Direct observation of time and temperature dependent transition from spherical micelles to vesicles

An interesting transition from spherical micelles to vesicles, which was time and temperature dependent, was observed for the first time; it is tentatively attributed to the thermal hysteresis of temperature-responsive poly(N-isopropylacrylamide).     

Effect of temperature on the photoalignment of azo dyes in thin films

The temperature dependences of the induced dichroic ratios (DRs) of azo dyes after their photoalignment in thin films 80 to 200 nm thick are studied. It is found that the DR values of layers containing dyes of the benzeneazodiphenyl series fall from 6.0 to 1.6 as the temperature rises from 60 to 130°C, respectively. A reduction in induced DR as the temperature rises (from 20 to 100°C) is also observed for the thin films of the dyes of benzeneazo-5,5’-dioxodibenzothiophene group. The absence of induced DR after irradiation with polarized light at 100°C indicates there is no alignment of molecules at this temperature.     

Microenvironment in the corona region of triblock copolymer micelles: temperature dependent solvation and rotational relaxation dynamics of coumarin dyes

Dynamic Stokes' shift and fluorescence anisotropy measurements using coumarin-153 (C153) and coumarin-151 (C151) as the fluorescence probes have been carried out in aqueous poly(ethylene oxide)20-poly(propylene oxide)70-poly(ethylene oxide)20 (P123) and poly(ethylene oxide)100-poly(propylene oxide)70-poly(ethylene oxide)100 (F127) block copolymer micelles with an aim to understand the water structures and dynamics in the micellar corona region. It has been established that the probes reside in the micellar corona region. It is indicated that the corona regions of P123 and F127 micelles are relatively less hydrated than the Palisade layers of neutral micelles like Triton-X-100 and Brij-35. From the appraisal of total Stokes' shift values for the probes in the two block copolymer micelles, it is inferred that the F127 micelle is more hydrated than the P123 micelle. It is observed that the dynamic Stokes' shift values for both of the probes remain more or less similar at all the temperatures studied in the P123 micelle. For C153 in F127, however, the observed Stokes' shift is seen to decrease quite sharply with temperature, though it remains quite similar for C151. Moreover, the fraction of the unobserved initial dynamic Stokes' shift is appreciably higher for both the probes in the F127 micelle compared to that in P123. Over the studied temperature range of 293-313 K, the spectral shift correlation function is described adequately by a bi-exponential function. Rotational relaxation times for C153 in both the micelles show a kind of transition at around 303 K. These results have been rationalized assuming collapse of the poly(ethylene oxide) (PEO) blocks and formation of water clusters in the corona region due to dehydration of poly(ethylene oxide) blocks with an increase in temperature. A dissimilar probe location has been inferred for the differences in the results with C153 and C151 probes in F127. Comparison of the microviscosity and the hydration of the block copolymer micelles has also been made with those of the other commonly used neutral micelles, for a better understanding of the results in the block copolymer micelles.     

Studies on the voltammetric behavior of azo dyes and its determination in cosmetic products1

The voltammetric behaviors of azo dyes on glassy carbon electrode were investigated in an aqueous containing various supporting electrolyte. The possible reaction mechanisms were discussed by the relations of scan rate and peak potentials and currents. The electroreduction process is applied for the quantitative determination of Lithol Rubine B azo dyes cosmetic products. Comparison with results obtained from high performance liquid chromatography shows good agreement.     

Solvatochromism effects on the dipole moments and photo-physical behavior of some azo sulfonamide dyes

Absorption and emission spectra of three azo sulfonamide dyes with various molecular structures have been studied in different solvents. The solute photo-physical behavior depends strongly on the solvent-solute interactions and solvent microenvironment. In order to understand the effect of intermolecular interactions on spectral behaviors of these dyes in different solvents and to conceive nature and extent of solvent-solute interactions the spectral variations were analyzed by the linear solvation energy relationships concept. In addition, by means of solvatochromic method the dipole moments of these dyes, in ground and excited states, were investigated.     

