Synthesis,characteristics, and phase behavior of a thermosensitive and pH‐sensitive polyelectrolyte

A series of poly(N‐isopropylacrylamide‐co‐methacrylic acid‐co‐octadecyl acrylate) (poly(NIPAM‐co‐MAA‐co‐ODA)) with different monomer molar ratios was synthesized. Critical micelle concentration (CMC) of the polyelectrolyte solution was determined and the CMC increase with methacrylic acid content in the polyelectrolyte. The phase behaviors of the polyelectrolyte solution were studied, and the effects of various factors on the phase transition were discussed. The experimental results indicate that the lower critical solution temperature and the phase transition pH depend on the monomer molar ratio in the polyelectrolyte. Effect of polyelectrolyte concentration on phase transition pH was studied, and results shown that the phase‐transition pH is independent of the polyelectrolyte concentration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Determination of critical micelle concentration (CMC) of nonionic surfactants by donor-acceptor interaction with lodine and correlation of CMC with hydrophile-lipophile balance and other parameters of the surfactants

The nonionic surfactants form donor-acceptor complexes with iodine in aqueous medium. The spectral absorption and the shift in the λ_max of l₂ upon complexation have been exploited to determine the critical micelle concentration (CMC) of Tweens, Brijs, and Triton X-100. The CMC values obtained closely agree with those determined by other methods, including measurements of static surface tension, differential refractive index, and iodine solubilization. The spectral characteristics of the complex salt Kl₃ can be utilized as well to derive similar information. The CMC and the spectral shift can be correlated with the weight fraction of the polyoxyethylene groups and the hydrophile-lipophile balance (HLB) in various ways, with the parameters in these relationships depending on the series to which the surfactant belong. Because both CMC and HLB depend on temperature, the results and the relations obtained are temperature-dependent; those presented are with reference to 298 K.     

硫辛酸钠的表面活性对制备无溶剂硫辛酸的影响

对硫辛酸制备工艺中水相法纯化过程进行了研究,结果表明硫辛酸钠具有表面活性,若其浓度高于临界胶束浓度,则会加剧硫辛酸聚集,不利于结晶,进而发生聚合反应生成黏稠物质。因此,需要加大水量,降低硫辛酸钠的浓度,当浓度低于临界胶束浓度时,收率会大幅增加。采用电导法测定硫辛酸钠的临界胶束浓度为0.253 mol/L,对应的水量为19.2倍,这与测定硫辛酸水量与收率关系的工艺实验得到的最适宜水量正好吻合。     

Crosslinkable micelles from diblock amphiphilic copolymers based on vinylbenzyl thymine and vinylbenzyl triethylammonium chloride

Polymeric micelles (PMs) composed of self‐assembled amphiphilic block copolymers were synthesized from vinylbenzyl thymine (VBT) and vinylbenzyl triethylammonium chloride (VBA) exhibiting improved physical stability. Three diblock copolymers of different chemical compositions and similar molecular weights (polydispersities below 1.5) were obtained via nitroxide mediated radical polymerization. Critical micelle concentration (CMC) was determined by dye micellization method, the shift of the absorption peak of the anionic (EY) due to the interactions with non‐assembled chains and auto‐assembled copolymers was followed. Polymeric systems exhibited good stability revealing that a higher proportion of cationic monomers in the diblock reduce the CMC. Furthermore, after the core of PMs was photocrosslinked by UV irradiation, the CMC decreases notably. Kinetic release studies using EY dye as probe demonstrated that both, higher VBA ratios in the polymer and higher UV‐irradiation, slow down the dye release. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41947.     

