Micropolarity and microviscosity of Pluronics L62 and L64 core–shell aggregates in water at various concentrations and additives examined by absorption and fluorescence probes

The microstructure of aggregates formed in aqueous solutions of the triblock copolymers poly(ethylene oxide) (PEO)–poly(propylene oxide)–PEO, Pluronics L62 and L64, and the effect of additives (n-butanol, n-hexanol, and o-xylene) on the local polarity and viscosity were investigated using several absorption and fluorescence probes with different hydrophilic/hydrophobic trade-offs. The absorption probe was 2,2,6,6-tetramethylpiperidine-1-oxyl and the fluorescence probes pyrene (P), 1-anilinonaphthalene-8-sulfonic acid (ANS), 1,10-bis(1-pyrene) decane (PD), and N-[5-(dimethylamino)naphthalene-1-sulfonyl]hexadecylamine (Dansyl). The specific absorption and fluorescence parameters, sensitive to changes in micropolarity and microviscosity, were related to the hydration calibration curves carried out in homogeneous tetraethylene glycol/water mixtures. Thus, the effective local hydration of the molecular probe solubilized in the guest aggregate was quantified, and at the same time, the probe location is established with respect of the corona and core aggregate. The ANS and PD probes evidence differences in microviscosity and track the effect of the block copolymer structure and additive concentration on microviscosity.     

阴离子疏水单体改性的P(AM-co-DMC)的合成及絮凝性能

在少量阴离子疏水单体4-(ω-丙烯酰氧乙氧基)苯甲酸(PEBA)的参与下,合成了丙烯酰胺(AM)-丙烯酰氧乙基三甲基氯化铵(DMC)共聚物。通过表观黏度及芘探针发射谱测定了疏水改性P(AM-co-DMC)溶液的临界缔合浓度(CAC)。透射电镜观察表明:在水溶液中,当疏水改性P(AM-co-DMC)浓度高于CAC时,因静电及疏水作用可形成微球状缔合体。对高岭土悬浮液的絮凝表明,与普通P(AM-co-DMC)共聚物相比,疏水改性P(AM-co-DMC)具有较好的絮凝能力及较宽的窗体用量。pH对絮凝效果的影响表明,除疏水作用外,高分子链间的静电作用是提高絮凝效果的另一原因。     

Spectroscopic probing of the effect of alkanols on the properties of the head group region in reverse micelles of AOT-heptane-water

The effects of addition of alkanols (ethanol, n-hexanol, and 3-ethyl-3-pentanol) on the micropolarity and microviscosity of the head group region in reverse micelles of AOT-heptane-water have been investigated by fluorescence probing methods (ANS fluorescence yield and TMADPH fluorescence anisotropy), complemented by the use of the solvatochromic probe E(T)(30) in absorption spectroscopy. For all the alkanols considered, ANS fluorescence in AOT reverse micelles (at W=3) is quenched by additive incorporation, being the effect elicited almost independent of the alkanol chain length and topology. As sensed by the E(T)(30) parameter, the micropolarity of the micelle surface increases, remains unmodified, and decreases upon addition of ethanol, 3-ethyl-3-pentanol, and hexanol, respectively. While ethanol barely modifies the fluorescence anisotropy of TMADPH, 3-ethyl-3-pentanol and n-hexanol addition strongly decrease it. The similarity of the tendencies of ANS data to TMADPH anisotropies and the differences between ANS data and E(T)(30) values would indicate that, at least for 3-ethyl-3-pentanol and n-hexanol, microviscosity, rather than micropolarity, must be considered to interpret the effect of the alkanols upon the fluorescent behavior of ANS.     

