Adhesion and Physicochemical Properties of Soy Protein Modified by Sodium Bisulfite

Soy protein adhesives with a high solid content (28–39 %) were extracted from soy flour slurry modified with sodium bisulfite (NaHSO₃) at different concentrations. 11S‐dominated soy protein fractions (SP 5.4) and 7S‐dominated soy protein fractions (SP 4.5) were precipitated at pH 5.4 and pH 4.5, respectively. The objective of this work was to study the effects of NaHSO₃ on adhesion and physicochemical properties of soy protein. The adhesion performance of NaHSO₃‐modified SP 4.5 was better than SP 5.4; the wet strength of these two fractions was from 2.5 to 3.2 MPa compared with 1.6 MPa of control soy protein isolate. SDS‐PAGE results revealed the reducing effects of NaHSO₃ on soy protein. The isoelectric pH of soy protein decreased as NaHSO₃ increased due to the induced extra negative charges (RS‐SO₃^?) on the protein surface. The rheological properties of soy protein adhesives were improved significantly. Unmodified samples SP 5.4 and SP 4.5 had clay‐like properties and extremely high viscosity, respectively; with 2–8 g/L NaHSO₃ modification, both SP 5.4 and SP 4.5 had a viscous cohesive phase with good flowability. Overall, NaHSO₃‐modified soy protein adhesives in our study have many advantages over the traditional soy protein isolate adhesive such as better adhesion performance, higher solid content but with good flowability and longer shelf life.     

Biopolymer-stabilized emulsions on the basis of interactions between β-lactoglobulin and ι-carrageenan

ι-Carrageenan and β-lactoglobulin (β-lg) stabilized oil-in-water (O/W) emulsions, which can be used for the oral administration of bioactive but environmentally sensitive ingredients, have been successfully prepared. The effects of protein/polysaccharide ratios, total biopolymer concentration, environmental stress (thermal processing and sonication), and pH on the complex formation between ι-carrageenan and β-lactoglobulin have been investigated. We found that β-lactoglobulin and ι-carrageenan stabilized emulsions can be formed at pH values of 6.0, 4.0, and 3.4. However, the microstructures of emulsions stabilized by β-lactoglobulin and ι-carrageenan was identified by optical microscopy, and it indicated that the emulsion prepared at pH 6.0 flocculated more extensively, while its hydrodynamic radius was much bigger than those prepared at pH 4.0 and 3.4. Regarding rheological properties, the emulsion of pH 6.0 showed a more solid-like behavior but with a lower viscosity than those of pH 4.0 and 3.4. The optimum concentration ranges for β-lg and ι-carrageenan to form stable emulsions at pH 4.0 and 3.4 were 0.3 wt-%–0.6 wt-% and 0.4 wt-%–0.7 wt-%, respectively.     

Adsorption behavior of β-lactoglobulin onto polyethersulfone membrane surface

The adsorption of whey protein onto polyethersulfone (PES) membrane was investigated by static adsorption experiments to understand fouling mechanism and optimize the process condition to minimize the membrane fouling. Adsorption isotherm was applied to calculate the isotherm parameters such as adsorption capacity (K_F) and surface heterogeneity (1/n). The K_F values increased about 3.7 times at pH 3.0, 1.5 times at pH 5.2, and 2.3 times at pH 9.0 compared to that at pH 7.0. The hydrophobic interaction by dissociation of dimer structure of β-lactoglobulin to monomer structure at acidic and alkaline conditions showed the greatly increasing of the amount of protein adsorption by the protein and membrane interaction which might form the strong and rigid protein layer on the polymeric membrane surface. The addition of salt reduced the protein adsorption on PES membrane because of the interactions between charged protein molecules and salt ions.     

