二甲基硅氧烷甘醇乙酸基共聚物水溶液的表面活性

通过表面张力的测定, 考察了不同无机盐和温度对二甲基硅氧烷甘醇乙酸基共聚物(PSEP)表面活性的影响, 进而研究PSEP在不同介质中胶束形成热力学性质. 研究表明, NaCl、NaBr和CaCl2的存在可提高PSEP的表面活性. 而且, PSEP的胶束化焓变对熵变呈线性相关, 说明存在焓/熵补偿现象.     

Formation of intermediate micellar phase between hexagonal and discontinuous cubic liquid crystals in brine/N-acylamino acid surfactant/N-acylamino acid oil system

The phase behavior in the brine/sodium N-dodecanoyl sarcosinate (Sar)/isopropyl N-dodecanoyl sarcosinate (SLIP) system has been investigated by means of phase study, static light scattering, and small-angle X-ray scattering. The liquid crystal phases, hexagonal (H(1)) and discontinuous cubic (I(1)), melt upon the addition of NaCl, which shows the similar effect to the increasing of temperature. The addition of SLIP to the brine/Sar solution at high Sar concentration induces the phase transition from H(1) to I(1) via the isotropic micellar solution (W(m2)). The micellar structure in the W(m2) phase also changes from the wormlike to the globular micelle with SLIP concentration. Adding NaCl reduces the repulsive force between the Sar head groups and simultaneously the space of the solubilized SLIP in the palisade layer, leading SLIP to shift their location further into the micelle core. As a consequence, the hexagonal symmetry breaks into the micelle solution and the liquid crystal order is destabilized entropically.     

Micellization of non-surface-active diblock copolymers in water. Special characteristics of poly(styrene)-block-poly(styrenesulfonate)

Strongly ionized amphiphilic diblock copolymers of poly(styrene)-b-poly(styrenesulfonate) with various hydrophilic and hydrophobic chain lengths were synthesized by living radical polymerization, and their properties and self-assembling behavior were systematically investigated by surface tension measurement, foam formation, hydrophobic dye solubilization, X-ray reflectivity, dynamic light scattering, small-angle neutron scattering, small-angle X-ray scattering, and atomic force microscope techniques. These copolymer solutions in pure water did not show a decrease of surface tension with increasing polymer concentration. The solutions also did not show foam formation, and no adsorption at the air/water interface was confirmed by reflectivity experiments. However, in 0.5 M NaCl aq solutions polymer adsorption and foam formation were observed. The critical micelle concentration (cmc) was observed by the dye solubilization experiment in both the solutions with and without added salt, and by dynamic light scattering we confirmed the existence of polymer micelles in solution, even though there was no adsorption of polymer molecules at the water surface in the solution without salt. By the small-angle scattering technique, we confirmed that the micelles have a well-defined core-shell structure and their sizes were 100-150 A depending on the hydrophobic and hydrophilic chain length ratio. The micelle size and shape were unaffected by addition of up to 0.5 M salt. The absence of polymer adsorption at the water surface with micelle formation in a bulk solution, which is now known as a universal characteristic for strongly ionized amphiphilic block copolymers, was attributed to the image charge effect at the air/water interface due to the many charges on the hydrophilic segment.     

Swelling of poly(ethylene oxide) gel in aqueous solutions of sodium dodecyl sulfate with added sodium chloride

The swelling behavior of poly(ethylene oxide) (PEO) gels in aqueous solutions of sodium dodecyl sulfate (SDS) with and without NaCl was investigated. In the absence of NaCl, PEO gels with different degrees of cross-linking began to swell from a concentration lower than the critical micelle concentration (cmc) of SDS, then showed sigmoidal enhancements of swelling in a higher SDS concentration region until the degrees of swelling reached maximum values. The SDS concentration at which the swelling began to appear was in reasonable agreement with the critical aggregation concentration (cac) value reported for the aqueous PEO system. For the cases where NaCl was present, the swelling behavior of PEO gel was different from that when NaCl was absent in the following way. The concentrations where the swelling begins to appear, and hence those where the degree of swelling rises steeply, decreased with an increase in NaCl concentration. The ultimate degrees of swelling at higher concentration regions also decreased with an increase in the NaCl concentration. The lowering of the SDS concentrations at which the PEO gel began to swell is in line with the decreases in the cmc of SDS solutions containing NaCl and also with the decreases in the cac of PEO solution. Electronic Publication     

pH-induced micelle formation of poly(histidine-co-phenylalanine)-block-poly(ethylene glycol) in aqueous media

