Effect of the thickness of a dicarbocyanine dye layer on the conformational composition and spatial orientation of layer components

The conformational and aggregate structure and the spatial orientation of polyatomic organic molecules on solid substrates are investigated by the example of molecular layers of symmetric and asymmetric dicarbocyanine dyes. It is shown that the structure of a dicarbocyanine dye layer is determined by two mechanisms: (i) the change in the symmetry of the intramolecular charge distribution in the monomeric components of the layer as a result of the intermolecular interaction with the substrate, which leads to closer values of the equilibrium concentrations of two monomers with different spatial structure (rotational stereoisomers), and (ii) the association of monomer molecules with formation of dimers and J aggregates. The relative position of the spectra of the layer components, the spatial orientation of the components, and the concentration ratio of different monomeric forms depend on the structure and the electron-donating ability of terminal groups. In going from a monomolecular layer to multilayered structures, the asymmetry of the intramolecular charge distribution induced by the substrate and the ratio of different stereoisomeric forms first change and then become stabilized.     

Formation mechanisms of equilibrium component composition of molecular layers of polymethine dyes

We study the concentration dependences for the absorption spectra and component composition of molecular layers from three homologous series of symmetric polymethine dyes of different electron-donating ability of their terminal heterocyclic groups. We find that a change in the layer thickness leads to a change in the width and position of the spectrum due to a change in the number of absorption bands. The number of bands of monomers increases with increasing chain length and electron-donating ability. The concentration ratio of monomers and associated forms depends on the spatial orientation of molecules in the layer. The electron-donating ability of terminal groups affects the angle between the chromophores of molecules that form a dimer and the intensity ratio between the short- and long-wavelength absorption bands of dimers. We conclude that the effect of the thickness of the layer on its spectral parameters is determined by the degree of intramolecular electron asymmetry that arises as a result of the interaction of chemically symmetric molecules with charges of the substrate surface and upon intermolecular interaction. This asymmetry leads to changes in free energies of ground states of monomeric molecules and, as a consequence, to an increase in equilibrium concentrations of cis-stereoisomeric forms in the layer.     

Optical properties and component composition of layers of cyanine dyes on dielectric supports: influence of asymmetry of the molecular electron density distribution

The component composition of molecular layers of dicarbocyanine dyes of cationic type on glass is determined by the absorption spectroscopy methods. For symmetric and asymmetric molecules the component composition depends on the chemical structure of a molecule and its interaction with the substrate, which are responsible for the electron density distribution in a molecule. The interaction with the substrate depends on the thickness of a layer and the orientation of a layer molecule on the substrate. The increase in the separation between the molecule and the substrate in thicker layers decreases the interaction with the substrate and the asymmetry of a molecule. In symmetric and slightly asymmetric dyes the value of the charge difference on the end groups decreases with increasing layer thickness, whereas in dyes with a large asymmetry, both the value and the sign of the charge difference change. The above results are confirmed by data on the computer simulation of the charge distribution in a dicarbocyanine cation upon its interaction with the oxygen anion on the substrate.     

1-羟基-5-十二烷氧基-萘LB膜结构和取向的光谱研究

用红外透射,反射光谱及紫外可见吸收光谱方法研究了１－羟基－５－十二烷基－萘ＬＢ膜及溶液状态下的结构,分子取向。研究结果表明分子在溶液中主要是以单体形式存在;在ＬＢ膜中是以聚集体形式存在。     

Optical Spectroscopy and the Structure of Polyfunctional Hydrocarbon Compounds and Oil Products

