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.     

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.     

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.     

Studies of novel monomeric and polymeric azo disperse dyes

A series of polymeric dyes were synthesized by free‐radical addition polymerization of monomeric dyes that were derived from diazotized 2‐amino‐3,5‐bis‐(ethoxycarbonyl)‐4‐methylthiophene by coupling with various N‐arylmaleimides. All the polymeric dyes were characterized by elemental analysis, IR and visible spectroscopy, viscometry, and TGA. Color and dyeability of the polymeric dyes are discussed by comparing them with those of the corresponding monomeric dyes. All the dyes have been found to give various color shades with good to very good depth and levelness on the fiber. The dyeing of the monomeric dyes shows good fastness to light and very good to excellent fastness to washing, perspiration, sublimation, and solvents. The corresponding polymeric dyes show excellent fastness properties. The percentage dyebath exhaustion and fixation on the fiber have been found to be good to very good (60–90%). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1380–1389, 2002; DOI 10.1002/app.10276     

Factors affecting the adsorption of cationic dyes on polymeric hydrogels prepared by gamma irradiation

The adsorption of the cationic dyes Rhodamine B (RB) and Crystal Violet (CV) on polyacrylamide/poly(acrylic acid) (poly(AAm/AAc), 25:25 % weightwise) and polyacrylamide/poly(sodium acrylate) (poly(AAm/AAcNa), 25:25 % weightwise) hydrogels was studied, employing the Langmuir and Freundlich isotherms. The results of swelling tests at pH 5.5 indicate that poly(AAm/AAcNa) hydrogel shows maximum percentage swelling (%S) was 4400 %. Moreover, the results show that the adsorption capacity is pH‐ and concentration‐dependent. At pH >5 adsorption of RB and CV increases due to ionization of ? COOH and ? COONa groups of (poly(AAm/AAc) and (poly(AAm/AAcNa) and interactions with the cationic groups of the dyes. However, at pH lower than 5, adsorption is still high, which can be explained by considering the formation of hydrogen bonds between the amino groups of the dyes and the ? COOH groups of the polymeric hydrogels. Moreover, the kinetics of adsorption follows a first‐order equation. Furthermore, scanning electron microscopy (SEM) micrographs of polymeric hydrogels doped with CV and RB have morphological differences from the pure form. Our data show that Rhodamine B adsorbs more efficiently on both polyacrylamide/poly(acrylic acid) and polyacrylamide/poly(sodium acrylate) hydrogels than CV. Copyright © 2004 Society of Chemical Industry     

BODIPY荧光二向性液晶染料的制备及性能

以8-(4-碘苯基)氟硼吡咯为原料,与4-乙炔基苯基胆甾醇酯或4-乙炔基苯戊基双环己基甲醇酯进行Sonogashira偶联反应,制备了两个含氟的荧光二向性液晶染料DC-1和DC-2,其化学结构均由1HNMR、13CNMR和HRMS鉴定。将染料DC-1和DC-2进行光谱测试,最大吸收波长和最大发射波长分别在503和517 nm,发亮绿色荧光。基于宾-主(G-H)效应,将染料DC-1和DC-2作为宾体组分溶于主体液晶E7中,测得DC-2在液晶E7中的吸收二向色比高达8.91,有序参数为0.73,可应用在宾-主型液晶显示器(GH-LCD)中。经差热扫描量热仪(DSC)测试,染料DC-1和DC-2在一定温度范围内具有介晶性质,并通过偏光显微镜(POM)验证了DC-1和DC-2的液晶织构。     

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。     

基于二氟化硼-二吡咯甲烷(BODIPY)染料类汞离子荧光探针的研究进展

Hg2+是一种极具生理毒性的化学物质,对人类和环境危害极大,其检测方法在化学传感器领域得到广泛研究。荧光探针法因具有检测灵敏度高、快速便捷等优点而成为Hg2+检测的重要手段之一。综述了近年来BODIPY类染料汞离子的研究进展,着重总结了Hg2+荧光探针的设计合成、性能及其检测机制;展望了该类荧光探针的研究方向。     

Synthesis and application of polymeric dyes containing the anthraquinone structure

Two polymeric dyes containing the anthraquinone structure were prepared via solution polycondensation. Their monomers were prepared through reactions between 1,5‐dichloroanthraquinone and nucleophiles. The polymeric dyes were characterized with NMR and thermogravimetry. Their ultraviolet spectra, intrinsic viscosity, and solubility were also measured. Then, the polymeric dyes were applied to the mass coloration of poly(ethylene terephthalate) with good compatibility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1252–1257, 2002     

Design of polymeric materials: Experiences and prescriptions

As process engineering has matured, research interest has shifted towards polymer product quality. In the past 20 years or so, the shift has progressed even further, as interest in polymer product quality has morphed into polymer product design. Product design is intended to be a targeted pursuit of optimal conditions that will yield polymers with desirable properties for a specific application. This can be achieved by following a systematic design framework that employs sequential, iterative steps informed by prior knowledge and experience. This overview provides some background information regarding the need for design (including some examples from previous experience), especially in terms of structure‐property relationships. When links between kinetics (synthesis conditions), polymer structure, and application properties are well‐understood, it becomes possible to essentially reverse‐engineer the polymeric material; the researcher can start with known application requirements and synthesize polymers with tailor‐made properties using an optimized recipe (according to the polymerization kinetics). A suggested design approach is presented herein, followed by the application of the design approach to two large case studies. The number of applications for polymeric materials is essentially limitless; the current work provides typical examples of a systematic polymeric material design framework (and related case studies).     