Poly[(L-histidine)-co-(L-phenylalanine)]-block-poly(ethylene glycol) (HF-b-PEG) diblock copolymers were synthesized to be used for preparation of pH-sensitive polymeric micelles. First, HF block was synthesized by ring opening copolymerization of L-histidine and L-phenylalanine N-carboxyanhydride, and then the resulting copolymer was coupled with PEG. The pKa value of diblock copolymer can be controlled by adjusting the histidine/phenylalanine ratio in HF block. It is observed that the block copolymers form micelles in aqueous media and that the micelles are spherical in shape with a unimodal distribution. The micelle is formed at pH higher than pKa of block copolymer while it is not formed at lower pH. This is because the protonation of histidine residue in the HF block converts the hydrophobic core into hydrophilic one at lower pH. Acid-Base titration profile of HF41(5600)-b-PEG, HF56(5500)-b-PEG, H(5100)-b-PEG and 0.1 N NaCl.     

Highly luminescent SiO(2) beads with multiple QDs: Preparation conditions and size distributions

Multiple CdTe quantum dots (QDs) were incorporated in SiO(2) beads using a reverse micelle route (i.e., a water-in-oil emulsion) and a precursor solution of SiO(2)-coated CdTe QDs as the water phase. The QDs in the beads retained their initial photoluminescence efficiency (56%) because they had a thin SiO(2) shell that prevented removal of the ligands from their surface during incorporation. Because of the SiO(2) sol in the precursor solution, the size of the water pools in water-in-oil emulsion increased to 700±320nm compared to 25±5nm when an aqueous CdTe QD solution was used. The size of the beads prepared in the water pools depended strongly on the preparation parameters (water phase injection speed, tetraethyl orthosilicate concentration, reaction time). The beads were easily separated into three size ranges (60±23, 160±40, and 650±200nm) by filtering for further application.     

Molecular dynamics study of salt effects on micellization of N-dodecyl-N,N-dimethyl-3-ammonio-1-propane-sulfonate

In this paper, molecular dynamics simulation methods were used to investigate salt effects on micellization of N-Dodecyl-N,N-Dimethyl-3-Ammonio-1-Propane-sulfonate (SB12-3) in aqueous solution. It is proved that micelle shapes transform from spherical to prolate spherical shape after 30.0?ns simulation with different NaCl and CaCl₂ concentration. By comparison with the eccentricity value without salt addition, SB12-3 shows salt tolerance behaviors due to its unique “inner salt” structure of amphiphilic surfactant. Radial distribution function (RDF), hydrophobic groups solvent accessible surface area (SASA), hydrogen bond, and the deuterium order parameter (S_CD) are to elucidate salt effects on SB12-3 micelle formation. The radius of micelle is achieved by the related RDF value and in accordance with other researches. The addition of NaCl and CaCl₂ didn’t change the structure of micelle significantly and have little effects on the interactions between SB12-3 and water molecule. By comparison with the results without salt system, SASA of hydrophobic groups is almost the same, and SASA of hydrophilic groups and total molecule fluctuates only slightly. This further indicates that the surface of micelles is more hydrophilic due to the strong interactions between SB12-3 and water molecules. The existence of NaCl and CaCl₂ will enhance the hydrophilic interactions.     

