Formation and microstructure transition of F127/TX-100 complex

Formation and structure transition of the complex composed of triblock copolymer F127 and nonionic surfactant TX-100 have been investigated by 1H NMR spectroscopy, dynamic light scattering (DLS), and isothermal titration calorimetry (ITC). Three TX-100 concentration regions are identified, within which TX-100/20 mg/mL F127 complex undergoes different temperature-induced structure transitions. In low concentration region (< 9.42 mM), F127 single molecular species (unimers) wrap around TX-100 micelles forming F127/TX-100 complex with TX-100 micelle as the skeleton at a lower temperature (5 degrees C), and the skeleton transfers to F127 micelle at higher temperature (40 degrees C); in intermediate TX-100 concentration region (9.42-94.85 mM), the skeleton of F127/TX-100 complex transfers from TX-100 micelle successively into F127 micelle and TX-100 micelle again upon heating. The interaction of F127 with TX-100 is saturated in high TX-100 concentration region (> 157.57 mM), and free TX-100 micelles coexist with larger clusters of F127/TX-100 complexes. In addition, TX-100-induced F127/TX-100 complex formation and structure transition are also investigated at constant temperatures. The results show that within 5-10 degrees C, F127 unimers mainly adsorb on the surface of TX-100 micelles just like normal water soluble polymers; in the temperature region of 15-25 degrees C, TX-100 micelles prompts F127 micelle formation. Within 30-40 degrees C, TX-100 inserts into F127 micelles leading to the breakdown of F127 aggregates at higher TX-100 concentrations, and the obtained unimers thread through TX-100 micelles forming complex with TX-100 micelle as skeleton.     

Cinnamoyl Pluronic F127 as a Stimuli-Sensitive Amphiphile

Cinnamoyl Pluronic F127 (CP F127) was prepared by reacting cinnamoyl chloride and Pluronic F127. On the ¹H NMR spectrum of CP F127, 1.2 moiety of cinnamoyl group was found to be attached to one molecule of CP F127. Using pyrene as a fluorescence probe, it was found that not only Pluronic F127 but also CP F127 could be readily assembled into micelles, and the critical micelle concentration was around 0.015 mg/ml and 0.03 mg/ml, respectively. Pluronic F127 in aqueous solution (2% w/v) could form no particles in 10–20°C, but particles (ca. 30 nm in diameter) were detected on a dynamic light scattering machine in 25–40°C possibly due to the thermal micellization. However, CP F127 was assembled into particles (ca. 230 nm) even in the lower temperature range, possibly because of the intermolecular hydrophobic interaction of the cinnamoyl group. The particle size of CP F127 strongly depended on the medium temperature and UV irradiation time. CP F127 was a good emulsifier for the preparation of O/W emulsions. The oil droplet size markedly increased upon UV irradiation (254 nm, 6 W), possibly because of the photo-dimerization of cinnamoyl group, but it was little affected by the temperature change (10–40°C).     

Effect of solvent–matrix interactions on structures and mechanical properties of micelle‐crosslinked gels

Previous studies on hydrogels crosslinked by acrylated PEO₉₉–PPO₆₅–PEO₉₉ triblock copolymer (F127DA) micelles demonstrate outstanding strength and toughness, which is attributed to the efficient energy dissipation through the hydrophobic association in the micelles. The current study further focuses on how the solvent property affects the structures and the mechanical properties of F127DA micelle crosslinked polyacrylamide gels. Binary solvents comprised of dimethyl sulfoxide (DMSO) and water are used to adjust the polymer/solvent interactions, which consequently tune the conformations of the polymer chains in the network. The presence of DMSO significantly decreases the strength but increased the stretchability of the gels, whereas the overall tensile toughness remained unchanged. In situ small‐angle X‐ray scattering measurements reveal the deformation of micelles along with the stretching direction. A structure evolution mechanism upon solvent change is proposed, according to the experimental observations, to explain influence of solvent quality on the mechanical properties of the micelle‐crosslinked gels. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 473–483     

Mechanisms of micellization and rheology of PEO-PPO-PEO triblock copolymers with various architectures

