Location of Solubilization of 2′-ethylhexyl Salicylate in Micelles

Absorption and excited state intramolecular proton transfer (ESIPT) fluorescence of 2′-ethylhexyl salicylate (EHS) were examined in the presence of cationic, non-ionic, and anionic surfactants. It was found that linear EHS molecule was solubilized in micelles with its flexible and hydrophobic 2′-ethylhexyl chain toward the micellar core and with its rigid salicyl moiety toward the micelle-water interface. The UV absorption of EHS was improved and the intramolecular hydrogen bonding formation of EHS was favored, resulting in greatly enhanced ESIPT fluorescence. The excited EHS molecules decay via visible luminescence and non-radiative deactivation. The binding sites of EHS in micelles were explained at a molecular level in terms of molecular structures and sizes of EHS and surfactants. Dynamic fluorescence quenching and spectral measurements of ester hydrolysis of EHS provide further evidences for the binding sites of EHS in different micelles.     

水杨酸-2’-乙基己基酯在胶束中的增溶位点

考察了阳离子、非离子和阴离子表面活性剂存在下水杨酸-2’-乙基己基酯(EHS)的吸收光谱和激发态分子内质子转移(ESIPT)荧光光谱. 结果表明, EHS可增溶在胶束中, 2’-乙基己基碳链朝向胶束内核, 而水杨酸基朝向胶束-水界面; 胶束环境有利于EHS分子对紫外光的吸收和分子内氢键的形成, 从而使ESIPT 荧光显著增强, 激发态分子以发射可见光和非辐射去活化方式衰减; 并根据EHS和表面活性剂分子的结构和大小, 解释了EHS分子在胶束中的结合位点, 荧光猝灭和酯水解的光谱测量进一步为此结合位点提供了佐证.     

Studies of bio-mimetic medium of ionic and non-ionic micelles by a simple charge transfer fluorescence probe N,N-dimethylaminonapthyl-(acrylo)-nitrile

In this report we have studied micellization process of anionic, cationic and non-ionic surfactants using N,N-dimethylaminonapthyl-(acrylo)-nitrile (DMANAN) as an external fluorescence probe. Micropolarity, microviscosity, critical micellar concentration of these micelles based on steady state absorption and fluorescence and time resolved emission spectroscopy of the probe DMANAN show that the molecule resides in the micelle-water interface for ionic micelles and in the core for the non-ionic micelle. The effect of variation of pH of the micellar solution as well as fluorescence quenching measurements of DMANAN provide further support for the location of the probe in the micelles.     

Dye–Surfactant Interaction: Modulation of Photophysics of an Ionic Styryl Dye

The interesting modulation of multibond rotation–induced intramolecular charge transfer photophysics of 2-(4-(dimethylamino) styryl)-1-methylpyridinium iodide in different micelles due to different contributions of twisted intramolecular charge transfer (TICT) and hydrogen bonding deactivation channels have been reported in this paper. 2-(4-(dimethylamino) styryl)-1-methylpyridinium iodide enters into all the micelles in different positions from the water solution due to active hydrophobic force and electrostatic field, as revealed from the shift and intensity of intramolecular charge transfer (ICT) band. The presence of mechanically trapped water with the addition of salt and inherent thermodynamic water controls the ICT emission. Analysis of spectral data before and after the addition of salt confirms the orientation of 2-(4-(dimethylamino) styryl)-1-methylpyridinium iodide in cationic and anionic micelles.     

水杨酸-2′-乙基己基酯在胶束中的增溶位点

考察了阳离子、非离子和阴离子表面活性剂存在下水杨酸-2′-乙基己基酯(EHS)的吸收光谱和激发态分子内质子转移(ESIPT)荧光光谱.结果表明,EHS可增溶在胶束中,2′-乙基己基碳链朝向胶束内核,而水杨酸基朝向胶束-水界面;胶柬环境有利于EHS分子对紫外光的吸收和分子内氢键的形成,从而使ESIPT荧光显著增强,激发态分子以发射可见光和非辐射去活化方式衰减;并根据EHS和表面活性剂分子的结构和大小,解释了EHS分子在胶束中的结合位点,荧光猝灭和酯水解的光谱测量进一步为此结合位点提供了佐证.     