Microviscosity in poly(ethylene oxide)‐polypropylene oxide‐poly(ethylene oxide) block copolymers probed by fluorescence depolarization kinetics

Triblock copolymers [poly(ethylene oxide) (PEO) and polypropylene oxide (PPO)], Pluronic F127 with 100 PEO blocks on each end, and 65 blocks of PPO in the center were examined in aqueous solution. The “sol” and “gel” phase diagram was determined as a function of concentration and temperature. For further study, the concentration was fixed at 20 wt %, and the temperature dependence of the dynamic viscosity differed from the temperature dependence of fluorescence emission spectra and the microviscosity probed by the fluorescence depolarization kinetics of rhodamine 123 dye, which was dissolved in the continuous hydrophilic phase. The depolarization measurements used single‐photon counting after two‐photon excitation with a Ti‐sapphire femtosecond laser. Although the viscoelastic modulus increased by an order of magnitude when the sol‐to‐gel transition was crossed, the microviscosity of the hydrophilic continuous medium showed only minor changes. At different temperatures the fluorescence lifetime was the same with a single‐exponential time constant, but the fluorescence depolarization displayed a double‐exponential decay. After comparison with fluorescence depolarization of the dye in PPO melt and PEO whose molecular weight and aqueous concentrations were varied, the relative proportions of faster and slower components of the fluorescence depolarization were tentatively attributed to varying ratios of the dye in free solution and associated with micelles. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2883–2888, 2002     

Interaction of slightly cross-linked gels of poly(diallyldimethylammonium bromide) with sodium dodecyl sulfate. Diffusion of surfactant ions in gel

The dynamics of the changing microenvironment of the fluorescent probe pyrene in slightly cross-linked networks of poly(diallyldimethylmmonium bromide) during diffusion of sodium dodecyl sulfate (SDS) in the gel phase has been investigated by fluorescence spectroscopy. Values of the spectral ratio I₃/I₁ for pyrene monomer included in SDS micelles in the swollen networks fall between the corresponding values for pyrene in water and for pyrene dissolved in SDS micelles in aqueous solution. In the narrow interval of the surfactant concentrations in the gel phase, the formation of pyrene excimers is observed. The values of the critical micelle concentration in the gel phase (ca. 5 × 10^?4 to 8 × 10^?4 mol/L) are tenfold lower than in aqueous solutions of the surfactant. The effective micellar diffusion coeffecient D in the gel phase increases with increasing swelling of the network. © 1993 John Wiley & Sons, Inc.     

A fluorescence study of the excited-state dynamics of boron dipyrrin molecular rotors

Noticeable viscosity dependence has been revealed for fluorescence spectra of three phenyl derivatives of boron dipyrrin in aqueous glycerol solutions. This dependence is less pronounced for the fluorescence lifetimes. Such behavior is characteristic of molecular rotors used as media microviscosity sensors. A significant growth of the radiative deactivation constant is observed in the range 298-150 K. Quantumchemical calculation of the model fluorophore support the assumption on barrier-free relaxation of the excited state from the pretwisted to the flattened conformation. The spectral-kinetic parameters of fluorophores have been determined, and viscosity graduation curves are presented.     

A photophysical study of the urea effect on micellar properties of sodium dodecylsulfate aqueous solutions

With the aim of studying the effect of urea on micellar properties of aqueous solutions of sodium dodecylsulfate (SDS), steadystate fluorescence experiments were carried out with different luminescence probes incorporated into the micellar phase. The increase of critical micelle concentration (CMC) of the surfactant with urea addition was followed by changes in the relative intensities of the vibrational fine structure of the pyrene fluorescence spectra. Micellar aggregation numbers were obtained from the analysis of fluorescence quenching data using ruthenium tris(bipyridyl) chloride and 9-mehylanthracene as a donorquencher pair. It was found that the decrease in the aggregation number is mainly controlled by rise in the surface area per headgroup of the surfactant. From fluorescence measurements, using several ionic probes (8-anilino-1-naphthalen-sulfonic acid, rhodamine B, and auramine O), it was found that urea decreases the polarity and increases the microviscosity of the micellar interface. These effects, which are dependent on the concentration of urea, can be explained according to a direct interaction of urea at the micellar surface.     

