The optical properties of triphenylmethane dye molecules and chromogens

Industrial dye monomers, including malachite green, crystal violet, brilliant green, and methyl violet, were isolated by extraction with the use of heptane. UV light absorption bands characteristic of pure molecules were determined. The molecules of the dyes studied, which were ion pairs (formed by dye cations and oxalate or chlorine anions), did not absorb light in the visible range; that is, they were not chromogens. The conclusion was drawn that chromogen particles responsible for chromaticity were supramolecular dimers of nonchromogenic triphenylmethane series molecules. This conclusion was substantiated by trends in spectral transformations with the participation of immonium hydroxides obtained from dyes and side products of the synthesis of industrial dyes with quinoid molecular structures.     

The optical properties of molecules and chromogenic aggregates of xanthene dyes

The UV absorption spectra of rhodamine B and G molecules isolated from industrial dye samples were obtained. Two procedures were used. In one of them, rhodamine B molecules were displaced with water into a heptane layer from a solution of the dye in an alcohol-heptane mixture. The second procedure involved heating of the dye introduced into cellulose triacetate films. Individual rhodamine molecules (namely, dye cation-chlorine anion ion pairs) prepared by both methods did not absorb visible light. The spectra of individual rhodamine molecules coincided with the spectra of so-called pseudoleucobases of xanthene dyes reported in the literature. The conclusion was drawn that the chromaticity property in the series of xanthene dyes appeared because of the formation of supramolecular dimeric and larger aggregates, as was earlier established for triphenylmethane dyes (TPMDs) and copper phthalocyanine (CuPc). At the same time, individual xanthene dye molecules, like TPMD and CuPc molecules, are not chromogens.     

ZnS光催化剂对不同偶氮类染料光降解的光催化性能的比较

在表面活性剂十六烷基三甲基溴化铵(CTAB)存在时,合成了ZnS光催化剂。 采用X射线衍射和透射电子显微镜等测试技术结果表明,制得的ZnS粒子尺寸均一,无团聚现象,平均粒径约为3.5 nm。 研究了ZnS光催化剂在紫外光下对不同染料的光催化降解效率,结果表明,ZnS光催化剂对一些含-N=N-基团的偶氮类染料,如甲基橙(MO)、酸性嫩黄(AY)、酸性橙Ⅱ(AOⅡ)光催化降解效率高达88％以上,甲基红(MR)的光催化降解效率也达59.63%。 表明-N=N-基团容易降解。 染料分子本身的吸光性也起一定的作用,虽然二甲酚橙(XO)和亚甲基蓝(MB)分子中均不含-N=N-基团,但由于XO的最大吸收峰分布于430 nm的紫外光区,其光催化降解效率可达43.83％,而MB最大吸收峰分布于664 nm可见光区,因此,其光催化降解效率则非常低。     

Dye,fluorophores and pigment coloration of nanofibers produced by electrospinning

Polymeric nanofibers produced by the electrospinning technique are widely used in industrial scale production. Nanofibers chiefly find applications in filtration media and active–barrier surfaces for medical, biological, and military applications. In such applications, the quantity and the uniformity of the nanofibers distribution play a leading role in the product characteristics. For this reason, there is considerable interest regarding the nanofibers recovering quantification and simplification of the qualitative analysis. With the aim to improve and simplify the nanofibers relevability, a coloration approach for nanofibers has been designed and tested. The coloration has been carried out by organic dyes, pigments, and organic fluorophores and the consequent nanofibers' color has been analyzed by optical analysis, colorimetry, and spectroscopy. The coloration obtained by different dyes has been compared and their effect on the nanofibers relevability has been investigated. Moreover, the leading role of the light scattering phenomenon on the nanofiber coloration efficacy has been investigated by comparing the coloration response of nanofibers and film samples on equal terms of dye content. The study has been carried out using polyamide‐6 (PA6) as the testing polymer but the recovering quantification, the coloration approach, and the interaction between light and nanofibers can be extended to all the electrospinnable polymers. Copyright © 2008 John Wiley & Sons, Ltd.     

Polymethine dyes,derivatives of imidazopyridine

Certain new polymethine dyes of the cyanine, merocyanine, and merocyaninocyanine series containing residues of the quaternary salt of 1-methyl-1H-imidazo[4, 5-c]pyridine have been synthesized. A study was made of the coloration of synthesized dyes. Replacement of the benzimidazole residue in the cyanine dyes by the residue of the quaternary salt of 1-methyl-1H-imidazo[4, 5-c]pyridine leads to the intensification of the color of the dyes.     

