Styryl Dyes as Two-Photon Excited Fluorescent Probes for DNA Detection and Two-Photon Laser Scanning Fluorescence Microscopy of Living Cells

Spectral-fluorescent properties of benzothiazole styryl monomer (Bos-3) and homodimer (DBos-21) dyes in presence of DNA were studied. The dyes enhance their fluorescence intensity in 2–3 orders of magnitude upon interaction with DNA. Studied styrylcyanines in DNA presence demonstrate rather high values of two-photon absorption (TPA) cross-section, which are comparable with the values of TPA cross section of the rhodamine dyes. An applicability of the styrylcyanines as probes for the fluorescence microscopy of living cells was studied. It was shown that both dyes are cell-permeable but homodimer dye DBos-21 produces noticeably brighter staining of HeLa cells comparing with monomer dye Bos-3. Molecules of DBos-21 initially bind to the nucleic acids- containing cell organelles (presumable mitochondria) and are able to penetrate into the cell nucleus. Thus, homodimer styryl DBos-21 dye is viewed as efficient stain for single-photon and two-photon excitation fluorescence imaging of living cells.     

Spectroscopic study of interaction of styrylcyanine dye Sbt and its derivatives with bovine serum albumin

The spectral-fluorescent characteristics of styrylcyanine dye Sbt ((E)-2-(4-(dimethylamino) styryl)-3-methylbenzo[d]thiazol-3-ium iodide) and homodimers, dyes conjugated with two chromophores in aqueous solutions without and in the presence of bovine serum albumin (BSA), are studied. It is established that in the presence of BSA for dyes Dbt-5 and Dbt-10, an increase of the absorptivity, a slight broadening and the emergence of new band on the short wavelength range with λ_max=410 nm is observed; also hypsochromic shift of the absorption and fluorescence at 30 nm and 7 nm, respectively for the dye D-183 is observed. The intensity of the fluorescence emission fundamental band in all the studied dyes in the presence of BSA increases by 3.5 to 55 times. The binding constant (K) and number of binding sites (N) of studied dyes with BSA are determined. The dependence of the binding constants with BSA from the dipole moment of dye molecules is identified, which shows that in addition to the electrostatic attraction forces between molecules of styrylcyanine dyes with BSA, hydrophobic interactions are essential. It is shown that the aggregation of dye affects the processes of interaction of the dyes with the BSA.     

Effect of hydrophobicity of cationic carbocyanine dyes DiOC<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> on their binding to anionic surfactant micelles

The interaction of a series of cationic dialkyloxacarbocyanine perchlorate (DiOC _n ) dyes of different degrees of hydrophobicity with micelles of an anionic surfactant, sodium dodecylsulfate (SDS), has been studied spectrophotometrically in aqueous solutions. The Benesi–Hildebrand equation was used to calculate binding constants (K _b ) of the dyes to surfactant micelles, the fraction of dye bound to the micelles (f _mic ), and the standard free-energy change (ΔG ⁰) for the transfer of dye from the aqueous to micellar phase. It has been shown that the interaction of oppositely charged dye molecules and surfactant micelles is controlled by both electrostatic and hydrophobic interactions. A small increase in dye hydrophobicity due to lengthening of the hydrocarbon radical has been shown to cause an abrupt nonlinear increase of the fmic value. This points to a key role of hydrophobic interactions in the binding of dye molecules with the micelles.     

Synthesis and Spectra of a Kind of Novel Longer-Wavelength Benzoxazole Indole Styryl Cyanine Dye with a Carbazole-Bridged Chain

Based on cyanine dye probe oxazole yellow (YO) and Cy₃, a series of novel styryl cyanine dyes were designed and synthesized. Carbazole was inserted into the structures of YO and Cy₃ to act as a bridge to link the benzoxazole and indole group. This modification resulted in a novel kind of benzoxazole indole styryl cyanine dye with a carbazole-bridged chain. The dyes were characterized by ¹HNMR and MS. The spectra of the novel dyes were also performed and the results showed that the maximum emission wavelength of the carbazole styryl cyanine dye was shifted red, the Stokes shift increased and the fluorescence intensity enhanced compared with those of YO and Cy₃. These results indicated that the novel dye could be used as an excellent fluorescent probe in biological labeling.     