Binding of 8-anilino-1-naphthalenesulfonate to lecithin:cholesterol acyltransferase studied by fluorescence techniques

The solvatochromic fluorescent probe 8-anilino-1-naphthalenesulfonate (ANS) has been used to study the hydrophobicity and conformational dynamics of lecithin:cholesterol acyltransferase (LCAT). The ANS to LCAT binding constant was estimated from titrations with ANS, keeping a constant concentration of LCAT (2 microM). Apparent binding constant was found to be dependent on the excitation. For the direct excitation of ANS at 375 nm the binding constant was 4.7 microM(-1) and for UV excitation at 295 nm was 3.2 microM(-1). In the later case, not only ANS but also tryptophan (Trp) residues of LCAT is being excited. Fluorescence spectra and intensity decays show an efficient energy transfer from tryptophan residues to ANS. The apparent distance from Trp donor to ANS acceptor, estimated from the changes in donor lifetime was about 3 nm and depends on the ANS concentration. Steady-state and time-resolved fluorescence emission and anisotropies have been characterized. The lifetime of ANS bound to LCAT was above 16 ns which is characteristic for it being in a hydrophobic environment. The ANS labeled LCAT fluorescence anisotropy decay revealed the correlation time of 42 ns with a weak residual motion of 2.8 ns. These characteristics of ANS labeled LCAT fluorescence show that ANS is an excellent probe to study conformational changes of LCAT protein and its interactions with other macromolecules.     

New three-arm amphiphilic and biodegradable block copolymers composed of poly(epsilon-caprolactone) and poly(N-vinyl-2-pyrrolidone). Synthesis, characterization and self-assembly in aqueous solution

The synthesis, characterization and the self-assembly process of a novel biodegradable block copolymer containing a poly(epsilon-caprolactone), PCL, central block and three poly(N-vinyl-2-pyrrolidone), PVP, arms are reported. Three samples with different amounts of PVP were investigated. The copolymers were characterized by FTIR spectroscopy, (1)H NMR and viscosity measurements. The composition and the molecular weights of the block copolymers were established using size exclusion chromatography SEC and (1)H NMR. Micelle formation by these copolymers was monitored by using the vibrational fine structure of pyrene monomer fluorescence and the critical aggregation concentrations, cac, of the copolymers in aqueous solution were determined using sigmoid Boltzmann-type fitting of the fluorescence data. Dynamic light scattering measurements showed a bimodal size distribution for the copolymers in solution, indicating that the micellization is an intermolecular process. Partitioning coefficients of pyrene between copolymer micelles and water were also determined and increase in magnitude with increasing epsilon-caprolactone content of the copolymer.     

Effect of leucinyl-phenylalanyl-valine on DMPC liposome membrane

Leucinyl-phenylalanyl-valine (LFV) is a hydrophobic tripeptide with a flat egg shaped structure with the long axis dimension of about 12 A. The effect of LFV on dimyristoylphosphatidylcholine (DMPC) liposome membrane has been studied by differential scanning calorimetry (DSC) and fluorescence spectroscopy. Calorimetric studies shows that incorporation of LFV completely abolishes the pretransition temperature with broadening of main transition temperature. Four conceptually different fluorescence probes, 1-naphthol (1-ROH) an excited state proton transfer probe, 8-anilino-1-naphthalenesulphonate (ANS) a solvent polarity probe, 1-6-diphenylhexatriene (DPH) an anisotropy probe and pyrene an excimer-forming probe have been used for fluorescence spectroscopic studies. For 1-ROH, ANS and DPH, a decreased partitioning with increasing mol.% of LFV was observed. Increasing LFV mol.% caused a decrease in the neutral form emission of 1-ROH, and a decrease in fluorescence intensity with red shift in ANS. The excimer formation ability of pyrene also decreased. The phase transition behavior of DMPC membrane in the presence of LFV was similar to the known effect of cholesterol on lipid bilayers. These results suggest that LFV cause an increased compactness of membrane.     

