Styrylquinolinium Dye Research Articles

Comparing the crystal structures and spectroscopic properties of a p-hydroxy styrylquinolinium dye with those of its p-dimethylamino analogue

Two previously synthesized styrylquinolinium dyes, namely (E)-1-butyl-4-(4-(dimethylamino)styryl)quinolinium iodide (D36) and (E)-1-butyl-4-(4-hydroxystyryl)quinolinium iodide (D34), were compared in terms of their properties by single-crystal X-ray diffraction (XRD), Hirshfeld surface analysis, Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR), fluorescence, and ultraviolet–visible (UV–Vis) spectroscopy, and 1H- and 13C-NMR methods. Both dyes D36 and D34 crystallized in the triclinic and monoclinic systems in the centrosymmetric space groups P-1 and P21/n, respectively. The unit cell of D36 contains two molecules of the dye, participating in weak intermolecular interactions, whereas that of D34 contains four formula units. The phenolic hydroxy group of D34 participates in the formation of a hydrogen bond with the iodide anion. The 4-styrylquinolinium moieties of the cationic dye molecules are nearly planar. The dihedral angle between the mean planes through the ten-membered quinolinium system and the benzene ring is 7.5° in D36 and 5.9(1)° in D34. The structural parameters planarity and bond length alternation (BLA) are discussed, which are important for the evaluation of the first hyperpolarizability β at the molecular level, even in a centrosymmetric crystal. The UV–visible spectra of the dyes in 14 solvents of different polarities were investigated. The reversible solvatochromic behavior of the dyes is demonstrated experimentally and compared with known “binuclear dyes” by evaluating the Rezende model. Dye D36 does not fluoresce, and D34 has a very low emission in the solvents tested.

Applying styryl quinolinium fluorescent probes for imaging of ribosomal RNA in living cells

The detection of subcellular domains in cells can be obtained by specific fluorescent markers. Here we report the use of styryl quinolinium dyes that selectively stain ribosomal RNA (rRNA) in nucleoli and in the cytoplasm of mammalian cells. Specifically, we synthesized a series of 1-methyl-4-(substituted) styryl-quinolinium derivatives, 12a–l. We developed highly efficient microwave-assisted synthesis which prevents the formation of side-products, leading to the products in yields greater than 90%. Compounds 12c-f and 12i in various solvents exhibited maximum absorbance at 500–660 nm, molar extinction coefficient of 25400–49000 M−1cm−1, and emitted at 630–715 nm. Dyes 12a–l are highly photochemically stable. Dye 12e specifically stained nucleoli and the cytoplasm and is non-toxic. Various tests showed the markedly higher affinity of the dye for rRNA. We demonstrate that 12e is an attractive staining reagent for visualizing and assessing rRNA in both fixed and living cells.

Tuning the selectivity of N-alkylated styrylquinolinium dyes for sensing of G-quadruplex DNA.

Selective and sensitive detection of G-quadruplex DNA structures is an important issue and attracts extensive interest. To this end, numerous small molecular fluorescent probes have been designed. Here, we present a series of N-alkylated styrylquinolinium dyes named Ls-1, Ls-2 and Ls-3 with varying side groups at the chain end. We found that these dyes exhibited different binding behaviors to DNAs, and Ls-2 with a sulfonato group at the chain end displayed sensitivity and selectivity to G-quadruplex DNA structures in vitro. The characteristics of this dye and its interaction with G-quadruplex DNA were comprehensively investigated by means of UV-vis spectrophotometry, fluorescence, circular dichroism and molecular docking. Furthermore, confocal fluorescence images and MTT assays indicated dye Ls-2 could pass through membrane and enter the living HepG2 cells with low cytotoxicity.

Electrodeposited styrylquinolinium dye as molecular electrocatalyst for coupled redox reactions

Modification of carbonaceous materials with different conductive coatings is a successful approach to enhance their electrocatalytic activity and thus to increase the electrical outputs when used as electrodes in biofuel cells. In this study, a methodology for electrodeposition of styrylquinolinium dye on carbon felt was developed. The produced dye electrodeposits were characterized by means of AFM, ESI-MS/MS and NMR spectroscopy. The obtained data reveal that the dye forms overlaid layers consisting of monomer molecules most likely with an antiparallel orientation. The UV–VIS spectroscopy, CV and EIS analyses show that the dye molecules preserve their redox activity within the coating and a charge transfer between NADH/NAD+ and electrodeposit is possible as a coupled redox reaction. The fabricated nano-modified electrodes were also tested as anodes in batch-mode operating yeast-based biofuel cell. The results indicate that the electrodeposited dye acts as an immobilized exogenous mediator, contributing to enhanced extracellular electron transfer.

