Biscyanine Dye Research Articles

Photochemical properties of new bis-cyanine dye as a promising agent for in vivo imaging

Photochemical properties of a new bis-cyanine dye have been investigated, including spectral kinetic characteristics of singlet and triplet excited states as well as affinity to BSA as a representative blood protein. The results obtained reveal, that the dye is a promising agent for imaging and fluorescent labeling of biomacromolecules.

Synthesis and Electronic Transitions of the Dye Based on 1-{2-[4-(3-Hydroxy-2-oxo-2H-chromen-4-yl)phenyl]-2-oxoethyl}-4-methylpyridinium Bromide

4-[4-(2-Bromoacetyl)phenyl]-3-hydroxy-2H-chromen-2-one reacted with pyridine and 4-methylpyridine to give the corresponding quaternary pyridinium salts. The condensation of 1-{2-[4-(3-hydroxy-2-oxo-2H-chromen-4-yl)phenyl]-2-oxoethyl}-4-methylpyridinium bromide with 4-(dimethylamino)benzaldehyde afforded a new biscyanine dye whose electronic spectrum showed two absorption maxima originating from interactions of chromophores. The nature of electronic transitions in the dye molecule was analyzed by quantum chemical calculations.

Phototransformation of cyanine dye with two chromophores. Effects of oxygen and dye concentration

Abstract Phototransformation of a cyanine dye with two chromophores (biscyanine dye, BCD) subject to visible light in phosphate buffer was studied using optical absorption and fluorescence spectroscopic techniques. The effects of the dye concentration and molecular oxygen were demonstrated. The monoexponencial dependence of optical absorption of the BCD solution on the irradiation time was observed. The increase of the characteristic phototransformation time with the dye concentration is explained in terms of the dye aggregation. The explanation is confirmed by experiments in the presence of SDS micelles, where the concentration effect is absent, since at binding with SDS micelles BCD does not aggregate. The dye phototransformation rate increase in the presence of oxygen is explained in terms of singlet oxygen formation due to energy transfer from the dye excited triplet state to molecular oxygen. Singlet oxygen was detected, and its quantum yield was determined by an indirect chemical method. The effect of singlet oxygen on the BCD phototransformation was confirmed by reduction of its phototransformation rate in the presence of 2,5-dimethylfuran, a known singlet oxygen water soluble quencher. Singlet oxygen may destroy the π-conjugation of the BCD chromophores. A possible structure of the dye photoproduct is proposed based on the similarity of its spectral characteristics and those of monochromophoric cyanine dye and confirmed by quantum chemical modelling.

Synthesis, nature of electronic transitions, and absorption spectra of the dye based on 4-(methyl-1-{2-[4-(1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)phenyl]-2-oxoethyl}pyridinium bromide

The reaction of 3-(4-bromoacetylphenyl)-1-methylquinolin-2(1Н)-one with pyridine and 4-methylpyridine has afforded the corresponding pyridinium salts. Condensation of 4-methyl-1-{2-[4-(1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)phenyl]-2-oxoethyl}pyridinium bromide with 4-dimethylaminobenzaldehyde has given a new biscyanine dye, 1-{1-[4-(1,2-dihydro-1-methyl-2-oxo-3-quinolinyl)benzoyl]-2-[4-(dimethylamino)-phenyl]ethynyl}-4-{2-[4-(dimethylamino)phenyl]ethynyl}pyridinium bromide. Its electronic spectrum has been analyzed, and quantum-chemical simulation of spatial and electronic structure of its possible isomers has been performed.

Titanium dioxide sensitization with a biscyanine dye in the photocatalytic reduction of methylene blue

Photosensitive heterostructures containing titanium dioxide and a sensitizer, viz., a cyanine dye with two conjugated chromophores have been obtained. Their absorption spectra have been studied, and their photocatalytic activity has been demonstrated to depend on the dye content and irradiation conditions. The energetics of possible electronic processes induced by light of various spectral ranges is considered. Some explanationsare proposed for the observed regularities.

New biscyanine dye based on 1-{2-oxo-2-[4-(2-oxo-2H-chromen-3-yl)phenyl]ethyl}-4-methylpyridinium bromide. Electron transitions and electronic spectra

New biscyanine dye, 4-{2-[4-(dimethylamino)phenyl]ethenyl}-1-{2-[4-(dimethylamino)phenyl]-1-[4-(2-oxo-2H-chromen-3-yl)benzoyl]ethenyl}pyridinium bromide, has been prepared via condensation of 4-dimethylaminobenzaldehyde with 4-methyl-1-{2-oxo-2-[4-(2-oxo-2H-chromen-3-yl)phenyl]ethyl}pyridinium bromide. The latter has been synthesized via the Meerwein reaction of coumarin with 4-acetylphenyldiazonium chloride with subsequent bromination and quaternization of the formed α-bromoketone under the action of 4-methylpyridine. Electronic spectra are analyzed, and quantum-chemical simulation of possible isomers of the biscyanine dye has been performed.

ChemInform Abstract: Unique UV/VIS and CD Behavior Due to Exciton Coupling in a Biscyanine Dye.

