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.     

Interaction of bovine serum albumin with nonionic surfactant Tween 80 in aqueous solutions: Complexation and association

It is shown by the methods of precision tensiometry, quasi-elastic light scattering, and UV, IR, and fluorescent spectroscopies that the properties of binary aqueous solutions with a constant concentration of bovine serum albumin and different concentrations of the nonionic surfactant Tween 80 (1 × 10^–7−6 × 10⁻² M) are determined mainly by the complexation and formation of a new phase. The complexation occurs owing to specific interactions (hydrogen bonding) between polar groups of Tween 80 and protein molecules. The solubility in water and surface activity of a 1: 1 Tween 80-protein complex are determined. At the concentrations above the break point on surface tension isotherms (conditionally corresponding to critical association concentration), the particles are formed with radii varying from 16 to 350 nm. At a molar nonionic surfactant/protein ratio in the range of 6–10, the additional binding of Tween 80 molecules by the particles of the new phase due to hydrophobic interactions is observed. Original Russian Text ? N.M. Zadymova, G.P. Yampol’skaya, L.Yu. Filatova, 2006, published in Kolloidnyi Zhurnal, 2006, Vol. 68, No. 2, pp. 187–197.     

Characterization of Binary Surfactant Mixtures (Cetylpyridinium Chloride and Tween 60) in an Aqueous Medium

Abstract

Micellar properties of the binary surfactant mixtures of cetylpyridinium chloride (CPC) and polyoxyethylene (20) sorbitan monostearate (Tween‐60) have been investigated in detail using tensiometric, conductometric, spectrophotometric, and fluorimetric techniques. The critical micelle concentration (CMC), counterion binding, interfacial adsorption, energetics of micellization, and micellar dielectric constant have been evaluated. The theories of Clint, Motomura, Rubingh, and Sarmoria, Puvvada and Blankschtein have been followed to understand the CMC, composition, activity coefficients, and synergism of the binary surfactant systems.     

Probing of ferrocenylanilines on model micelle/reverse micelle membrane and their enhanced reactivity for reactive oxidants

Reactive oxygen species are formed in the human body but can be removed by suitable antioxidants. In this study we synthesized and characterized three ferrocene derivatives, 4‐ferrocenylaniline (pFA), 3‐ferrocenylaniline (mFA) and 3‐methyl‐4‐ferrocenylaniline (MeFA), having significant potential to be used as antioxidants. The synthesized compounds are insoluble in water, with the solubility of these compounds increasing in micelle solution. The micelle and reverse micelle solutions were considered as model membranes. The synthesized compounds were probed on the model membranes, made by sodium dioctylsulfosuccinate reverse micelle and tetradecyltrimethylammonium bromide micelle, using ¹H NMR spectroscopy. The ¹H NMR results indicated that these compounds are present in the polar region of the model membrane interface. Quantitative measurements showed that mFA has the greatest ability to penetrate into the micelle membrane among these compounds, and pFA is least penetrating in this respect. Solubilization of these compounds in aqueous micelle solution facilitates crystallization (of mFA) and enhances the antioxidant potential of these compounds. X‐ray crystal structure analysis revealed that mFA captures water molecules during crystallization in micelle solution. Their ability to act as antioxidants was evaluated, in dimethylsulfoxide (DMSO) and in micelle solution, using standard 1,1‐ diphenyl‐2‐picrylhydrazyl (DPPH) assay. It was found that their antioxidant potential is good in DMSO and that potential increases on the interface of the model membrane. The highest increase (by 19.6%) in the antioxidant potential, on the model membrane interface, was observed for mFA.     

EGCG在Tween80胶束体系中的性质(英文)

通过离子萃取技术,从黄山绿茶中提取高纯度儿茶素没食子酸酯(EGCG).在Tween 80/EGCG/H2O体系中,随着EGCG浓度增加,Tween 80临界胶束浓度和胶束动力学半径增大;随着Tween 80浓度增加,EGCG和Tween 80扩散系数减小,而EGCG的紫外-可见吸收光强度和荧光强度增加.对EGCG在Tween 80胶束中的定位也进行了讨论.     