High performance biocompatible cellulose‐based microcapsules encapsulating gallic acid prepared by inverse microsuspension polymerization

In this study, the preparation of biocompatible cellulose‐based microcapsules encapsulating gallic acid (GA), an important antioxidant of Bambara groundnut extracts, by water‐in‐oil inverse microsuspension polymerization was studied. GA and carboxymethyl cellulose (CMC) were selected as core and shell materials, respectively. For high encapsulation efficiency, CMC was firstly modified (modified‐CMC (m‐CMC)) with 3‐(trimethoxysilyl)propyl methacrylate (MPS) as a silane coupling agent. It was subsequently polymerized with methacrylic acid (MAA) monomer through a radical route, forming a PMAA grafted m‐CMC (m‐CMC‐g‐PMAA) biocompatible polymer shell. Using CMC:MPS in a ratio of 75:25 (w/w %), highly water‐soluble m‐CMC containing a C=C bond for further radical polymerization was obtained. After inverse microsuspension polymerization at various ratios of m‐CMC:MAA, highly stable spherical m‐CMC‐g‐PMAA microcapsules encapsulating GA were formed in all ratios. It was observed that the encapsulation efficiency increased with increase in MAA content. m‐CMC:MAA in a ratio of 33:67 (w/w%) presented the highest encapsulation efficiency which may due to the increase of hydrophilicity of the aqueous phase. It also presented rapid release and non‐cytotoxic characteristics, suited for use in cosmetic products. © 2018 Society of Chemical Industry     

Synthesis of Gemini‐Like Methyl Acrylate‐Acrylic Acid‐Methyl Acrylate Triblock Copolymers Surfactants by RAFT Polymerization in Solution and Investigation of their Behavior at the Air–Water Interface

A series of methyl acrylate‐acrylic acid amphiphilic triblock copolymers (PMA‐PAA‐PMA) were prepared by solution polymerization using S,S′‐bis (α,α‐dimethy1acetic acid) trithiocarbonate (BDAT) as a reversible addition fragmentation chain transfer (RAFT) agent and methyl acrylate (MA) as the first monomer. The triblock copolymers and their common MA homopolymer precursors were characterized in terms of their compositions, molecular weights and behavior at the air–water interface using ¹H‐NMR spectroscopy, thermogravimetric analysis, gel permeation chromatography, surface tension, transmission electron microscopy (TEM) and dynamic light scattering respectively. The results indicated that PMA‐PAA‐PMA was successfully synthesized through RAFT polymerization. The polydispersity index (PDI) decreased when the molar ratio [n(MA)/n(AA)] increased, the lowest PDI was obtained at 5.23 wt% RAFT and the molecular weights were consistent with the theoretical value as the RAFT agent percentage varied. The polymer neutralized by sodium hydroxide solution shows a low critical micelle concentration (CMC), which was <10^?2 mol L^?1 in water. The A_min values increased and showed a maximum with decreased AA chain length. TEM showed that the neutralized polymer formed a special vesicle structure with large pore structure which led to a low CMC and surface tension of water.     

Aggregate Formation of Glycyrrhetic Acid 3-<Emphasis Type="Italic">O</Emphasis>-Glucuronide

The molecular structure of glycyrrhetic acid 3‐O‐glucuronide consists of an aglycone and glucuronic acid as hydrophobic and hydrophilic groups, respectively. In general, this amphiphile is obtained from glycyrrhizic acid (a major component of licorice root) by hydrolysis of the terminal glucuronic acid. Glycyrrhetic acid 3‐O‐glucuronide is used as a substitute for glycyrrhizic acids, which are potent sweeteners. In this work, the surface and aggregation properties of glycyrrhetic acid 3‐O‐glucuronide were studied using general surface chemistry techniques. The surface tension of a glycyrrhetic acid 3‐O‐glucuronide solution (pH 7) gradually decreased with increasing concentration and the critical micelle concentration (CMC) was determined to be 1.6 mmol L^?1 (γ_CMC = 54 mN m^?1). Similar values of CMC were further confirmed by the pyrene fluorescent probe method and light scattering measurements. According to the dynamic light scattering method, the average radius of aggregate was 200 nm over a concentration of 3 mmol L^?1. Transmission electron microscopy showed that glycyrrhetic acid 3‐O‐glucuronide forms large spherical aggregates. These results suggested that its potential for surface activity is almost equivalent to that of glycyrrhizic acid, even though the two amphiphiles have a different number of hydrophilic groups in them. The removal of one glucuronic acid group significantly influenced the shape of the aggregate formed by glycyrrhetic acid 3‐O‐glucuronide. Furthermore, it was confirmed that glycyrrhetic acid 3‐O‐glucuronide can also be used as a plant‐derived surfactant, similar to glycyrrhetic acid.     