Miniemulsion copolymerization of styrene and butyl acrylate initiated by redox system at lower temperature-preparation and polymerization of miniemulsion

Miniemulsions of styrene and butyl acrylate with sodium dodecyl sulfate (SDS) as the surfactant and hexadecane (HDE) and cetyl alcohol (HDL) as cosurfactants were prepared under high-speed stirring or ultrasonification. Results indicate that the stability of miniemulsions produced with HDE is more stable than that with HDL, when the feeding method, in which the cosurfactant is mixed with monomers, is used. There is an optical ratio (¼) of the surfactant to the cosurfactant for maximum stabilization of the miniemulsions. The miniemulsions prepared by ultrasonification are much more stable than those by high-speed stirring. Also, a stable miniemulsion can be prepared at lower temperature (45°C) when homogenizing way of ultrasonification is used. The emulsions were of a droplet-size range common to miniemulsions and some of them exhibited long-term stabilities (3 months). When these emulsions were initiated, particle formation occurred predominantly by monomer droplet nucleation. The effects of temperature, ultrasonification time, ratio of monomers, and concentrations of surfactant, cosurfactant, and initiator on the polymerization rate, conversion, and particle size were determined. It was found that the miniemulsion copolymerization of styrene and butyl acrylate with a midial amount of a redox initiator ((NH₄)₂S₂O₈/NaH SO₃) at lower temperature (45°C) can be carried out successfully by using a suitable amount of the surfactant SDS (10 mM) and the cosurfactant HDE (40 mM), when a homogenizing way of ultrasonification is applied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2029–2039, 1998     

Characterization of fish oil-in-water emulsions using light-scattering,nuclear magnetic resonance,and gas chromatography-headspace analyses

The effect of the molecular environment on the physical and oxidative properties of homogenized or microfluidized fish oil-in-water emulsions (5% w/w tuna oil in pH 7 phosphate buffer) stabilized by whey protein isolate (WPI, 1 or 5% w/w) or lecithin (2.5% w/w) was examined. Laser light-scattering measurements showed that WPI-stabilized emulsions had smaller particle sizes than lecithin-stabilized emulsions, and that higher pressures reduced the particle size. WPI afforded more protection against oil oxidation than did lecithin, as evidenced by the lower headspace propanal of emulsions as measured by GC-headspace analysis, despite the larger interface in WPI-stabilized emulsions. Reducing the concentration of WPI in emulsions from 5 to 1% decreased the oxidative stability of WPI-stabilized emulsions. The ¹H NMR transverse relaxation times (T ₂) of FA chains in emulsion droplets stabilized by the same surfactants made by homogenization or microfluidization were different and not always related to particle size. The higher mobility (i.e., longer T ₂) of the unsaturated parts of the FA chains within an oil droplet, compared with the saturated parts, suggests that the unsaturated components tended to stay in the core of the oil droplets. This experimental result supports the hypothesis reported in other literature that the more unsaturated FA are buried in the oil core of oil-in-water emulsions. The lack of a universal correlation between particle size and oxidation suggests that the mobility of particles in an emulsion has an influence on the rate of oxidation.     

The effect of micellar lifetime on the rate of solubilization and detergency in sodium dodecyl sulfate solutions

The slow relaxation time (τ₂) of sodium dodecyl sulfate (SDS) micelles, measured by the pressure-jump technique, was maximum at 200 mM concentration at 25°C, indicating that the most stable micelles are formed at this concentration. This is presumably related to the optimum molecular packing in the micelle. The rate of solubilization of benzene and Orange OT dye into SDS solutions was also maximum at 200 mM concentration. The results are explained as follows: The distance between micelles (i.e., intermicellar distance) decreases as the surfactant concentration (or the number of micelles) increases, resulting in a stronger electric repulsion between micelles. Therefore, the micelles become more rigid, due to the compressive force of intermicellar repulsion, as the concentration increases up to 200 mM SDS. With further increase in the SDS concentration, the micellar shape changes from spherical to cylindrical to accommodate more surfactant molecules in the solution and to minimize the free energy of the system. The interior of the tightly packed micelles is more hydrophobic than that of loosely packed micelles and, therefore, the tightly packed micelles induce rapid solubilization of nonpolar molecules (e.g., benzene, Orange OT) into these micelles.     