Synthesis and Characterization of Silicone Modified Polyurethane Surfactant Useable at High Temperature

A series of novel silicone modified polyurethane (Si-PU) surfactants were successfully synthesized by using hydroxypropyl-terminated polydimethylsiloxane (HPMS), polyethylene glycol (PEG), dimethylolpropionic acid (DMPA) and isophoronediisocyanate (IPDI). The chemical structure of the surfactant was confirmed by FTIR and ¹H-NMR. TEM photographs showed that the micelles of the Si-PU surfactants dispersed in aqueous solution were spherical with the particle size in the range of 100–400 nm. Surface tension measurements indicated that these surfactants had low surface tension to 29.9 mN·m^?1and a definite critical micelle concentration to, approximately 5.0×10^?4–7.5×10^?4mol·L^?1. When the content of HPMS was 20 wt%, the surfactant's, emulsifying performance was superior to the traditionally available Span80/Tween80 mixed emulsifiers. In addition to that, no phase transition temperature was detected from 20°C to 90°C by fluorescence probe and DSC measurements, confirming the high thermal stability of the micelles.     

Determination of alkylphenols and their short-chained ethoxylates in Polish river waters

A simple and robust analytical method for analysis of octyl- and nonylphenol as well as their short-chained ethoxylates in river water was proposed. Quantification of these analytes was performed by high-performance liquid chromatography with fluorescence detection after isolation using solid phase extraction with polytetrafluoroethylene sorbent. The method allowed one to obtain about 80–100% recovery for octylphenol and its ethoxylates and 70–80% for nonylphenol and its ethoxylates. Also, there was no need for additional sample cleaning before chromatographic analysis. The limit of detection was 0.01?µg?L^?1 for octylphenol and its ethoxylates and 0.03?µg?L^?1 for nonylphenol and its ethoxylates. The proposed method was used for quantitation of octyl- and nonylphenol together with their short-chained ethoxylates. Nonylphenol, nonylphenol mono- and diethoxylates were detected at concentrations ranging from 0.12 to 0.53?µg?L^?1. Octylphenol, octylphenol mono- and diethoxylates were detected in four out of eleven samples at concentrations ranging from 0.03 to 0.17?µg?L^?1. High concentrations of nonylphenol and its ethoxylates were found in the samples, despite the fact that their use in European countries was forbidden several years ago.     

SURFACE STRUCTURE OF THE MICELLE OK AN AMPHOTERIC AMPHIPHILE DERIVED FROM LYSINE

ABSTRACT

Micelle structure in aqueous colloid of an amphoteric amphiphile N^αN^α-dimethyl-N^? -lauroyl lysine (DMLL), which was derived from lysine, was studied through light scattering, SAXS and a rheological method. The critical micelle concentration of the colloid system is 216 UM and the weight average molecular weight of the micelle is 2.40 × 10⁴, i.e. the aggregation number is 67.4. The diameter of the micelle is about 43.4 Å and the spherical micelle is likely to be retained in a concentration up to about 20 %, The SAXS measurements show that the electron density Fluctuation in the micelle is almost negligible and that the surface area of the micelle is approximately 3.5 times larger than that of a completely smooth sphere.     

Deaggregation of acacia emulsions

Summary Emulsions aggregated by the hydrocolloid potassium arabate through interparticular bridging, are deaggregated by shear and added surface active agent but are unaffected by simple electrolyte. The minimum shear rate for almost complete deaggregation is in the region of 550 sec⁻¹ and the process is irreversible. In terms of critical micelle concentrations (c.m.c), potassium laurate (anionic) is more effective than hexadecyl-trimethylammonium bromide (cationic) which in turn is very much more effective than Tween 20 (non-ionic). The rate of deaggregation by surface active agent is rapid.     

