反胶束体系中水团的笼效应

在反胶束体系中研究了菁染料的吸收光谱以及ω值对菁染料荧光光谱的影响.讨论了不同粒径的AgCl纳米粒子对反胶束体系中菁染料的吸附状态及J-聚集体形成的影响.特别研究了反胶束水团空间限定效应对菁染料荧光量子产率及J-聚集体的影响.     

反胶束中菁染料与AgCl粒子相互作用的光谱研究

在阴离子型和非离子型表面活性剂组成的反胶束体系中研究了直径为11～14nm的AgCl微粒子与菁染料之间的作用,讨论了AgCl纳米粒子对菁染料的吸附及荧光猝灭现象.     

不同表面活性剂反胶束对纳米AgCl性能的影响

在反胶束中研究了直径10～14nm的AgCl微粒子与曙红间的作用,比较了阴离子型和非离子型表面活性剂组成的反胶束微环境效应.考察了AgCl粒子对曙红吸收光谱、荧光光谱及荧光寿命的影响.讨论了AgCl粒子对曙红荧光猝灭的机制,初步研究了稳定剂苯基巯基四氮唑及四氮茚对曙红-AgCl粒子反胶束体系的影响.     

反胶束笼对纳米氯化银反应性能的微环境限定

研究了反映束中直径为１０￣１７ｎｍ的ＡｇＣｌ微料与亚甲基蓝之间的作用，比较了阴离子型和非离子型表面活性剂组成的反胶束微环境的影响，讨论了亚甲基蓝在粒子上的吸附，二聚体形成的钠米ＡｇＣｌ粒子对亚甲基蓝荧光猝灭机制。     

反胶束笼对纳米氯化银反应性能的微环境限定

研究了反胶束中直径为10～17nm的AgCl微粒与亚甲基蓝之间的作用，比较了阴离子型和非离子型表面活性剂组成的反胶束微环境的影响，讨论了亚甲基蓝在粒子上的吸附，二聚体形成和纳米AgCl粒子对亚甲基蓝荧光猝灭机制．     

Effects of the water content on the growth rate of AgCl nanoparticles in a reversed micelle system

The effects of water content on the growth rate and the final particle size of AgCl nanoparticles in a reversed micelle (RM) system of polyoxyethylene (6) nonylphenyl ether (NP-6)/water/cyclohexane were investigated using a double-jet technique, in which RM solutions of AgNO(3) and KCl were added concurrently to a RM solution containing the excess concentration of chloride ion. As a result, the particle growth rate and the final particle size at a constant Rw ( identical with[water]/[surfactant]) below 5 were found to be in excellent agreement with our theoretical prediction based on a dynamic Ostwald ripening mechanism governed by the overall solubility of the solid and the diffusivity of the reversed micelles, whereas the final particle size was far beyond the size of the water pool of a reversed micelle. Thus, the dramatic reduction of the particle size in the RM system can be explained by the drastic reduction of the overall solubility of the solid and the small diffusivity of the bulky reversed micelles as a carrier of silver ion, and not by the size of the water pool of a reversed micelle as conventionally explained. Some additional contribution of a coagulation process was also suggested in a high Rw range above 5. Significant coagulation of AgCl particles was observed in a RM system with AOT in place of NP-6 even under the standard conditions for the NP-6 system.     

Calorimetric investigation of the formation of ZnS nanoparticles in w/o microemulsions

The enthalpies of precipitation of ZnS nanoparticles within water containing reversed micelles of sodium bis(2-ethylhexyl) solfosuccinate, L-α phosphatidylcholine, tetraethyleneglycol-mono-n-dodecyl ether and didodecyldimethylammonium bromide as a function of the molar concentration ratioR (R=[water]/[surfactant]) were measured by calorimetric technique. The results indicate that the energetic state of ZnS nanoparticles confined in the aqueous core of the reversed micelles is different from that in bulk water. Effects due to nanoparticle size, adsorption of HS⁻ ions on the nanoparticle surface and interactions between nanoparticles and water/surfactant interfaces are discussed. This work has been supported by MURST.     

