BODIPY类荧光染料的研究进展

BODIPY(氟化硼二吡咯)类荧光染料作为一类新兴的荧光染料,因其良好的光物理性质,在过去的二十年内得到广泛的研究。对BODIPY的中心骨架进行官能化,可形成一系列衍生物用于环境监测和生物科学等领域研究。文章主要对近年来有关BODIPY的官能化及作为荧光探针、荧光标记、光敏剂的应用加以综述。     

Near-infrared emissive BODIPY polymeric and copolymeric dyes

Novel near-Infrared emissive BODIPY polymeric dyes (polymers A and B) were prepared by Sonogashira cross-coupling reaction of 2,6-diiodo BODIPY dyes bearing one and two styryl groups at 3,5 positions (5, 6) with 2,6-diethynyl BODIPY dye, respectively. These polymeric dyes (A and B) display absorption maxima at 697 and 738 nm, and emission maxima at 715 and 760 nm, respectively. These polymeric dyes exhibit significant red shifts in absorption and emission maxima due to their extended π-conjugation systems compared with their BODIPY monomeric dyes. The thin films of polymers A and B display further red shift with emission maxima 764 and 810 nm, respectively. Near-infrared BODIPY copolymeric dye (C) was prepared by Sonogashira polymerization of 2,6-diiodo BODIPY dye bearing two styryl groups with 2,5-diethynyl-3-decylthiophene. For comparison in optical properties, deep-red and red emissive BODIPY copolymeric dyes (D and E) were prepared by Sonogashira polymerization of 2,6-diiodo BODIPY dye bearing monostyryl group and 2,6-diiodo BODIPY dye with 2,5-diethynyl-3-decylthiothene, respectively. These polymers display their absorption maxima at 649 nm and 634 nm, and emission maxima at 694 nm and 669 nm, respectively. All the polymers displayed good thermal stability and solubility in dichloromethane, and their lifetimes ranged from 0.7 to 3.4 ns.     

基于氟硼二吡咯的共轭聚合物研究进展

氟硼二吡咯（BODIPY）类功能染料因具有良好的光子及电子性质已经得到广泛的应用,对其共轭聚合物的研究则在近年受到广泛关注。与BODIPY单体相比,BODIPY的共轭聚合物具有更窄的带隙、吸收光谱的红移及更强的电子传导能力。BODIPY共轭聚合物在有机半导体材料及有机太阳能电池等方面具有广泛的应用前景。总结了BODIPY共轭聚合物的制备方法、结构与性质的关系以及应用等方面,提出了BODIPY共轭聚合物设计合成策略及未来的发展趋势。     

Fluorophore-Functionalized and Top-Covered Resorcin[4]arene Cavitands

This review describes our recent developments in the field of resorcin[4]arene cavitands. We present the syntheses of cavitands bearing pyrene, anthracene, and BODIPY dyes as fluorophores on the cavitand walls. These systems have been used to examine the conformational switching process between the closed vase and the open kite forms that are characteristic for this class of cavitands. In a second research direction, we prepared top-covered resorcin[4]arene-based, switchable container molecules, and investigated their binding and switching properties.     

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.     

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(...     

BODIPY-based polymeric dyes as emerging horizon materials for biological sensing and organic electronic applications

The design, synthesis, and characterization of BODIPY (4,4′-difluoro-4-bora-3a,4a-diaza-s-indacene)-based small molecules has undergone tremendous progress in the past two decades. BODIPYs and their dipyrrin precursors have been recently reviewed with emphasis placed on their syntheses, reactions and applications including biochemical labelling, fluorescent switches, chemosensors, and electroluminescent devices. Compared to other dye classes, these systems offer unique attractions such as excellent thermal/photochemical stability, intense absorption/emission profiles, negligible triplet-state formation, and small Stokes shifts. Their optoelectronic and semiconductor properties can be finely tuned via facile synthetic modifications on the dipyrromethene core, while their optical characteristics are relatively insensitive to medium polarity and the pH of the environment. On the contrary, the optoelectronic and photophysical properties of BODIPY-based polymeric semiconductors the newest developed family in BODIPY-based organic materials (the first BODIPY based conjugated polymers were published in 2008) are still not well understood. For fully resolving these open questions, it will be shown in this review that the optoelectronic and photophysical properties of the BODIPY-based conjugated polymers are depending on various parameters including: (i) the positions where the BODIPY core will be attached into the polymer backbone (α-, β-, meso positions, or fluorine substitution) and (ii) the number of methyl substituents on 1, 2, 3, 5, 6, and 7 positions and finally (iii) if BODIPY functions as electron rich or electron deficient building block in “donor-acceptor” (D-A) conjugated polymers. This is a very significant advance in the emerging field of BODIPY chemistry since it opens the path for further optimization of the recent and new developed BODIPY-based polymeric semiconductors with predetermined optoelectronic and photophysical properties by providing new design rules to organic and material chemists as well as physical (bio)chemistry and device (bio)engineering scientists.     

