Push-pull amino succinimidyl ester thiophene-based fluorescent dyes: synthesis and optical characterization

The design and synthesis of new fluorescent dyes with emission range at 490-650 nm are described. Their structural and electronic properties have been characterized by both experimental techniques and quantum-chemical calculations. The chromophores are donor-π-bridge-acceptor push-pull compounds with a π bridge of phenyl and thiophene rings and their combination. Compared with previous thiophene fluorophores, these dyes show significant redshift in the absorption and emission spectra and offer compact, red-emitting fluorophores. The dyes have amino succinimidyl active ester and can be readily conjugated to proteins, polymers and other amino-group-containing materials.     

Fluorescence of dyes adsorbed on highly organized,nanostructured gold surfaces

It is shown that fluorescent dyes can be adsorbed selectively on gold nanoparticles which are immobilized on a glass substrate and that the fluorescence originating from the adsorbed dyes exhibits significantly less quenching when compared to dyes adsorbed on bulk gold. Self-assembled monolayers of lissamine sulfide molecules have been studied both on bulk gold and on glass surfaces bearing gold nanoparticles. Gold nanoparticles have been arranged in ordered, two-dimensional patterns, with periodicity in the microm range and used as substrate for the fluorescent dyes. Optical resolution of the fluorescence originating from the pattern has been achieved with laser-scanning confocal microscopy.     

Solid-phase methods for the synthesis of cyanine dyes

We report here a series of studies that explore solid-phase methodologies for the synthesis of various cyanine dyes. The scope of the previously reported catch-and-release method using sulfonyl chloride resin(1) has now been extended to include pentamethine and water-soluble cyanine dyes. We also report a new and chemically distinct synthetic strategy, employing the stepwise attack of heterocyclic carbon nucleophiles on immobilized polyene-chain precursors, allowing the clean synthesis of hydrophobic and hydrophilic trimethine and pentamethine dyes from more easily obtained starting materials. Overall, both approaches appear to be robust and versatile strategies to delivering a wide range of cyanine-based dyes in high purity.     

Indicator characteristics of bromothymol blue derivatives

Some Bromothymol Blue derivatives with a nitro, amino, isothiocyanato or sulfonamide group substituted on the sulfonated ring of the dibromothymolsulfonephthalein have been studied spectrometrically. All the dyes have two characteristic absorption peaks which can be used to measure pH in the physiological range. The molar absorptivities, wavelengths of maximum absorption and pK(a) values have been determined from the absorbances, and are similar for all four dyes.     

New indolium and quinolinium dyes sensitive to aqueous halide ions at physiological concentrations

Twelve new highly fluorescent dyes have been produced by the reaction of two heterocyclic nitrogen bases with 8-bromooctanoic acid, 11-bromoundecanoic acid and 15-bromopentadecanoic acid. The bromide counter ions of the first six dyes have been replaced with the tetraphenylborate ion. Unlike the bases themselves, the quaternary salts are water soluble and have fluorescence characteristics independent of pH in the pH range 7–11. Both the fluorescence intensity and fluorescence lifetime of dyes 1–12 are reduced in the presence of aqueous halide ions allowing halide concentrations to be determined accurately at physiological levels. All the dyes have been characterised in terms of steady state fluorescence spectra and steady-state Stern-Volmer analysis.     

Conformationally restricted dipyrromethene boron difluoride (BODIPY) dyes: highly fluorescent, multicolored probes for cellular imaging

Novel fluorescent, conformationally restricted dipyrromethene boron difluoride (BODIPY) dyes have been prepared by introducing a naphthalenyl group at the meso position of the BODIPY core. These BODIPY dyes exhibit increased fluorescence quantum yields compared with dyes that have a meso-position phenyl group with internal rotation. The absorption and emission wavelengths of such conformationally restricted BODIPY dyes can be easily tuned to the near-IR range by derivatization through a condensation reaction with benzaldehyde derivatives. The two-photon absorption properties of these BODIPY dyes were also investigated and the results show that they exhibit increased two-photon excited fluorescence compared to analogue dyes that contain a phenyl group. The one- and two-photon fluorescence imaging of living cells by using selected BODIPY dyes has been successfully demonstrated.     