Study on the Synthesis and Spectra of a Novel Kind of Carbozole Benzothiazole Indole Styryl Cyanine Dye with a Carbazole Bridged Chain

Based on the frequently-used cyanine dye probe thiazole orange (TO) and Cy3, a novel kind of styryl cyanine dye was designed and synthesized. Carbazole was inserted into the structures of two cyanine dyes, TO and Cy3, to act as a bridge to link the benzothiazole and indole. This modification resulted in a novel kind of carbozole benzothiazole indole cyanine dye with a carbazole-bridged chain. The dyes were characterized by HNMR and MS. The spectra of the novel dyes were also studied and the results showed that the fluorescence wavelength of novel carbazole benzothiazole indole cyanine dye shifted red, the Stokes shift and Fluorescence quantum yields increased and the fluorescence intensity was enhanced compared to that of TO. These results indicated that the novel dye could be used as an excellent fluorescent probe in biological labeling.     

Synthesis of Novel Carbazole based Styryl: Rational Approach for Photophysical Properties and TD-DFT

The synthesis and solvatochromic behavior of four novel carbazole based fluorescent styryl dyes were explained. In chlorinated solvents such as DCM and chloroform, these dyes show bathochromic shift in their absorption as well as emission. The styryl dyes 6b and 6c show solid state yellow fluorescence. DFT and TD-DFT computations were performed to study structural, molecular, electronic and photophysical properties of these dyes. The computed absorption and emission wavelength values are found to be in good agreement with the experimental results. The photophysical properties of these 1-styryl carbazole dyes are also compared with the recently reported 3-styrl carbazole dyes. The unique behavior of dye 6d is well explained by its optimized geometry found in the excited state. Ratio of ground to excited state dipole moment of the synthesized novel styryl compounds were calculated by Bakhshiev and Bilot-Kawski correlations.     

Studies on the Spectral-Luminescent Properties of the Novel Homodimer Styryl Dyes in Complexes with DNA

Series of homodimer styryls containing on (p-dimethylaminostyryl) pyridinium residues that are connected with aliphatic linkage group was synthesized. Spectral luminescent properties of obtained dyes in free state and in nucleic acids presence were studied. It was shown that DNA binding affinity of the novel homodimers exceeds that of parent monomer (p-dimethylaminostyryl)pyridine iodide. For homodimers with the linkage 4–10 carbon atoms preference in binding to DNA than to RNA was observed. It could be concluded that parent monomer has different mechanisms of binding to nucleic acids than corresponding homodimer dye.     

Spectroscopic Study of the Interaction of Styrylcyanine Dyes Sbo,Sil and Their Derivatives with Bovine Serum Albumin

The spectral-luminescent characteristics of newly synthesized styrylcyanine dyes on the base of dyes Sbo ((E)-2-(4-(dimethylamino)styryl)-3-methylbenzo[d]oxazol-3-ium iodide) and Sil ((E)-2-(4-(dimethylamino)styryl)-1,3,3-trimethyl-3H-indolium perchlorate) in aqueous solutions without and in the presence of bovine serum albumin (BSA) were studied. It was established that the absorption spectra of dyes Tol-6, Dbo-10 and Dil-10 with increasing amount of BSA appear new bands with λ_max = 505 nm, λ_max = 512 nm and λ_max = 566 nm, respectively, whose intensity increases in proportion to the amount of albumin. The intensity of the glow of the main band of fluorescence in the presence of BSA sharply increases. The binding constant (K) and the number of binding sites (N) of studied dyes with BSA were determined. The dependence of binding constants with BSA on the dipole moment of dye molecules was determined, which indicates that besides electrostatic forces of attraction between molecules styrylcyanine dyes with BSA, hydrophobic interactions are essential.     

Photoquenching parameters for commonly used laser dyes

Laser dyes which are commonly used in pulsed laser pumped dye laser (PLPDL) systems have been investigated. It is shown that photoquenching plays an important role in the pumping process of all laser dyes, determining the efficiency of the PLPDL. Molecular parameters, such as absorption cross sections at various pumping wavelengths and fluorescence lifetimes of theS _n (n>1) excited electronic states of laser dyes, have been determined utilizing the photoquenching technique.     

