Electrochemical Oxidation of L-Cystenine in SDS／BA／H2O Microemulsion

The electrochemical oxidation of L-cysteine in an SDS/BA/H2O microemulsion system was studied with the methods of ultramicroelectrode cyclic voltammetry and AC impedance. The catalytic efficiency of the microemulsion on the electrochemical oxidation increases with the increase of BA or SDS content, but decreases with the increase of the water content because of the effects of BA, SDS and water on the solubilization of Lcysteine in the microemulsion. Furthermore, the catalytic efficiency of the bicontinuous structure is greater than that of an O/W microemulsion system. The results derived from both the rate constant k^0 and Gibbs free energy △G^≠ accord with those from the catalytic efficiency.     

Effects of additives on the aggregation of surfactants: binding domination

The effects of electrolytes, alcohols, and urea on the aggregation of SDS, CTAB, and TritonX-100 at 25℃ have been investigated by fluorescence probing of pyrene. Both electrolytes and alcoholsreduce the critical micelle concentration (CMC) of the ionic surfactants, while the effect of the former ismore pronounced. It is shown that the effects of electrolytes mainly depend on the concentrationsand especially the valence of the opposite charge ions, and only slightly depend on the same charge ionsin respect of ion aggregate of micelle. The logarithm of CMC is not linearly correlated with theconcentrations of the counter ion or the electrolytes. The results are rationalized in terms of Hartley'smodel. Propanol increases the CMC of TX-100, while electrolytes and urea do not. In all the threekinds of surfactant micelles the excitation spectrum of pyrene slightly red-shifts (ca. 4 nm) from thatin water, but is not affected by the additives. The micropolarity of the environment in which pyrenemolecule resides in SDS micelle decreases with the increase of the concentrations of electrolytes. Thisis not the case when alcohols and urea were added to SDS or to TX-100. It is suggested that theaddition of electrolytes would result in more orderly orientation of SDS molecules. It is the bindingstrength of the counter ions that dominates the effects of additives on the aggregation of surfactants.     

CATALYTIC ACTIVITY OF Pd-Sn COMPLEX CARBONYLATION OF ACETYLENE

The influence of different concentration of HO, SnCl2, Cl- and n-BuOH on the carbonylation of acetylene has been studied. The results show that the yield of n- butyl propionate increases with the increase of HC1 concentration and the catalytic activity is depressed when Cl" concentration increases. However, the stability of catalytic complex is promoted by Cl-. The key to the carbonylation of acetylene lies in the addition of SnCl2, which promotes the formation of the complex of C2H2, CO with catalyst and plays an important role in the hydrogen removal from n-BuOH. The hydrogen removed from n BuOH is the hydrogen source of this reaction. Meanwhile, the principle of the effect of HCl, Cl- and SnCl2 on reaction has been discussed. The reaction model has also been proposed.     

MICELLIZATION STUDIES OF DODECYL BENZENESULFONIC ACID AND ITS INTERACTION WITH POLYVINYLPYRROLIDONE

Dodecyl benzenesulfonic acid (DBSA) surfactant was used in the present study to find the effect of concentration on its electrical conductance in solution from 293-323K above and below the critical micelle concentration (CMC). The micellization parameters i.e. degree of counter ion binding (β), aggregation number (n) and number of counter ion micelle(m) were measured. The interaction of DBSA with polyvinylpyrrolidone (PVP) was also studied at 293K throughconductance and surface tension measure ments. A number of important parameters i.e. critical aggregation concentration (CAC), Gibb‘s free energy (△G) and binding ratio (R) were determined and the effect of NaCl on the CAC and polymer saturation point (PSP) was also investigated.     