表面活性剂双水相的性质及其应用 Ⅰ. 表面活性剂双水相的微环境性质

阴、阳离子表面活性剂混合体系, 在一定浓度及混合比范围内, 可以形成两个互不相溶、平衡共存的水相, 称为表面活性剂双水相。其中阳离子表面活性剂过量的双水相体系, 称为阳离子双水相。本文分别以芘和罗丹明B作为探针, 用荧光探针法研究了摩尔比为1.6:1的C12NE和SDS混合体系成形成的阳离子双水相,测定其上层和下层的胶束微环境的极性和微粘度, 取得了有意义的结果。     

聚酰胺-胺接枝PPO-PEO两亲嵌段树状分子的合成与表面性质

合成了一系列以1.0 代(G1)聚酰胺-胺(PAMAM)为核心、以聚环氧丙烷-聚环氧乙烷(PPO-PEO)为辐射臂的新型树状分子, 通过傅里叶变换红外(FTIR)光谱、质谱(MS)、核磁共振谱(1H NMR)和凝胶渗透色谱(GPC)等方法对其结构进行了表征与分析. 用表面张力与稳态荧光法对其表面性质与聚集行为进行研究, 结果表明, 临界聚集浓度(CAC)随PPO-PEO两亲嵌段长度的增加而增大, 同时聚集体的生成对芘探针有增溶作用, 并使其微环境的极性明显减弱. 通过动态激光光散射(DLS)法得到聚集体的尺寸分布均为窄分布, 其平均尺寸约为100 nm. 对该体系水溶液pH效应的研究发现, 两亲嵌段的长度对于质子化进程有着较大影响.     

Modulating properties of aqueous sodium dodecyl sulfate by adding hydrophobic ionic liquid

Altering and modifying important physicochemical properties of aqueous surfactant solutions is highly desirable as far as potential applications of such systems are concerned. Changes in the properties of aqueous solutions of a common anionic surfactant sodium dodecyl sulfate (SDS) are assessed in the presence of a common and popular 'hydrophobic' ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF(6)). Upon addition of up to approximately 0.10 wt% bmimPF(6), a dramatic decrease in critical micelle concentration (cmc) is accompanied by an increase in the degree of counterion dissociation (alpha) and micellar aggregation number (N(agg)) indicating micellar growth. However, in the range 0.10 wt% < or = bmimPF(6) 2.00 wt%, relatively gradual decrease in alpha and N(agg) is observed along with no change in cmc. Significantly decreased microfluidity of the aqueous SDS solutions on addition of bmimPF(6) is indicated by a fluorescence microviscosity probe 1,3-bis-(1-pyrenyl)propane which suggests partitioning of bmimPF(6) into the SDS micellar phase. Behavior of solvatochromic fluorescence probes, pyrene, pyrene-1-carboxaldehyde, and 2-(p-toluidino)naphthalene-6-sulfonate, confirms interaction, and possible complexation, between IL bmimPF(6) and anionic micellar surface. Increased solubility of bmimPF(6) with increasing SDS concentration further confirms SDS-bmimPF(6) interactions. Presence of strong electrostatic attraction between bmim(+) and anionic micellar surface is proposed to be the most dominant reason for these observations. All-in-all, unique role of a hydrophobic ionic liquid bmimPF(6) in modifying the properties of aqueous anionic sodium dodecyl sulfate is demonstrated.     

pH-Sensitivity and pH-dependent structural change in polymeric nanoparticles of poly(vinyl sulfadimethoxine)-deoxycholic acid conjugate

pH-Sensitive nanoparticles of poly(vinyl sulfadimethoxine) (PSDM)-deoxycholic acid (DOCA) conjugates were prepared by dialysis at pH 9.0. The average size and the critical aggregation concentration (CAC) of the nanoparticles were 340 nm and 2.5 × 10⁻¹ g/l, respectively. The CAC decreased with decreasing pH as a result of the increase in the hydrophobic nature of the PSDM. Nanoparticle aggregation was observed at pHs ranging from 6.6 to 7.2. The photophysical characteristics of the nanoparticles were examined using a fluorescence probe technique. The microviscosity in the nanoparticle core was measured by 1,6-diphenyl-1,3,5-hexatriene (DPH). The microviscosity changed significantly with decreasing pH from 8.0 to 6.8, indicating a decrease in the rigidity of the inner cores. One interesting feature was that the microviscosity increased sharply at pHs below 6.8. This suggests that in this pH range most of the PSDM became deionized, which caused the reconstitution of new hydrophobic domains inside the nanoparticles.     