The optical and physicochemical properties associated with the change (oxidation, thermolysis and photolysis), during the operation, of the spatial and electronic structures of the polyfunctional hydrocarbon compounds, oils, oil products, and N-, O-, and S-containing heteroaromatic compounds and additives, which comprise a variety of fuel and lubricant compositions involved in the structural and phase rearrangements, as well as in the formation of colloidal and micelle aggregates altering the structure with respect to their hydrocarbon, chemical, and fractional compositions, are investigated. The spectroscopic-luminescent properties of the compounds and their ion-radical forms were studied using optical and spectroscopic methods and quantum-chemical calculations when the excitation energy in the full spectra of singlet and triplet (for the ion, quartet and doublet) electronic excited states was deactivated. Intramolecular mechanisms of the hyperfine electron–nucleus interaction between the active groups of quasi-oscillators in the structure of polyfunctional compounds in the paramagnetic states of hydrocarbons, which form the electronic structure of the triplet–triplet transitions induced by pumping in the optical absorption spectra, are studied. It is shown that the mechanism of multistep ionization, fragmentation, and appearance of radicals and the electronic-vibrational mechanism of an increase in the vibration temperature up to T = 6000–7000 K are developed during the action of the ultraviolet (UV) pumping pulse of a nanosecond duration until the light emission, which gives rise to thermolysis and recombination that create the conditions for the combustion and explosion when the excitation energy is localized on a limited number of groups of quasi-oscillators in the structure.     

Anomalous aggregation of squaraine dyes in confined solutions

Enhanced aggregation of squaraine (SQ) dyes in solution capillary layers in contrast to the monomer behavior of the bulk solutions has been observed through differences in electronic absorption spectra of the capillary and bulk SQ solutions of the same concentration. The spectra of the capillary solutions were also different from spectra of SQ condensed films. The spectral differences were dependent on both chemical structure of the dye used and the solvent. It was found that aggregation was stronger in dimethylformamide (DMFA) capillary solutions when compared to the chloroform capillary solutions where aggregation was negligible. It is proposed that the driven force of the observed phenomena is enhanced adsorption of SQ molecules and formation of a liquid crystalline state of the solution near the liquid/solid interface.     

Excitation transfer between components of molecular layers of cyanine compounds

Using the example of layers of symmetric polymethine dyes, we have studied the optical excitation energy transfer processes between nanocomponents of a molecular layer. The fluorescence yields and life-times of excited states of monomeric stereoisomers have been estimated, and the stereoisomerization yields have been determined. We show that the excitation transfer yield between the S ₁ states of monomeric stereoisomers (tens of percent) is considerably higher than the fluorescence yield (several percent) and depends on the structure of terminal groups of the molecule.     

Monomerization of photosensitizers by ultrasound irradiation in surfactant micellar solutions

The absorption and fluorescence properties of pheophorbide-a, Sodium salt of pheophorbide-a and its long chain (C₂₀H₃₉) ester (Pheophytine) were investigated in air-saturated micellar aqueous solutions before and after ultrasound irradiation (48 kHz, 10 min). The absorption spectra changed depending on the surfactant; cetyltrimethyl ammonium bromide (CTAB) or sodium dodecyl sulfate concentrations. The formation of different molecular species in various micellar solutions was estimated from the analysis of the absorption spectra. The absorption bands resulted from an aggregated form of the chromophore present in 50 mM phosphate buffer and in pre-micellar solutions. The specific bands of the aggregate disappeared with a simultaneous increase of the bands of monomer in normal micellar solution. The fluorescence spectra, the lifetimes and the fraction of each component (with a characteristic lifetime) of the chromophore in the micellar solutions changed significantly before and after ultrasound irradiation although the changes in absorption spectra were small. The fluorescence emission band at 710 nm due to the aggregate almost disappeared in the pre-micellar solution after ultrasound irradiation. The fraction of the short-lifetime component estimated for the aggregates decreased 55% in H₂O or 85% in 2 mM CTAB, however the long-lifetime components increased after the ultrasound treatment. From these fluorescence properties, it was concluded that the aggregated molecules were converted to a stable monomeric form by ultrasound. Extrapolation of these data to in vivo situations suggests that pretreatment of certain photosensitizers with ultrasound in micellar solutions may lead to increased efficiency of photodynamic therapy since only the monomers are photodynamically active.     