Synthesis of antibacterial polypropylene film with surface immobilized polyvinylpyrrolidone‐iodine complex

A novel antibacterial material with surface immobilized polyvinylpyrrolidone‐iodine complex was synthesized facilely by a two‐step approach. First, N‐vinylpyrrolidone (NVP) was photografted onto polymeric substrates, and subsequently the surface‐grafted polyvinylpyrrolidone (PVP) underwent complexation of iodine. In the UV‐induced photografting process, PVP was efficiently grafted onto the polypropylene (PP) film surface by a unique film interlayer photopolymerization (FIP) technique; the grafting yield (Y_g) could be controlled by varying the irradiation time or the monomer concentration. Further, we demonstrated that the grafted PVP chains could readily perform the complexation reaction with iodine as the homopolymer PVP does, which was characterized by UV–vis spectroscopy. The antibacterial activity of the modified polymer against Escherichia coli, Staphylococcus aureus, and Candida albicans was investigated. The results show that the modified PP film with surface‐immobilized PVP‐I complex has a desirable antibacterial property, with broad spectrum and high efficiency. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2026–2031, 2005     

Design and cell cytotoxicity assessment of palmitoylated polyethylene glycol‐grafted chitosan as nanomicelle carrier for paclitaxel

Amphiphilic graft copolymers were synthesized using chitosan with varying substitution degrees of methoxy polyethylene glycol and palmitic acid. FT‐IR, ¹H‐NMR, differential scanning calorimetry, and elemental analysis showed successful chitosan modification. Amphiphilic copolymers are able to produce nano ssemblies with low critical micelle concentration (CMC). It was demonstrated that particle size (PS) analysis and drug solubilization methods could be used to determine CMC, beside fluorescent pyrene assay. Paclitaxel was efficiently loaded (up to 12.8%) without significant change in the nanomicelles’ PS. In addition, without significant change in size and loading, nanomicelles could be freeze‐dried. Hemolysis assay exhibited biocompatibility of copolymers and cell cytotoxicity assay on MCF‐7 cell line showing the encapsulated drug had a higher cytotoxic effect. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43233.     

阳离子型表面活性单体(2-丙烯酰胺基)乙基十四烷基二甲基溴化铵的合成及其胶束化行为

以丙烯酸、N,N-二甲基乙二胺及溴代十四烷为主要原料合成了阳离子型表面活性单体(2-丙烯酰胺基)乙基十四烷基二甲基溴化铵(AM C14AB);通过红外光谱与核磁共振谱对AM C14AB的化学结构进行了确认;使用紫外分光光度法测定了N aAM C14S在水中的溶解度,同时采用表面张力测定(环法)与电导测定两种方法测定了AM C14AB在不同温度下的临界胶束浓度(CM C)。实验结果表明,通过酰氯化、酰胺化与季铵化三步反应成功地合成出了丙烯酰胺型阳离子表面活性单体AM C14AB;其K rafft点为21.3℃;25℃下其CM C为6.51×10-4m o.lL-1,对应的表面张力为46.3mN.m-1。     

Surface and Aggregation Properties of Synthesized Cetyl Alcohol Based Bis-Sulfosuccinate Gemini Surfactants in Aqueous Solution