Application of Polyglycerol Diisostearate Ethoxylates in Microemulsion

Effect of surfactants [polyglycerol diisostearate ethoxylates (PGDIS-E31, PGDIS-E36 and PGDIS-E40) and Tween-80], alcohols (1,2-propandiol, ethanol, 1-propanol, 1-butanol, 2-butanol and 1-pentanol), oils [isopropyl palmitate (IPP), isooctyl palmitate (IOP), dioctyl carbonate (DOC), and dioctyl hexanediate (DOH)], temperature and sodium chloride on the microemulsion formation of the surfactant/alcohol/oil/water system has been investigated by the pseudo-ternary phase diagrams. The capacities of the four surfactants in the microemulsion formation of the surfactant/alcohol/IPP/water system at surfactant/alcohol of 2:1 are in the order of PGDIS-E31 > PGDIS-E36 > Tween-80 > PGDIS-E40, whatever alcohol (ethanol, 1-propanol, and 1-butanol) is used. PGDIS-E31 and 1-butanol exhibit best synergism in the microemulsion formation. In addition, the volume, structure and polarity of oil all influence the microemulsion formation. At the optimum weight ratio 2:1 of PGDIS-E31/1-butanol, the microemulsion region of the PGDIS-E31/1-butanol/IPP/water system is the largest among the studied systems. The microemulsion system of PGDIS-E31/1-butanol/IPP/water is not sensitive to lower temperature such as 40°C. It is also not sensitive to sodium chloride when the concentration of sodium chloride is in the range of 0 to 1.0%.     

Synthesis,surface activity,and corrosion inhibition of dentritic quaternary ammonium salt-type tetrameric surfactants

The dentritic quaternary ammonium salt-type tetrameric surfactant (4C₁₂tetraQ) was synthesized, and the molecular structure was confirmed by ¹H NMR and FTIR. The surface activity of 4C₁₂tetraQ was investigated by surface tension, and surface chemical parameters, such as critical micelle concentration (cmc), efficiency (pC₂₀), effectiveness (π_cmc), the surface tension value at cmc (γ_cmc), minimum surface area (A_min), maximum surface excess (Γ_max), and cmc/C₂₀ were obtained from the measurement results. The results show that the 4C₁₂tetraQ surfactant has higher surface activity than the traditional monomeric surfactants (dodecyl trimethyl ammonium bromide, DTAB). The Krafft points were taken as <0°C, indicating that the synthesized tetrameric surfactants had good water solubility. Free energies of micellization and adsorption show that 4C₁₂tetraQ display greater propensity to absorb at the interface than form micelle in the bulk of the aqueous solution, and that the two processes are spontaneous. The measurement results show that 4C₁₂tetraQ has good emulsification power and foam performance. The corrosion efficiency was evaluated with the loss weight method in 1?mol/L HCl solution, and the results show that the 4C₁₂tetraQ surfactant has good corrosion inhibition, and can be considered as a corrosion inhibitor.     

The Total Solubility of the Co-Solubilized PAHs with Similar Structures Indicated by NMR Chemical Shift

The synergism/inhibition level, solubilization sites and the total solubility (S_t) of co-solubilization systems of phenanthrene, anthracene and pyrene in Tween 80 and sodium dodecyl sulfate (SDS) are studied by ¹H-NMR, 2D nuclear overhauser effect spectroscopy (NOESY) and rotating frame overhauser effect spectroscopy (ROESY). In Tween 80, inhibition for phenanthrene, anthracene and pyrene is observed in most binary and ternary systems. However, in SDS, synergism is predominant. After analysis, we find that the different synergism or inhibition situation between Tween 80 and SDS is related to the different types of surfactants used and the resulting different co-solubilization mechanisms. In addition, we also find that three polycyclic aromatic hydrocarbons (PAHs) have similar solubilization sites in both Tween 80 and SDS, which are almost unchanged in co-solubilization systems. Due to the similar solubilization sites, the chemical shift changes of surfactant and PAH protons follow the same pattern in all solubilization systems, and the order of chemical shift changes is consistent with the order of changes in the St of PAHs. In this case, it is feasible to evaluate S_t of PAHs by chemical shift. In both Tween 80 and SDS solutions, the ternary solubilization system has relatively high S_t rankings. Therefore, in practical applications, a good overall solubilization effect can be expected.     