Aggregation of sodium 1-(n-alkyl)naphthalene-4-sulfonates in aqueous solution: micellization and microenvironment characteristics

In aqueous solution, the micellization and microenvironment characteristics of the micelle assemblies of three anionic surfactants, sodium 1-(n-alkyl)naphthalene-4-sulfonates (SANS), have been investigated by steady-state fluorescence and time-resolved fluorescence decay techniques using pyrene, Ru(bpy)3(2+), and 1,6-diphenyl-1,3,5-hexatriene as fluorescence probes. The critical micelle concentrations (cmc's), effective carbon atom numbers (neff's), hydrophilic-lipophilic balances (HLBs), mean micelle aggregation numbers, micropolarities, and microviscosities of these surfactant micelles have been determined. The logarithmic cmc of the alkylnaphthalene sulfonates decreases linearly with an increase in the neff. The logarithmic aggregation number of the alkylnaphthalene sulfonates increases linearly with an increase in the neff. However, in contrast to the alkylsufonates and the alkylbenzene sulfonates, the aggregation for these alkylnaphthalene sulfonate molecules is less sensitive to the increase in the neff. The micropolarity of these alkylnaphthalene sulfonate micelles is less sensitive to the increase in the alkyl chain length and is lower than that of sodium dodecyl sulfate (SDS). The microviscosity of these alkylnaphthalene sulfonate micelles increases with an increase in the alkyl chain length and is lower than those of nonionic surfactants and zwitterionic surfactants. These results suggest that naphthyl rings have a notable effect on the micellization of SANS.     

芘在改性硅胶上的光物理研究——以芘为探针研究改性硅胶的表面特性

研究了芘在正十碳烷氧基和三甲基硅氧基改性硅腔表面上的荧光光谱和寿命。在这二种硅胶上,激基缔合物是由基态聚积体直接受光和受激发的单分子和基态的单分子所形成、在硅胶≡Si—O—C_(10)H_(21)-n上比在硅胶≡Si—O—SiMe_3上所形成的聚积体较少。化学改性与物理改性相结合可使芘在较大的浓度范围内主要以单分子分散。激基缔合物的形成主要是由动力学过程所控制。研究了温度对芘的荧光光谱和寿命的影响。激基缔合物形成过程的活化能约为7kcal mol~(-1)。讨论了环境对单分子荧光光谱结构的影响。     

Electrochemical, microscopic, and spectroscopic characterization of prevesicle nanostructures and vesicles on mixed cationic surfactant systems

Several experimental techniques (conductivity, zeta potential, transmission electronic microscopy, and steady-state fluorescence spectroscopy) have been used to study the formation of mixed colloidal aggregates consisting of a cationic double-chain surfactant, di-dodecyldimethylammonium bromide (di-C12DMAB), and a single-chain alkyltrimethylammonium bromide with 10 and/or 14 carbon atoms (decyltrimethylammonium bromide, C10TAB, and/or tetradecyltrimethylammonium bromide, C14TAB). Special interest has been devoted to the prevesicle domain, within which the formation of aggregated nanostructures was first reported in our laboratory. For that purpose, studies have been carried out on the very dilute region by means of conductivity experiments, confirming the existence of two critical aggregation concentrations in that concentration domain: the so-called mixed critical aggregate concentration, CAC, and the mixed critical vesicle concentration, CVC. By carrying out TEM experiments on negatively stained samples, we were surprised to find a number of aggregates without a clear aggregation pattern and with a variety of sizes and shapes at concentrations below CAC, where only monomers were expected. However, the nanoaggregates found at concentrations between CAC and CVC, also by TEM microscopy, show a clear and ordered "fingerprint"-like aggregation pattern similar to the liquid-crystalline phases reported for DNA-liposome complexes and/or DNA packed with viral capsids. Finally, at total surfactant concentrations above CVC, the aggregates were confirmed, by means of cryo-TEM micrographs and zeta potential measurements, to be essentially unilamellar spherical vesicles with a medium polydispersity and a net-averaged surface density charge of around 12 x 10(-3) C m(-2). The fluorescence emission of two probes, TNS (anionic) and PRODAN (nonionic), allows for the analysis of the micropolarity and microviscosity of the different microenvironments present in aqueous surfactant solutions where the above-mentioned vesicle and prevesicle aggregates are present.     