A series of cetyl alcohol based anionic bis‐sulfosuccinate gemini surfactants (BSGSCA1,4; BSGSCA1,6 and BSGSCA1,8) with different spacer lengths was prepared using dibromoalkanes. The surfactant structure was elucidated using elemental analysis, Fourier transform infrared spectroscopy (FT‐IR) and nuclear magnetic resonance spectroscopy (NMR). Surface tension measurements were used to determine the critical micelle concentration (CMC), the surface tension at the CMC (γ_CMC), surface pressure at the CMC (π_CMC) and efficiency of adsorption (pC20). On the basis of surface studies, the CMC and γ_CMC decreases with increasing length of the spacer group. The micelle aggregation number, determined by fluorescence quenching studies, increases with increasing surfactant concentration above the CMC. The micropolarity in the micelle increases with increasing length of the spacer and decreases with increasing surfactant concentration.     

无患子皂苷及其复配体系的泡沫性能研究

测定了无患子皂苷的表面活性特征参数，包括HI。B值、浊点、酸值、皂化值、临界胶柬浓度（CMC）、表面张力值（γcmc）等。研究了无患子皂苷与阴离子、非离子和两性表面活性剂复配后的起泡和稳泡结果．从微观结构上分析了复配体系，为无患子皂苷在洗涤剂配方中的应用提供了理论依据。     

Synergisms in Binary Mixtures of Anionic and pH‐Insensitive Zwitterionic Surfactants and Their Precipitation Behavior with Calcium Ions

This work aims to investigate synergy in anionic and zwitterionic surfactant mixtures, as they result in better interfacial properties and micellization behavior. Various mixtures of the pH‐insensitive zwitterionic surfactant 3‐(decyldimethylammonio) propanesulfonate (Zwittergent 3–10) and sodium dodecylsulfate (SDS) were prepared in aqueous solution at a range of pH values between 2 and 13. The thermodynamic parameters during mixed surfactant adsorption at the air/water interface are obtained and the results show the mixed surfactant systems having superior properties to the constituent surfactants. Experimentally, the mixed surfactant solutions clearly improve the surface activities by lowering the critical micelle concentration (CMC) and lowering the surface tension at the air/water interface. The synergisms are investigated through the interaction parameters estimated from regular solution theory that is used to quantitatively describe the nonideality of surfactant mixtures. High negative interaction parameters are obtained from these surfactant mixtures. Experimental precipitation phase boundaries of SDS in the presence of CaCl₂ were also investigated in mixtures containing pH‐insensitive zwitterionic surfactant at different pH levels from 2 to 13 and SDS mole fractions of 0.25, 0.50, 0.75, and 1.00. Changes in the precipitation phase boundaries are due to the changes in the speciation or activities of the major components both below and above the CMC. As a result, the precipitation phase boundaries are pH dependent. In addition, mixed micellization and counterion binding to the micelle also change the precipitation phase boundary above the CMC. The activity‐based solubility product of calcium dodecylsulfate is also determined from the precipitation phase boundaries below the CMC. X‐ray diffraction patterns and SEM images confirm that only calcium dodecylsulfate precipitates in the soap scum for all pH and surfactant compositions studied.     

表面活性单体2-丙烯酰胺基十四烷磺酸钠的合成及其胶束化行为的研究

以丙烯腈与1-十四烯为主要原料合成了表面活性单体2-丙烯酰胺基十四烷磺酸钠(N aAM C14S),用红外光谱与核磁共振谱确认了N aAM C14S的化学结构,用紫外光谱测定了N aAM C14S在水中的溶解度,用表面张力法(环法)与电导法测定了N aAM C14S在不同温度下的临界胶束浓度(CM C)。结果表明,以丙烯腈与1-十四烯为原料可较顺利地合成N aAM C14S,其K rafft点为22℃,25℃下CM C为9.2×10-4m o l.L-1,且CM C随温度变化很小,25℃的表面张力为48.2mN.m-1,表明N aAM C14S具有较高的表面活性。     