Synthesis of amphiphilic poly(ether-amide) dendrimer endcapped with poly(ethylene glycol) grafts and its solubilization to salicylic acid

An amphiphilic dendrimer (DPEA-PEG) grafting polyethylene glycol at the terminals was prepared by endcapping of dendritic poly(ether-amide) (DPEA) with isocyanate terminated linear polyethylene glycol (PEG-NCO). The molecular structure was verified by gel permeation chromatography (GPC), ¹H NMR and FT-IR. The micelle characteristic of DPEA-PEG in water was investigated. The critical micelle concentration (CMC) was determined by a fluorescence technique to be 55.5 mg/L. The hydrodynamic radius of micelles was measured by dynamic light scattering (DLS) to be 76.2 nm. The UV–vis spectrum showed that the solubility of salicylic acid increased from 1.91 to 2.78 mg/L when the concentration of DPEA-PEG attained 5 mg/mL in an aqueous solution.     

Synthesis and micelle formation of triblock copolymers of poly(methyl methacrylate)-b-poly(ethylene oxide)-b-poly(methyl methacrylate) in aqueous solution

Amphiphilic triblock copolymers of poly(methyl methacrylate)-b-poly(ethylene oxide)-b-poly(methyl methacrylate) (PMMA-b-PEO-b-PMMA) with well-defined structure were synthesized via atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) initiated by the PEO macroinitiator. The macroinitiator and triblock copolymer with different PMMA and/or PEO block lengths were characterized with ¹H and ¹³C NMR and gel permeation chromatography (GPC). The micelle formed by these triblock copolymers in aqueous solutions was detected by fluorescence excitation and emission spectra of pyrene probe. The critical micelle concentration (CMC) ranged from 0.0019 to 0.016 mg/mL and increased with increasing PMMA block length, while the PEO block length had less effect on the CMC. The partition constant K_v for pyrene in the micelle and in aqueous solution was about 10⁵. The triblock copolymer appeared to form the micelles with hydrophobic PMMA core and hydrophilic PEO loop chain corona. The hydrodynamic radius R_h,app of the micelle measured with dynamic light scattering (DLS) ranged from 17.3 to 24.0 nm and increased with increasing PEO block length to form thicker corona. The spherical shape of the micelle of the triblock copolymers was observed with an atomic force microscope (AFM). Increasing hydrophobic PMMA block length effectively promoted the micelle formation in aqueous solutions, but the micelles were stable even only with short PMMA blocks.     

Thermosensitive sol–gel transition behaviors of poly(ethylene oxide)/aliphatic polyester/poly(ethylene oxide) aqueous solutions

The thermoreversible gelation of Pluronic [poly(ethylene oxide) (PEO)–polypropylene oxide (PPO)–PEO] aqueous solutions originates from micelle formation and micelle volume changes due to PEO–water and PPO–water lower critical solution temperature behavior. The micelle volume fraction is known to dominate the sol–gel transition behavior of Pluronic aqueous solutions. Triblock copolymers of PEO and aliphatic polyesters, instead of PPO, were prepared by hexamethylene diisocyanate coupling and dicyclohexyl carbodiimide coupling. Through changes in the molecular weight and hydrophobicity of the polyester middle block, the hydrophobic–hydrophilic balance of each block was systematically controlled. The following aliphatic polyesters were used: poly(hexamethylene adipate) (PHA), poly(ethylene adipate) (PEA), and poly(ethylene succinate) (PESc). With the hydrophobicity and molecular weight of the middle block increasing, the critical micelle concentration at the same critical micelle temperature decreased, and the absolute value of the micellization free energy increased. The micelle size was rather insensitive to temperature but slightly decreased with increasing temperature. PEO–PHA–PEO and PEO–PEA–PEO triblock copolymers needed high polymer concentrations to form gels. This was ascribed to the tight aggregation of PHA and PEA chains in the micelle core due to strong hydrophobic interactions, which induced the contraction of the micelle core. However, because of the relatively hydrophilic core, a PEO–PESc–PEO aqueous solution showed gelation at a low polymer concentration. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 772–784, 2004     

Probing the micellization of diblock and triblock copolymers of poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide) and poly(ethylene glycol) in aqueous and NaCl salt solutions