Micelle formation was followed by micro-DSC and rheology for aqueous solutions of two copolymers of PEO-PPO-PEO, the Pluronic F127 (from BASF) and the EG56 (from PolymerExpert), a branched copolymer built with three chains of F127 type. It is shown that micellization is endothermic and that, for both polymers, the enthalpy of formation/melting is proportional to total concentration. The rheology of the solutions was carefully analyzed, before gelation for F127, and it reveals firstly the progressive changes of solubility of the unimers (decease of relative solution viscosity), followed by micelle formation over a 10 degrees C range. In this range, the micelle concentration dependence on temperature was deduced from enthalpy measurements and the corresponding volume fractions were derived. Viscosity was interpreted within the framework of well-known theories for hard sphere suspensions (Krieger-Dougherty or Quemada) based on an analogy between micelles and nanosized hairy grain suspensions. The gel state is achieved due to formation of the colloidal crystal. For EG56, the rheology is quite different; as the aggregation increases with temperature, a progression is observed from Newtonian to visco-elastic liquid. The characteristic frequency, defined by the relation G(') = G('), for EG56 varies with temperature and the corresponding times increase by two orders of magnitude according to an Arrhenius law. The frequency dependence of G(') and G(') at different temperatures can be superposed with a horizontal shift factor and a small amplitude adjustment. There is no elastic solid formation in this case. The "gelation" of these two copolymers is compared to the physical gelation of cold-set gels (gelatin).     

Competitive Destabilization/Stabilization of β‐Lactoglobulin Foam by PEO‐PPO‐PEO Polymeric Surfactants

The effect on β‐lactoglobulin foamability and foam stability of the poly(ethylene oxide)‐poly(propylene oxide) block copolymers F127 (PEO₉₉‐PPO₆₅‐PEO₉₉), molecular weight 12500 g/mol, and P85 (PEO₂₆‐PPO₃₉‐PEO₂₆), molecular weight 4600 g/mol, has been investigated at constant protein concentration, 10 µM (0.2 mg/L), and varying block copolymer concentrations, ranging from 0.02 to 1600 µM. Foam was generated by means of air sparging and the foam volume and liquid volume of the foam were measured for one hour. It was found that foam stabilized by F127 or P85 in the concentration range 20–1600 µM contained a larger liquid volume initially than pure β‐lactoglobulin foam. Furthermore, β‐lactoglobulin foamability was only marginally affected by the presence of F127, while it was reduced in an interval of low P85 concentrations. The protein foam stability was retained in the presence of the larger polymer F127, whereas P85 largely reduced the stability, indicating that the size of the polymeric surfactant is important. The results are discussed in relation to surface rheological properties and forces acting across foam films. Steric repulsion generated between the surfaces of foam films is suggested to be the main stabilizing factor in dry foam containing F127. The instability of the mixed β‐lactoglobulin/P85 system is suggested to be caused by two effects. First, there are incompatible stabilization mechanisms of block copolymer and protein, as supported by previous surface rheological data. Second, there is a reduced importance of long‐range steric repulsion when P85 is added, compared to the case where F127 and β‐lactoglobulin are mixed.     

Formation of Vesicles and Micelles in Aqueous Systems of Tetrameric Acids as Determined by Dynamic Light Scattering

A comprehensive dynamic light scattering (DLS) study on the system BP10Na₄/water is presented. BP 10Na₄ is a tetrameric fatty acid in sodium form. In order to change molecular packing conditions both electrolyte (NaCl) and alcohol (1-butanol, 1-pentanol) are added to the surfactant system. Phase diagrams of the systems reveal not only an extensive micellization, but also the occurrence of a lamellar liquid crystalline D phase. The DLS study shows an existence of vesicles at very dilute BP10Na₄ concentrations ( ?cmc) and also a co-existence of micelles and vesicles at higher BP10Na₄ concentrations. Cryo-TEM pictures verify the existence of the vesicles. Based on the DLS and SLS experiments the weight-average molar mass of the micelles are estimated to be 13500 g/mol at 100 mM NaCl and 22700 g/mol at 600 mM. The corresponding aggregation numbers are 13 and 22, respectively.     