ChemInform Abstract: Unique UV/VIS and CD Behavior Due to Exciton Coupling in a Biscyanine Dye.

Benzodipyrrolenine-based biscyanine dyes: Synthesis, molecular structure and spectroscopic characterization

A novel method of synthesizing long-wavelength absorbing and emitting bis-trimethine dyes that consists of condensing benzodipyrrolenine dialdehyde with quaternized heterocyclic CH-acidic compounds was used to prepare a series of biscyanines. The new method is more convenient than its conventional counterepart, which relies upon condensation of a quaternized benzodipyrrolenine with Fisher's aldehyde, for the synthesis of a symmetrically substituted dyes that contain various heterocyclic end-groups. Investigations of the spectral and luminescent properties of the dyes in solution revealed that the absorption (596–717 nm) and emission (629–773 nm) maxima of the biscyanines were red-shifted by ∼100 nm compared to the parent “monomeric” cyanine that contained only one chromophoric polymethine system. The prepared dyes have high extinction coefficients (≤251,000 M −1 cm −1) and quantum yield (≤28%). Substitution of both terminal benzoxazole moieties with indolenine, benzothiazole, 2- and 4-quinoline imparted a red-shift in the absorption and emission maxima but lowered quantum yield.

Determination of the stoichiometry of DNA–dye interaction and application to the study of a bis-cyanine dye–DNA complex

Some, though not all, cationic dyes exhibit enhanced fluorescence in the presence of DNA. Based on this phenomenon a simple and rapid method has been developed for determining the stoichiometry of interaction of such dyes with DNA. The method was validated using the well-characterised dyes Ethidium Bromide and Thiazole Orange dimer TOTO [1,1′-(4,4,7,7-tetramethyl-4,7-diazaundecamethylene)-bis-4-[3-methyl-2,3-dihydro-(benzo-1,3-thiazole)-2-methyl-idene]-quinolinium tetraiodide] as well as the butyl homologue of Thiazole Orange. In each case the stoichiometries thus determined were consistent with those already reported. Using this protocol the stoichiometry of interaction, with DNA, of a novel type of bis-cyanine dye was studied, and shown to involve binding of an unexpectedly large molar ratio of dye to DNA. Possible mechanisms of binding are suggested.

Investigation of Conformational and Electron Properties of Biscyanine Dyes

ABSTRACT The spectral and luminescent characteristics of four biscyanine dyes and corresponding monomer dye in ethanol solutions and in polyvinyl butyral have been investigated. The influence of angle between chromophores of biscyanine molecules on splitting and intensity of absorption bands has been discussed. It has been shown that the splitting of the biscyanine excited electron level S1 is caused both dipole and resonant chromophor interactions. It has been found that the fluorescence quantum yields of the biscyanines in ethanol at room temperature are 0.005–0.02. The introduction of biscyanines in a polymer matrix, which provides rigidity of a polymethine chain, results in reduction of molecules trans-cis isomerization and consequently increase of fluorescence quantum yields.

Spectroscopic studies of the interaction of bichromophoric cyanine dyes with DNA. Effect of ionic strength

Spectroscopic characteristics of a cyanine dye with two chromophores (biscyanine dye, BCD) in aqueous solutions and effects of NaCl and DNA upon these characteristics have been studied by optical absorption, circular dichroism (CD) and fluorescence spectroscopies. In homogeneous solutions, BCD is characterized by intense optical absorption ( ε=1.33×10 5 M −1 cm −1) and weak fluorescence ( ϕ fl=0.018) in the wavelength region greater than 600 nm. The dye forms H-aggregates at low concentrations (10 −6 M). NaCl stimulates the formation of both H- and J-aggregates of the dye at much lower dye concentrations, while DNA in low concentrations (<10 −6 M) stimulated the formation of just J-aggregates on the surface of the DNA molecule. Higher DNA concentrations induce the dye to disaggregate, and there exists an equilibrium between three dye forms: free monomers, J-aggregates and bound monomers, the maximum content of J-aggregates was observed at [DNA]/[BCD]=0.6±0.2 and total disaggregation at [DNA]/[BCD]=190±20. J-aggregates are characterized by ϕ fl=0.05 and bound monomers by ϕ fl=0.44. In the presence of NaCl, total disaggregation was observed at [DNA]/[BCD]=570±10 due to competition between Na + and the dye molecules for DNA electronegative binding sites.

Magnetic-dipole, quadrupole-dipole and electron-vibration manifestations inchirality

For the first time, quantum chemical and Car–Parinello molecular dynamicssimulations of rotation strength dispersion, using restricted Hartree–Fock (RHF)and density functional theory (DFT) approaches, for a biscyanine dye with Schiffbase (BDSB) molecule as a model have been performed. We have found that mostof the DFT approaches give substantially better agreement with the experimentalstructural and optical data than the RHF. Contributions of the magnetic-dipoleand quadrupole-dipole interactions to the rotation strength spectra wereseparated. For this reason independent measurements of the rotational strengths(RSs) for the oriented and disordered BDSB molecule were performed. Asignificant contribution of the anharmonic electron-vibration interaction to the RSwas found.