Fluorescence of Styryl Dyes-DNA Complexes Induced by Single- and Two-Photon Excitation

The series of novel monomer and homodimer styryl dyes based on (p-dimethylaminostyryl) benzothiazolium residues were synthesized and studied as possible fluorescent probes for nucleic acids detection. Spectral-luminescent and spectral-photometric properties of obtained dyes in the unbound state and in DNA presence were studied. Fluorescence emission induced by two-photon excitation of dye-DNA complexes in aqueous buffer solution was registered. Two-photon absorption cross section values of the studied dyes in DNA presence were evaluated.     

Adsorption study of dimethylaminostyryl benzazoles onto Na-montmorillonite

The adsorption of 2-(4′-dimethylaminostyryl)benzoxazole (DMASBO) and its benzothiazole analogue (DMASBT) onto Na-montmorillonite (Na⁺-MMT) was studied. The adsorption data have been fitted with Freundlich and Dubinin-Radushkevich (D-R) equation to find the characteristic parameters of each model. From D-R isotherm, it was concluded that the adsorption is of chemical nature. The equilibrium adsorption constant, K_c, was determined and has been used to calculate the enthalpy and entropy of the adsorption process. The mechanism of the adsorption has been investigated by fluorescence, IR, X-ray and ESR spectroscopic measurements. These measurements indicate oxidation of the styryl dyes by the Lewis acidic sites of the clay and formation of radical cations at Na⁺-MMT surface without intercalation into the interior.     

Studies of Benzothiazole and Benzoselenazole Squaraines as Fluorescent Probes for Albumins Detection

Series of squaraine benzothiazole and benzoselenazole dyes were studied as possible fluorescent probes for the detection of proteins, particularly albumins. It was shown that majority of the studied squaraines give significant fluorescent response on the human serum albumin (HSA) and bovine serum albumin presence. For squaraine dyes with N-hexyl pendent groups (P-1, P-2, P-3, P-5) about 100−540-fold fluorescence intensity increase upon albumins addition was observed. At the same time in presence of other proteins, namely insulin, avidin from hen egg white, immunoglobulin G (IgG), carbonic anhydrase fluorescence enhancement values were considerably lower —up to 43 times in IgG presence. It was noted that generally, squaraines with long N-hexyl pendent groups demonstrate higher emission increase values upon proteins addition comparing with their analogues with short N-ethyl tails. It was shown that fluorescence intensity enhancement for benzothiazole squaraine dye P-3, relates linearly to the HSA concentration over the wide range—from 0.2 to 500 μg/ml. Together with noticeable selectivity of this dye to albumins, existence of wide dynamic range gives possibility to propose P-3 dye as probe for HSA quantification.     

Novel Thiazole Based Styryl Dyes with Benzimidazole Unit - Synthesis,Photophysical and TD-DFT Studies

Three new Y-shaped styryl dyes were designed and synthesized from thiazole carbaldehyde with different active methylene compounds as acceptor moieties. All the dyes were characterized by IR, ¹HNMR, MS/LCMS/HRMS. Spectroscopic properties and non-linear optical properties styryl derivatives were analyzed and the effect of change in solvent polarity on their absorption and emissive properties has been investigated. The dye with (1-phenylethylidene) propanedinitrile unit shows red shift absorption/emission profile among all the dyes. Density Functional Theory and Time Dependent-Density Functional Theory computations have been used for comparative study with the experimental data and also to understand the structural, molecular, electronic and photophysical parameters of the styryl dyes. The computational method was also employed to investigate the nonlinear optical properties of the styryl dyes in different organic solvent. The unsubstituted benzimidazolyl thiazole styryl dyes possess good non-linear optical properties.     