Photochromic,Thermochromic, and Fluorescent Spirooxazines and Naphthopyrans: A Spectrokinetic and Thermodynamic Study

The photochromic and thermochromic behavior of four commercially available Reversacol dyes are presented. The compounds studied belong to the class of spirooxazines and naphthopyrans, which are typically thermoreversible photochromic molecules. On stimulation with UV light, these compounds become colored and exhibit spectra which extend over the whole visible region. Increasing the temperature causes spontaneous coloration (thermochromism). Herein, absorption and fluorescence spectra, molar absorption coefficients of the colorless and colored forms, fluorescence and photochemical quantum yields, and kinetic parameters of thermal bleaching (rate constant, frequency factor, and activation energy) are determined in acetonitrile solution. The thermal ground‐state reaction is exhaustively described in terms of thermodynamic parameters (equilibrium constant, free energy, enthalpy, and entropy). Temperature effects on photochemical and thermal colorabilities are evaluated. The results indicate that the two spirooxazines are good photochromes below room temperature, whereas they are efficient thermochromic compounds above room temperature. Naphthopyrans are better photochromes but worse thermochromic compounds than spirooxazines.     

DNA-mediated delivery of lipophilic molecules via hybridization to DNA-based vesicular aggregates

A scheme is presented for stabilizing hydrophobic molecules and releasing them into aqueous solution via DNA hybridization. A tetradecyl hydrophobic tail is covalently attached to synthetic oligomers, and the resulting amphiphilic molecules take up substantial amounts of orange OT and pyrene dyes in aqueous environments. The resulting structures do not affect the surface tension and are predominantly spherical as shown by light scattering and TEM, and the pyrene fluorescence is consistent with a hydrophobic environment. It is concluded that the amphiphilic DNA creates vesicular domains upon which the hydrophobic dyes reside and are stabilized in solution. Upon exposure to the complementary strand, the pyrene dye is released from the structures, showing that the scheme can be used for unlabeled or DNA-mediated drug delivery.     

Fluorescent DNA nanotags: supramolecular fluorescent labels based on intercalating dye arrays assembled on nanostructured DNA templates

Fluorescence detection and imaging are vital technologies in the life sciences and clinical diagnostics. The key to obtaining high-resolution images and sensitive detection is to use fluorescent molecules or particles that absorb and emit visible light with high efficiency. We have synthesized supramolecular complexes consisting of a branched DNA template and fluorogenic intercalating dyes. Because dyes can intercalate up to every other base pair, high densities of fluorophores are assembled yet the DNA template keeps them far enough away from each other to prevent self-quenching. The efficiency with which these noncovalent assemblies absorb light is more than 10-fold greater than that of the individual dye molecules. F?rster resonance energy transfer from the intercalated dyes to covalently attached acceptor dyes is very efficient, allowing for wavelength shifting of the emission spectrum. Simple biotinylation of the DNA template allows for labeling of streptavidin-coated synthetic microspheres and mouse T-cells.     

Theoretical Study of Origin of Triple Fluorescences of a Squaraine Dye, Bis[4-(N,N-dimethylamino)phenyl]-squaraine

A new scheme of photo‐fluorescent emission origin, described as S₀ (relaxed state)→S_n (Frank‐Condon state)→ S_m (relaxed state)→S₀ (Frank‐Condon state), is presented to explain the multiple fluorescent emissions of squaraine dyes observed experimentally according to the configuration interaction singles calculations of relaxed excited states of a model compound, bis[4‐(N,N‐dimethylamino)phenyl]squaraine (SQ). It is exhibited that all triple fluorescent emissions of SQ have their significant origin in vertical electron transitions of different relaxed excited states. In addition, some important absorption peaks appearing in higher energy region are most likely to be responsible for the higher energy band observed in solid states of many squaraine dyes.     

Rotational diffusion of dyes in solvents of low viscosity from transient-dichroism experiments

Rotational diffusion data from pulsed laser experiments are presented for dye molecules dissolved in alcohols and non-alcohols. Cresyl violet and fluorescein both exhibit strong dependence of the rotational motion upon solvent molecular structure. In complete contrast the rotational diffusion of the oblong dyes pyronine G and acridine orange do not reveal any specific solute-solvent interaction.     