Effects of protonation on the thermodynamic properties of alkyl dimethylamine oxides

The effects of protonation on alkyldimethyl amine oxide micelles are reviewed, mainly with regard to dodecyl and tetradecyl homologs. The topics discussed are hydrogen ion titration properties, critical micelle concentration (CMC), area per surfactant and micelle aggregation number. A hydrogen bond hypothesis is proposed to interpret the several characteristic results associated with protonation: between two cationic species as well as between the non-ionic-cationic pair. The dipole-dipole interaction of the non-ionic micelle is discussed in relation to both: (a) the unusually high CMC values of the non-ionic micelles compared with other non-ionic surfactants with the same hydrocarbon chain; and (b) the reversal of the stability of the non-ionic and the cationic micelles at high ionic strengths. Two different approaches of the salting out effect on the ionic micelles are compared, the Chan-Mukerjee approach and ours, in relation to the non-linear Corrin-Harkins relation. The obtained salting out constants of the surfactants carrying a dodecyl chain decreased as the head group becomes more polar. Infrared and 13C-NMR spectra data are examined from the point of the specific interaction claimed by the hydrogen bond model. Mixed surfactant systems including amine oxides and the solid state phase behavior of amine oxides are both briefly reviewed.     

On the investigation of the bilayer functionalities of 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine (DOPC) large unilamellar vesicles using cationic hemicyanines as optical probes: a wavelength-selective fluorescence approach

The behavior of the cationic hemicyanines trans-4-[4-(dimethylamino)-styryl]-1-methylpyridinium iodide (HC) and 4,(4-(dihexadecylamino)styryl-N-methyl-pyridinium iodide (DIA) were studied in large unilamellar vesicles (LUV) of 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine (DOPC) using absorption, emission, depolarization and time resolved spectroscopies. Also, thorough spectroscopic studies were performed in homogeneous media to investigate the different interactions that the dyes can experience with its microenvironment. These results help us to comprehend the dye performance under different media and, consequently find interesting features of the DOPC membrane properties. The studies in homogeneous media analyzed by the Kamlet and Taft's solvatochromic comparison method demonstrate, for the first time, that the cationic hemycianines undergo specific interactions with the medium through the solvents ability to donate an electron pair as measured by the beta parameter. Thus, the absorption bands shifts bathochromically with beta while, the emission band shifts hypsochromically. In addition, for the relaxed hemicyanines the 00 energy, nu00, is invariant with the solvent properties. The results in LUV of DOPC show that, DIA undergoes a strong association with the vesicle bilayer while HC partitions between the water and the bilayer pseudophases. To monitor directly the microenvironment and dynamics around HC and DIA inside the DOPC bilayer, we use the wavelength-selective fluorescence approach, which is based on the red edge effect in fluorescence spectroscopy, in addition with the nu00 energy of the hemicyanines. The results show that the fluid state of the DOPC bilayer resembles the microenvironment of sodium bis (2-ethylhexyl) sulfosuccinate (AOT) reverse micelles at W=[H2O]/[AOT] below 10 where there is no free water forming the water pool. Moreover, it is demonstrated for the first time, that the region of the bilayer close to the polar head of DOPC is a powerful electron donor environment.     