Specifics of the formation of J-aggregates of cyanine dyes in solutions of AOT/water/hexane reverse micelles

The behavior of a cyanine dye (3,3′-di-(gamma-sulfopropyl)-4,5,4′,5′-dibenzo-9-ethylthiacarbocyanine betaine pyridinium salt) was studied in AOT/water/hexane reverse micelles over a wide range of W at various concentrations of the dye, AOT, and reverse micelles. The processes occurring during the formation of the AOT/water/hexane micellar solution were studied in detail. It has been shown that, before the formation of the stable microemulsion, the dye aggregation processes occur by virtue of the interaction of the dye with the AOT anion. The amount of J-aggregates is proportional to the logarithm of the ratio of the amount of AOT molecules to the amount of dye molecules. The time behavior of J-aggregates after the formation of a micellar structure depends on the concentration of reverse micelles, thereby indicating an important role of intermicellar exchange.     

Protein‐Sized Bright Fluorogenic Nanoparticles Based on Cross‐Linked Calixarene Micelles with Cyanine Corona

The key challenge in the field of fluorescent nanoparticles (NPs) for biological applications is to achieve superior brightness for sizes equivalent to single proteins (3–7 nm). We propose a concept of shell‐cross‐linked fluorescent micelles, in which PEGylated cyanine 3 and 5 bis‐azides form a covalently attached corona on micelles of amphiphilic calixarene bearing four alkyne groups. The fluorescence quantum yield of the obtained monodisperse NPs, with a size of 7 nm, is a function of viscosity and reached up to 15 % in glycerol. In the on‐state they are circa 2‐fold brighter than quantum dots (QD‐585), which makes them the smallest PEGylated organic NPs of this high brightness. FRET between cyanine 3 and 5 cross‐linkers at the surface of NPs suggests their integrity in physiological media, organic solvents, and living cells, in which the NPs rapidly internalize, showing excellent imaging contrast. Calixarene micelles with a cyanine corona constitute a new platform for the development of protein‐sized ultrabright fluorescent NPs.     

The role of molecular size in the excited state behavior of aminocoumarin dyes in restricted media--2: study of BC I in AOT-formamide reversed micelles

Ground and excited state properties of a pre-twisted 7-diethylaminocoumarin dye (BC I) belonging to the family of coumarinyl benzopyrano pyridines are reported in isooctane-AOT-formamide reversed micelles. In reversed micelles, BC I, albeit soluble in formamide, is found to remain out of the polar solvent pool. But the photophysical properties of the probe dye are sensitive to the changes in the polarity of the interfacial region caused by increase in F0 = [formamide]/[AOT]. The spectroscopic properties and dynamics are indicative of dual emission due to the solubilization of the dye in two different environments (the nonpolar solvent and the interfacial region). Results of the steady-state fluorescence anisotropy experiments also support the presence of two different environments. The present study once again proves that molecular size is an important parameter in the study of the photophysical properties of the flexible aminocoumarin dyes in reversed micelles.     

反胶束法合成CdS纳米粒子及其表征

以AOT为保护剂,采用反胶束法合成CdS纳米粒子。利用水洗法洗去保护剂AOT,通过加入不同量的无水乙醇调节分散介质的极性,改变CdS纳米粒子在分散介质中的"溶解度",从而实现不同尺寸粒子的分离。采用紫外-可见(UV-vis)吸收光谱、透射电子显微镜(TEM)、荧光光谱法对其进行表征。     

Direct potentiometric titration of chloride and fluoride ions in reversed micelles of an ethoxylated surfactant

The possibility of the potentiometric titration of Cl^– and F^– ions directly in reversed micelles of the ethoxylated surfactant (Neonol APh₉-4) in n-decane is shown. The potential change of the indicator electrode (silver chloride and lanthanum fluoride) only depends on the ion concentration in the aqueous pseudophase of the reversed micelles and is independent of the aqueous phase concentration in n-decane in the region of concentrations from 4 to 0.2 vol %. The determination of the micelle size of Neonol APh₉-4 in the precipitation titration of Cl^– and F^– ions by photon correlation spectroscopy showed the formation of nanoparticles of AgCl and LaF₃ of dimensions limited by original micelle size (r_hd = 6 to 11 nm). The growth of AgCl and LaF₃ nanoparticles was studied at a shortage and excess of the titrant and in the point of equivalence.     