Diffusion Coefficients and Structure Properties in the Pluronic F127/n‐C4H9OH/H2O System

Abstract

Diffusion coefficients of different aggregates in aqueous solutions formed by an amphiphilic block copolymer, Pluronic F127 (F127), were determined by cyclic voltammetry, and the critical micelle concentration (CMC, 4.31 × 10^?4 mol L^?1) of F127 was obtained. The added n‐butanol facilitates the formation of micelles from the monomers of F127 and makes the critical micelle temperature (CMT) of F127 solutions decrease. The diffusion coefficient of the F127 micelles decreases relatively fast at first with increasing n‐butanol and then the decreasing trend slows after the solubilization of n‐butanol in micelles reaches maximum.     

Metallo‐supramolecular block copolymer micelles: Improved preparation and characterization

Micelles prepared from amphiphilic block copolymers in which a poly(styrene) segment is connected to a poly(ethylene oxide) block via a bis‐(2,2′:6′,2″‐terpyridine‐ruthenium) complex have been intensely studied. In most cases, the micelle populations were found to be strongly heterogeneous in size because of massive micelle/micelle aggregation. In the study reported in this article we tried to improve the homogeneity of the micelle population. The variant preparation procedure developed, which is described here, was used to prepare two “protomer”‐type micelles: PS₂₀‐[Ru]‐PEO₇₀ and PS₂₀‐[Ru]‐PEO₃₇₅. The dropwise addition of water to a solution of the compounds in dimethylformamide was replaced by the controlled addition of water by a syringe pump. The resulting micelles were characterized by sedimentation velocity and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission electron microscopy of negatively stained samples. Sedimentation analysis showed virtually unimodal size distributions, in contrast to the findings on micelles prepared previously. PS₂₀‐[Ru]‐PEO₇₀ micelles were found to have an average molar mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly less than after micelle preparation by the standard method) and an average hydrodynamic diameter (d_h) of 18 nm. For PS₂₀‐[Ru]‐PEO₃₇₅ micelles, the corresponding values were M = 603,000 g/mol (31 protomers per micelle) and d_h = 34 nm. The latter particles were found to be identical to the “equilibrium” micelles prepared in pure water. Both micelle types had a very narrow molar mass distribution but a much broader distribution of s values and thus of hydrodynamic diameters. This indicates a conformational heterogeneity that is stable on the time scale of sedimentation velocity analysis. The findings from electron microscopy were in disagreement with those from the sedimentation analysis both in average micelle diameter and in the width of the distributions, apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4458–4465, 2004     

Rheology and phase behavior of thermo‐reversible pentablock terpolymer hydrogel

Thermo‐reversible phase behaviors and rheological properties of a pentablock terpolymer solution, poly(N‐isopropylacrylamide)‐b‐poly(ethylene oxide)‐b‐poly(propylene oxide)‐b‐poly(ethylene oxide)‐b‐poly(N‐isopropylacrylamide) (PNIPAM₁₅₀‐PEO₁₃₆‐PPO₄₅‐PEO₁₃₆‐PNIPAM₁₅₀), are investigated in comparison with its precursor, PEO₁₃₆‐PPO₄₅‐PEO₁₃₆ (F108). It is found that the critical gelation concentration of the terpolymer solution is only about 11 wt %, which is significantly lower than that of F108 solution (～22 wt %). The 11 wt % terpolymer solution displays higher viscosity, stronger gel strength, and fast thermo‐responsive behavior compared with the 22 wt % F108 solution. The 11 wt % terpolymer solution shows a typical Newtonian fluid behavior at 30 °C due to the presence of individual spherical micelles, and presents an elastic gel property at 41 °C because of the formation of the close‐packed micelle aggregates. Cryogenic transmission electron microscopy (cryo‐TEM) and variable‐temperature ¹H NMR results demonstrate that the sol–gel phase transition mechanism is mainly related to the hydrophilic/hydrophobic transition of PPO and PNIPAM groups by external temperature stimulus. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1335–1342     

Thermodynamic studies of interaction between cetylpyridinium bromide and lysozyme by means of calorimetric titrations