G-quadruplex DNA fluorescence sensing by a bis-amine-substituted styrylquinolinium dye

Searching for specific G-quadruplex DNA probes is important for study of the function of G-rich gene sequence, as well as design of novel effective anticancer drugs. In this paper, a novel bis-amine-substituted styrylquinolinium dye (BSAQ) was designed and synthesized to enhance the performance for the application as a G-quadruplex DNA probe. The studies on BSAQ with different DNA forms showed that it could be used as a colorimetric and red-emitting fluorescent probe for G-quadruplex DNA. The limits of detection of BASQ with various G-quadruplex DNAs were found to below 1 nM. CD spectroscopy analysis revealed that BSAQ did not induce the G-rich sequence folding into G-quadruplex structure. These results of this study gave some crucial factors on developing of effective probes for G-quadrupex DNA applications.

Comparing of the crystal structure and spectroscopic properties of some stilbazolium dyes with enlarged π-conjugated system I. Chromophores with p-dimethylamino group

A comparative study of the structures and spectroscopic properties of two styrylquinolinium dyes: 4-{(E)-2-[4-(dimethylamino)naphthalen-1-yl]ethenyl}-1-methylquinolinium iodide in an anhydrous (Structure I), and monohydrate (Strucuture II) forms and the newly synthesized dye 4-{(E)-2-[4-(dimethylamino)naphthalen-1-yl]ethenyl}-1-pentylquinolinium bromide dihydrate (III) has been conducted by single crystal X-ray diffraction, IR- and Raman spectroscopy, UV–Vis, steady-state and time-resolved fluorescence spectroscopy, 1H and 13C NMR spectroscopy, and TG/DTA analyses. The structures I, II and III belong to a monoclinic system, space groups P21/c, P21/n, and C2/c, respectively. In all of the crystal structures the molecules in the asymmetric unit are in an E configuration and the naphthyl and quinolinium aromatic rings are nearly planar. The angle between the mean planes of the aromatic rings is in the range 1.43–3.65°. Calculated BLA (Bond Lengths Alternation) parameters are close to the optimal. Solvatochromism in 12 organic solvents has been investigated by using absorption and emission spectroscopy. Reversal in solvatochromic behavior of the absorption spectra has been observed. The data in solutions indicate a significant charge transfer (CT) band shifting up to 84 nm, corresponding to a great molecular first hyperpolarizability values, and very large Stokes shift up to 245 nm. The average lifetime of the fluorescence of the dye III, determined from the measured data by multi-order exponential decay curve fitting as 34.71 ns in benzene and 2.98 ns in DMSO.

Mechanisms of electron transfer between a styrylquinolinium dye and yeast in biofuel cell

In the present study, the influence of the recently synthesized styrylquinolinium dye 4-{(E)-2-[4-(dimethylamino)naphthalen-1-yl]ethenyl}-1-methylquinolinium iodide (DANSQI) on the intracellular processes as well as the electrical outputs of Candida melibiosica 2491 yeast-based biofuel cell was investigated. The addition of nanomolar quantities of DANSQI to the yeast suspension results in an increase of the current outputs right after the startup of the biofuel cells, associated with an electrooxidation of the dye on the anode. After that, the formed cation radical of the dye penetrates the yeast cells, provoking a set of intracellular changes. Studies of the subcellular anolyte fractions show that 1μM dye increased the peroxisomal catalase activity 30-times (1.15±0.06Unit/mg protein) and over twice the mitochondrial cytochrome c oxidase activity (92±5Unit/mg protein). The results obtained by electrochemical and spectrophotometric analyses let to the supposition that the dye acts as subcellular shuttle, on account of its specific intramolecular charge transfer properties. The transition between its benzoid, quinolyl radical and ion forms and their putative role for the extracellular and intracellular charge transfer mechanisms are discussed.

Computational studies on linear, second and third-order nonlinear optical properties of novel styrylquinolinium dyes

The electric dipole moments (μ), static dipole polarizabilities (α) and first hyperpolarizabilities (β) of styrylquinolinium dyes, D8 and D21, have been computed by density functional theory (DFT). The one-photon absorption (OPA) characterizations have been investigated using UV–vis spectroscopy and further interpreted using computational chemistry. The time-dependent Hartree–Fock (TDHF) method has been used to describe the dynamic dipole polarizabilities, dynamic second-order and also static and dynamic third-order nonlinear optical (NLO) properties. D8–D21 have rather high β and second hyperpolarizabilities (γ). The highest occupied molecular orbitals (HOMO), the lowest unoccupied molecular orbitals (LUMO) and the HOMO–LUMO band gaps for D8–D21 have been evaluated by DFT.