Preparation of cadmium sulfide nanoparticles in self-reproducing reversed micelles

Octyl octanoate (O-OL) underwent hydrolysis in sodium octanoate (NaOA) reversed micelles in 85:15 = isooctane:octanol (OL) (v/v), containing w = [H2O]/[NaOA] = 40. The products of the hydrolysis, octanoic acid (OA) and octanol (OL), lead to the formation of additional (albeit smaller) reversed micelles; hence the process is considered to be self-reproducing. Self-reproduction was found to be catalyzed by lithium hydroxide, solubilized in the water pools, as well as by hydrogen sulfide, added to the solution of the reversed micelles. Addition of hydrogen sulfide to cadmium perchlorate containing self-reproducing reversed micelles resulted in the formation of cadmium sulfide (CdS) nanoparticles. Diameters of the CdS containing nanoparticles could be altered from 5.4 to 1.8 nm by changing the [Cd2+]/[H2S] ratios from 0.25 to 10. The CdS nanoparticles formed were capped by mercaptopropionic acid, isolated as solids, and could be repeatedly redispersed in water without changing their sizes. Additional CdS nanoparticles were generated in the supernatants removed from the precipitated capped CdS nanoparticles.     

N,N′-对羧苄基吲哚三菁敏化纳米TiO2电极的研究

应用光电化学方法研究了N, N′-对羧苄基吲哚三菁（Cy5）染料敏化TiO2纳米晶电极的光电化学行为,优化了敏化的条件.结合Cy5的循环伏安曲线和光吸收阈值,初步确定Cy5电子基态和激发态能级位置.结果表明,Cy5电子激发态能级位置能与TiO2纳米粒子导带边位置相匹配,因而使用该染料敏化可以显著提高TiO2纳米晶的光电流,使TiO2纳米晶电极吸收波长由紫外光区红移至可见光区和近红外区,光电转换效率得到明显改善,在膜厚为6.5μm、敏化时间为6 h的条件下IPCE值（incident photo-to-electricity conversion efficiency）最高可达46.4％,总的光电转换效率η为1.70％.     

Fluorescence quenching of bovine serum albumin.

The fluorescence emission spectra and 3D fluorescence spectra of bovine serum albumin (BSA) in cetyltrimethylammonium bromide (CTAB) reversed micelles were affected by the microenvironment. Blue shifts of the fluorescence emission peaks were found when BSA was present in CTAB reversed micelles. The fluorescence intensity changed with the water content. Similar changes in the peak regions of the 3D fluorescence spectra were also observed. CdS nanoparticles prepared in CTAB reversed micelles quenched the fluorescence of BSA significantly. The fluorescence of BSA was more effectively quenched by negative CdS nanoparticles than by positive or neutral CdS ones. The quenching degree increased linearly with increasing the concentration of negative CdS nanoparticles over the range of 5.0 x 10(-6) - 3.0 x 10(-5) mol L(-1). The quenching mechanism is discussed and the quenching constant is 1.32 x 10(4) L mol(-1).     

