断中吸收波长短、水溶性和生物相容性差的问题,设计开发了2种吸收波长达到近红外区的BODIPY分子,并通过与DSPE-PEG2000-MAL-RGD(PC-RGD)自组装形成具有良好水溶性和生物相容性的纳米粒子.研究了纳米粒子的荧光成像能力,结果表明:单取代分子3a和双取代分子...     

Small BODIPY Probes for Combined Dual 19F MRI and Fluorescence Imaging

The combination of the two complementary imaging modalities ¹⁹F magnetic resonance imaging (MRI) and fluorescence imaging (FLI) possesses high potential for biological and medical applications. Herein we report the first design, synthesis, dual detection validation, and cytotoxic testing of four promising BODIPY dyes for dual ¹⁹F MRI–fluorescence detection. Using straightforward Steglich reactions, small fluorinated alcohols were easily covalently tethered to a BODIPY dye in high yields, leaving its fluorescence properties unaffected. The synthesized compounds were analyzed with various techniques to demonstrate their potential utility in dual imaging. As expected, the chemically and magnetically equivalent trifluoromethyl groups of the agents exhibited a single NMR signal. The determined longitudinal relaxation times T₁ and the transverse relaxation times T₂, both in the lower second range, enabled the imaging of four compounds in vitro. The most auspicious dual ¹⁹F MRI–fluorescence agent was also successfully imaged in a mouse post‐mortem within a 9.4 T small‐animal tomograph. Toxicological assays with human cells (primary HUVEC and HepG2 cell line) also indicated the possibility for animal testing.     

Efficient Acid‐Catalyzed 18F/19F Fluoride Exchange of BODIPY Dyes

Fluorine‐containing fluorochromes are important validation agents for positron emission tomography imaging compounds, as they can be readily validated in cells by fluorescence imaging. In particular, the ¹⁸F‐labeled BODIPY‐FL fluorophore has emerged as an important platform, but little is known about alternative ¹⁸F‐labeling strategies or labeling on red‐shifted fluorophores. In this study we explore acid‐catalyzed ¹⁸F/¹⁹F exchange on a range of commercially available N‐hydroxysuccinimidyl ester and maleimide BODIPY fluorophores. We show this method to be a simple and efficient ¹⁸F‐labeling strategy for a diverse span of fluorescent compounds, including a BODIPY‐modified PARP‐1 inhibitor, and amine‐ and thiol‐reactive BODIPY fluorophores.     

Synthesis and Biochemical Evaluation of an Artificial,Fluorescent Glucosinolate (GSL)

The synthesis of the first example of a fluorescent glucosinolate (GSL)–BODIPY conjugate based on an azide-containing artificial GSL precursor (GSL-N₃) is reported. Biochemical evaluation of the artificial GSLs revealed that the compounds are converted to the corresponding isothiocyanates in the presence of myrosinase. Furthermore, myrosinase-catalyzed hydrolysis in the presence of plant specifier proteins yielded the expected alternative products, namely nitriles. The easy assembly of the fluorescent GSL–BODIPY conjugate by click chemistry from GSL-N₃ holds potential for application as a fluorescence labeling tool to investigate GSL-associated processes.     

DNA分子荧光探针

本文综述了各种DNA荧光探针的结构特征荧光性质和与DNA的作用方式，主要涉及了6类化合物：吖啶和菲啶类、菁类染料、荧光素和罗丹明类、噻嗪和恶嗪类染料、BODIPY类染料以及其它类别的探针，概述了DNA探针在生物分子分析方面的应用，并展望了DNA荧光探针的发展趋势和应用前号。有47篇参考文献。     

Synthesis of Cholesterol Analogues Bearing BODIPY Fluorophores by Suzuki or Liebeskind–Srogl Cross‐Coupling and Evaluation of Their Potential for Visualization of Cholesterol Pools

We report a synthetic route to BODIPY–cholesterol conjugates in which the key steps were Suzuki or Liebeskind–Srogl cross‐coupling of cholesterol phenyl moieties with structurally diverse BODIPY scaffolds. All conjugates feature single‐bonded and hydrophobic linkages between the fluorophore and sterol that are devoid of heteroatoms. Using HeLa cells, we show that these BODIPY–cholesterol analogues can be used simultaneously with the parent BODIPY–cholesterol for cell imaging and flow cytometry. The BODIPY–cholesterol analogues exhibit similar cellular localization in HeLa cells and show similar cholesterol efflux properties from THP‐1 cells to HDL acceptors. These results demonstrate that the red‐shifted BODIPY–cholesterol analogues behave in a manner similar to unlabeled cholesterol and are useful probes for simultaneous visualization of intracellular cholesterol pools and for monitoring cholesterol efflux from cells to extracellular acceptors.     