Determination of sunset yellow and tartrazine by differential pulse polarography

A study has been made of the polarographic (DC and DPP) behaviour of the food dyes Sunset Yellow and Tartrazine in acid and alkaline media and in the absence and presence of polyvinylpyrrolidone. Methods are proposed for the determination of both dyes by DPP over a concentration range of 0.1-10 ppm. The methods have been applied to their determination in soft drinks.     

Intramolecular triplet energy transfer in multi-chromophoric dyes and its influence on the photostability

The photostability of organic dyes plays a very important role in practically all aspects of the development and applications of these dyes. In recent years, intramolecular transfer of triplet excitation energy between isolated chromophores on the same molecule has been a subject of intensive studies. Many multi-chromophoric organic dyes with covalent linkage between the chromophores, one of which can act as a triplet acceptor of the excess energy, have been synthesized and studied. The significant increases in photostability of such assembled dyes have been reported, suggesting that some chromophores can act as internal photostabilizers. These modified dyes have enhanced photostability and hence potential applications in a wide range of areas such as laser dyes, electroluminescent (EL) devices and solar cells.     

Radical CH Alkylation of BODIPY Dyes Using Potassium Trifluoroborates or Boronic Acids

A one‐step synthetic procedure for the radical C?H alkylation of BODIPY dyes has been developed. This new reaction generates alkyl radicals through the oxidation of boronic acids or potassium trifluoroborates and allows the synthesis of mono‐, di‐, tri‐, and tetraalkylated fluorophores in a good to excellent yield for a broad range of organoboron compounds. Using this protocol, multiple bulky alkyl groups can be introduced onto the BODIPY core thus creating solid‐state emissive BODIPY dyes.     

A fluorogenic ‘click’ reaction of azidoanthracene derivatives

Fluorogenic reactions have broad applications in biolabeling, combinatorial synthesis of fluorescent dyes, and materials development. It was recently reported that the highly selective and efficient Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction can be employed in designing new types of fluorogenic reactions. In this study, we report a fluorogenic reaction using anthracene azides as starting materials. The fluorescence of the anthryl core can be greatly inhibited upon introducing electron-donating azido groups in the proximity. Such weakly fluorescent anthracene azides demonstrate high reactivity with a variety of alkynes under the CuAAC conditions producing a strongly fluorescent triazole product with high quantum yields. This reaction can be used in the synthesis and screening of fluorescent dyes combinatorially. Compared with most existing methods, the fluorogenic CuAAC reaction is a much milder and simpler technique to prepare large libraries of fluorescent dyes without further purification. In order to demonstrate the efficiency of using anthracene azides for biolabeling applications, both small molecules and biomolecules including the multialkyne-derivatized cowpea mosaic virus and tobacco mosaic virus had been studied.     

Iodine substituted phosphorus corrole complexes as possible photosensitizers in photodynamic therapy: Insights from theory

The search for new dyes to be used as photosensitizers in photodynamic therapy (PDT) is a field of great interest from both experimental and theoretical viewpoints. In this study, the main photophysical properties (excitation energies, singlet-triplet energy gap, and spin orbit coupling matrix elements) of some unsubstituted and iodine substituted phosphorus corrole complexes have been determined by using density functional theory and its time-dependent formulation. Results show that these compounds can be proposed as photosensitizers in PDT. The heavy atom effects have been rationalized on the basis of El-Sayed rules.     