The micelle formation of a series of amphiphilic block copolymers in aqueous and NaCl solutions was studied by a fluorescent probe technique using pyrene as a "model drug". These copolymers were synthesized from poly (ethylene glycol) (PEG) and l-lactide by a new calcium ammoniate catalyst. They had fixed PEG block lengths (44, 104 or 113 ethylene oxide units) and various poly(l-lactide) (PLLA) block lengths (15–280 lactide units). The critical micelle concentration (cmc) was found to decrease with increasing PLLA content. The distinct dissimilarity of the cmc values of diblock and triblock copolymers based on the same block length of PEG provided evidence for the different configurations of their micelles. It was also observed that the introduction of NaCl salt significantly contributed to a decrease in the cmcs of the copolymers with short PEG and PLLA blocks, while it had less influence on the cmcs of copolymers with long PEG or PLLA blocks. The dependence of partition coefficients ranging from 0.2×10⁵ to 1.9×10⁵ on the PLLA content in the copolymer and on the micelle configuration was also discussed. The contribution of NaCl salt to increasing the partition of pyrene into a micellar phase was observed.     

2-(Acylaminoethyl)trimethylammonium chloride surfactants: synthesis and properties of aqueous solutions

The title cationic surfactants have been synthesized by reaction of carboxylic acids with N, N-dimethylethylenediamine to give an intermediate amidoamine. The latter was quaternized with methyl iodide; the product was transformed into the corresponding chloride surfactant by ion-exchange on a macroporous resin. Adsorption and aggregation of these surfactants in H ₂O have been studied by surface tension measurement. Additionally, solution conductivity, electromotive force (H ₂O), and Fourier transform IR spectroscopy (D ₂O) have been employed to investigate micelle formation. Increasing the length of R resulted in the following changes: an increase in the micelle aggregation number; a decrease in the minimum area per surfactant at the solution/air interface, the critical micelle concentration, and the degree of counterion dissociation. Gibbs free energies of adsorption at the solution/air interface and micelle formation in water were calculated and compared to those of alkyltrimethylammonium chlorides. The contribution to these free energies from surfactant methylene groups (in the hydrophobic tail) and the head group was calculated. The former are similar to those of other cationic surfactants. The corresponding free-energy contributions of head groups are smaller (i.e., more negative), indicating that the transfer of this group from bulk water to the interface (for adsorption) and/or to the micelle (aggregate formation) is more favorable. This is attributed to intermolecular hydrogen bonding of monomers at the interface, and/or in the aggregate, via the amide group, in agreement with our Fourier transform IR data. Our results are compatible with a micellar interface closer to the amide nitrogen than to the quaternary ammonium ion.     

Synthesis and micellization of amphiphilic poly(sebacic anhydride)–poly(ethylene glycol)–poly(sebacic anhydride) block copolymers

Amphiphilic biodegradable block copolymers [poly(sebacic anhydride)–poly(ethylene glycol)–poly(sebacic anhydride)] were synthesized by the melt polycondensation of poly(ethylene glycol) and sebacic anhydride prepolymers. The chemical structure, crystalline nature, and phase behavior of the resulting copolymers were characterized with ¹H NMR, Fourier transform infrared, gel permeation chromatography, and differential scanning calorimetry. Microphase separation of the copolymers occurred, and the crystallinity of the poly(sebacic anhydride) (PSA) blocks diminished when the sebacic anhydride unit content in the copolymer was only 21.6%. ¹H NMR spectra carried out in CDCl₃ and D₂O were used to demonstrate the existence of hydrophobic PSA domains as the core of the micelle. In aqueous media, the copolymers formed micelles after precipitation from water‐miscible solvents. The effects on the micelle sizes due to the micelle preparation conditions, such as the organic phase, dropping rate of the polymer organic solution into the aqueous phase, and copolymer concentrations in the organic phase, were studied. There was an increase in the micelle size as the molecular weight of the PSA block was increased. The diameters of the copolymer micelles were also found to increase as the concentration of the copolymer dissolved in the organic phase was increased, and the dependence of the micelle diameters on the concentration of the copolymer varied with the copolymer composition. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1271–1278, 2006     