疏水链长对聚氧乙烯失水山梨醇脂肪酸酯界面扩张流变性质的影响

利用悬挂滴方法研究了系列聚氧乙烯失水山梨醇脂肪酸酯(TweenX)在正癸烷-水界面的扩张流变性质. 实验结果表明, 疏水烷基链长较短的Tween20 分子在界面上吸附量较大, 分子排列更紧密, Tween40 和Tween60具有大致相同的“有效截面积”, 导致饱和吸附时界面张力(γ_cmc)比较接近. TweenX浓度大于临界胶束浓度(cmc)时, 由于Tween20 分子排列的更加紧密, 模量和弹性大于Tween40 和Tween60. 当TweenX的疏水烷基链长达到一定长度时, TweenX的界面膜性质受疏水链长的影响减弱, Tween40和Tween60的扩张参数相差不大.     

C12 hydroxyester ethoxylates as nonionic surfactants

A series of ethoxylates of 2,2,4-trimethyl-1,3-pentanediol mono-isobutyrate representing a synthetic C12 hydroxyester hydrophobe was obtained. The solubility parameters, surface tension and critical micelle concentrations for model solutions were investigated. The new surfactants were found to produce extremely low foam levels and a non-standard surface interfacial behavior was determined. It was observed that the ethoxylates of the C12 hydroxyester formed an oriented monolayer at the interface regardless of their average polyaddition degree. Such behavior is different from the surface activities of commonly known linear nonionic surfactants and it indicates self organization of the surfactants at the interface. This feature offers possibility for application of these surfactants in nanotechnology as well as in the conventional cleaning processes.     

Spectroscopic Study on the Interaction between Bovine Serum Albumin and Tween‐20

The interaction between nonionic surfactant Tween-20 and bovine serum albumin (BSA) is studied in Tris‐HCl buffer solution by spectroscopic methods. The intrinsic fluorescence of BSA is quenched by the addition of Tween‐20. The UV‐visible absorption spectra and the synchronous fluorescence spectra show that the addition of Tween‐20 changes the polarity of the environment around tryptophan (trp) residues of BSA. The fraction of trp residues on the surface of BSA with and without Tween- 20 is calculated via I^? quenching experiments.     

Thermosensitive t‐PLA‐b‐PNIPAAm tri‐armed star block copolymer nanoscale micelles for camptothecin drug release

Thermosensitive polylactide‐block‐poly(N‐isopropylacrylamide) (t‐PLA‐b‐PNIPAAm) tri‐armed star block copolymers were synthesized by atom transfer radical polymerization (ATRP) of monomer NIPAAm using t‐PLA‐Cl as macroinitiator. The synthesis of t‐PLA‐Cl was accomplished by esterification of star polylactides (t‐PLA) with 2‐chloropropionyl chloride using trimethylolpropane as a center molecule. FT‐IR, ¹H NMR, and GPC analyses confirmed that the t‐PLA‐b‐PNIPAAm star block copolymers had well‐defined structure and controlled molecular weights. The block copolymers could form core‐shell micelle nanoparticles due to their hydrophilic‐hydrophobic trait in aqueous media, and the critical micelle concentrations (CMC) were from 6.7 to 32.9 mg L^?1, depending on the system composition. The as‐prepared micelle nanoparticles showed reversible phase changes in transmittance with temperature: transparent below low critical solution temperature (LCST) and opaque above the LCST. Transmission electron microscopy (TEM) observations revealed that the micelle nanoparticles were spherical in shape with core‐shell structure. The hydrodynamic diameters of the micelle nanoparticles depended on copolymer compositions, micelle concentrations and media. MTT assays were conducted to evaluate cytotoxicity of the camptothecin‐loaded copolymer micelles. Camptothecin drug release studies showed that the copolymer micelles exhibited thermo‐triggered targeting drug release behavior, and thus had potential application values in drug controlled delivery. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4429–4439     

Optimization of modified dispersive liquid–liquid microextraction coupled with high‐performance liquid chromatography for the simultaneous preconcentration and determination of nitrazepam and midazolam drugs: An experimental design