In this study, we have investigated the micellization characteristics of n-cetylpyridinium bromide (CPB) and lysozyme–CPB system using isothermal titration calorimetry (ITC) technique. The ITC operates in a stepwise addition mode, providing an excellent method of determination of critical micelle concentration (CMC) and enthalpy of demicellization (and hence micellization). The micellization characteristics of CPB have been investigated by microcalorimetric technique at 25, 30, 35, and 40 °C in a buffer solution of Tris(hydroxymethyl)aminomethane and pH of 7.3. A scheme to describe lysozyme–CPB interaction has also been proposed on the basis of ITC technique in a buffer solution of Tris(hydroxymethyl)aminomethane at 30 °C, pH of 7.3, 0 mM NaCl, and 1 mM NaCl. The enthalpy changes associated with micelle dissociation were temperature and lysozyme concentration dependent, indicating the importance of hydrophobic interactions. The ΔG _mic was found to be negative, implying that, micellization, as expected, occurs spontaneously once the CMC has been reached. The values of ΔG _mic were found to become more negative with increasing temperature (in case of micellization of CPB) and with increasing the lysozyme concentration (in the case of lysozyme–CPB). The ΔS _mic was also found to decrease with increasing temperature in both cases. The presence of NaCl (1 mM) in the solutions decreased the CMC of CPB.     

Self-assembly control of a pyridine-containing diblock copolymer by perfluorinated counter anions during salt-induced micellization

The micelle formation of poly[(4-pyridinemethoxymethyl)styrene]-block-polystyrene (PPySt-b-PSt) was studied in the nonselective solvent using perfluoroalkyl carboxylic acids. PPySt-b-PSt showed no self-assembly into micelles in THF, because this solvent was nonselective for the copolymer. Dynamic light scattering demonstrated that the diblock copolymer formed the micelles in the solvent in the presence of perfluoroalkyl carboxylic acids in which the number of carbons in the perfluoroalkyl chains was over eight. ¹H NMR revealed that the micellization proceeded through the salt formation of the pyridinium perfluoroalkyl carboxylate and through the aggregation of the perfluoroalkyl chains in the counter anions. The hydrodynamic radius and the aggregation number of the micelles increased with an increase in the length of the perfluoroalkyl chain. The copolymer needed less carboxylic acid with longer perfluoroalkyl chain to form the micelles. The copolymer produced the micelles with lower aggregation number and higher critical micelle concentration at higher temperature, although the micellar size was almost independent of the temperature. The micelles were unstable with respect to the variation in the temperature, and were dissociated into the unimers with the increase in the temperature. The micelles, however, were reconstructed by decreasing the temperature. This dissociation–reconstruction of the micelles was controlled reversibly not only by the temperature but also by the concentration of the perfluoroalkyl carboxylic acid. An increase in the acid concentration suppressed the dissociation into the unimers, while promoting the reconstruction of the micelles.     

Facile fabrication of thermally responsive Pluronic F127-based nanocapsules for controlled release of doxorubicin hydrochloride

Novel core–shell-structured Pluronic-based nanocapsules with thermally responsive properties were successfully prepared using a modified emulsification/solvent evaporation method. The nanocapsules were constructed through the cross-linking reaction between p-nitrophenyl-activated Pluronic F127 and hyaluronic acid (HA) (named Pluronic F127/HA) or poly(ε-lysine) (PL) (named Pluronic F127/PL) at the organic/aqueous interface. The formation, size, and thermal responsiveness of the nanocapsules were characterized by ¹H NMR, transmission electron microscopy (TEM) and dynamic light scattering (DLS). The resultant shell-cross-linked nanocapsules exhibit a larger volume transformation (26 times change in volume for Pluronic F127/HA and 31 times for Pluronic F127/PL) over a temperature range of 4–37 °C because of the temperature-dependent dehydration of cross-linked Pluronic F127 polymer chains. The nanocapsules are about 72?±?4 nm (polydispersity index [PDI]?=?0.08) for Pluronic F127/PL (69?±?5 nm, PDI?=?0.10 for Pluronic F127/HA) at 37 °C with narrow size distribution and expand to about 226?±?23 nm (PDI?=?0.34) for Pluronic F127/PL (206?±?20 nm, PDI?=?0.3) for Pluronic F127/HA at 4 °C with broad size distribution in aqueous solutions. The nanocapsules were used to encapsulate and control the release of doxorubicin hydrochloride (DOX·HCl) in aqueous solution. DOX·HCl was physically encapsulated in the nanocapsules using a soaking–freeze-drying–heating procedure. The release curve and release kinetics disclosed that the thermally responsive hollow nanocapsules are good carries for drug delivery.     