Fluorescence Probe Studies of Ionic Micelles in Concentrated Salt Solutions

We have investigated the effect of salt concentration and temperature on the average aggregation number and micro-polarity of the interior of micelles of sodium dodecyl sulfate (SDS). sodium tetradecyl sulfate (STDS) and lithium dodecyl sulfate (LiDS). The transient fluorescence decay of micelle-solubilized pyrene has been measured and analyzed. An exponent weighted average aggregation number <n>_e was obtained by this technique. For SDS and STDS in NaCl solution, <n>_e increases as the temperature is lowered or salt concentration is increased <n>_e increased from ～ 50 to ～ 250 over [NaCl] = 0 to 0.8 M. Due to the strong counterion binding of lithium in the micellar solution, the LiDS micelle is much, smaller and does not increase appreciabily even at [LiCl] =0.8 M. From the fluorescence spectrum fine structure of pyrene and the fluorescence decay of the monomer and excimer, we can understand the local polarity and the water penetration to the interior of the micelle upon addition of salts and with changing temperature. The interior of the micelle becomes more nonpolar as the salt concentration is increased and the temperature is lowered. A complete kinetic analysis of the time–dependence of the fluorescence is given. The kinetic analysis is in agreement with the results reached by fluorescence spectral analysis.     

荧光探针法研究新型Gemini表面活性剂在水溶液中的聚集行为

以芘为荧光探针、二苯酮为猝灭剂,用稳态荧光探针法测定了新型Gemini表面活性剂的临界胶团浓度(CMC)、胶团聚集数(N_agg)及胶团微极性.研究了Gemini表面活性剂结构和氯化钠浓度对CMC、N_agg、胶团微极性的影响.结果表明,新型Gemini表面活性剂的CMC比常规表面活性剂的CMC低1—2个数量级.当疏水基碳原子数增加时,CMC依次降低,N_agg增大,胶团微极性减小.当氯化钠浓度增大时,N_agg增大,胶团微极性减小.     

Porous thin films based on photo-cross-linked star-shaped poly(D,L-lactide)s

Self-assembly processes and subsequent photo-cross-linking were used to generate cross-linked, ordered microporous structures on the surfaces of well defined four-arm star-shaped poly(D,L-lactide) (PDLLA) thin films. The four-arm star-shaped PDLLAs were synthesized using an ethoxylated pentaerythritol initiator. Solutions of the PDLLAs were cast in a humid environment, and upon solvent evaporation, ordered honeycomb structures (or breath figures) were obtained. Correlations between molar mass, polymer solution viscosity, and pore dimensions were established. The average pore dimension decreased with increasing polymer solution concentration, and a linear relationship was observed between relative humidity and average pore dimensions. Highly ordered microporous structures were also developed on four-arm star-shaped methacrylate-modified PDLLA (PDLLA-UM) thin films. Subsequent photo-cross-linking resulted in more stable PDLLA porous films. The photo-cross-linked films were insoluble, and the honeycomb structures were retained despite solvent exposure. Free-standing, structured PDLLA-UM thin films were obtained upon drying for 24 h. Ordered microporous films based on biocompatible and biodegradable polymers, such as PDLLA, offer potential applications in biosensing and biomedical applications.     

Physicochemical characterization of polymeric micelles constructed from novel amphiphilic polyphosphazene with poly(N-isopropylacrylamide) and ethyl 4-aminobenzoate as side groups

An amphiphilic graft polyphosphazene (PNIPAm/EAB-PPP) composed of oligo-poly(N-isopropylacrylamide) (PNIPAm) as hydrophilic segments and ethyl 4-aminobenzoate (EAB) as hydrophobic groups was synthesized via ring-opening polymerization and subsequent substitution reaction. The molar ratio of the PNIPAm segment to EAB group was 1.85:0.15. The lower critical solution temperature (LCST) of copolymer was 32.6 degrees C as determined by turbidity method. Micellization behavior of PNIPAm/EAB-PPP in an aqueous phase was characterized by fluorescence technique, 1H NMR, dynamic light scattering (DLS) and transmission electron microscopy (TEM). The critical micelle concentration (CMC) of the graft copolymer in aqueous solution was 0.1mg/ml. The number-averaged particle size of spherical micelles was 80 nm at 25 degrees C with a narrow distribution. TEM also revealed that inter-micellar aggregation was induced in the micelle solution at temperature above LCST of graft copolymer. The thermosensitive PNIPAm/EAB-PPP micelles may be of help to regulate the loading and release of hydrophobic drugs.     