Thermally induced variations in the conformational composition and spatial orientation of molecular components of a dicarbocyanine dye layer

The effect of heating on the spatial orientation and concentration of the components of dicarbocyanine dye layers on a glass substrate is studied experimentally. Layers of two types differing in the spatial orientation angles of all their components (monomeric all-trans and β-mono-cis isomers, dimers, and J aggregates) are considered. It is shown that storing of samples at temperatures of 150–200°C causes partial thermal destruction but does not change the absorption spectra of the molecular components. Heating of the layer of the first type changes neither the orientation nor the relative concentration of the components. Heating of the layer of the second type leads to irreversible changes in the orientation angles of all the molecular components and causes the β-mono-cis isomer and the dimer to transform into the all-trans isomer and the J aggregate. The dependences of the orientation angle on the heating time have the form of saturating functions. The rate of variation of the orientation angle and its limiting value in the saturation region increase with increasing temperature of heating. At high temperatures, the layer of the second type transforms completely into the layer with the first type of spatial orientation. A mechanism of the changes in the angles of the spatial orientation of the layer components, which includes the stages of thermal isomerization and reorientation of each molecular component, as well as rearrangement of its environment, is proposed. Energetic and kinetic parameters of all the stages of layer reconstruction satisfying the experimental results obtained in the region from 150 to 230°C are determined.     

Fluorescence Study on the Structure of Ionic Liquid Aggregates in Aqueous Solutions

Although ionic liquids are a relatively novel class of materials, it is well documented that they form micelles through aggregation of cation aliphatic tails. However, anion self-assembly has not yet been reported. In this study, we analyzed the intrinsic fluorescence of p-toluenesulfonate groups (tosylate) as part of the ionic liquid 1-ethyl-3-methylimidazolium tosylate ([emim][TOS]) and p-toluenesulfonic acid (pTSA), in aqueous solution. pTSA was found to have overlapping monomer and excimer emissions for chromophore concentrations from 10⁻³ to 1 M, whereas [emim][TOS], in the same conditions, showed monomer emission slightly broadened by much weaker excimer emission. These different photophysical behaviors of the same chromophore in the two compounds are explained by the formation of ion pairs by [emim][TOS], which can also be inferred from the loss of vibrational structure of the absorption spectra with respect to pTSA. Despite this different behavior regarding ion pairing, anion aggregation was observed in the excitation spectra of both pTSA and [emim][TOS]. While the absorption spectra corresponded to single chromophores, the excitation spectra changed from those characteristic of a single chromophore (below 10⁻³ M) to red-shifted narrow bands (above 0.1 M) typical of J aggregates. Between those concentrations, the excitation spectra split into blue- and red-shifted bands with relative intensities that changed with concentration as the chromophores rearranged in their clusters from head-to-head to head-to-tail aggregates. Differences between the absorption and excitation spectra were ascribed to aggregation-induced fluorescence enhancement.     

Mutual modification of silver-nanoparticle plasmon resonances and the absorptive properties of polymethine-dye molecular layers on a sapphire surface

Extinction spectra of a hybrid material comprised of molecular layers of polymethine dyes and granulated silver films preliminarily deposited onto sapphire substrates are studied experimentally. Specific features of the dye layer composition and broadening of plasmon absorption bands are discussed. In hybrid samples, both an increase and a decrease in the silver-nanoparticle plasmon resonance frequency upon spreading of dyes have been observed, as well as a considerable increase in the dye molecule absorption. Possible mechanisms of the phenomena are discussed.     

黄腐酸对菁染料超分子组装及手性调控研究

利用菁染料超分子作为分子探针对黄腐酸进行标记,检测黄腐酸和药效机制,对于生命科学和药物化学领域的发展具有重要意义。采用紫外-可见吸收光谱和圆二色谱研究黄腐酸作为模板对不同结构菁染料超分子的组装及手性调控。结果表明：黄腐酸能诱导三种菁染料J-聚集体解聚为单体并伴有体系表观颜色的变化,并与菁染料单体之间具有很高亲和力。黄腐酸作为模板不仅可以诱导MTC形成具有一定手性的H-聚集体,而且能使MTC的H-聚集体的手性出现两次反转;还可以诱导ETC的J-聚集体发生分子间的重排,最终形成具有左手螺旋性的J-聚集体。除此之外,黄腐酸还对PTC的J-聚集体圆二色谱信号有显著的影响。同时,菁染料中位取代基影响到相互作用的能力：中位取代基越小,菁染料聚集体与黄腐酸的作用越强。菁染料与黄腐酸的结合能力大小为MTC>ETC>PTC。菁染料超分子可作为一类优良的分子探针对黄腐酸进行特异性识别并可达到可视化的检测效果。     