Water-soluble ABC triblock copolymers based on vinyl ethers: Synthesis by living cationic polymerization and solution characterization

Water-soluble ABC triblock copolymers of methyl vinyl ether (MVE), ethyl vinyl ether (EVE), and methyl tri(ethylene glycol) vinyl ether (MTEGVE) of various block sequences and carrying 20 monomer units in each block were synthesized by living cationic polymerization. In addition to the triblocks, one AB diblock, one BA diblock, and one statistical copolymer of MVE and MTEGVE carrying 20 units of each type of monomer were synthesized as controls. Moreover, three homopolymers each carrying 20 units of MVE and end groups of varying hydrophobicity were synthesized using three different initiators. The molecular weights and molecular weight distributions of all the polymers were determined by gel permeation chromatography (GPC) in tetrahydrofuran (THF). The number average degrees of polymerization (DP_ns) and composition of all the polymers were calculated by proton nuclear magnetic resonance (¹H-NMR) spectroscopy. The molecular weights and degrees of polymerization corresponded to the values expected from the monomer/initiator ratios. The calculated polydispersities were reasonably narrow at 1.3. Aqueous GPC studies at room temperature on the triblock copolymers showed that the polymers exist as isolated chains (unimers) in solution but they tend to assemble and form micelles in the presence of a sufficiently high salt concentration apparently due to the insolubility of the EVE units under the latter conditions. Triblocks with a different block sequence exhibited a different susceptibility to salt-induced micellization, as indicated by the retention volume of the micelles and the relative micelle/unimer peak areas. Similarly, the cloud points of the triblock copolymers covered a relatively wide temperature range from 56 to 72°C. These differences in micellization and cloud points suggest a profound effect of the location of the hydrophilic MTEGVE block on copolymer association. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1181–1195, 1997     

Polymerized mixed aggregates containing gadolinium complex and CCK8 peptide

Two novel amphiphilic unimers containing an aliphatic hydrophobic chain (PDA) with two C≡C triple bonds and hydrophilic heads presenting the chelating agent DTPAGlu and the CCK8 bioactive peptide, respectively, have been prepared by solid phase synthesis. Aggregates obtained by mixing together PDA-DTPAGlu, or its Gd(III) complex, and PDA-L2-CCK8 in 70/30 molar ratio before and after a polymerization process carried out by UV irradiation have been structurally characterized by means of small angle neutron scattering. The relaxivity properties of aggregates containing Gadolinium complexes have also been investigated. Elongated mixed micelles have been observed, in which the relaxivity value r _1p for each Gadolinium complex, measured at 20 MHz and 298 K, is around 12 mM^–1 s^–1.     

Synthesis,CMC determination and influence of the micelles, β-cyclodextrin,ionic liquids and liposome(dipalmitoylphosphatidylcholine) vesicles on the kinetics of an outer-sphere electron transfer reaction