Influence of anthocyanin co-pigment on electron transport and performance in black rice dye-sensitized solar cell

This work reports the novel contribution of chlorophyll b as natural anthocyanin co-pigment in unpurified black rice extract for improved electron transport and performance of natural dye-sensitized solar cell. The dyes are extracted as prominent photosensitizers by considering the concentration, the dye electronic structure, the extraction, and immersion time. The anthocyanin dye containing 1.92 mM cyanidin-3-O-glucoside structure has been extracted without purification. Interestingly, 0.33 mM chlorophyll b is found as a natural co-sensitizer in unpurified anthocyanin. The role of chlorophyll b supporting the electron transfer of anthocyanin dye will be investigated for improved cell performance. Both purified and unpurified dyes are compared in the same anthocyanin concentration. The combined Tauc plot and voltametric method will be conducted to show the interfacial electronic band edges of TiO₂-dye-electrolyte. Electrochemical impedance spectroscopy method will investigate electron transfer dynamic in both cell systems. As a result, chlorophyll b has dominantly acted as two intermediate states in boosting electron injection and dye regeneration to improve cell efficiency from 1.31 to 2.17 % due to the narrower LUMO–TiO₂ conduction band gap and the narrower HOMO-iodide (I ^?) potential gap, respectively. According to the electron transport, the co-sensitizer contributes to the smaller transport resistance (R _t?=?21.9 Ω), the higher chemical diffusion coefficient (D_n?=?1.696?×?10^?3 cm²/s), the higher chemical capacitance (C_μ?=?14.32 μF), and the faster electron transport (τ_d?=?39.88 μs).     

IR absorption spectrum (4200–3100 cm) of H2O and (H2O)2 in CCl4. Estimates of the equilibrium constant and evidence that the atmospheric water absorption continuum is due to the water dimer

IR absorption spectra, 4200–3100 cm⁻¹, of water in CCl₄ solutions are presented. It is shown that for saturated solutions significant amounts of water are present as dimer (ca. 2%). The IR spectra of the monomer and dimer are retrieved. The integrated absorption coefficients of the monomer absorption are significantly enhanced relative to the gas phase values. The dimer spectrum consists of 5 bands, of which 4 were expected from data from cold beams and cold matrices. The origin of the “extra” band is discussed. In addition it is argued that the dimer absorption bands intensities must be enhanced relative to the gas phase values. Based on recent calculations of band strengths, and observed frequency shifts relative to the gas phase, the intensity enhancement factors are estimated as well as the monomer/dimer equilibrium constant in CCl₄ solution at T=296 K (K_c=1.29 mol⁻¹ L). It is noted that the observed dimer spectrum has a striking resemblance with the water vapour continuum determined by Burch in 1985 which was recently remeasured by Paynter et al. and it is concluded that the atmospheric water absorption continuum in the investigated spectral region must be due to water dimer. Based on the newly published spectral data a revised value of the gas phase equilibrium constant is suggested (K_p=0.035 atm⁻¹ at T=296 K) as well as a value for the standard enthalpy of formation, ΔH⁰=15.4 kJ mol⁻¹.     

Water adsorption on the Be(0001) surface: from monomer to trimer adsorption

In this paper, the density functional theory has been used to perform a comparative theoretical study of water monomer, dimer, trimer, and bilayer adsorptions on the Be(0001) surface. In our calculations, the adsorbed water molecules are energetically favoured adsorbed on the atop sites, and the dimer adsorption is found to be the most stable with a peak adsorption energy of ～437 meV. Further analyses have revealed that the essential bonding interaction between the water monomer and the metal substrate is the hybridization of the water 3a₁-like molecular orbital with the (s, p_z) orbitals of the surface beryllium atoms. While in the case of the water dimer adsorption, the 1b₁-like orbital of the H₂O molecule plays a dominant role.     

Synthesis and phase transition studies on non-symmetric liquid crystal dimers: N-(4-(n-(4-(benzothiazol-2-yl)phenoxy)alkyloxy)-benzylidene)-4-chloroanilines

A new series of non-symmetric liquid crystal dimers N-(4-(n-(4-(benzothiazol-2-yl)phenoxy)alkyloxy)benzylidene)-4-chloroaniline containing benzothiazole and benzylideneimine units connected by a flexible alkyl spacer, –(CH₂) _n –, with n ranging from 4 to 12 in even parity have been prepared. All five members of this homologous series exhibit an enantiotropic nematic phase. The compounds with greater n of 8–12 exhibit both nematic and smectic phases upon cooling. A notable feature among this series is that for the member with n?=?10, the smectic–nematic transition is also present. The nematic–isotropic transition temperatures and associated entropy changes with respect to all compounds in this series exhibit a dramatic dependence on the length of the flexible spacer. A comparison of the transitional properties of this series with those of α-(4-benzylidenechloroaniline-4′-oxy)-ω-[4-(thiophene-2-carboxyl)benzylideneaniline-4′-oxy]alkanes reveals that replacing benzothiazole moiety at one side of the flexible alkyl spacer reduces the nematic–isotropic transition temperature.     