Effect of different donors and a polymer environment on photophysical and energy transfer studies using C540 as the acceptor

The dyes (C450, C480 and C540) and their dye mixtures (C450:C540 and C480:C540) were doped in polymer matrices (solid). Their photophysical studies were recorded. These results were analysed by comparing them with the data of the dyes and the dye mixtures in monomer compositions (liquid). The absorption and fluorescence spectral profiles of the dyes in the polymer matrix were found to be identical to those in the monomer compositions. The effect of different donors on the energy transfer technique using C540 as acceptor, in polymer matrix and monomer compositions, was studied in detail. The results obtained for the energy transfer technique in two binary dye mixtures containing different donors but same acceptor, in solid and liquid media, were intercompared. The gain of the acceptor without donor and with different donors was determined experimentally. The gain coefficient in the polymer matrix (solid) was less than that in the monomer medium (liquid). Also, the gain of the acceptor C540 was found to be more when C450 was used as the donor compared to that when C480 was used as the donor. Using nitrogen laser, the photobleaching effect in the two binary dye-doped polymer rods (with different donors but same acceptor) was studied. It was observed that photobleaching of the acceptor C540 in the presence of C450 as donor is slower than that in the presence of C480 as donor.     

Structure and Orientation of 1-Hydroxyl-5-Hexadecyloxy-Naphthalene LB Films Studied By UV-VIS and FTIR Spectroscopy

Ultraviolet-visible (UV-Vis), infrared transmission, and reflection absorption(RA) spectra have been measured for one-and multi-monolayer Langmuir-Blodgett(LB) films of C₁₆H₃₃30Naph(1,5)OH at various temperature to investigate dependencies of the aggregation and phase transitions on the number of monolayers. The UV-vis spectra of the LB films have revealed that the C₁₆H₃₃ONaph(1,5)OH forms aggregates in the LB film. From the temperature dependence of UV-vis absorption spectra, it is clear that the aggregate is gradual converted to monomer upto 80 °C. A comparison of the infrared transmission and RA spectra reveals that the hydrocarbon chains are tilted considerably in the LB film. As for the naphthalene ring part, the result suggest that the ring plane is oriented approximately perpendicular to the substrate surface. The Temperature dependence of infrared transmission spectra have been measured for 1-, 3-, and 11-monolayer LB films to investigate dependence of phase transitions on the number of monolayers. These observations show that the one-monolayer LB films does not have a clear order-disorder transition, while the three-and eleven-monolayer films have a phase transition near 60 °C. Therefore, it seems that the title angles of both the alkyl chain and chromophore part change largely concomitantly with the conversion from the aggregate to the monolayer.     

The effect of an electrostatic field on the photoluminescence and photoconductivity of polymer films doped by cationic polymethine dyes with end groups with different electron-donating properties

The effect of an external electrostatic field on the photoluminescence spectra and photoconductivity of symmetric and asymmetric cationic polymethine dyes with end groups possessing different electron-donating properties (basicity) in polymer films based on photoconductive poly-N-epoxypropylcarbazole and nonphotoconductive polyvinylethylal is studied. It is found that application of an electric field to films can both decrease and increase their luminescence intensity. The strongest decrease in the luminescence intensity is observed for symmetric dyes in poly-N-epoxypropylcarbazole films with either a decrease in the electron-donating ability of the end groups or with a decrease in the length of the polymethine chain. Colored polyvinylethylal films exhibit both a negative and a positive effect of the field on the photoluminescence intensity. The character of changes in the luminescence spectra does not depend on the electron-donating ability of the end groups. The spectral effects are explained by a change in the probability of vibronic transitions due to the redistribution of the electron density in the chromophore of the dye in the ground and excited states in an external electric field.     