Ab-initio and DFT methodologies for computing hyperpolarizabilities and susceptibilities of highly conjugated organic compounds for nonlinear optical applications

In this talk, after a short introduction on the methodologies used for computing dipole polarizability (α), second and third-order hyperpolarizability and susceptibility; the results of theoretical studies performed on density functional theory (DFT) and ab-initio quantum mechanical calculations of nonlinear optical (NLO) properties for a few selected organic compounds and polymers will be explained. The electric dipole moments (μ) and dispersion-free first hyperpolarizabilities (β) for a family of azo-azulenes and a styrylquinolinium dye have been determined by DFT at B3LYP level. To reveal the frequency-dependent NLO behavior, the dynamic α, second hyperpolarizabilities (γ), second (χ(2)) and third-order (χ(3)) susceptibilites have been evaluated using time-dependent HartreeFock (TDHF) procedure. To provide an insight into the third-order NLO phenomena of a series of pyrrolo-tetrathiafulvalene-based molecules and pushpull azobenzene polymers, two-photon absorption (TPA) characterizations have been also investigated by means of TDHF. All computed results of the examined compounds are compared with their previous experimental findings and the measured data for similar structures in the literature. The one-photon absorption (OPA) characterizations of the title molecules have been theoretically obtained by configuration interaction (CI) method. The highest occupied molecular orbitals (HOMO), the lowest unoccupied molecular orbitals (LUMO) and the HOMO–LUMO band gaps have been revealed by DFT at B3LYP level for azo-azulenes, styrylquinolinium dye, push–pull azobenzene polymers and by parametrization method 6 (PM6) for pyrrolo-tetrathiafulvalene-based molecules.

Novel Styrylquinolinium Dye Thin Films Deposited by Pulsed Laser Deposition for Nonlinear Optical Applications

The nonlinear optical (NLO) properties of novel styrylquinolinium dye thin films for photonic applications have been studied by the Z-scan, second harmonic generation (SHG), and third harmonic generation (THG) techniques, providing both the second- and third-order nonlinear optical parameters. The styrylquinolinium dye (E)- 1-ethyl-4-(2-(4-hydroxynaphthalen-1-yl)vinyl)quinolinium bromide was synthesized by the Knoevenagel condensation, and its structure and physicochemical properties were determined by 1 H NMR, 13 C NMR, FTIR, UV−vis spectros- copy, and elemental analysis. Functional thin films were deposited by pulsed laser deposition (PLD) using UV TEA N2 laser onto glass substrates and KCl, NaCl monocrystals at room temperature and vacuum at 10 −3 mbar/0.1 Pa. Further characterization of the films and target from native material by FTIR spectroscopy revealed that there was no difference between the deposited films and the initial material. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) measurements have been also performed in order to provide information about the morphology and topology of the thin films.

Solvent Effects on the Spectroscopic Properties of Styrylquinolinium Dyes Series

The study on the relationship between the structure and spectroscopic properties of styrylquinolinium dyes were carried out by measuring the electronic visible absorption, steady-state and time-resolved fluorescence spectra of quinoline based hemicyanine dyes. The influence of the solvent on absorption and emission spectra and the solvatochromic properties, observed for both ground and first excited states, for all the dyes were applied for the evaluation of their excited state dipole moments. The ground state dipole moments of dyes under the study were established by applying ab initio calculations. The measured, using solvatochromic methods, excited state dipole moments of tested hemicyanines are in the range from 5.38 to 18.90 D and the change in the dipole moments caused by excitation were found to differ from 1.88 to 6.64 D. It was observed that for all tested dyes the dipole moments of the excited states were higher than those of a ground states. The fluorescence lifetime measurements with picosecond resolution was performed for entire series of hemicyanine dyes possessing different dialkylamino groups attached to the phenyl ring. The average lifetimes of the dye fluorescence, determined from the measured data by multi-order exponential decay curve fitting, were in the range from about 120 to 1200 ps at the fluorescence peak wavelength. The fluorescence lifetime measurements were performed for dyes in ethyl acetate solutions. The time-resolved fluorescence spectra measurements allowed to propose the mechanism of the dyes excited states deactivation.

Novel, N-ethyl-2-styrylquinolinum iodides as fluorophores for monitoring of polymerization process, Part I

A series of of p-substituted 2-styrylquinolinium iodides were prepared by the condensation of N-ethyl-2-methylquinolinium salts with p-substituted benzaldehydes. The spectroscopic properties of the styryl quinolinium dyes are characterized in organic solvents of varying polarities. The electronic absorption and fluorescence emission spectra of the dyes demonstrate their high sensitivity to the nature of substituents introduced into the aromatic ring. The dyes were investigated as fluorescent probes for monitoring the progress of the photochemically initiated free-radical polymerization of a mixture of 2-ethyl-2-(hydroxymethyl)-1,3-propanediol triacrylate and 1-methyl-2-pyrrolidinone. During the course of the polymerization an increase in the fluorescence intensity of the dyes by at least one order of magnitude was recorded; a feature which renders the dyes as good fluorescent probes for such polymerization reactions. The term “probe sensitivity” has been defined and appears in the range from 0.08 to 11 for the styryl dyes.