Production of thermostable alkaline lipase on vegetable oils from a thermophilic Bacillus sp. DH4, characterization and its potential applications as detergent additive

BACKGROUND: The alkaline lipase production on vegetable oils as sole carbon source, its characterization and effect of different commercial detergents and surfactants on enzymatic activity from thermophilic Bacillus sp. DH4 was investigated. RESULTS: The organism grew on mannose, but the amount of lipase secreted was significantly less than on vegetable oils. This study identified a simple substrate for lipase production and established the utility of groundnut oil for increasing the lipase yield. The enzyme was compatible with various ionic and non‐ionic surfactants as well as commercial detergents. Lipase activity was strongly inhibited by sodium dodecyl sulfate (SDS), but not by Triton X‐100 or Triton X‐114. The best assay conditions observed for this lipase was found to be pH 9.0 and 50 °C. The enzyme was stable at alkaline pH and considerable activity was observed at pH 10 and it retained 93% of the residual activity at 60 °C. The lipase showed a novel property of marked activation at alkaline pH. Wash performance analysis of commercial detergent for removal of fatty stains improved upon addition of lipase. CONCLUSION: The production on cheap vegetable oils, novel properties and resistance towards various surfactants and tolerance to commercial detergents make this lipase a potential additive for detergent formulations. Significance and impact of the study: Bacillus sp. produces alkaline and thermostable lipase on cheap vegetable oils and its compatibility can find use in the detergent industry. Copyright © 2008 Society of Chemical Industry     

Interaction between bisphenol A and micelles of ionic surfactants

Interactions between bisphenol A (BPA) and ionic surfactants—cationic hexadecyltrimethylammonium bromide (HTAB) and anionic sodium dodecylsulfate (SDS)—were studied by measuring interfacial tensions and the intensities of pyrene fluorescence. The critical micellar concentrations (CMC) decreased with an increase in the BPA concentration, and the degree of that decrease was greater in HTAB than in SDS. In those micelles, BPA interacted more strongly with HTAB than with SDS. Conversely, BPA adsorbed on the air-water interface cooperatively with the surfactants, even though almost no adsorption of BPA itself was observed. This cooperative adsorption was more enhanced with HTAB than with SDS. Thus, BPA worked on the surfactants to stabilize the micelles and interfacial adsorption. The stability gained by the addition of BPA was greater on the interface than in the micelle. This was evidence of decreased hydrophilicity of the head group of the ionic surfactant, which interacted with BPA, because this decrease acted on the surface activities of the surfactants more directly than on the micelle stabilities. Pyrene fluorescence measurements yielded identical results for the effect on micelle stabilities. It is noteworthy that the fluorescence intensity of peak 1, l ₁, decreased with an increase in BPA concentrations at constant concentrations of surfactant greater than the CMC, but the peak ratio, l ₁/l ₃, remained almost unchanged. This fact was also related to the interaction of BPA with the hydrophilic head groups in the surfactant micelle.     

Foamability of Detergent Solutions Prepared with Different Types of Surfactants and Waters

In the development of new detergent products, it is important to test the foaming behavior of different types of surfactants. Different types and concentrations of surfactant solutions prepared with three types of water are expected to present differences in their foamability. In this study, foam volumes produced by cetyl trimethyl ammonium bromide (CTAB; C₁₉H₄₂BrN), Tween 80^® (T80; C₆₄H₁₂₄O₂₆) and sodium dodecylsulfate (SDS; C₁₂H₂₅NaO₄S) aqueous solutions (0.5, 1.0 and 1.5%, w/v) were compared using a stirring system, rotating at 8,000, 9,500 and 13,500 rpm. The foamability produced by CTAB, SDS and T80 solutions, in a concentration range between 0.2 and 1.0% (w/v), prepared using deionized, hard and hypersaline water were also compared. Foam volumes were higher at a stirring speed of 9,500 rpm than at 8,000 rpm. However, the results obtained at 9,500 and 13,500 rpm were not significantly different. In general, SDS solutions produced higher foam volumes than CTAB and T80 solutions. Water characteristics did not seem to influence significantly the foamability of the three types of surfactants in the studied concentrations. These studies related with foaming behavior appear to be an important step in the pre-formulation of detergent products, particularly in cosmetics and pharmaceutics.     