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.     

Raman spectroscopic investigations on intermolecular interactions in aggregates and crystalline forms of trans‐astaxanthin

Astaxanthin is a carotenoid naturally found in microbial organisms, microalgae, and many crustaceans. Its consumption has led to beneficial effects such as pigmentation of marine animals, and it favorably addresses several human health issues as a result of its high important antioxidant property. Several companies produce synthetic trans‐astaxanthin for dietary purposes in aquaculture, where it is mainly used for pigmentation. It is known that trans‐astaxanthin manifests itself as a monomer in organic solvents, as aggregates in aqueous solutions of organic solvents, or as crystalline solids. These forms display unique optical and structural properties, which have an impact on biological systems. In this work, we report on detailed Raman investigations, in conjunction with optical absorption spectroscopy, of monomer, aggregates, and crystalline forms of trans‐astaxanthin. The Raman and optical absorption spectroscopic investigations of trans‐astaxanthin aggregates were performed as a function of time, showing the formation of card‐packed aggregates after 2 h, and head‐to‐tail aggregates after 24 h in a 10% acetone–water astaxanthin solution. For the crystalline trans‐astaxanthin, a pointwise Raman mapping evidenced the presence of two distinct crystal structures. The Raman modes of these crystal structures (A and B) were correlated with the intermolecular interactions present in chloroform solvated (AXT‐Cl) and unsolvated (un‐AXT) trans‐astaxanthin single crystals. Both crystal structure A and the card‐packed aggregates have similar intermolecular π stacking interactions as AXT‐Cl. The crystal structure B and the head‐to‐tail aggregates showed linear chain features as in un‐AXT. This work also clearly demonstrates that Raman spectroscopy is a powerful tool to distinguish the crystal structures present in crystalline powder of trans‐astaxanthin. Copyright © 2012 John Wiley & Sons, Ltd.     

Spectral properties of naphthalimide dyes mixed with 4-heptyl-4′-cyanobiphenyl (7CB) in Langmuir-Blodgett films

Langmuir-Blodgett (LB) films formed of some fluorescent dyes, namely derivatives of 4-aminonaphthalimide, and their binary mixtures with the liquid crystal 4-heptyl-4′-cyanobiphenyl (7CB) have been studied. The electronic absorption and fluorescence spectra were recorded. On the basis of these spectra, the spectral properties of the dyes and the intermolecular interactions in ultrathin ordered films were determined. The conclusions about the tendency to the creation of aggregates by dye molecules in LB films have been drawn. The measurements of absorption by using linearly polarised light have allowed us to determine the arrangement of the dye and liquid crystal molecules on the air-solid substrate interface.     

LB薄膜中四新戊氧基酞菁锌和四壬基酞菁铜分子聚集体的吸收光谱的温度特性

本文制备了四新戊氧基酞菁锌(Tetra-neopentoxy phthalocyanine zine)(TNPPeZn)和四壬基酞菁铜(Tetra-nonyl phthalocyanine copper)(TNPeCu)两种酞菁衍生物的Langmuir-Blodgett(LB)薄膜.通过测量10～473K温度下的吸收光谱,研究了两种薄膜的分子聚集状态.TNPPeZn的LB薄膜中,存在着分子单体和分子二聚体,在吸收光谱中分别表现为680nm和620nm的吸收峰.随着温度的升高,分子单体逐渐转变为分子二聚体,这个过程是不可逆的.TNPeCu的LB薄膜中,除了分子单体和分子二聚体以外,还有吸收为740nm的分子J聚集体存在.随着温度的变化,J聚集体发生可逆变化.     

Extinction Spectra of Bilayer Organometallic Nanoplatelets

Spectra of light extinction by metal nanoprisms and nanostars coated with molecular aggregates of organic dyes are calculated and theoretically analyzed. Qualitatively different nature of the spectra of organometallic nanoparticles under study is established when using J-aggregates of various cyanine dyes as their capping layer, as well as silver and gold as the cores. This results from the implementation of various plasmon-exciton coupling modes in the systems under consideration.