The surfactant–cobalt(III) complex, cis-[Co(trien)(4AMP)(DA)](ClO₄)₃, trien = triethylenetetramine, 4AMP = 4-aminopyridine, DA = dodecylamine was synthesized and characterized by various spectroscopic and physico-chemical techniques. The critical micelle concentration (CMC) value of this surfactant–cobalt(III) complex in aqueous solution was found out from conductance measurements. The conductivity data (at 303, 308, 313, 318 and 323 K) were used for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔG _m ^° , ΔH_m and ΔS _m ^° ). Also the kinetics of reduction of this surfactant–cobalt(III) complex by hexacyanoferrate(II) ion in micelles, β-cyclodextrin, ionic liquids (ILs) and in liposome vesicles (DPPC) media were studied at different temperature. The rate constant for the electron transfer reaction in micelles was found to increase with increase in the initial concentration of the surfactant–cobalt(III) complex. This peculiar behaviour of dependence of second-order rate constant on the initial concentration of one of the reactants has been attributed to the presence of various concentration of micelles under different initial concentration of the surfactant–cobalt(III) complex in the reaction medium. Inclusion of the long aliphatic chain of the surfactant complex ion into β-cyclodextrin leads to decrease in the rate constant. Below the phase transition temperature of DPPC, the rate decreased with increasing concentration of DPPC, while above the phase transition temperature the rate increased with increasing concentration of DPPC. It is concluded that below the phase transition temperature, there is an accumulation of surfactant–cobalt(III) complex at the interior of the vesicle membrane through hydrophobic effects, and above the phase transition temperature the surfactant–cobalt(III) complex is released from the interior to the exterior surface of the vesicle. In the presence of ionic liquid medium the second order rate constant for this electron transfer reaction for the same complex was found to increase with increasing concentration of ILs has also been studied. An outer-sphere mechanism is proposed for all these reactions and the results have been explained based on the hydrophobicity of the ligand and the reactants with opposite charges.     

Conductivity and Surface Tension Study for Cucurbit[7]uril Inclusion Complex of Cetyltrimethylammonium Chloride in Aqueous Solution

Conductivity and surface tension measurements have been carried out at temperatures between 298.15 K for cetyltrimethylammonium Chloride (CTAC) + H₂O and CTAC + Cucurbit[7]uril (CB[7]) + H₂O systems. The apparent critical micelle concentrations, the dissociation degree of the micelle, the hydrophobic contribution of the transfer free energy for the hydrocarbon chain of CTAC, the stoichoimetry and inclusion constants for the inclusion complex of CTAC with CB[7] have been determined. The influence of CB[7] and its complex on the micellization processes of CTAC is analyzed. It is shown that CB[7] partly screened the hydrophobic hydrocarbon chain of CTAC molecules from contact with the surrounding medium, and retarded the formation of CTAC micelles in a certain extent. CB[7] and the inclusion complex do not have any surface activity. The CB[7] and its complexes do not participate the formation of micelles of CTAC, and the complex has no effect on the micelle properties once the micelles are formed. The result suggests that β-CB[7] forms strong complex with CTAC, and the stoichoimetry is found to be 1:1, and the inclusion constants of CB[7]-CTAC complex are almost the same in different CB[7] solutions.     

Physicochemical Investigation of the Micellar Behavior of a Diblock (PEO)62-b-(PBO)33 Copolymer in Water and its Interaction with Ionic Surfactants

The physicochemical investigations on the associative, micellar, and thermodynamic properties of a diblock (PEO)₆₂-b-(PBO)₃₃ copolymer in aqueous medium and its interaction with ionic surfactants were carried out by using surface tensiometry, laser light scattering, and steady-state fluorescence spectroscopy. Surface tension and fluorescence measurements were used to find out the critical micelle concentration (CMC) and related thermodynamic parameters of micellization copolymer at various temperatures. The data from dynamic light scattering (DLS) were helpful to obtain the values of hydrodynamic radii (R_h), volume (υ_h), and hydrodynamic expansion parameter (δ_h) of the copolymer micelle. Likewise, the measurements from static light scattering (SLS) were employed to determine weight-average molar (M_w), association number (N_w), thermodynamic radius (R_t), thermodynamic volume (υ_t), anhydrous volume (υ_a), and thermodynamic expansion parameter (δ_t) of the copolymer micelles in the temperature range of 20–50°C. Similarly, the interactions between (PEO)₆₂-b-(PBO)₃₃ and two ionic surfactants, sodium dodecyl sulfate (SDS) and hexadecyltrimethylammonium bromide (CTAB), have also been investigated by fluorescence spectroscopy and DLS at 30°C. Similarly, the interactions between (PEO)₆₂-b-(PBO)₃₃ and two ionic surfactants, sodium dodecyl sulfate and hexadecyl trimethylammonium bromide, have also been investigated by fluorescence spectroscopy and DLS in detail.     