Phase behavior of charge stablized colloid dispersion with added water soluble polymers

Demixing and colloidal crystallization in the mixture of charge stabilized colloidal poly(methyl methacrylate) particles and soluble poly(ethylene oxide) were investigated by means of synchrotron small-angle X-ray scattering (SAXS) technique. Phase diagram of the mixture was obtained based on visual inspection and SAXS results. The phase behavior is determined as a function of the concentration of the polymer as well as the volume fraction of the colloidal particles. The system shows a one phase region when the concentration of the polymer is low, whereas a two-phase region is present when the concentration of the polymer is larger than a critical concentration at certain volume fraction of the colloids. Interestingly, a face centered cubic colloidal crystalline structure was formed under certain conditions, which has been rarely observed in experiments of colloid-polymer mixtures with competing interactions.     

Location of ethanol in sodium dodecyl sulfate aggregates

The hexagonal liquid crystalline phase of SDS (Sodium dode-cyl sulfate)/H2O system changes into lamellar liquid crystal and the effective length of surfactant molecule d0/2 in the lamellar liquid crystal decreases with the addition of ethanol. The micellar aggregation number N of SDS decreases and the micellar diffusion coefficient increases with the added ethanol. Under a constant concentration of SDS, the molecule number ratio of ethanol to SDS in the micelle increases with the concentration of ethanol and even exceeds 10 when ethanol concentration is 1. 085 mol/L. All these results show that ethanol, even though a short chain alcohol and soluble in water, can partly exist in the interphase of the amphiphilic aggregates showing some properties of co-surfactant.     

EFFECT OF ANIONIC SURFACTANT UPON THE VISCOSITY OF POLYMER GUAR GUM SOLUTIONS

The reduced viscosity of polymer guar gum solutions containing a certain concentration of sodium dodecyl benzene sulfonate （SDBS） was measured. It has been found that the Huggins coefficient kH of polymer solutions is very sensitive to the concentration of the surfactant, CSDBS, in solutions. If CSDBS is lower than CMC, the critical micelle concentration of SDBS, kH increases rapidly with CSDBS. On the other hand, if CSDBS is larger than CMC, kH decreases rapidly with CSDBS. Comparatively, the intrinsic viscosity of polymer solution does not show a notable change with CSDBS. The experimental results indicate that the interchain association of polymer guar gum in solution is greatly associated with SDBS interacted with polymer chains through hydrogen bonds. However, the effect of SDBS upon the intrachain association of polymer guar gum solution is negligible, presumably due to the fact that guar gum is a slightly stiffened random-coil chain polymer.     

Using PVP/SDS Complex as a Probe to Study the Inclusion Complex of β-cyclodextrin with SDS in Aqueous Solution

PVP/SDS complex was applied as a probe to study the interaction between β-cyclodextrin （β-CD） and sodium dodecyl sulfate （SDS） in aqueous solution. It has been found that a critical concentration, namely cs, exists in the relative viscosity of solution containing PVP/SDS complex versus β-CD concentration plot. As the β-CD concentration is less than cs, the relative viscosity of solution decreases sharply by adding β-CD into solution successively. On the other hand, as the β-CD concentration is greater than cs, the relative viscosity of solution increases gradually by adding β-CD into solution. The decrease of the relative viscosity of solution containing PVP/SDS in the presence of β-CD is just due to the inclusion complex of β-CD with the guest molecule SDS. And, this inclusion interaction takes down SDS from the PVP chains in solution. The ratio of the host molecule β-CD to the guest molecule SDS can be calculated from Cs. In our experiment the inclusion ratio of β-CD to SDS is 1/1. The further experimental results indicate that cs is associated with SDS but free from PVP in PVP/SDS complex. However, the inclusion ratio of β-CD to SDS has proved to be independent of either SDS or PVP in PVP/SDS complex.     

INTERMOLECULAR AND INTRAMOLECULAR INTERACTIONS OF POLYMER GUAR GUM IN SOLUTIONS

The tetrahedral borate ion can crosslink with polymer guar gum in aqueous solutions. If the concentration of guar gum is less than 0.045 g/dL, the intramolecular interaction between guar gum and borate ion increases due to the formation of crosslinks. As a result, the polymer chains of guar gum in solution shrink in size and the reduced viscosity of polymer solution decreases accordingly. On the other hand, if the concentration of guar gum is greater than 0.045 g/dL, the intermolecular interaction becomes apparent due to the same reason. The polymer chains, therefore, associate together and the reduced viscosity of polymer solution increases considerably. According to this technique, the critical concentration c^＊, presented by de-Gennes, is determined successfully.     