Synthesis of copolymeric hydrogels using gamma radiation and their utilization in the removal of some dyes in wastwater

Copolymer hydrogels were prepared by γ‐radiation copolymerization of maleic acid (MA) and 2‐hydroxyethylacrylate (HEA) or acrylamide (AAm). The effect of AAm/MA and HEA/MA composition and irradiation dose on the gel fraction yield in the prepared hydrogels was determined. It was found that as the content of MA increased, the gel fraction yield decreased. The increase of irradiation dose resulted in increasing the crosslinked network structure and consequently the gel percent. The parameters of equilibrium swelling, maximum swelling, initial swelling rate, diffusion exponent, and diffusion coefficient of the hydrogels were calculated and evaluated, and it was found that water diffusion to the hydrogels generally was a non‐Fickian diffusion type. Characterization of the prepared hydrogels was studied and accordingly the possibility of its practical use in the treatment of waste dyes from aqueous solution was studied. The effect of treatment time, the pH of the feed solution, initial feed concentration, and temperature on the dye uptake was also investigated. The maximum uptake of the investigated dyes was higher for HEA/MA hydrogel than that for AAm/MA hydrogel. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3720–3731, 2006     

Synthesis and characterization of new monomeric and polymeric phthalocyanines

Monomeric (M = 2Li or 2H) and polymeric (M = 2H, Zn, Cu, Co, or Ni), where M is metal or hydrogen, phthalocyanines were prepared by the tetramerization reaction of bisphthalonitrile monomer with appropriate materials. The electrical conductivities of the polymeric phthalocyanines, which were measured as gold sandwiches, were found to be 10⁻¹⁰–10⁻⁷ S/cm in vacuo and in air. The binding property of a Co‐containing polymeric phthalocyanine ( 10 ) toward alkali, alkaline‐earth, and some heavy cations was studied in tetrahydrofuran. The extraction affinity of 10 for K⁺ was found to be the highest in the heterogeneous phase extraction experiments. The disaggregation property of a Ni‐containing polymeric phthalocyanine ( 11 ) was investigated with K⁺, Na⁺, and NH₄⁺ cations. The intrinsic viscosities of all polymers were also measured by means of viscometry. All the novel compounds were characterized with elemental analysis, ultraviolet–visible, Fourier transform infrared, NMR, and mass spectrometry spectral data, and differential thermal analysis/thermogravimetry. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Self‐curable aqueous polymeric dyes for printing and dyeing applications

An epoxy resin (NPES‐904, epoxy equivalent weight is 815) with a repeating unit, n > 4 was selected as a polymer backbone of polymeric dye. Water‐reducible epoxy resin was prepared by a semiesterification of its secondary hydroxy group with succinic anhydride and then dispersed to aqueous phase after it was neutralized with triethylamine. An aqueous polymeric dye was obtained from a ring opening reaction of that epoxy resin with amino group of a direct dye (soluble dye such as C. I. Acid Blue 62, C. I. Direct Orange 39 or C. I. Direct Red 2). These aqueous polymeric dye dispersions carried the average particle sizes between 50 and 90 nm. A polyaziridine was added as a latent curing agent and forming a self‐curable system of aqueous polymeric dye solution, which was stable in aqueous phase when its pH remained above 8.0. This aqueous polymeric dye was self‐cured on drying at ambient temperature and results in the formation of waterproof and solvent‐resistant polymeric dye. These self‐curable polymeric dyes had potential for jet ink printing and dyeing applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1919–1931, 2006     

Electrochemical formation of poly(thionine) thin films: The effect of amine group on the polymeric film formation of phenothiazine dyes

The electropolymerization of thionine in an aqueous solution has been carried out by using both cycling voltammetry and chronoamperometry experiments. Electropolymerization has been applied at various pHs by using different working electrodes. The characterization of poly(thionine) thin films is performed by using cyclic voltammetry, current–time transients, atomic force microscopy, scanning tunnelling microscopy, ATR‐FTIR, and UV–vis absorption spectroscopy techniques. It is deduced from current–time transients and morphological data that poly(thionine) film forms with random adsorption process and exhibits an irregular polymeric film. Poly(thionine) film formation was compared with that of previously published results of phenothiazine derivatives of poly(azure A) and poly(methylene blue). It has been concluded that type of amine functional group of phenothiazine dyes is very effective on the formation of polymeric film structure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39686.     