Effect of micelles on the spectral characteristics of the prototropic species of 2-(2'-aminophenyl)benzimidazole

The absorption and fluorescence spectra of 2-(2'-aminophenyl)benzimidazole (2-APBI) have been studied in anionic (sodium dodecylsulphate, SDS), cationic (cetyltrimethylammonium bromide, CTAB) and non-ionic micelles (Tween-80, TritonX-100) at different acid-base concentrations. Spectral characteristics of 2-APBI at various acid concentrations have established only one kind of monocation (MC) in Tween-80 and TritonX-100 (TX-100), whereas two kinds of MCs are present in SDS. Above study has further shown that there is a strong hydrogen bonding interaction between the polar polyoxyethylene groups of non-ionic micelles and the MCs of 2-APBI. This interaction is responsible for the stabilization of the MC III to MC III' which is more planar than either MC II or MC III, which is otherwise less stable in water. This is substantiated by the lifetime data, fluorescence excitation spectra and the pKa values of the monocation-neutral (MC-N) equilibrium.     

Non-ionic and cationic micelle nanostructures as drug solubilization vehicles: spectrofluorimetric and electrochemical studies

The use of colloidal organized media, such as micelles, to solubilize tetracaine hydrochloride (TC.HCl), a local anaesthetic drug, in aqueous solution has been studied by means of fluorescence spectroscopy at 298.15 K. Because tetracaine molecule is a fluorescent probe, changes in the fluorescence emission spectra of the drug when it is solubilized by the micelles enable the study of the micelles–drug association process through the calculation of the association constants. Two kinds of micelles have been selected to solubilize the drug: non-ionic micelles and cationic micelles. Complementary conductometric experiments were also done to determine the critical aggregation concentration of the surfactants in the presence of the drug. The micelle–drug association process has been also analyzed by deconvoluting the fluorescent of the drug into several Gaussian components, each of which assigned to the solubilization of the drug within different microenvironment inside and outside the cationic and/or non-ionic micelles.     

Fluorescence behavior of intramolecular charge transfer probe in anionic, cationic, and nonionic micelles

The intramolecular charge transfer (ICT) property of trans-ethyl p-(dimethylamino) cinnamate is used to probe the anionic, cationic, and nonionic micelles by steady-state and picosecond time-resolved fluorescence spectroscopy. The ICT fluorescence band intensity was found to increase with concomitant blue shift with addition of surfactants. All the experimental results suggest that the probe molecule resides in the micelle-water interface rather than going into the core. However, the penetration is more toward the micellar core in nonionic surfactants when compared with ionic micelles. The decrease in nonradiative decay constants in micellar environments indicate restricted motion of the probe toward the formation of ICT state. Critical micelle concentrations were determined from the sharp change in fluorescence intensity and effective dielectric constants of the micelle-water interface were calculated from the correlation diagram of 0,0 transition energy with polarity of the medium.     

Solubilization of 5-methoxy tryptamine molecular probes in CTAB and SDS micelles: a cmc and binding constant study

To understand the change in environmental conditions when a probe is incorporated in micelles, an absorption and fluorescence spectral study on the solubilization behaviour of 5-methoxy tryptamine (5-MT) and N,N-dimethyl-5-methoxy tryptamine (5-NMT) has been made in CTAB and SDS for their neutral and cationic forms. The blue shift in emission wavelength is accompanied by increase in intensity with increasing surfactant concentration for almost all the cases except for the cationic probe in CTAB surfactant. This exceptional behaviour can be attributed to the quenching of emission intensity caused by Br(-) ions. Spectral correlations with solvent polarity parameters indicate relatively less polar binding sites in CTAB and SDS as compared to water. The binding constant and cmc values have been determined for CTAB and SDS using both the neutral and the cationic probes, which are in good agreement with the literature values. Higher value of binding constant and lower polarity of the binding sites justify 5-NMT as a better binding probe as the two methyl groups make the molecule more hydrophobic and drag it to the interior of both the micelles.     