Synthesis and pH-sensitive micellization of doubly hydrophilic poly(acrylic acid)-b-poly(ethylene oxide)-b-poly(acrylic acid) triblock copolymer in aqueous solutions

A doubly hydrophilic triblock copolymer poly(acrylic acid)-b-poly(ethylene glycol)-b-poly(acrylic acid) (PAA-b-PEO-b-PAA) with M _w/M _n = 1.15 was synthesized by atom transfer radical polymerization of t-butyl acrylate (tBA), followed by acidolysis of the PtBA blocks. The pH-sensitive micellization of PAA-b-PEO-b-PAA in acidic solution was investigated by potentiometric titration, fluorescence spectrum, dynamic light scattering and zeta potential. The pK _a was 6.6 and 6.0 in deionized water and in 0.1 mol/L NaCl solution, respectively. The copolymer formed micelles composed of a weakly hydrophobic core of complexed PAA and PEO and a hydrophilic PEO shell in 1 mg/mL solution at pH < 5.5 due to hydrogen bonding. The critical micelle concentration was 0.168 mg/mL at pH 2.0. At pH < 4.5, steady and narrow distributed micelles were formed. Increasing pH to 5.0, unsteady and broad distributed micelles were observed. At pH > 5.5, the micelle was destroyed owing to the ionization of the PAA blocks.     

Micelle formation of N-(1,1-dihydroperfluorooctyl)- and N-(1,1-dihydroperfluorononyl)-N,N,N-trimethylammonium chlorides

Micelle formation of N-(1,1-dihydroperfluorooctyl)-N,N,N- and N-(1,1-dihydroperfluorononyl)-N,N,N-trimethylammonium chloride was investigated by analyzing the concentration dependence of the electric conductivity and of the activity of the counterion (Cl(-)) of the solution. The three micellization parameters for ionic surfactants, the micellization constant K(n), the micelle aggregation number n, and the number of counterions per micelle m, were determined by combination of electric conductivity and counterion concentration. The present analysis employed two slopes of the plots of specific conductivity against surfactant concentration below and above the critical micelle concentration and the mass action model of micelle formation. The aggregation numbers thus obtained were relatively small, while the degrees of counterion binding to the micelle (m/n) were found to be quite large, much larger than expected from the small aggregation numbers. Thermodynamical parameters of the micellization were evaluated from the temperature dependence of the three parameters, and the micellization of the fluorinated surfactant was found to be enthalpy-driven. A CF(2) group in the perfluorocarbon chain was found to be 1.44 times larger in hydrophobicity for micellization than a CH(2) group in the hydrocarbon chain.     

Effects of additives on the structure of rhamnolipid (biosurfactant): a small-angle neutron scattering (SANS) study

Pollution of soils and sediments by heavy metals is an environmental concern. Among the remedial techniques, soil washing is proving to be reliable. Biosurfactant rhamnolipid has shown its potential as a washing agent. In this research, small angle neutron scattering (SANS) was employed to investigate the size and morphology of rhamnolipid aggregates and micelle structure in the presence of heavy metals Cu, Zn, and Ni. The results indicate the importance of the pH of the system in the morphology of the aggregates in the rhamnolipid solution. Creation of a basic condition by addition of 1% NaOH led to the formation of large aggregates (>2000 A) + micelles with RG approximately 17 A while in the acidic environment with 1% NaCl, large polydisperse vesicles with a radius about 550-600 A were formed. The size of the aggregates in both acidic and basic condition is fine enough to ease the flow of the rhamnolipid solution through the porous media with the pore sizes as small as 200 nm.