Decay pathways of small gold clusters

The decay pathway competition between monomer and dimer evaporation of photoexcited cluster ions Au ⁺ _n, n = 2-27, has been investigated by photodissociation of size-selected gold clusters stored in a Penning trap. For n > 6 the two decay pathways are distinguished by their experimental signature in time-resolved measurements of the dissociation. For the smaller clusters, simple fragment spectra were used. As in the case of the other copper-group elements, even-numbered gold cluster ions decay exclusively by monomer evaporation, irrespective of their size. For small odd-size gold clusters, dimer evaporation is a competitive alternative, and the smaller the odd-sized clusters, the more likely they decay by dimer evaporation. In this respect, Au ⁺ ₉ shows an anomalous behavior, as it is less likely to evaporate dimers than its two odd-numbered neighbors, Au ⁺ ₇ and Au ⁺ ₁₁. This nonamer anomaly is typical for copper-group cluster ions M ⁺ ₉ (M = Cu, Ag, Au) and a similar behavior is found in the anionic heptamers M ^- ₇. It is discussed in terms of the well-known electronic shell closing at n _e = 8 atomic valence electrons. Received 2 November 2000     

Basis set limit binding energies of hydrogen bonded clusters

The utility of the recently developed extrapolation method to estimate the binding energies of weakly bound clusters at the basis set limit exploiting the similar basis set convergence behaviour of correlation energies of the monomer and cluster in correlated calculations (J. chem. Phys., 116, 5389 (2002)) was tested for small to medium (HF)_n and (H₂O)_n (n = 2–5) clusters using various correlation consistent cc-pVXZ (X= D,T,Q,5) basis sets containing different numbers of diffuse functions and 6–31G type basis sets at the MP2 and CCSD(T) level for which accurate basis set limits are available for comparison. It is shown that the basis set limit binding energies estimated by this extrapolation method with modest size of basis sets (cc-pVDZ/cc-pVTZ or 6–3 1 G(d,p)/6-3 IG(2df,2pd)) are much closer to the exact basis set limits than the estimates by commonly used X ^?3 extrapolation or counterpoise corrected binding energies, signifying the importance of this extrapolation method for the study of large weakly bound clusters. It is also shown that the inclusion of appropriate diffuse functions in the basis sets can significantly improve the accuracy of the estimated basis set limits by this extrapolation method. For (HF)_n clusters the MP2 and CCSD(T) basis set limits estimated by this extrapolation method with aug-cc-pVDZ and aug-cc-pVTZ basis sets are 18.4 (18.5) and 18.9 (18.9) for the dimer, 61.8 (62) and 63.2 (63) for the trimer, 113.5 and 114.7 (116) for the tetramer, and 155.2 and 156.3 (158) for the pentamer, respectively, with the values in parentheses representing the apparent basis set limits, with the numbers in units of kJ mol^?1. The corresponding results for (H₂O)_n clusters are 20.5 (20.5) and 20.6 (20.7) for (H₂O)₂, and 60.5 (61) and 60.1 (60) for (H₂O)₃, respectively.     

Unsymmetrical dyes derived from 7,8‐dihydrobenzo[c,d]furo[2,3‐f]indole

On the basis of the 7,8‐dihydrobenzo[c,d]furo[2,3‐f]indole nucleus, a number of unsymmetrical carbocyanines as well as styryl dyes have been synthesized and their absorption spectra have been measured. Starting from the deviations of long‐wavelength maxima, the value of electron‐donor ability D has been estimated for the heterocycle under study and a number of dye end groups have been ranked by their electron‐donor properties. Experimental inferences are supported by the quantum chemically calculated bond length alternations and energy levels for the dyes concerned. Copyright © 2009 John Wiley & Sons, Ltd.