Erlotinib-Modified BODIPY Photosensitizers for Targeted Photodynamic Therapy

Photodynamic therapy (PDT) is an innovative, non-invasive and highly selective therapeutic modality for tumours and non-malignant diseases. BODIPY based molecules can function as new generation photosensitizers (PSs) in various PDT applications. Despite numerous conjugated PS systems are available, BODIPYs containing erlotinib lagged behind other photosensitizer units. In this study, smart photosensitizers containing BODIPY, erlotinib and hydrophilic units were prepared for the first time, their physicochemical properties and PDT effects were investigated. Compared with non-halogenated compound, halogenated derivatives possessed much lower fluorescence profile as well as the good ROS generation ability under red light. In vitro PDT studies were performed on both healthy (PNT1a) and prostate cancerous cells (PC3) to determine the selectivity of the compounds on cancerous cells and their effects under light. The halogenated conjugates, exposed to low dose of light illumination exhibited potent activity on cancer cell viability and the calculated IC₅₀ values proved the high phototoxicity of the photosensitizers. It was also determined that the PSs have very low dark toxicity and that the light illumination and ROS formation are required for the initiation of the cell death mechanism. As a result, erlotinib modified BODIPYs could serve as promising agents in anticancer photodynamic therapy.     

Click‐coupling of anthraquinone dyes with β‐cyclodextrin: formation of polymeric superstructures

Two novel cyclodextrin‐modified anthraquinone dyes were synthesized and investigated for their complexation behaviour and formation of superstructures. Therefore, 1‐fluoro‐4‐N‐(propargylamino)anthraquinone and 1,4‐bis(propargyloxy)anthraquinone were prepared via nucleophilic aromatic displacement and subsequently covalently ‘click‐coupled’ in a copper(I)‐catalysed azide–alkyne cycloaddition with β‐cyclodextrin monoazide. Both the propargyl‐modified precursor and the click‐coupled anthraquinone dyes were evaluated as hosts and guests, respectively, in β‐cyclodextrin interactions. The anthraquinone dye bearing two cyclodextrins, 1,4‐bis((1‐β‐cyclodextrin‐1H‐1,2,3‐triazol‐5‐yl)methoxy)anthraquinone, enables the reversible formation of supramolecular crosslinked poly[(N,N‐dimethyl acrylamide)‐co‐(N‐(ferrocenoylmethyl)acrylamide)] ( 11 ), whereas the monofunctionalized compound 1‐fluoro‐4‐(((1‐β‐cyclodextrin‐1H‐1,2,3‐triazol‐5‐yl)methyl)amino)anthraquinone can be supramolecularly linked to 11 resulting in coloured polymers. These features of β‐cyclodextrin‐linked anthraquinone dyes can be verified with either ¹H ¹H NMR rotating frame nuclear Overhauser effect spectroscopy or the naked eye. © 2016 Society of Chemical Industry     

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。     

Process control for thin organic coatings using fluorescence dyes

The fluorescence dyes rhodamine B and auramine O were added to a coating material based on hybrid polymers (ORMOCER^®s) in concentrations of 10 ppm each. The fluorescence intensity of the auramine depends on the curing state of the lacquer while rhodamine is almost insensitive to this variation of the molecular environment. With the combination of both these dyes, the curing state as well as the thickness of the coating can be measured.Due to the low concentration the dyes do not degrade the properties of the lacquer coating.     

Preparation and coagulation performance of hybrid coagulant polyacrylamide–polymeric aluminum ferric chloride

In this study, we synthesized a novel hybrid coagulant, polyacrylamide (PAM)–polymeric aluminum ferric chloride (PAFC), by the polymerization of acrylamide monomer with the redox system (NH₄)₂S₂O₈–NaHSO₃. The factors affecting the PAM–PAFC hybrid coagulant were investigated in an orthogonal experiment. The maximum intrinsic viscosity was observed at an initiator mass fraction of 0.5%, a polymerization temperature of 50 °C, a monomer mass fraction of 20%, and a polymerization time of 4 h, which were the optimum synthesis parameters. The spatial network structure of the PAM–PAFC hybrid coagulant was graphically determined by scanning electron microscopy. Hybrid PAM–PAFC was adopted to treat the kaolin–humic acid suspension and the synthetic dye wastewater. The effect of the coagulant dosage and pH on the coagulant experiments were examined. The coagulant experiment on the kaolin–humic acid suspension showed that the optimum treatment efficiency was achieved at a coagulants dosage of 0.6 mg/L, at which level the turbidity reductions with the inorganic PAFC coagulant, PAM–PAFC composite, and PAM–PAFC hybrid were 95.30%, 95.84%, and 98.38%, respectively. Treatment with the PAM–PAFC hybrid coagulant was also effective in removing Congo Red and Direct Fast Turquoise Blue GL; the color‐removal efficiencies for these dyes were higher than 93% and 94%, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46355.