Dipolar relaxation within the protein matrix of the green fluorescent protein: a red edge excitation shift study

The fluorophore in green fluorescent protein (GFP) is localized in a highly constrained environment, protected from the bulk solvent by the barrel-shaped protein matrix. We have used the wavelength-selective fluorescence approach (red edge excitation shift, REES) to monitor solvent (environment) dynamics around the fluorophore in enhanced green fluorescent protein (EGFP) under various conditions. Our results show that EGFP displays REES in buffer and glycerol, i.e., the fluorescence emission maxima exhibit a progressive shift toward the red edge, as the excitation wavelength is shifted toward the red edge of the absorption spectrum. Interestingly, EGFP displays REES when incorporated in reverse micelles of sodium bis(2-ethylhexyl)sulfosuccinate (AOT), independent of the hydration state. We interpret the observed REES to the constrained environment experienced by the EGFP fluorophore in the rigid protein matrix, rather than to the dynamics of the bulk solvent. These results are supported by the temperature dependence of REES and characteristic wavelength-dependent changes in fluorescence anisotropy.     

Theoretical study of non-radiative deactivation pathways for some heterocyclic compounds. I. Pyrrolyl-izoxazole derivatives

We perform an experimental and theoretical study on some pyrrolyl-izoxazole derivatives with single bridged donor (D) and acceptor (A) moieties, potentially Twisted Intramolecular Charge Transfer (TICT) state forming compounds. The emission spectra in solvent of different polarities and at different excitation wavelengths were performed. The fluorescence quantum yield is very low and the emission band shifts towards long wavelengths in polar solvents and on increasing the excitation wavelength. Solvent dependent semiempirical calculations were performed. The ground and excited states potential energy surfaces were built in terms of the torsion angle about the single bond joining D and A. The ground states have quasiplanar geometry, but the minimum of the excited states corresponds to the orthogonal conformation, stabilised in methanol due to the large charge separation between the D and A fragments. The possibility of forming TICT excited states for the studied pyrrolyl derivatives is discussed.     

火菇素酪氨酸微区的研究

用紫外差光谱和荧光光谱技术对火菇素的酪氨酸微区进行了研究,结果表明火菇素表现典型的酪氨酸残基紫外275nm吸收峰,ε~m~a~x=20322L·mol^-^1·cm^-^1,紫外差光谱滴定发现,当10.1相似文献   

新型近红外试剂的合成及其现场二聚体与DNA作用的研究

合成了一种新型近红外阴离子染料,并对其水溶液及阳离子表面活性剂ＣＴＡＢ存在下的吸收荧光光谱进行了研究。结果表明,低浓度的ＣＴＡＢ与该近红外阴离子染料形成离子缔合物而使阴离子染料的荧光强度降低,当ＣＴＡＢ的浓度进一步加大时,其胶束前预聚集促使该染料形成非荧光二聚体,导致荧光急剧猝灭。     

利用荧光探针溶致变色效应研究有机改性蒙脱土的层间环境性质

利用荧光探针的溶致变色行为,研究了以不同阳离子表面活性剂处理过的化学修饰蒙脱土内腔的极性.清楚地观察到随所用表面活性剂长链碳原子数目的增多,荧光探针N,N-二甲氨基查尔酮在蒙脱土内的荧光光谱峰值波长移向短波,表明蒙脱土内腔的极性随活性剂疏水链长的增长而不断减小.本工作所得结果将对具体的插层材料(包括不同极性的聚合单体或聚合物分子)在插层时选择合适的表面处理剂有所帮助.     

Comparative study of the photophysical behavior of fisetin in homogeneous media and in anionic and cationic reverse micelles media