Wavelength Dependence of the Fluorescence Quenching Efficiency of Nearby Dyes by Gold Nanoclusters and Nanoparticles: The Roles of Spectral Overlap and Particle Size

The efficiency of the glutathione monolayer-protected gold nanocluster (NC) Au(25) (1.2 nm metal core diameter (d)) in quenching the emission of dyes intercalated into DNA is compared to that of 2 and 4 nm gold nanoparticles (NPs). In all cases, the DNA/dye moieties and the gold particles are not covalently attached but rather form non-covalent ground state complexes. Under these conditions, steady-state measurements reveal that the quenching efficiency of Au(25) is a factor of 10 lower than that of plasmonic 4 nm gold NPs but comparable to that of 2 nm particles which do not show a distinct plasmon band. Nonetheless, significant emission quenching is observed even at very low (nM) concentrations of Au(25). The quenching efficiency of the 4 nm NPs is significantly higher for dyes emitting near the wavelength of the plasmon peak whereas that of the 2 nm gold NPs is well described by the nano-surface energy transfer (NSET) model proposed by the Strouse group (J. Am. Chem. Soc. 127, 3115 2005). Interestingly, for Au(25) the maximum quenching efficiency occurs for dyes emitting in the same wavelength range as that of the 2 and 4 nm NPs (490-560 nm), where it shows no discrete absorption features, rather than for wavelengths coincident with its HOMO-LUMO, intra-band or inter-band transitions. The fluorescence quenching properties of Au(25) NCs are therefore found to be distinct from those of larger NCs and NPs but do not appear to conform to theoretical predictions advanced thus far.     

Natural dyes based on chlorophyll and protoporphyrin derivatives

The utility of natural dyes (chlorophyll, protoporphyrin, and their derivatives) as ecologically pure new-generation dyes that are safer than common synthetic arene-based dyes is discussed. New dyes were obtained from chlorophyll and protoporphyrin derivatives such as pheophorbide (a+b), chlorin e₆, 6-N-(2-aminoethylamido)chlorin e₆ dimethyl ester, and 6-N-(2-aminoethylamido)deuteroporphyrin methyl ester and tested in coloration of wool, cotton, and acetate fibers.     

Artificial light-harvesting arrays: electronic energy migration and trapping on a sphere and between spheres

A sophisticated model of the natural light-harvesting antenna has been devised by decorating a C(60) hexa-adduct with ten yellow and two blue boron dipyrromethene (Bodipy) dyes in such a way that the dyes retain their individuality and assist solubility of the fullerene. Unusually, the fullerene core is a poor electron acceptor and does not enter into light-induced electron-transfer reactions with the appended dyes, but ineffective electronic energy transfer from the excited-state dye to the C(60) residue competes with fluorescence from the yellow dye. Intraparticle electronic energy transfer from yellow to blue dyes can be followed by steady-state and time-resolved fluorescence spectroscopy and by excitation spectra for isolated C(60) nanoparticles dissolved in dioxane at 293 K and at 77 K. The decorated particles can be loaded into polymer films by spin coating from solution. In the dried film, efficient energy transfer occurs such that photons absorbed by the yellow dye are emitted by the blue dye. Films can also be prepared to contain C(60) nanoparticles loaded with the yellow Bodipy dye but lacking the blue dye and, under these circumstances, electronic energy migration occurs between yellow dyes appended to the same nanoparticle and, at higher loading, to dye molecules on nearby particles. Doping these latter polymer films with the mixed-dye nanoparticle coalesces these multifarious processes in a single system. Thus, long-range energy migration occurs among yellow dyes attached to different particles before trapping at a blue dye. In this respect, the film resembles the natural photosynthetic light-harvesting complexes, albeit at much reduced efficacy. The decorated nanoparticles sensitize amorphous silicon photocells.     

Impact of molecular surface characteristics on the reversed-phase retention behaviour of synthetic dyes

The lipophilicity and specific hydrophobic surface area of 42 synthetic dyes were determined on reversed-phase alumina layers using water-methanol mixtures as eluents, and their relationship with the molecular surface characteristics was elucidated by principal component analysis followed by a two-dimensional nonlinear map and cluster analysis. Four dyes remained on the origin in each eluent system. Except for two dyes, the majority showed regular retention behaviour with their retention decreasing steadily with increasing concentration of methanol in the mobile phase. Calculations indicated that both hydrophobicity parameters decrease with increasing polar surface area of the molecules.     