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...     

Some observations relating to the stability of the BODIPY fluorophore under acidic and basic conditions

4,4-Difluoro-4-bora-1,3,5,7-tetramethyl-2,6-diethyl-8-methyl-3a,4a-diaza-s-indacene (BODIPY) fluorophore was transformed into its corresponding 4,4-dimethyl, 4,4-dimethoxy and 4,4-diphenyl analogues. The stabilities of these BODIPY fluorophores in acidic (di- and trichloroacetic acid) and basic conditions (aqueous ammonium hydroxide) were investigated using ¹¹B NMR spectroscopy.     

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...     

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.     

Effect of glucose on photocatalytic decolorization of dyes by TiO2

The effect of saccharides, such as glucose, on the photocatalytic decolorization of various dyes has been investigated using TiO₂ as a photocatalyst in an aqueous solution saturated with nitrogen. An azo dye, such as Orangell, used as a typical dye, was reduced by cleavage of the azo linkage, as evidenced by the production of sulfanilic acid. All of the dyes tested were decomposed with first‐order kinetics. The rate constants of decolorization in the aqueous solution saturated with nitrogen increased with the addition of a saccharide such as glucose. Furthermore, the effect of the reductive saccharides on the photocatalytic decolorization of dyes was quantitatively correlated with their dispersion force. The reaction rate of the photocatalytic decolorization of dyes in the aqueous solution saturated with nitrogen, including glucose, is 7 times that in the solution saturated with oxygen.     

Acid-base equilibria of sulfonephthalein dyes in aqueous polymer-surfactant media

The acid-base equilibria of three anionic sulfonephthalein dyes, viz., bromothymol blue (BTB), thymol blue (TB), and cresol red (CR), were studied spectroscopically in aqueous media containing the water-soluble noninonic polymers polyvinyl alcohol (PVA) and polyethylene glycol (PEG) in the presence of an anionic surfactant, sodium dodecyl sulfate (SDS). A partition equilibrium method was used to determine the equilibrium constant of partition of the dyes between the micellar pseudo phase and aqueous phase in the presence of PVA and PEG. The critical aggregation concentrations (CAC) of the surfactants in buffered aqueous systems containing the neutral polymers were also determined. The CAC of the polymer-surfactant systems were found to be lower than the critical micelle concentration of such systems in the absence of polymer, in otherwise identical conditions. The pH-dependent association constants, K _ass, of the sulfonephthalein dyes with the SDS-PVA system increased with the increase in molecular weight of the polymer. The interactions of the dyes with the buffered aqueous SDS-PVA and SDS-PEG systems were found to be endothermic and entropy oriented. In the polymer domain, the head group region of the micelles was more exposed at lower concentrations of the polymer, but under excess polymer concentration they were increasingly shielded, which impaired their electrostatic interaction with the dyes.     

In2S3-Polymer Hybrid Gels Derived from In(III) Metal–Organic Gels for Dye Adsorption,Photodegradation, and Bacteria Removal

Currently, the treatment of wastewater that contains organic dyes and bacteria attracts a considerable amount of attention, and the fabrication of photoinduced catalytic materials to address the problem is still a challenge. In this work, indium(III) sulfide hybrid gels are prepared by in situ polymerization and sulfurization using In(III) metal–organic gels as sacrificial templates. Two In(III) metal–organic gels are fabricated by the coordination interaction between multitopic pyridyl ligands and indium ions, where the assembled structure of the gel templates can be tuned by employing different multitopic ligands to obtain the networks of nanofibers and nanoparticles. After templated fabrication, the resulting In₂S₃-polymer hybrid gels show improved mechanical strength, and can be used as novel photocatalysts for the photodegradation of organic dyes, such as rhodamine B and methylene blue, and efficient adsorbents for the adsorption of anionic dyes, such as Congo red. Experiments that involve pure and mixed bacteria demonstrate the bacteria-removing activities of the hybrid gels due to their electrostatic adsorption and photoinduced sterilization of the bacteria. Therefore, this new kind of hybrid gel might have potential applications in the photoinduced purification of water by scavenging organic dyes and bacteria in the aqueous phase.     