Biscyanine dye with Shiff base as new chirooptical materials

We have revealed a giant chirooptical effects in the biscyanine dye with Shiff base (BDSB) molecule. For the first time, quantum-chemical and molecular dynamics simulations of rotation strength's dispersion using restricted Hartree–Fock (RHF) and density functional theory (DFT) approaches with inclusion of electron–vibration interactions (EVI) for the biscyanine dye with Shiff base (BDSB) molecule as a modelling one were performed. We have found that the DFT approach gives substantially better agreement with the experimental structural data than the RHF. Contributions of the magnetic dipole (MD) and quadruple dipole (QD) interactions to the spectrum of the rotation strengths were separated. For this reason, independent measurements of the RS for the oriented and disordered BDSB molecule were carried out. Significant contribution of the anharmonic electron–vibration interaction to dispersion of the RS was found.

Simulation of chirally-induced excitonic optical effects in biscyanine dye with shiff base (optical and molecular structure simulations)

ABSTRACTFor the first time simulations of chirally-induced excitons have been carried out, using molecular dynamic simulations and self-consistent quantum chemical calculations within the RHF [Restricted Hartree-Fock ] and DFT [Density Functional Theory] approaches. We found that the DFT approach gave substantially better agreement than the RHF. Comparison of theoretical and experimental results for biscyanine dye with a Shiff base showed a sufficiently good level of agreement.

Influence of interaction of chromophores, linked by the unconjugated chain, on the luminescence properties of biscyanine dyes

Deactivation of electronically excited state of chemically bound dimers – biscyanines with two chromophores linked by unconjugated chains and corresponding monomer dye was investigated. It was found that the quantum yield of dimer fluorescence is lower than that of a monomer dye. The amount of quantum yield of fluorescence decreases with the increase of chromophores interaction degree (the decrease of the isolating polymethylene bridge length). It is shown on the basis of the external heavy-atom effect studies that the decrease of biscyanines fluorescence ability is connected with the enhancment of singlet–triplet intersystem crossing ( S 1⤳ T 1 ). It has been established that the probability of the triplet states population in biscyanines with chromophores in parallel arrangement is considerably higher than that in similar compounds with an angular arrangement of chromophores. The delayed fluorescence was observed in the case of dyes with parallel arrangment of chromophores.

Unique ultraviolet-vis absorption and circular dichroic exciton-split spectra of a chiral biscyanine dye: origin and nature

The exciton coupling between two cyanine dyes, characterized by intense and sharp absorption bands in the visible region, has been studied by UV-vis and CD spectroscopy because it provides a unique system of theoretical and applicational interests. Biscyanine dye 4b prepared from (1S,2S))-(+)-trans-1,2-cyclohexanediamine (1) shows two well-separated and strong electronic absorption bands at λ max 550 (e 182 00) and 480 nm (e 191 000)

Unique ultraviolet-visible and circular dichroism behavior due to exciton coupling in a biscyanine dye

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTUnique ultraviolet-visible and circular dichroism behavior due to exciton coupling in a biscyanine dyeDario Gargiulo, Fadila Derguini, Nikolina Berova, Koji Nakanishi, and Nobuyuki HaradaCite this: J. Am. Chem. Soc. 1991, 113, 18, 7046–7047Publication Date (Print):August 1, 1991Publication History Published online1 May 2002Published inissue 1 August 1991https://doi.org/10.1021/ja00018a058RIGHTS & PERMISSIONSArticle Views191Altmetric-Citations30LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (268 KB) Get e-Alerts Get e-Alerts

Spectroscopic manifestation of association of biscyanine dyes with nonconjugated chromophores in low polarity solvents

Spectroscopic manifestation of association of biscyanine dyes with nonconjugated chromophores in low polarity solvents

Effect of ?-electron conjugation of the chromophores on the reactivity of the triplet states of dyes with two chromophores in electron-transfer reactions

1. An increase in the degree of ir-electron conjugation of the chromophores of biscyanine dyes results in an increase in the quenching constants of their triplet states by electron acceptors and a decrease of the quenching constant of the triplet states by electron donors. 2. The change in the reactivity of the triplet states of biscyanine dyes when the degree of conjugation of the chromophores is changed is caused, apparently, by a decrease in the ionization potential and an increase in the electron affinity of the dyes when the degree of conjugation of the chromophores is increased.

Polymethine dyes with several conjugated chromophores

Triscyanine dyes with three successively conjugated chromophores were obtained from diquaternary salts of four isomeric dimethylbenzobisthiazoles and two isomeric hexamethylbenzodipyrrolenines. The spectra of the dyes contain three absorption bands, the intensities of which depend on the angles formed by the directions of the interacting chromophores and are determined by the structure of the heteroring. The magnitude of the separation of the frequencies of the two extreme absorption maxima of the triscyanines exceeds the magnitude of the separation of the frequencies of the maxima of the corresponding biscyanine dyes by a factor of √2. A dye with four successively conjugated chromophores was obtained from centrosymmetric hexamethylbenzodipyrrolenine, and its absorption spectrum was examined.