Polyelectrolyte effects on the quenching of pyrene fluorescence in solutions of a pyrene substituted poly(acrylic acid)

The quenching of pyrene fluorescence by nitromethane, Tl⁺, Cu²⁺, I^?, and 4-dimethylaminopyridine (DMAP) in aqueous solutions of a pyrene substituted poly(acrylic acid) ( 1 ) was influenced by the “polyelectrolyte effect” of 1 . The efficiency of quenching in solutions of 1 was measured in terms of the Stern–Volmer constants for dynamic and static quenching which were obtained from comparison of the intensity and lifetime of pyrene fluorescence in solutions of 1 and a monomer model compound. The efficiency of quenching in solutions of 1 was always greater at high pH ( 9 ) in comparison to that at low pH ( 4 ). The ionization of carboxylic groups in 1 caused an expansion of the polymer mainchain and concomitant exposure of the pyrene molecules to the aqueous phase and quencher. The polyanion domain of 1 favored the condensation of cationic quenchers and could account for very efficient quenching in case of Cu²⁺ and Tl⁺. A very efficient quenching of pyrene fluorescence in solutions of 1 by DMAP at high pH was attributed to the hydrophobic interactions of DMAP and pyrene moiety. The iodide ions were less efficient quenchers of pyrene fluorescence due to electrostatic repulsion from the polyanion. The efficiency of quenching by nitromethane was not significantly affected by ionization of the carboxylic groups in 1 .     

Hydrophobie effects on photophysical and photochemical processes: VI. Character of aggregates formed by hydrocarbon with long chain in poor solvents

Dodecyl β-naphthoate and 3-octadecyl pyrene were used as fluorescence probes for estimation of microscopic polarity in aggregates formed by long chain hydrocarbon Cn (n-10, 12, 14, 16, 18) in dimethyl sulfoxide-water mixed solvent. The polarity in the aggregates is similar to that in cyclohexane. The average aggregation number (N?) was determined by using time resolved fluorescence technique. N? is dependent on substrate chain length and varies from 15 to 30. The microviscosity was also measured by fluorescence depolarization method. Above phase transition temperature, the microviscosity in aggregates is slightly larger than that in micelle, but below this temperature, the microviscosity in aggregates is as large as that in solid phase.     

Host-guest interactions in aqueous media withp-tert.-butylcalix[4]arene bearing polyoxyethylene chains

The interactions ofp-tert.-butylcalix[4]arene bearing polyoxyethylene chains (C3) with pyrene (Py), 1-anilino-8-naphthalenesulfonate (ANS) andN-phenyl-naphthylamine (NPN) in aqueous solution were studied by absorption and fluorescence measurements. Absorption spectral changes and fluorescence enhancements reveal that C3, which has a hydrophobic cavity, can include organic molecules and ions in aqueous solution and form 11 host-guest complexes with ANS and NPN. C3 forms inclusion complexes with Py at different stoichiometries depending on the host: guest molar ratio. Binding constants of 2.2×10⁴, 2.0×10⁴ and 3.6×10⁵ dm³ mol^–1 were calculated for the C3Py, C3ANS and C3NPN complexes (11), respectively, based on the Benesi-Hildebrand equation.Author for correspondence.