Efficient degradation of methyl orange via multilayer films of titanium dioxide and silicotungstic acid

We report layer-by-layer (LbL) assembly of TiO2 and H4 SiW12 O40 (SiW 12 ) multilayer film on silicon wafers and glass slides for photocatalytic degradation of methyl orange (MO). The photocatalytic efficiency of the obtained multilayer film increases along with the decrease of pH and salt concentration of the incubation solution. The results show that MO can be almost removed in pH2.0 solution without salt addition in the first 60 min incubation when MO concentration is lower than 15 mg/L. Different salts show an apparent inhibitory effect on photocatalytic degradation of MO with the order of ZnCl2 >KCl> NaCl>LiCl. The TiO2 /SiW12 multilayer film maintains photocatalytic activity even after five degradation cycles. The reaction of MO photodegradation accords with an apparent first-order dynamics.     

Removal of cadmium ions using micellar-enhanced ultrafiltration with mixed anionic-nonionic surfactants

Micellar-enhanced ultrafiltration (MEUF) was used to remove cadmium ions from wastewater efficiently. In this study the nonionic surfactants polyoxyethyleneglycol dodecyl ether (Brij35) and polyoxyethylene octyl phenyl ether (TritonX-100) were for micellar-enhanced ultrafiltration to lower the dosage of the anionic surfactant sodium dodecyl sulfate (SDS). The surfactant critical micelle concentration (CMC) and the degree of micelle counterion binding were investigated. The effects of nonionic surfactant addition on the efficiency of cadmium removal, the residual quantities of surfactant, the permeate flux and the secondary membrane resistance were investigated. A comparison between MEUF with SDS and MEUF with mixed anionic–nonionic surfactants was undertaken. The results show that the addition of Brij35 or TritonX-100 reduced the CMC of SDS and the degree of counterion binding for the micelles. Due to these variations the Cd²⁺ rejection efficiency was at a maximum when the Brij35:SDS and the TritonX-100:SDS molar ratio was 0.5. The Cd²⁺ rejection efficiency in MEUF with SDS is higher than for MEUF with mixed surfactants when the total dose of surfactant is constant. The permeate flux of MEUF with SDS is higher than that for MEUF with mixed surfactants while the secondary resistance of MEUF with SDS is less than that of MEUF with mixed surfactants.     

Interaction of (hydroxypropyl) cellulose with anionic surfactants in dilute regime

(Hydroxypropyl)cellulose (HPC) dilute aqueous solutions in the presence of sodium cholate (CS), sodium deoxycholate (DC), and sodium dodecylsulphate (SDS) were investigated. The hydrophobicity parameter (I ₁/I ₃) from fluorescence has shown a critical aggregation concentration (CAC) lower than the critical micellar concentration (CMC). One or two breakpoints were observed in the curve conductivity vs surfactant concentration. The thermodynamic parameters of aggregation (, and ) and the degree of counterion dissociation were calculated. Evidences for the secondary aggregation of CS/water system were found. The relative viscosity increases for HPC/bile salt solutions only at high surfactant concentrations, whereas for HPC/SDS, it passes through a maximum. The cloud points of both HPC/bile salt solutions at higher surfactant concentrations reach a temperature plateau value around 324 K, while for HPC/SDS, it exceeds 373 K at low SDS concentrations. Dynamic light scattering has demonstrated that the surfactants bind to HPC already at concentrations lower than CAC.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Chitosan/sodium dodecylsulfate interactions