A simple, sensitive, and rapid microextraction method, namely, ultrasound‐assisted surfactant‐enhanced emulsification microextraction based on the solidification of floating organic droplet method coupled with high‐performance liquid chromatography was developed for the simultaneous preconcentration and determination of nitrazepam and midazolam. The significant parameters affecting the extraction efficiency were considered using Plackett–Burman design as a screening method. To obtain the optimum conditions with consideration of the selected significant variables, a Box–Behnken design was used. The microextraction procedure was performed using 29.1 μL of 1‐undecanol, 1.36% (w/v) of NaCl, 10.0 μL of sodium dodecyl sulfate (25.0 μg mL^?1), and 1.0 μL of Tween80 (25.0 μg mL^?1) as an emulsifier in an extraction time of 20.0 min at pH 7.88. In order to investigate the validation of the developed method, some validation parameters including the linear dynamic range, repeatability, limit of detection, and recoveries were studied under the optimum conditions. The detection limits of the method were 0.017 and 0.086 ng mL^?1 for nitrazepam and midazolam, respectively. The extraction recovery percentages for the drugs studied were above 91.0 with acceptable relative standard deviation. The proposed methodology was successfully applied for the determination of these drugs in a number of human serum samples.     

Solubility of methane in pure non-ionic surfactants and pure and mixtures of linear alcohols at 298 K and 101.3 kPa

The emissions of methane (CH₄), a powerful greenhouse gas (GES), contribute to the increase in GES concentration level in the atmosphere. For this reason, the importance of controlling CH₄ emissions of anthropogenic origin has increased over the last decades. Physicochemical and biological processes are available for treating CH₄. For this reason, such properties as the solubility of CH₄ in aqueous solutions and organic solvents are of great relevance in different applications in environmental engineering and biotechnology. In this study, the solubility of CH₄ was determined at 298 K and 101.3 kPa in organic solvents, such as polyoxyethylenesorbates (Tween 20, Tween 40, and Tween 60), and linear alcohols (methanol, ethanol, and butan-1-ol) alone and in their admixtures. Admixtures of methanol with butan-1-ol exhibited the highest solubility of CH₄, of around 0.49 g m⁻³ of solvent, whereas the solubility of CH₄ in linear alcohols varied from 0.167 g m⁻³ to 0.41 g m⁻³ of solvent. In the case of Tweens, CH₄ solubility decreased with the hydrophilic-lipophilic balance (HLB) number.     

Poly(vinyl alcohol)-based Amphiphilic Copolymer Aggregates as Drug Carrying Nanoparticles

A series of amphiphilic polyisobutylene-block-poly(vinyl alcohol) (PIB-b-PVA) copolymers of constant PIB and varying PVA block length was synthesized by living carbocationic polymerization and their solution behavior was studied. The synthesis involved the preparation of polyisobutylene-b-poly(tert.-butyl vinyl ether) followed by hydrolysis with hydrogen bromide. The copolymers were characterized by gel permeation chromatography, ¹H-NMR, and MALDI-TOF MS methods. The micellization behavior of the copolymers was investigated in aqueous media by direct dissolution and dialysis using static and dynamic light scattering. The critical micelle concentration, micelle size, aggregation number, and micelle shape were determined. The ability of the aggregates as drug carrying nanodevices was also investigated by doping them with indomethacin. UV-Vis measurements showed that the solubility of indomethacine increased significantly. Our findings suggest that the solubility is largely dependent upon the block segment ratios.     

Study of Partitioning and Solubilization of Some New Chalcones Between Aqueous and Micellar Phases

The partitioning behavior of four newly synthesized chalcones between aqueous and micellar phases of ionic surfactants (SDS and CTAB) was investigated using ultraviolet-visible spectroscopy. The simple absorption spectra were recorded to study the interaction between these drugs and surfactants (in the concentration range below critical micelle concentration to above critical micelle concentration). The absorption data is also used to determine the number of additive molecules incorporated per micelle of the surfactant. The partition coefficient (K_x) of additives between bulk water phase and the micellar phase was determined in the range of 5.52 × 10⁺⁴ to 5.06 × 10⁺⁵ at 298 K by differential spectroscopic method. The corresponding standard free energy of partition ΔG°_p obtained was in the range of ?27.05 kJmol^?1 to ?32.54 kJmol^?1. The relative solubility of additives between aqueous and micellar phases in different micellar concentrations was also estimated. The results showed that the chalcones are preferably soluble in cationic surfactant micelles.