Complex formation of amphiphilic polymers with azo dyes and their photoviscosity behavior

The hydrophobic interaction of amphiphilic copolymers, which contain 2-hydroxyethyl methacrylate(HEMA) and 1vinyl-2-pyrrolidone (VPy), with Methyl Orange (MO) was compared with that of HEMA-acrylamide (AAm) copolymers to deduce the correlation between their complexation ability in a photochromic azo dye and the photoviscosity effect in aqueous copolymer/dye complex solution. On the basis of the dialysis data and fluorometric analysis it appeared that the complexation dependence on HEMA content in the copolymers was due to the hydrophobic interaction between the polymer and the dye. For a comparable HEMA content AAm copolymers bound less MO than VPy copolymers. It was confiied by photoviscosity measurements that the conformation of the complex composed of photochromic azo dye and HEMA copolymer changed reversibly in response to the photo- and thermal isomerization of the dye. In HEMA-AAm copolymer systems the photoviscosity effect was small compared with that of HEMA-VPy copolymer systems. From these results it was concluded that the complexation ability of polymers due to the hydrophobic interaction was an important factor in producing a large photoinduced conformational change in water.     

镍铁类水滑石对偶氮阴离子染料的吸附脱色作用

采用镍铁类水滑石作为吸附剂,对偶氮阴离子染料酸性大红G、活性艳红X-3B和直接耐酸大红4BS废水进行脱色处理,研究了时间、镍与铁的物质的量之比、初始pH和无机电解质添加剂等因素对脱色率的影响,并结合红外光谱和X射线衍射分析结果讨论了其吸附脱色机理.结果表明,三种染料在镍铁类水滑石上的吸附均为层间的阴离子交换吸附和外表面的吸附.通过阴离子交换进入层间后,不同于直接耐酸大红4BS阴离子,酸性大红G和活性艳红X-3B两种阴离子与水滑石层间水分子之间产生氢键作用;在化学键合过程中,染料分子被镍铁类水滑石表面Fe3+氧化,同时偶氮键断裂导致脱色.     

Synthesis and two-photon absorption property of novel salen complexes incorporated with two pendant azo dyes

New salen compounds have been developed to possess two pendant azo dye chromophores. The two-photon absorption properties have been observed which result from the chromophores. The additive property has been found to exist as a result of no detrimental dipole-dipole interaction between chromophores.     

基于QSAR对偶氮染料光响应性及降解路径研究

采用密度泛函理论方法计算偶氮染料类化合物的量子化学参数,研究该类化合物结构与光响应活性的定量构效关系(QSAR),应用多元回归方法建立的方程具有显著统计学意义,并结合紫外光谱结果进行降解过程预测.结果表明:光催化体系中会最先造成偶氮染料的N=N键与萘环的断开,然后再生成其他副产物,副产物再经过电子转移、开环等一系列反应...     

Effect of TiO2 colloids on the fluorescence behavior of two cyanine dyes

The photophysical properties of two typical cyanine dyes [3,3'-diethyl-9-methyl-thiacarbocyanine iodide (dye A) and anhydro-3,3'-disulfopropyl-5,5'-diphenyl-9-ethyloxacarbocyanine hydroxide (dye B)] in the absence and presence of TiO(2) colloids have been investigated by UV-visible spectroscopy, (1)H-NMR spectroscopy, fluorescence spectroscopy, fluorescence lifetime measurements, and ESR measurements. It was found from the absorption spectra and NMR results that there are two isomers in the ground state of these dyes. Steady-state fluorescence spectra show that the fluorescence intensities of dye A and dye B are enhanced and quenched by TiO(2) colloids, respectively. Time-resolved fluorescence lifetime measurements indicate that the lifetimes of dye A and dye B in the presence of TiO(2) colloids are longer and shorter than those obtained in the absence of TiO(2) colloids, respectively. ESR measurements demonstrate that the electron transfer efficiency from (1)dye B* to the conduction band of TiO(2) is much larger than that from (1)dye A* to the conduction band of TiO(2). The different fluorescence behavior of dye A and dye B can be intepreted in terms of whether phi(Tr,nr)(0)-phi(Tr,nr) (the reduction of the quantum yield for radiationless transition in the excited singlet state (1)dye* caused by the TiO(2) colloids) is larger or smaller than phi(ET) (the quantum yield of electron transfer from (1)dye* to the conduction band of TiO(2) colloids).     

Dielectric behavior of lipid vesicles: the case of L-alpha-dipalmitoylphosphatidylcholine vesicles as a function of size and temperature