Effect of β-Cyclodextrin on the Micellization of Cetyltrimethylammonium in Aqueous Solution at High Temperature

Molar volume and conductivity measurements have been carried out at 338.2 K for cetyltrimethylammonium chloride (CTAC) + H₂O and CTAC + β-cyclodextrin (β-CD) + H₂O systems. The apparent critical micelle concentrations, the dissociation degree of the micelle, the transfer free energy for the hydrocarbon chain of CTAC, the standard partial molar volumes of CTAC in aqueous β-CD solution and the stoichoimetry for the inclusion complex of CTAC with β-CD have been determined. The influence of β-CD and its complex on the micellization processes of CTAC are analyzed under this temperature. It is shown that β-CD partly screened the hydrophobic hydrocarbon chain of CTAC molecules from contact with the surrounding medium, and retarded the formation of CTAC micelles in a certain extent. The thermodynamic activity of CTAC is decreased. The β-CD and its complexes do not participate the formation of micelles of CTAC, and the complex have no effect on the micelle properties once the micelles are formed. Based on a simple model, the number of CH₂ groups entered the cavity of β-CD was calculated. The result suggests that β-CD forms strong complex with CTAC, and the stoichoimetry is found to be 2:1. This supports our conductivity results.     

Self-Assembling Behavior of Polyglyceryl-Modified Silicone Surfactant in Aqueous Solution

We report interesting self-assembly behavior of a polyglyceryl-modified silicone surfactant in the aqueous solution; the sample has been characterized through measurements of surface tension, transmission electron microscopy (TEM), dynamic light scattering (DLS), and small-angle x-ray scattering (SAXS). Aqueous solutions of this surfactant had a low critical aggregation concentration (CAC) and surface tension (21.5 mN · m^?1), substantially lower than those reported for polyether-modified silicone surfactants with a similar molecular architecture. DLS and TEM revealed self-assembled spherical micelles with a narrow size distribution. At higher concentrations (10 wt%), linear packing of micelles was observed, while the micelle size distribution remained similar (50–90 nm). SAXS data could be fitted through the use of a core–shell model and implied that the core radius remained roughly 4.3–6.0 nm for all solutions of the surfactant analyzed. The origin of its curious aggregates behavior is attributed to hydrogen bonding, steric effects, and the directionality of bond angle from the polyglyceryl block of this novel class of silicone surfactant. This type of surfactant coupling lipophilic segments assembles the cores of the micelles in water which may find positive factors for potential applications such as microreaction compartmentalization.     

Synthesis and self‐assembling of poly(N‐isopropylacrylamide‐block‐poly(L‐lactide)‐block‐poly(N‐isopropylacrylamide) triblock copolymers prepared by combination of ring‐opening polymerization and atom transfer radical polymerization

Novel thermo‐responsive poly(N‐isopropylacrylamide)‐block‐poly(l ‐lactide)‐block‐poly(N‐isopropylacylamide) (PNIPAAm‐b‐PLLA‐b‐PNIPAAm) triblock copolymers were successfully prepared by atom transfer radical polymerization of NIPAAm with Br‐PLLA‐Br macroinitiator, using a CuCl/tris(2‐dimethylaminoethyl) amine (Me₆TREN) complex as catalyst at 25 °C in a N,N‐dimethylformamide/water mixture. The molecular weight of the copolymers ranges from 18,000 to 38,000 g mol^?1, and the dispersity from 1.10 to 1.28. Micelles are formed by self‐assembly of copolymers in aqueous medium at room temperature, as evidenced by ¹H NMR, dynamic light scattering (DLS) and transmission electron microscopy (TEM). The critical micelle concentration determined by fluorescence spectroscopy ranges from 0.0077 to 0.016 mg mL^?1. ¹H NMR analysis in selective solvents confirmed the core‐shell structure of micelles. The copolymers exhibit a lower critical solution temperature (LCST) between 32.1 and 32.8 °C. The micelles are spherical in shape with a mean diameter between 31.4 and 83.3 nm, as determined by TEM and DLS. When the temperature is raised above the LCST, micelle size increases at high copolymer concentrations due to aggregation. In contrast, at low copolymer concentrations, decrease of micelle size is observed due to collapse of PNIPAAm chains. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3274–3283