Rotational diffusion of dyes in micellar media from transient absorption

Solubilizer effects in dye solutions have been investigated by subnanosecond laser-pulse photometry. Different models for the transient dichroism of dye-micelle solutions are proposed. Computer fits of the experimental curves indicate that the model where dye molecules rotate within the liquid-like interior of the micelles is the most realistic one. Since the measured rotational diffusion times differ for different dyes in almost the same way as for pure highly-viscous solvents, the dye molecules do not act merely as labels for the rotation of the micelles, but rotate themselves considerably. It is shown that the rotational diffusion of dye molecules and micelles can be separated giving reasonable results for the size of the micelles. The results are compared with previous steady-state experiments.     

Highly selective uptake and release of charged molecules by pH-responsive polydopamine microcapsules

A systematic study of the permeation of small molecules through Pdop microcapsules is reported. The zwitterionic Pdop microcapsules are prepared by oxidative polymerization of dopamine on polystyrene microspheres followed by core removal with THF. Rhodamine 6G, methyl orange and alizarin red are chosen as differently charged probing dyes. The loading amount is affected by pH and dye concentration. Highly selective and unidirectional uptake and release of charged molecules through Pdop microcapsules can be achieved by controlling pH value: at low pH, the Pdop particles incorporate cationic dye (rhodamine 6G); at high pH, they incorporate anionic dyes (methyl orange and alizarin red). In each case, the uptake is highly selective.     

Spectrophotometric determination of aliphatic aldehyde 2,4-dinitrophenylhydrazones with 3-methyl-2-benzothiazolinone hydrazone

A sensitive new spectrophotometric procedure is described for the analysis of aliphatic aldehyde 2,4-dinitrophenylhydrazones. The chromogens formed in the procedure absorb at 667 mμ and are approximately three times as intense at this band as the starting aldehyde derivatives are in neutral and alkaline solvent at their wavelength maxima. With further improvement the procedure is capable of even greater sensitivity. Other aliphatic aldehyde derivatives also should be analyzable by this procedure, but 2,4-dinitrophenylhydrazones of ketones do not react.     

Synthesis and modification of sulfur dyes

An integrated approach to sulfur utilization by synthesis of sulfur dyes derived from m- and p-phenylenediamine was suggested. The sulfur dyes obtained were modified by the reaction with butyl bromide. The possibility of dyeing cotton fabrics by the dyes prepared was examined, and the coloration fastness was evaluated.     

The effect of pulsed laser radiation on polyelectrolyte capsule shells modified with fluorescent dyes

Polyelectrolyte capsules containing rhodamine 6G and fluorescein isothiocyanate in their shells are obtained by successive adsorption on spherical microscopic CaCO₃ particles followed by the dissolution of the latter. Suspensions of the capsules are irradiated with a laser operating at a wavelength corresponding to the absorption bands of the dyes, and it is shown that shell modification with the selected dyes promotes photosensitized disruption of these structures. The mechanism proposed for this disruption is realized via energy transfer from photoexcited dye molecules to the polymer matrix. Therewith, the dye-modified capsules are disrupted due to their nonuniform local heating.     

Reversible isomerization of chromogenic dimers and the nature of azulene chromaticity

The spectra of azulene solutions in siloxane and heptadecane were studied. The VIS band (435–714 nm) associated with the color blue was shown to transform reversibly as a result of a temperature increase and to assume a likeness to the less intensive VIS band typical for solutions in polar ethanol and dibutyl phthalate. It was concluded that supramolecular dimers rather than individual molecules are the chromogens of azulene, just as in the case of phthalocyanine, triphenylmethane, xanthene, and thiazine dyes. Clar’s conclusions regarding the nature of the visible band of azulene absorption and the mechanism of reversible thermal discoloration of azulene solutions in high-boiling-point hydrocarbons are consequently wrong. It was established that the thermochromism of azulene solutions is actually not associated with the isomerization of azulene molecules into nonplanar nonaromatic molecules but with the reversible isomerization of dimeric structures, accompanied by a change in the positions of the aromatic molecules relative to one another. The corresponding equilibrium is somewhat endothermic: ΔH = 6.6 kJ/mol, ΔG ^o ≈ − 1.45 kJ/mol. Based on these results, it was concluded that light absorption changes the energetic state of the dimeric structures (transition S _D→ S _D^*) without leading to electron transfer in single molecules according to the scheme S ₀ →S ₁. That is, the traditional idea that Kasha’s law is violated when azulene fluoresces is incorrect, since the radiation comes from the S ₁ level and not from the S ₂ level, as is stated in the literature.