We present an extensive set of radio wave dielectric relaxation spectroscopy measurements of aqueous suspensions of different size unilamellar L-alpha-dipalmitoylphosphatidylcholine (DPPC) vesicles, in a temperature range between 15 and 55 C, where the lipidic bilayer experiences structural transitions from the gel to the rippled phase (at the pretransition temperature) and from the rippled to the liquid phase (at the main transition temperature). The dielectric spectra have been analyzed in the light of the Cole-Cole relaxation function, and the main dielectric parameters-the dielectric increment Deltaepsilon and the mean relaxation frequency omega(0)--have been evaluated as a function of temperature. These parameters display a very complex phenomenology, depending on the structural arrangement of the lipid-water interface. The structural parameters that govern the dielectric behavior of these systems associated with the lipid bilayer have been recognized within a recent dynamic mean-field model we have proposed, aimed to predict the dipolar relaxation of an array of strongly interacting dipoles anchored to a flat or corrugated surface. They are the prefactor A(T) of the distance-dependent part of the effective dipolar interaction energy, the term Gamma(vis), that takes into account the damping of the dipolar motion, the average dipolar distance related to the area a(0) per polar head, and the bilayer thickness. The present analysis furnishes, from a phenomenological point of view, the dependence of these parameters on the temperature and on the vesicle size.     

Sustainable approach on the biodegradation of azo dyes: A short review

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Effect of tautomerization on the fast-atom bombardment tandem mass spectra of azo dyes

The effect of tautomerization on the collision-induced dissociation of negative ions produced from sulfonated azo dyes by fast-atom bombardment (FAB) was studied by analyzing the product ion spectra of several related compounds. The mechanisms by which azo dyes fragment were found to depend on the formation and stability of tautomers. The extent of tautomerization was affected by the number and location of hydroxy groups on the dye, as well as by the FAB matrix. Ions that retained a sodium were often inhibited from forming tautomers and gave different product ions. Substitution of deuterium for hydrogen on the hydroxy groups aided in the identification of ions having more than one possible structure and provided verification of proposed mechanisms. Mechanisms involving ions retaining a sodium were verified by substituting potassium for the sodium.     

Oxazole ring cleavage in the course of the synthesis of heterocyclic azo dyes

The formation of azo dyes by coupling the diazonium salts of aminophenyloxazolopyridines with N,N-di-ethylaniline was shown to be a suitable probe to check the stability of the oxazole ring in the course of their preparation. Depending on experimental conditions, “closed” and “opened” systems could be obtained separately.     

Adsorption of three azo reactive dyes by metal hydroxide sludge: effect of temperature, pH, and electrolytes

Adsorption of azo reactive dyes by metal hydroxide sludge were investigated using CI Reactive Red 2 (RR-2), CI Reactive Red 120, (RR-120), and CI Reactive Red 141 (RR-141). The adsorption isotherms, including the Langmuir constants (Q degrees and b) and the Freundlich constant (K(f)), for RR-2 decreased with increasing temperature, but this was reversed for RR-120 and RR-141. This behavior implied an exothermic process for RR-2 but an endothermic process for RR-120 and RR-141. The enthalpy value of adsorption for RR-2, RR-120, and RR-141 was -5.56, 2.77, and 6.41 kJ/mol, respectively, indicating that the adsorption of the less charged dyes (RR-2) was mainly physical, but that of the more charged dyes (RR-120 and RR-141) was chemical. The optimum system pH of 8.6+/-0.3 was maintained even when the solution pH was varied from 3 to 10. Higher concentration or more valence of anions of electrolytes in dye solution caused decreasing dye adsorption efficiency of metal hydroxide sludge. A higher dosage of sludge is required for real textile wastewater (>1% w/v) than for the synthetic dye solution (0.2% w/v). The leachates of heavy metals from metal hydroxide sludge to the environment are very low, which are within the standard limit of industrial effluent and leachable substances.     

Synthesis,characterization and dyeing assessment of novel acid azo dyes and mordent acid azo dyes based on 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid on wool and silk fabrics

Novel acid mono azo and mordent acid mono azo dyes were synthesized by the coupling of diazonium salt solution of different aromatic amines with 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid. The resulting dyes were characterized by spectral techniques like elemental analysis, IR, ¹H-NMR and UV visible spectroscopy. The dyeing performance of all the dyes was evaluated on wool and silk fabrics. The dyeing of chrome pre-treated wool and silk fabrics showed better hues on mordented fabrics. Dyeing of wool and silk fabrics resulted in pinkish blue to red shades with very good depth and levelness. The dyed fabrics showed excellent to very good light, washing, perspiration, sublimation and rubbing fastness.     

Oxidation of azo dyes with inorganic peroxides in the presence of cationic surfactants

Degradation of Direct Red 23, Rective Red 45, and Orange II azo dyes with hydrogen peroxide and hydroperite in the presence of cationic surfactants alkyldimethylbenzylammonium chloride (Katamin AB) and cetyltrimethylammonium chloride and without them was studied by spectrophotometry. The reactivity of the azo dyes was correlated with their chemical structure.