Swelling and dye adsorption study of novel superswelling [Acrylamide/N-vinylpyrrolidone/3(2-hydroxyethyl carbamoyl) acrylic acid] hydrogels

Summary Super swelling acrylamide (Am)/N-vinylpyrrolidone (NVP)/3-(2-hydroxyethyl carbamoyl) acrylic acid (HECA) hydrogels were prepared by free radical polymerization of quaternary mixtures of Am, NVP, HECA and water. The hydrogels were used in experiments on swelling, diffusion and adsorption of some water-soluble monovalent cationic dyes such as Crystal Violet (CV), Malachite Green (MG) and Methylene Blue (MB). In the experiment of the adsorption of dyes from their aqueous solutions type-S adsorption isotherm were found. The diffusion of water within the hydrogel was found to have non Fickian character. The uptake of dyes within the hydrogel increased in the following order: MG > MB > CV. The binding ratio of the hydrogel/dye systems was gradually increased with the increase of HECA content in the AAm/NVP/HECA hydrogel.     

Novel Formulations Containing Fluorescent Sensors to Improve the Resolution of 3D Prints

Three-dimensional printing in SLA (stereolithography) and DLP (digital light processing) technologies has recently been experiencing a period of extremely rapid development. This is due to the fact that researchers recognise the many advantages of 3D printing, such as the high resolution and speed of the modelling and printing processes. However, there is still a search for new resin formulations dedicated to specific 3D printers allowing for high-resolution prints. Therefore, in the following paper, the effects of dyes such as BODIPY, europium complex, and Coumarin 1 added to light-cured compositions polymerised according to the radical mechanism on the photopolymerisation process speed, polymerisation shrinkage, and the final properties of the printouts were investigated. The kinetics of the photopolymerisation of light-cured materials using real-time FT-IR methods, as well as printouts that tangibly demonstrate the potential application of 3D printing technology in Industry 4.0, were examined. These studies showed that the addition of dyes has an effect on obtaining fluorescent prints with good resolution.     

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。     

Dual drug release from CO2‐infused nanofibers via hydrophobic and hydrophilic interactions

This study investigated the effects of hydrophobic–hydrophilic interactions on dual drug release from CO₂‐infused nanofibers scaffolds (PCL, PCL–gelatin, and PCL “core” PCL–gelatin “shell”) using BODIPY 493/503 and Rhodamine B fluorescent dyes as drug models. Favorable dye–scaffold interactions increased total dye loading and promoted steady, more linear release. Unfavorable dye–scaffold interactions reduced overall loading and led to a greater burst release of dye. However, when CO₂ was used to infuse dye into an unfavorable scaffold, the changes in loading and release were less pronounced. When two dyes were infused, these behaviors were accentuated due to interactions between the dissolved forms of the dyes. Core–shell composite nanofibers displayed radically different release properties versus pure PCL–gelatin fibers when treated with dyes via CO₂ infusion. Dye release from core–shell scaffolds was highly sensitive to both interactions with scaffolds and the phase of CO₂ used to infuse the compounds of interest. By using different phases of CO₂ to partition dyes into hydrophobic and hydrophilic sections of core–shell nanofibers, such interactions can be manipulated to develop a bimodal drug release system with potential application in drug delivery or tissue engineering. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42571.     

Biosorption of hazardous textile dyes from aqueous solutions by hen feathers: Batch and column studies

The biosorption potential of hen feathers (HFs) to remove hazardous textile dyes, namely congo red (CR) and crystal violet (CV), from their aqueous solutions was investigated in batch and dynamic flow modes of operation. The effect of biosorption process parameters such as solution pH, initial dye concentration, temperature, feed flow rate and bed height was studied. Biosorption equilibrium data were well described by the Langmuir isotherm model. Kinetic studies at different temperatures showed that the rate of biosorption followed the pseudo second-order kinetics well. A thermodynamic study showed that biosorption of both CR and CV was spontaneous and endothermic. Breakthrough time increased with increase in bed height but decreased with increase in flow rate. The Thomas model showed good agreement with the dynamic flow experimental data. Overall, the results suggest the applicability of HFs as an efficient biosorbent for removal of carcinogenic textile dyes from aqueous media.