Rapid energy transfer in cascade-type bodipy dyes

Three new molecular dyads, comprising a bora-3a,4a-diaza-s-indacene (Bodipy) dye linked to two aromatic polycycles via the boron center, have been synthesized and fully characterized. The polycyclic compounds are either pyrene or perylene, or a mixture of both. Whereas the absorption spectral profiles contain important contributions from each of the subunits, fluorescence occurs exclusively from the Bodipy fragment. Intramolecular excitation energy transfer is extremely efficient in each case, even though spectral overlap integrals for the pyrene-based system are modest. Although these polycycles are sterically congested, molecular dynamics simulations indicate that they are in dynamic motion, and this hinders proper computation of the orientation factors for F?rster-type energy transfer. These new dyes, especially the mixed polycycle system, greatly extend the range of excitation wavelengths that can be used for fluorescence microscopy.     

Fluorescent nanoprobes dedicated to in vivo imaging: from preclinical validations to clinical translation

With the fast development, in the last ten years, of a large choice of set-ups dedicated to routine in vivo measurements in rodents, fluorescence imaging techniques are becoming essential tools in preclinical studies. Human clinical uses for diagnostic and image-guided surgery are also emerging. In comparison to low-molecular weight organic dyes, the use of fluorescent nanoprobes can improve both the signal sensitivity (better in vivo optical properties) and the fluorescence biodistribution (passive "nano" uptake in tumours for instance). A wide range of fluorescent nanoprobes have been designed and tested in preclinical studies for the last few years. They will be reviewed and discussed considering the obstacles that need to be overcome for their potential everyday use in clinics. The conjugation of fluorescence imaging with the benefits of nanotechnology should open the way to new medical applications in the near future.     

Synthesis and spectral properties of non-symmetrical red and near IR emitter dibenzoBODIPYs

New symmetrical and non-symmetrical benzoBODIPYs have been synthesized from diketones. For the two series the 3 and 5 positions have been substituted by different aromatic rings and onto benzo sub-units different groups have been introduced. The methodology of diketones self-condensation provides symmetrical dyes. By cross-condensation reaction, these positions can be differentiated and specific functions connected to the desired positions. These molecules have been fully characterized and their optical properties analyzed by both experimental and theoretical means. They are red to NIR emitters with a range of emission from 679 to 780?nm in CH₂Cl₂. They show maxima of absorption between 651?nm and 732?nm, strong ε of around 100,000?M^?1?cm^?1 and quite good quantum yields from 16% to 75%. The thienyl moiety on α-positions of the nitrogens generates the highest red shifts. Meanwhile dimethylamino groups in the same positions bring, besides chemical properties, proton sensitive dyes. The bromine atom onto the dibenzo sub-units exhibits good reactivity through Sonogashira coupling reactions. This approach provides multifunctional red to NIR dyes with endless possibilities of combination of chemical properties.     

紫外吸收染料研究进展

紫外线具有高能特性,能够伤害人类皮肤和破坏有机化合物,而紫外吸收染料既吸收紫外线,赋予染料抗紫外整理功能,又可提高有机染料的光稳定性,是一类新型的纤维防护功能染料,现已成为染料化学工作者的一个新的研究热点.     

纤维染料分析方法的研究进展

纤维染料是使纤维着色的物质,其分析检测对纺织、环保、法庭科学、古文物研究等诸多领域都有重要的意义。然而纤维染料的种类繁多、成分复杂,加之高灵敏度以及原位无损检测的分析需求日益突出,使得纤维染料的分析面临挑战。尽管如此,研究人员一直致力于高效、灵敏、无损的纤维染料分析新方法和新技术的研究,目前已经开发了多种纤维染料的分析方法,这些方法可大致分为3类:光谱法、色谱法及质谱法。该文综述了纤维染料的特点及纤维染料的检测方法及最新研究进展,并对未来纤维染料检测方法的发展进行了展望,为更好地开展纤维染料的分析提供了参考。     