Effects of natural antioxidants on iron-catalyzed lipid oxidation of structured lipid-based emulsions

The effects of iron, pH, and natural antioxidants (α-tocopherol, gallic acid, and quercetin) on oxidation of structured lipid-based emulsions were evaluated. Ten percent oil-in-water emulsions were formulated with a canola oil/caprylic acid structured lipid and stabilized with 0.5% whey protein isolate. The PV, anisidine values, and Totox values of emulsions stored at 50°C were measured over a 15-d period. Iron significantly (P<0.05) increased lipid oxidation rates compared to control emulsions. Greater iron-catalyzed lipid oxidation occurred in the pH 3.0 emulsions compared to their pH 7.0 counterparts. Quercetin and gallic acid exhibited significant (P<0.05) prooxidant effects on total oxidation in the pH 3.0 emulsions. Emulsions at pH 7.0 were relatively stable to oxidation throughout the storage period. Because of the ability of some of these natural antioxidants to exhibit prooxidant activity, care should be exercised when adding them to food systems containing transition metals.     

Kinetic study of Hg(II)-promoted substitution of cyanide from hexacyanoferrate(II) in an anionic surfactant medium by 2,2′-bipyridine

The kinetic investigation of Hg(II)-promoted reaction between [Fe(CN)₆]⁴⁻ and 2,2′-bipyridine (Bipy) has been performed in anionic sodium dodecyl sulfate (SDS) micellar medium by recording the surge in absorbance at 400 nm, corresponding to ultimate reaction product [Fe(CN)₄ Bipy]²⁻ using UV–visible spectrophotometer. Pseudo-first-order condition has been used to examine the progress of reaction as a function of temperature, [Fe(CN)₆⁴⁻], ionic strength, [SDS], pH, [Hg²⁺], and [Bipy] by changing one parameter at a time. The results exhibit that [Hg²⁺], [SDS], and pH are the decisive parameter showing maximum reaction rate at 1.5 × 10⁻⁴ mol dm⁻³, 6.0 × 10⁻³ mol dm⁻³, and 3.8, respectively. [Fe(CN)₆]⁴⁻ does not show any appreciable effect on the critical micellar concentration (CMC) of SDS as the polar head of SDS and [Fe(CN)₆]⁴⁻ both are negatively charged. Variable order kinetics was observed for [Fe(CN)₆]⁴⁻ and Bipy in their examined concentration range. The reverse response observed in the reaction rate with [KNO₃] shows a negative salt effect. The K⁺ provided by K₄[Fe(CN)₆] and KNO₃ decreases the repulsion between the negatively charged heads of the surfactant molecules thereby decreasing the CMC of SDS. The negative value for the entropy of activation also supports the interchange dissociative (I_d) mechanism recommended by us.     

Permeability alterations in unilamellar liposomes due to betaine-type zwitterionic and anionic surfactant mixed systems

The alterations caused by betaine-type zwitterionic and anionic surfactant mixed systems in the permeability of unilamellar liposomes have been investigated. The partition coefficient of these systems, at different molar fractions, between the aqueous phase and the lipid bilayer of liposomes has been determined. These surfactant mixed systems were formed byN-dodecyl-N,N-dimethylbetaine (C₁₂-Bet) and sodium dodecyl sulfate (SDS) in the presence of 20 mM PIPES buffer and 110 mM Na₂SO₄, at pH 7.21. Unilamellar liposomes were prepared from egg phosphatidylcholine and phosphatidic acid (9:1 molar ratio). The release of the fluorescent agent 5-(6)-carboxyfluorescein induced by the systems has been studied at sub-solubilizing concentrations. When the molar fraction of C₁₂-Bet/SDS is about 0.4, the critical micelle concentration values of these systems exhibit a minimum, whereas their partition coefficient between the aqueous phase and lipid bilayer of lipid bilayers shows a maximum. There is a consistent correlation between the partition coefficient and the ability of the different systems of surfactants to modify the permeability of liposomes.     