Water-soluble BODIPY and aza-BODIPY dyes: synthetic progress and applications

In recent years, boron-dipyrromethene (BODIPY) and boron-azadipyrromethene (aza-BODIPY) dyes have attracted considerable multidisciplinary attention due to their diverse applications. By introducing various hydrophilic groups, such as quaternary ammonium, sulfonate or oligo-ethyleneglycol moieties into the BODIPY core, the solubilities of these dyes in aqueous solution can be greatly improved while maintaining their high fluorescence quantum yields. Accordingly, applying these fluorescent dyes in aqueous systems to areas such as chemosensors, biomacromolecule labeling, bio-imaging and photodynamic therapy has been achieved. In this article, the recent progress on the synthesis, optical properties and application of water-soluble BODIPY dyes and aza-BODIPY dyes is reviewed.     

A Structure-Activity Relationship Study of Bimodal BODIPY-Labeled PSMA-Targeting Bioconjugates

The aim of this study was to identify a high-affinity BODIPY peptidomimetic that targets the prostate-specific membrane antigen (PSMA) as a potential bimodal imaging probe for prostate cancer. For the structure-activity study, several BODIPY (difluoroboron dipyrromethene) derivatives with varying spacers between the BODIPY dye and the PSMA Glu-CO-Lys binding motif were prepared. Corresponding affinities were determined by competitive binding assays in PSMA-positive LNCaP cells. One compound was identified with comparable affinity (IC₅₀=21.5±0.1 nM) to Glu-CO-Lys-Ahx-HBED-CC (PSMA-11) (IC₅₀=18.4±0.2 nM). Radiolabeling was achieved by Lewis-acid-mediated ¹⁹F/¹⁸F exchange in moderate molar activities (∼0.7 MBq nmol⁻¹) and high radiochemical purities (>99 %) with mean radiochemical yields of 20–30 %. Cell internalization of the ¹⁸F-labeled high-affinity conjugate was demonstrated in LNCaP cells showing gradual increasing PSMA-mediated internalization over time. By fluorescence microscopy, localization of the high-affinity BODIPY-PSMA conjugate was found in the cell membrane at early time points and also in subcellular compartments at later time points. In summary, a high-affinity BODIPY-PSMA conjugate has been identified as a suitable candidate for the development of PSMA-specific dual-imaging agents.     

Effect of core structure on the fluorescence properties of hyperbranched poly(phenylene sulfide)

We functionalize the focal group of hyperbranched poly(phenylene sulfide) (HPPS) with benzyl, phenyl, and naphthyl group, respectively. DSC analysis shows that T_g of HPPS is increased from 55 to 93°C by functionalization of the focal group with a conjugated naphthyl group. The fluorescence properties of the three core‐functionalized HPPS' are studied under the comparison with the original HPPS. Functionalization by a non‐conjugated benzyl group has no effects on the fluorescence properties of HPPS at all. Both the phenyl‐cored and the naphthyl‐cored HPPS' give rise to a new highly polarized fluorescent peak around 500 nm due to the formation of intermolecular excimers with encumbered molecular rotation. Differing from the often reported significant increase in core fluorescence due to the so‐called “antenna effect,” the fluorescence of HPPS backbones is drastically enhanced after functionalization of the cores with naphthyl groups that is 10‐ to 18‐fold higher than the original HPPS' depending on the molecular weights of HPPS'. The phenyl‐cored HPPS does not show a notable increase in fluorescence intensities compared with the original HPPS. The clear comparison results are rationalized by the restriction of intramolecular rotations of the naphthyl cores against the HPPS periphery. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008