Synthesis and Properties of a Novel Linear Alkylated Diphenylmethane Sulfonate Gemini Surfactant

The linear alkylated diphenylmethane sulfonate (C₁₂‐DSDM) was synthesized by a four‐step reaction with lauric acid, diphenylmethane and chlorosulfonic acid as raw materials. The structure of the final product was characterized by MS. The air–liquid surface tensions at various temperatures and salt solutions (NaCl) were measured by using the drop‐volume technique and the thermodynamic parameters of the micellization were calculated. The results show that the critical micelle concentration (CMC) and γ_CMC of the surfactant are 1.452 mmol L^?1 and 38.49 mN m^?1 at 298 K. With an increase in temperature, the CMC gradually increases, the γ_CMC and the maximum surface adsorption capacity Γ_max decrease. The free energy of micelle formation is negative (?51.2 to ?60.5 kJ mol^?1).     

Hydrogel coating of RVNRL film by electron‐beam irradiation

The tackiness properties of radiation‐vulcanized natural rubber latex (RVNRL) film surfaces coated by various monomers were investigated in order to define the suitable hydrogels which reduce the tackiness of the film. In this context, different types of monomers, namely, N‐vinyl‐2‐pyrrolidone (NVP), N,N‐dimethylaminoethylamide (DMAEA), acrylic acid (AAc), n‐butyl acrylate (n‐BA), and 2‐hydroxyethyl methacrylate (HEMA) as well as the monomer mixtures were tried with varying degrees of success. Coating the RVNRL film with 80% HEMA/20% n‐BA by irradiation at 80 kGy using a low‐energy electron beam gave a remarkable reduction in the surface tackiness of the RVNRL film. Several other attempts were made such as priming the RVNRL film with acid and aluminum sulfate prior to coating, mixing the aluminum sulfate into the monomer mixtures, and dipping the partially wet RVNRL film into the monomer to enhance the wettability of the monomers with the film. The photomicrographs taken illustrate that the decrease in tackiness with the coating is due to the increase of the surface roughness at an 80‐kGy irradiation dose. The studies also revealed that the reduction in the contact angle and the increase in water absorption of the RVNRL film after irradiation are due to the formation of the hydrogel layer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1421–1428, 1999     

Synthesis and Surface Properties of a Novel Sodium 3‐(3‐Alkyloxy‐3‐oxopropoxy)‐3‐oxopropane‐1‐sulfonate at the Air–Water Interface

The present paper describes the synthesis and evaluation of surface properties of a novel series of anionic surfactant, namely sodium 3‐(3‐alkyloxy‐3‐oxopropoxy)‐3‐oxopropane‐1‐sulfonate with varying alkyl chain length (C8–C16). Synthesis involves initial formation of the 3‐alkyloxy‐3‐oxopropyl acrylate along with fatty acrylate during the direct esterification of fatty alcohol with acrylic acid in the presence of 0.5 % NaHSO₄ at 110 °C followed by sulfonation of the terminal double bond of the 3‐alkyloxy‐3‐oxopropyl acrylate. Synthesized compounds were evaluated for surface and thermodynamic properties such as critical micelle concentration (CMC), surface tension at CMC (γ_cmc), efficiency of surface adsorption (pC₂₀), surface excess (Γ_max), minimum area per molecule at the air–water interface (A_min), free energy of adsorption (?G°_ads), free energy of micellization (?G°_mic), wetting time, emulsifying properties, foaming power and calcium tolerance. Effect of chain length on CMC follows the classic trend, i.e. decrease in CMC with the increase in alkyl chain length. High pC₂₀ (>3) value indicates higher hydrophobic character of the surfactant. These surfactants showed very poor wetting time and calcium tolerance, but exhibited good emulsion stability and excellent foamability. Foaming power and foam stability of C14‐sulfonate were found to be the best among the studied compounds. Foam stability of C14‐sulfonate was also studied at different concentrations over time and excellent foam stability was obtained at a concentration of 0.075 %. Thus this novel class of surfactant may find applications as foam boosters in combination with other suitable surfactants.     