Summary The thermodynamics of the interaction of chitosan and sodium dodecylsulfate, SDS, was characterised by titration microcalorimetry to gain an insight into the binding process of amphiphilic molecules to this biocompatible polymer and its consequences on the behaviour of the solutions and chemically cross-linked hydrogels of chitosan. 0.2 M acetic acid was used as solvent medium, without or with 0.9% NaCl, in order to evaluate the influence of the ionic and hydrophobic interactions with two chitosans of different molecular mass and degree of deacetylation, DD. The critical micellar concentration, CMC, of SDS was ten times lower in the presence of the salt (0.35 vs. 3.5 mM, as estimated by surface tension measurements). Binding to chitosan (at 0.25%) began at concentrations significantly lower than CMC (critical aggregation concentration, CAC=0.035-0.17 mM) and saturation was reached at around 10 mM SDS, which corresponds to a positive/negative charges ratio of about 1. The process was in all cases enthalpy-driven (strongly exothermic) and, in the absence of the salt, also entropically favourable. The Gibbs free energy of interaction values were slightly greater for the chitosan with lower DD but greater molecular mass. The addition of increasing amounts of SDS resulted in a continuous decrease in the viscosity of chitosan solutions above the CAC, which ended in a macroscopic coacervation when around 1/3 of the positive charges were neutralised. In the same range of SDS concentrations, the hydrogel beads showed a continuous decrease in the swelling degree and a final collapsed state. The scarce tendency to redissolution or hydrogel reswelling in the presence of greater SDS concentrations can be attributed to that the binding process is mainly caused by the ionic interaction and did not go beyond the neutralisation point.     

Interactions between Adsorbed Layers of a Low Charge Density Cationic Polyelectrolyte on Mica in the Absence and Presence of Anionic Surfactant

Interactions between two negatively charged mica surfaces across aqueous solutions containing various amounts of a 10% charged cationic polyelectrolyte have been studied. It is found that the mica surface charge is neutralized when the polyelectrolyte is adsorbed from a 10–50 ppm aqueous solution. Consequently no electrostatic double-layer force is observed. Instead an attractive force acts between the surfaces in the distance regime 250–100 Å. We suggest that this attraction is caused by bridging. Additional adsorption takes place when the polyelectrolyte concentration is increased to 100 and 300 ppm, and a long-range repulsion develops. This repulsive force is both of electrostatic and steric origin. The polyelectrolyte layer adsorbed from a 50 ppm solution does not desorb when the polyelectrolyte solution is replaced with an aqueous polyelectrolyte-free solution. Injection of sodium dodecyl sulfate (SDS) into the measuring chamber to a concentration of about 0.01 CMC (8.3 × 10⁻⁵M) does not affect the adsorbed layers or the interaction forces. However, when the SDS concentration is increased to 0.02 CMC (0.166 mM) the adsorbed layer expands dramatically due to adsorption of SDS to the polyelectrolyte chains. The sudden swelling suggests a cooperative adsorption of SDS to the preadsorbed polyelectrolyte layer and that the critical aggregation concentration between the polyelectrolyte and SDS at the surface is about 0.02 CMC. The flocculation behavior of the polyelectrolyte in solution upon addition of SDS was also examined. It was found that 0.16–0.32 mol SDS/mol charged segments on the polyelectrolyte is enough to make the solution slightly turbid.     

Cationic surfmers with benzyl groups: Synthesis and copolymerization with acrylamide

A series of cationic surfmers with benzyl groups（QARBCs）with different R groups on the benzene ring were synthesized and characterized by IR,¹H-NMR,¹³C-NMR.The aggregation of QARBCs was studied by the steady-state fluorescence technique.It turned out that QARBCs had surface activity and their critical micelle concentration（CMC）values varied in the range of 10^-2—10^-3mol/L with slight increase with temperature.The copolymerization of acrylamide（M₁）and QARBCs（M₂）was studied below and above CMC,their reactivity ratios were determined by the Finemann-Ross method.It was found that below CMC,copolymerization took place in a homogeneous system and reactivity ratios of acrylamide and QARBCs were less than 1;while above CMC,reactivity ratios of QARBCs were greater than 1.The copolymerization mechanism of QARBC was observed to be similar to that of micellar polymerization.QARBCs tended to homopolymerization,which gave rise to micro-blocky sequences in the polymer backbone.The Q and e values of QARBCs were calculated according to the Alfrey-Price equation by using r_1（AM）and r_2（qarBC）.Samples of poly（AM-co-QARBC） were prepared above and below CMC and their hydrophobic associations were studied by the steady-state fluorescence spectra and 2D NOESY spectra,and their critical associating concentrations（CAC）were estimated.The results showed that samples of poly（AM-co-QARBC）prepared above CMC had stronger hydrophobic association in aqueous solution than those prepared below CMC.     