Extraction of erythromycin‐A using colloidal liquid aphrons: I. Equilibrium partitioning

Colloidal liquid aphrons (CLAs) are surfactant‐stabilised solvent droplets which have recently been explored for use in pre‐dispersed solvent extraction (PDSE). In this work, the equilibrium partitioning of a microbial secondary metabolite, erythromycin, has been studied using both CLAs (formulated from 1% (w/v) Softanol 120 in decanol and 0.5% (w/v) SDS in water) and surfactant‐containing, two‐phase systems. The equilibrium partitioning of erythromycin was found to be strongly influenced by the extraction pH, and exhibited a marked change either side of the pK_a of the molecule. A modified form of the Henderson–Hasselbach equation could be used as a simple design equation to predict the equilibrium partition coefficient (m_eryt = C_org /C_aq) as a function of pH. For extraction experiments with dispersed CLAs where pH > pK_a, m_eryt values as high as 150 could be obtained and the erythromycin could be concentrated by factors of up to 100. Experiments were also carried out in surfactant‐containing, two‐phase systems to determine the effect of individual surfactants used for aphron formulation on erythromycin partitioning. For extraction at pH 10 neither the Softanol (a non‐ionic surfactant) nor SDS (an anionic surfactant) had any influence on the equilibrium erythromycin partition coefficients. For stripping at pH 7, however, it was found that recovery of erythromycin from the organic phase decreased with increasing concentration of SDS, although again the Softanol had no influence on the equilibrium. The effect of SDS was attributed to a specific electrostatic interaction between individual erythromycin and SDS molecules under stripping conditions. The m_eryt values and concentration factors achievable in the two‐phase systems were considerably less than those for the PDSE experiments. The physical properties of the two‐phase systems, ie density, viscosity, interfacial tension, etc, and the equilibrium distribution of the surfactants were also determined in relation to subsequent studies on the kinetics of erythromycin extraction. © 2000 Society of Chemical Industry     

An octaethylene glycol monododecyl ether-based mixed micellar assay for determining the lipid acyl hydrolase activity of patatin

Patatin was extracted from potato tubers (Solanum tuberosum L. cv. Spunta) and purified to homogeneity by ammonium sulfate salt fractionation and one sole chromatographic step. A spectrophotometric mixed micellar assay for patatin lipid acyl hydrolase (LAH) activity was designed with the detergent octaethylene glycol monododecyl ether (C₁₂E₈). Patatin LAH used p-nitrophenyl butyrate (PNP-butyrate) as substrate when solubilized in (C₁₂E₈) micelles. In the mixed micellar system, patatin LAH responds to the PNP-butyrate surface concentration expressed as mol% (=[PNP-butyrate]·100/([detergent]-critical micellar concentration)) and not to the molarity of PNP-butyrate. The kinetic parameters were determinined; V _max was independent of the mixed micelle concentration, as was K _m, when expressed as mol%. However, K _m was dependent on C₁₂E₈ concentration when expressed in molar concentration. C₁₂E₈/PNP-butyrate proved to be a reliable system for assaying patatin LAH activity and is superior to the commonly used Triton X-100 and SDS methods. It permits investigation of the substrate requirements of patatin LAH activity because the concentration-independent K _m can be determined both in mol% and as the absolute number of substrate molecules per micelle. In addition, the detergent did not affect the enzyme activity.     

Production,Biochemical Characterization and Detergents Application of Keratinase from the Marine Actinobacterium Actinoalloteichus sp. MA-32