Double-Tailed Single-Head Amino Acid-Based Chiral Cationic Amphiphilic Molecules: Synthesis,Characterization, and Physicochemical Properties

Two double-tailed single-head amino acid-based chiral cationic amphiphilic molecules, l -aspartic acid hydrochloride dihexylester (L-ADHE, C₆–C₆) and l -aspartic acid hydrochloride dioctylester (L-ADOE, C₈–C₈), were synthesized. ¹H NMR, ¹³C NMR, and Fourier transform infrared (FT-IR) were used to characterize the structures of the esters. Micellization, surface, and structural properties of L-ADHE and L-ADOE in aqueous solution were studied by means of a number of techniques including conductivity, pH, surface tension, density, zeta potential, and dynamic light scattering (DLS). The critical micelle concentration (CMC) of L-ADHE and L-ADOE were found to be very low compared with those of corresponding single-tailed amino acid-based amphiphilic molecules. The pK_a values of L-ADHE and L-ADOE in aqueous solutions were determined via pH measurements, and it was observed that they had acidic properties giving low pK_a values. The excellent adsorption behaviors at the air/water interface of L-ADHE and L-ADOE in aqueous medium were obtained, i.e. they efficiently lowered the surface tension of water at CMC down approximately to 24.3 and 23.4 mN m⁻¹, respectively. From the density measurements, the volume change due to the micellization process for L-ADOE was found to be quite high compared to L-ADHE, i.e. about three times more. This result and the data obtained from the DLS revealed that the increase in aggregated structures of L-ADOE may be due to vesicle formation. The dye solubilization study was performed by UV–vis absorption spectroscopy for L-ADHE. Besides, the CMC value of L-ADHE was also successfully determined without using any dye through UV–vis spectroscopy.     

Physicochemical studies of hemp (Cannabis sativa) seed oil using enzyme‐assisted cold‐pressing

The effects of enzyme‐assisted cold‐pressing (EACP) on the physicochemical attributes of Cannabis sativa (hemp) seed oil were investigated using five enzyme preparations: Protex 7L, Viscozyme L, Kemzyme, Feedzyme, and Natuzyme. The oil contents (28.4–32.8%) offered by the enzyme‐treated hempseeds were found to be significantly (p <0.05) higher than that determined for the control (26.7%). The protein, fiber, and ash contents of the seeds were unaffected by the enzyme treatment. There were no significant (p >0.05) variations observed for the values of iodine number, refractive index, density, unsaponifiable matter and fatty acid composition between the enzyme‐extracted and control hempseed oils. The levels of saponification value, free fatty acids, iodine value and peroxide value were slightly varied between the oils tested. The color intensity of the enzyme‐extracted oils was also higher than that of the control oil. A relatively higher level of tocopherols (724.4–788.8 mg/kg) was observed in the enzyme‐extracted oils compared to the control (691.2 mg/kg), showing an enhancement of ca. 4.8–14.1% in the total tocopherols. The Rancimat profiles and sensory scores of the enzyme‐extracted oils were noted to be improved compared to the control. The results of the present analysis (with respect to the control) showed that the enzyme added during the hempseed cold‐pressing resulted in considerably higher oil yields, without adversely affecting the quality of the oil.     

分光光度法研究十二烷基硫酸钠的临界胶束浓度

在碘的水溶液和I<'-><,3>溶液2种体系中测定了十二烷基硫酸钠(SDS)的临界胶束浓度(CMC),并讨论了在I<'-><,3>体系中,不同硫酸钠和氯化钾2种盐对测定结果的影响,在碘的水溶液中研究了不同碘浓度对SDS的CMC的影响.采用分光光度法求得SDS在两种体系中的CMC值,硫酸钠与氯化钾对CMC的值有影响,且无...