Substituent effects on the assembly of helical cyanine dye aggregates in the minor groove of a DNA template

Double-helical DNA was used as a template for the assembly of helical cyanine dye aggregates. The aggregates consist of cofacial dimers aligned end-to-end in the minor groove of the DNA. The effect of methoxy or fluoro substituents placed on the periphery of the cyanine dye heterocycles on aggregation both in water and on the DNA template was studied by UV-vis and circular dichroism spectroscopy. Methoxy groups were found to be stronger promoters of aggregation than fluoro, and a dimethoxy dye exhibited a higher propensity to aggregate compared with an unsymmetrical methoxy/fluoro dye. Semiempirical calculations supported the experimental observation of methoxy substitution favoring aggregation. These results indicate that dispersion and hydrophobic effects contribute more to dimerization/aggregation than do electron donor-acceptor effects.     

Direct potentiometric titration of chloride and fluoride ions in reversed micelles of an ethoxylated surfactant

The possibility of the potentiometric titration of Cl^– and F^– ions directly in reversed micelles of the ethoxylated surfactant (Neonol APh₉-4) in n-decane is shown. The potential change of the indicator electrode (silver chloride and lanthanum fluoride) only depends on the ion concentration in the aqueous pseudophase of the reversed micelles and is independent of the aqueous phase concentration in n-decane in the region of concentrations from 4 to 0.2 vol %. The determination of the micelle size of Neonol APh₉-4 in the precipitation titration of Cl^– and F^– ions by photon correlation spectroscopy showed the formation of nanoparticles of AgCl and LaF₃ of dimensions limited by original micelle size (r_hd = 6 to 11 nm). The growth of AgCl and LaF₃ nanoparticles was studied at a shortage and excess of the titrant and in the point of equivalence. Received: 23 April 1999 / Revised: 15 July 1999 / Accepted: 19 July 1999     

Spectrophotometric study of anionic azo-dye light yellow (X6G) interaction with surfactants and its micellar solubilization in cationic surfactant micelles

Solubilization and interaction of azo-dye light yellow (X6G) at/with cationic surfactants cetyltrimethylammonium bromide (CTAB) and cetylpyridinium chloride (CPC) was investigated spectrophotometricaly. The effect of cationic micelles on solubilization of anionic azo dye in aqueous micellar solutions of cationic surfactants was studied at pH 7 and 25 degrees C. The binding of dye to micelles implied a bathochromic shift in dye absorption spectra that indicates dye-surfactant interaction. The results showed that the solubility of dye increased with increasing surfactant concentration, as a consequence of the association between the dye and the micelles. The binding constants, K(b), were obtained from experimental absorption spectra. By using pseudo-phase model, the partition coefficients between the bulk water and surfactant micelles, K(x), were calculated. Gibbs energies of binding and distribution of dye between the bulk water and surfactant micelles were estimated. The results show favorable solubilization of dye in CTAB micelles.     

Chiral transformation of cyanine dye aggregates induced by small peptides

Three small peptides (K4, K5, and K6) with different length were designed to induce the transformation of the assembled state and the chirality of cyanine dye supramolecule. The absorption and circular dichroism (CD) results indicated that, the peptides tend to induce cyanine dye to H-aggregation, competed with Na(+) in PBS, which would induce dye to J-aggregation. Meanwhile, all three peptides could influence the chirality of both J-aggregates induced by Na(+) and H-aggregates, among which K6 could induce chiral reversion of J-aggregates. Furthermore, molecular modeling and energy calculation results have shown that the peptides with different chain length have different conformations. This might be the reason for cyanine dye to form the different chiral assembly induced by these oligo-peptide templates.     

不对称菁染料敏化纳米TiO2的光生电流过程

用光电化学方法研究了不对称菁类染料敏化TiO2纳米结构电极的光电转换过程.结果表明,该染料的电子激发态能级位置与TiO2纳米粒子导带边位置匹配较好,光激发染料后,其激发态电子可以注入到TiO2纳米多孔膜的导带,从而使TiO2纳米结构电极的吸收光谱和光电流谱红移至可见光区,其 IPCE(Incident photon-to-electron conversion efficiency)值最高可达84.3%.并进一步结合现场紫外-可见吸收光谱研究了外加电势对激发态染料往TiO2纳米多孔膜注入电子过程的影响.