The present study is the first report on poultry feathers as a novel, inexpensive substrate for the production of a thermo‐ and detergent stable keratinase from a marine actinobacterium belonging to the genus Actinoalloteichus. Medium composition and culture conditions for the keratinase production by Actinoalloteichus sp. MA‐32 were optimized using two statistical methods: Plackett–Burman design was applied to find the key ingredients and conditions for the best yield of enzyme production and central composite design used to optimize the concentration of the five significant variables: whole chicken feather, soy flour, MgSO₄·7H₂O, KH₂PO₄ and NaCl. The medium optimization resulted in a 19.30‐fold increase with a 31.99 % yield with a specific activity of 3842.57 U mg^?1 and the molecular weight was estimated as 66 kDa. The enzyme was optimally active at pH 8–10 and temperature 50–60 °C and it was most stable up to pH 12 and 10–14 % of NaCl concentration. The enzyme activity was reduced when treated with Hg²⁺, Pb²⁺, Tween‐80, 1,10‐phenanthroline and EDTA and stimulated by Fe²⁺, Mg²⁺, Cu²⁺, Ca²⁺, Ni²⁺, Mn²⁺, SDS, ethoxylated (9.5EO) octylphenol, DMSO, sodium sulfite and β‐mercaptoethanol. The keratinase exhibited a significant stability and compatibility with most of the tested commercial laundry detergents, demonstrating its feasibility for inclusion in laundry detergent formulation. These results suggest that this extracellular keratinase may be a useful alternative and eco‐friendly route for handling the abundant amount of waste feathers or for applications in detergent formulation and other industrial processes.     

Synthesis and characterization of hollow polyaniline microtubes and microbelts with nanostructured walls in sodium dodecyl sulfate micellar solutions

Doped polyaniline in its emeraldine salt form (PANI‐ES) were successfully prepared by in situ chemical oxidative polymerization using various concentrations of sodium dodecyl sulfate (SDS) micellar solutions. Structural analysis using field‐emission scanning electron microscopy and high‐resolution transmission electron microscopy showed that the morphologies of fabricated PANI‐ES contain hollow tube‐like and belt‐like structures with thickness in the range of 100–200 nm, diameters in the range of 1–5 μm, and lengths up to several tens and hundreds of micrometers. The changes of morphology from particle‐like into microtube‐like or microbelt‐like structure with nanostructured walls are strongly dependent on the concentration of SDS. The conductivities of fabricated PANI‐ES with 0.1 M SDS content at room temperature are 80% higher than those of PANI‐ES without SDS, perhaps because SDS may serve as a dopant or the formation of one‐dimensional structure to improve the conductivity of PANI‐ES. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

The Clouding of an Anionic Surfactant in Acid Solution: Mechanistic and Analytical Implications

The clouding of sodium dodecyl sulfate (SDS) in strongly acidic solutions has seen analytical use, but its mechanism has generally been misinterpreted. In the present work it was found that as SDS slowly hydrolyzes to form dodecanol, the solution passes through a series of compositions at which the aggregation of surfactant is promoted by nucleation onto traces of insoluble dodecanol. This occurred at concentrations well below the critical micelle concentration of SDS and resulted in mixed aggregates that grew to macroscopic size, giving the solution a cloudy appearance. The increasing dodecanol content eventually caused coalescence into a coacervate phase which evolved into a solid layer of dehydrated dodecanol. The process, which continued over an extended period, depended on the temperature and the concentration and type of acid used. The early stages of SDS aggregation were monitored through the I ₁/I ₃ ratio of pyrene fluorescence, which confirmed the existence of micelle-like aggregates at low surfactant concentration. The mixed SDS/dodecanol systems formed in acid hydrolysis were mimicked in neutral solution by combining the appropriate amounts of SDS, dodecanol, and NaCl. Clouding and the formation of a coacervate phase generally proceeded in a similar manner in these solutions.     

Effect of Acid Modification of Soy Glycinin on Its Interfacial and Emulsifying Properties