Studying Effect of Typical Nonplanar Cyclic Alcohols (n = 5‐7) on Micellization of Sodium Dodecyl Sulfate (SDS) in Aqueous Solution and Locating Their Solubilization Site in SDS Micelles

Cyclic alcohols (n = 5‐7) are compounds of distinctive nonplanar structure. Effect of the alcohols on micellization of sodium dodecyl sulfate (SDS) in aqueous solution are examined by determining the critical micelle concentration (CMC) by conductometry and the micelle aggregation numbers (N_agg) by fluorometry, respectively. In general, the CMC of SDS decreases with increase in volume of a cyclic alcohol in water and increases further after attaining a minimum value. The N_agg of SDS varies little with small addition of a cyclic alcohol, but decreases when added in sufficient volume. Both the changes of the CMC and N_agg with carbon number in the ring of the alcohols occur irregularly due to their steric reasons and nonplanar nature. The irregularity makes a difference between the cyclic alcohols and their chain counterparts. Based on ¹H NMR chemical shift measurements, the cyclic alcohols are found to be solubilized in the palisade layer in SDS micelles.     

Sorption of sodium dodecyl sulfate by highly basic anion-exchange resins

The interaction in the system of sodium dodecyl sulfate (SDS) solution and AB-17 highly basic anion-exchange resins in OH⁻ and Cl⁻ forms were considered, and the distribution coefficients (K _d) of the substance in the resin-solution ion exchange system were calculated. It was found that K _d decreases with increasing concentration of the initial solution, reaching a maximum value at the critical micelle concentration (CMC) of SDS. The effective diffusion coefficients of the surfactant in the anion-exchange resin phase were calculated; based on the IR spectroscopy data, the mechanism of SDS absorption was proposed.     

Electrochemical polymerization of aniline in SDS admicelles

The electrochemical polymerization of aniline was studied in sodium dodecyl sulfate (SDS) admicelles. The results demonstrate that electrochemical polymerization of aniline can be catalyzed by admicelles. The catalytic efficiency in SDS solutions increased slowly with SDS concentration when the SDS concentration was very low, but increased rapidly when SDS admicelles formed on the electrode surface. The catalytic efficiency decreased with the addition of n-pentanol. The polyaniline films formed in SDS admicelles were nanometer films and the size of particles in the films increased with SDS concentration, but decreased with the addition of n-pentanol. Therefore, n-C₅H₁₁OH can be used to regulate the electrochemical polymerization of aniline in SDS admicelles.     

Effect of Alcohols on the CMC and Thermodynamic Functions of Anionic Surfactants in DMF/Long‐Chain Alcohol Using Microcalorimetric Method

The critical micelle concentration (CMC) of two kinds of anionic surfactant (including sodium laurate (SLA) and sodium dodecyl sulfate (SDS)) in mixed alcohol and N, N‐dimethyl formamide solvent (DMF) were investigated through measuring power‐time curves by titration microcalorimetry. From data of the lowest point and the area of the power‐time curves, their CMC and ΔH _m ⁰ can be obtained. According to standard thermodynamic equations, ΔG _m ⁰ and ΔS _m ⁰ also can be calculated. For different surfactant, the influences of the carbon number and the concentration of alcohol on the CMC and standard thermodynamic functions are different in DMF polar medium. These thermodynamic functions for micelle formation can be further interpreted.