The 3,3', 4',7 tetrahydroxiflavone (fisetin) is a natural therapeutically active and fluorescent polyhydroxyflavone, with important spectroscopic and biological behavior. Fisetin shows dual emission, with a normal band (N) from the S1 --> S0 transition and the one generated in the excited state (phototautomer; PT) from the intramolecular proton transfer (ESIPT) process. The influence of different interfaces on the ESIPT process of fisetin was investigated in reverse micelles media (RMs) made of the anionic sodium 1,4-bis (2-ethylhexyl) sulfosuccinate (AOT) and cationic benzyl n-hexadecyl dimethylammonium chloride (BHDC) surfactants, in benzene. The studies were carried out by absorption, emission spectroscopy, steady-state anisotropy and time-resolved fluorescence measurements. Fisetin behavior was also investigated in homogeneous media with special emphasis in water and benzene, which are the polar core and the organic pseudofase in the RMs, respectively. In addition, the effect of concentration in benzene and the variation of the pH in water were studied. Fluorescence lifetime measurements show that in water the ESIPT process is independent on the concentration, while in benzene it was possible to detect fluorescent aggregate species (Nas) formed in the ground state. The effect of the pH in water allowed us to identify the anionic fisetin (A-) emission. The studies in RMs show that fisetin interacts specifically with the head of the surfactants, which always results in diminishing the emission of the PT. Also the formation of A- is detected particularly at W0 > 0. Appreciable high anisotropy values are obtained in RMs, as compared with those in fluid homogeneous media, which are independent of the water content confirming that fisetin molecules are anchored in the anionic as well as in the cationic interfaces.     

ESIPT inspired fluorescent 2-(4-benzo[d]oxazol-2-yl)naphtho[1,2-d]oxazol-2-yl)phenol: experimental and DFT based approach to photophysical properties

ESIPT inspired fluorescent 2-(4-benzo[d]oxazol-2-yl)naphtho[1,2-d]oxazol-2-yl)phenol was synthesized from 1-amino-3-(1,3-benzoxazol-2-yl)naphthalen-2-ol. Photophysical behavior of the synthesized compound was studied using UV–visible and fluorescence spectroscopy in polar and non-polar solvents. The synthesized naphthoxazolyl benzoxazole is fluorescent and very sensitive to the micro-environment. It shows a single absorption and dual emission in non-polar solvents with large Stokes shift originating from Excited State Intramolecular Proton Transfer while in polar solvents only a single short wavelength emission is observed. Experimental absorption and emission wavelengths are in good agreement with those predicted using the Time-Dependent Density Functional Theory (TD-DFT) [B3LYP/6-31G(d)]. The largest wavelength difference between the experimental and computed absorption maxima was 16 nm (acetonitrile) and 7 nm (ethyl acetate, THF, and 1,4-dioxane) in the short and long wavelength regions, respectively. A largest difference of 25 nm was observed for the short wavelength emission in DMF and 22 nm for the longer wavelength emission in chloroform.     

Influence of micellar media on the fluorescence of various benzo- and methyl-quinolizinium salts

The bebaviour of several different micelar systems (anionic, cationic and non-ionic) on the fluorescence of quinolizinium salts is studied. Important factors, such as pH and ionic strength that influence fluorescence parameters, are discussed. Fourteen quinolizinium salts (benzo and methyl derivatives) are examined as fluorescent probes in micellar media. All of them showed a marked increase of fluorescence intensity when sodium dodecyl sulfate solutions of critical micelle concentration (CMC) are added. The presence of non-ionic surfactants did not change the fluorescent emission of the probes. The emission intensity is much decreased when N-cetyl-N,N,N- trimethylammonium bromide concentrations are above the CMC. Changes in pH ido not significantly affect the fluorescence intensity of the benzo derivatives. Increasing the ionic strength decreases the fluorescence. For 9-cyanobenzo[a]phenanthro [9,10-g] quinolizinium chloride, the spectrum changes when the surfactant concentration is high than the CMC thereforre this compound is considered to be a good fluorescent probe in icell     

Dye-surfactant interactions: a review

The present state of knowledge of the mechanisms of dye-surfactant interactions for "normal" aqueous micelles is surveyed. The nature of the forces which lead to the binding of dye molecules in micelles, the influence of the cationic, anionic or non-ionic character of a surfactant on the absorption and/or fluorescence behaviour (below and above the critical micelle concentration), ion-association processes and the influence of additives on these processes are discussed. Some discussion along these lines on related systems (reverse micelles, vesicles, polyelectrolytes) is included.