Soybean glycinin [11S] was modified by an acidic pH treatment to improve its emulsifying properties. Glycinin was obtained by isoelectric precipitation (11Sn) and then treated with acid (11St). The oil–water interfacial tension and rheology were measured. The rate constants of adsorption (k_a) and rearrangement (k_r) of proteins at the interface and the dilational (E), elastic (E_d), and viscous modulus (E_v) of the protein interfacial film were determined. Particle size distribution (PSD), interfacial protein concentration (Γ), and the creaming destabilization rate constants k_s (for the smaller droplets) and k_l (for the larger droplets) were analyzed in oil‐in‐water emulsions (25% v/v of oil and 75% v/v of 1 mg/mL protein solution in 10 mM sodium phosphate buffers, pH 7.0 and 2.5, respectively). Compared to the native protein, the acid treatment caused irreversible denaturation of 11S and significantly increased Г, k_a, E, E_d, and E_v (P ≤ 0.05), resulting in a greater rate of protein adsorption to the interface and a stronger interfacial film. PSD showed a bimodal distribution with peaks above and below 4 μm. Smaller droplets moved toward smaller diameters for 11St. It also showed lower values of creaming destabilization constants k_s (d ≤ 4 μm) and k_l (d ≥ 4 μm) than 11Sn. In conclusion, acid treatment of 11S enhances the creaming stability of its emulsions by improving the interfacial properties and reducing the droplet size.     

Micellization of pH‐sensitive poly(butadiene)‐block‐poly(2 vinylpyridine)‐block‐poly(ethylene oxide) triblock copolymers: Complex formation with anionic surfactants

The micellization of three tailor‐made triblock copolymers, such as PB₁₀₀–P2VP₁₀₀–PEO₁₀₄, PB₁₈₅–P2VP₁₀₈–PEO₁₅₄, and PB₃₇–P2VP₁₁₅–PEO₂₄₁, having similar total molecular weights and constant poly(2‐vinylpyridine) (P2VP) sequence lengths, was investigated as a function of pH and sodium dodecyl sulfate (SDS) concentration. At pH 7 the formation of intermicellar aggregates was observed, especially for copolymers of low poly(ethylene oxide) (PEO) content. A pH decrease from 7 to 3 leads to a particle size increase due to the electrostatic repulsion of the protonated P2VP chains. The influence of the PEO sequence length was also observed for zeta potential values. At pH 3, in the absence of SDS, core–shell–corona micelles are formed whereas in the presence of small amount of SDS (degree of neutralization DN = 0%–50%), a complex is formed between SDS and the protonated P2VP which leads to the shrinkage of the shell and thus to a decrease of the micellar sizes. For higher DN values, the micellar sizes increase due to the formation of large agglomerates and a transition occurs from a monomodal to a bimodal size distribution. Furthermore, it turned out that secondary aggregation, such as intermicellar aggregation, can completely be avoided if the degree of polymerization (DPn) of the water‐soluble block is significantly higher than the DPn of the water‐insoluble sequence. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45313.     

Preparation of poly(butyl methacrylate)/γ‐Al2O3 nanocomposites via ultrasonic irradiation

A new technique (ultrasonic irradiation) has been employed to prepare poly(n‐butyl methacrylate) PBMA/γ‐Al₂O₃ nanocomposites, taking advantages of the multiple effects of ultrasonic irradiation, such as dispersion, pulverization and activation. When subjected to ultrasonic irradiation, n‐butyl methacrylate (BMA) is polymerized to form poly(n‐butyl methacrylate) (PBMA) latex without any chemical initiators, and the monomer conversion reaches 72.5% in 25 min. At an appropriate pH, surfactant bilayers are formed through electrostatic interactions between γ‐Al₂O₃ nanoparticles and the anionic surfactant sodium dodecyl sulfate (SDS), which adsorb BMA. After ultrasonic induced polymerization of BMA in the presence of nanoparticles of γ‐Al₂O₃, the γ‐Al₂O₃ nanoparticles are encapsulated by PBMA shells formed. The influence of factors such as pH, surfactant concentration and the nanoparticle content is investigated. The FTIR spectra show that there are still polymers tightly adsorbed by nanoparticles even after extraction by acetone for 72 h. The difference observed in the XPS spectra of nanocomposite residues and the pure γ‐Al₂O₃ nanoparticles may indicate some interactions between γ‐Al₂O₃ nanoparticles and the PBMA matrix. Furthermore, the feasibility of SDS bilayer formation and encapsulating polymerization is proven by XPS characterization. © 2001 Society of Chemical Industry