Forensic Identification of Dyes in Ballpoint Pen Inks Using LC–ESI–MS

The aim of this work was to develop a new technique using flow injection analysis combined with LC–ESI–MS which allows identification of dyes in ballpoint pen inks. A sample preparation procedure for the extraction of dyes from ballpoint pen strokes has been developed. The characteristic group of ions for each sample of 21 studied ballpoint pen inks corresponding to the present dyes has been determined using flow injection method. LC separation conditions for identified dyes have been optimized on reversed-phase sorbent based on silica gel. The best composition of the mobile phase for the dyes mixture LC separation was 0.1% aqueous formic acid and acetonitrile. Detection of dyes was carried out using mass spectrometry with electrospray ionization in positive and negative modes after reversed-phase liquid chromatography separation. Dye composition of ink was additionally confirmed comparing the data obtained from the literature. Flow injection analysis allows obtaining intensive ions of unknown strokes. It is difficult to get this information using only chromatographic methods, because dyes peak intensity can be low and noise of basic line high. Flow injection method allows distinguishing the analyzed 21 ballpoint pens by determining a characteristic set of dyes. The developed flow injection technique is very simple and quick. As a result, a novel approach for the identification of dyes in the ballpoint pen inks by flow injection analysis with LC–ESI–MS and UV detection without using standard dye samples has been established. It can be an effective alternative to the existing LC–DAD–MS and IR spectroscopy methods.     

New Dyes Based on Extended Fulvene Motifs: Synthesis through Redox Reactions of Naphthoquinones with Donor–Acceptor Cyclopropanes and Their Spectroelectrochemical Behavior

Novel dyes based on extended fulvene motifs are reported. The carbon skeleton was generated by a catalyzed addition of donor–acceptor cyclopropanes to naphthoquinone. The hydroxy group at the central ring of the tricyclic fulvene motif was converted into the triflate, which reacted efficiently with a wide range of nucleophiles, resulting in substitution and thereby providing new derivatives. The synthetic versatility allowed us to investigate the absorption, electrochemical, and UV/Vis-NIR spectroelectrochemical properties of these dyes as a function of the substituents. The dyes were shown to participate in reductive electrochemistry, the reversibility of which can be improved by appropriate selection of the substituents. Additionally, first signs of NIR electrochromism are presented, opening new avenues for the future investigations of such dyes.     

Dimerization of Organic Dyes on Luminescent Gold Nanoparticles for Ratiometric pH Sensing

Synergistic effects arising from the conjugation of organic dyes onto non‐luminescent metal nanoparticles (NPs) have greatly broadened their applications in both imaging and sensing. Herein, we report that conjugation of a well‐known pH‐insensitive dye, tetramethyl‐rhodamine (TAMRA), to pH‐insensitive luminescent gold nanoparticles (AuNPs) can lead to an ultrasmall nanoindicator that can fluorescently report local pH in a ratiometric way. Such synergy originated from the dimerization of TAMRA on AuNPs, of which geometry was very sensitive to surface charges of the AuNPs and can be reversely modulated through protonation of surrounding glutathione ligands. Not limited to pH‐insensitive dyes, this pH‐dependent dimerization can also enhance the pH sensitivity of fluorescein, a well‐known pH‐sensitive dye, within a larger pH range, opening up a new pathway to design ultrasmall fluorescent ratiometric nanoindicators with tunable wavelengths and pH response ranges.     

Dipolar organic pyridyl dyes for dye-sensitized solar cell applications

New dipolar dyes containing arylamine as the electron donor, 2-cyanoacrylic acid as the acceptor, and a conjugated spacer with incorporation of 2,5-pyridyl entity have been synthesized. Photophysical and electrochemical measurements, and theoretical computation were carried on these dyes. The solar cell devices using these dyes as the sensitizers exhibited light-to-electricity efficiencies in the range of 4.28–5.27%, which reaches 60–72% of N719-based device fabricated and measured under similar conditions. Better DSSC performance can be achieved with the dye where pyridine group is attached to thienyl or fluorenyl group because of favorable resonance energy and/or coplanarity for more effective charge transfer.