Microstructures of Aqueous Two‐Phase Systems Formed by Mixture of Polymer and Cationic‐Anionic Surfactants

Microstructure and phase behavior of decyltriethylammonium bromide (C₁₀NE)/sodium decylsulfonate (C₁₀SO₃)/poly(ethylene oxide) (PEO)/water quaternary systems were studied by freeze‐fracture transmission electron microscopy, small angle X‐ray diffraction, and dynamic light scattering methods. Aqueous two‐phase systems (ATPS) could be prepared by properly mixing the aqueous solution of PEO and equimolar mixed C₁₀NE and C₁₀SO₃. It was shown that the top phase of the ATPS was surfactant‐enriched and mainly composed of multi‐lamellar structure, while the bottom phase of the ATPS was polymer‐enriched in which some vesicles were observed.     

Physicochemical Properties and Surface Tension Prediction of Mixed Surfactant Systems: Triton X‐100 with Dodecylpyridinium Bromide and Triton X‐100 with Sodium Dodecylsulfonate

Dependences of the surface tension of aqueous solutions of ionic (dodecylpyridinium bromide, sodium dodecylsulfonate) and nonionic (Triton X‐100) surfactants and their mixtures on total surfactant concentration and solution composition were studied, and the surface tension of the mixed systems were predicted using different Miller's model. It was found that how to select the model for calculation of ω is corresponding to the degree of the deviation from the ideality during the adsorption of mixed surfactants. The compositions of micelles and adsorption layers at air‐solution interface as well as parameters (β^m, β^ads) of headgroup‐headgroup interaction between the molecules of ionic and nonionic surfactants were calculated based on Rubingh model. The parameters (B₁) of chain‐chain interaction between the molecules of ionic and nonionic surfactants were calculated based on Maeda model. The free energy of micellization calculated from the phase separation model (ΔG ₂ ^m ), and by Maeda's method (ΔG ₁ ^m ) agree reasonably well at high content of nonionic surfactant. The excess free energy ΔG _ads ^E and ΔG _m ^E (except α=0.4) for TX‐100/SDSn system are more negative than that TX‐100/DDPB system. These can be probably explained with the EO groups of TX‐100 surfactant carrying partial positive charge.     

Phase Behavior and Densities of Aqueous Two‐Phase Systems Formed by 1,3‐Propanediyl bis(dodecyl dimethylammonium bromide) and Sodium Dodecyl Sulfonate Mixtures

Phase behavior of aqueous mixed surfactants, 1,3‐propanediyl bis(dodecyl dimethylammonium bromide) and sodium dodecyl sulfonate, has been studied at 318.15 K. The influence of added sodium halides (NaF, NaCl, and NaBr) has been investigated. For those systems studied, only one aqueous two‐phase region is formed in which cationic gemini surfactant is in excess. Different salt effects on the densities of the concentrated phases in aqueous two‐phase systems were observed for the three sodium halides. Density experiments indicate that contributions of various ions and water to the density of the solutions are near additive. Whether the concentrated phases in aqueous two‐phase systems are the bottom phases with higher densities or not are dependent on the different counterion binding ability and on the different contribution to the density of the three halides.     

Salinity Controlled Vesicle Formation and Growth in Aqueous Mixture of Aerosol OT/Triton X‐100

Mixed vesicles can be formed spontaneously from aqueous mixture of the double‐tailed anionic surfactant sodium bis(2‐ethylhexyl) sulfosuccinate (AOT) and the nonionic surfactant octylphenoxypolyethoxyethanol (Triton X‐100) under the inducement of salt, the formation mechanism of which should be attributed to the compression of salt on the electric bilayers of the head groups. The stability and the polydispersity of the vesicles are superior to single‐component AOT vesicles, which can be proved by the TEM image and visual observation. The vesicle region was presented in a pseudo‐ternary diagram of AOT/TX‐100/brine. The size of the vesicle was measured using dynamic light scattering. It is found that the vesicle size increases with the salinity but decreases with the content of TX‐100 in the mixture at the same salinity. Especially, the vesicle size is independent of the surfactant concentration at fixed salinity.     

The Influence of Sodium Phosphate on Extraction Phenomena of Aqueous Two‐Phase Cationic/Anionic Surfactant Systems

The phase behavior of dodecyltrimethylammonium bromide (DTAB)/sodium dodecyl sulfonate (AS)/H₂O system in the presence and in the absence of sodium phosphate has been studied. Two kinds of aqueous two‐phase systems (ATPSs) were formed, one is ATPS‐A in which anionic surfactant is in excess, the other is ATPS‐C in which cationic surfactant is in excess. For the CTAB/AS/H₂O system, the addition of sodium phosphate changes the extraction phenomena of both ATPS‐A and ATPS‐C. For the DTAB/AS/H₂O system, the addition of sodium phosphate changes the extraction phenomena of ATPS‐C. For ATPS‐C, the addition of trivalent PO₄ ^3? results in a strong extraction effect of ATPS‐C to cationic water‐soluble dye methylene blue.     

Fabrication of ZnO Nanorods in Colloidal Systems Formed by PEO‐PPO‐PEO Block Copolymers

One‐dimensional (1‐D) ZnO nanorods with various sizes were synthesized in colloidal systems formed by PEO‐PPO‐PEO block copolymers. The experimental results revealed that the growth of ZnO nanorods was dependent on the molecular structure of polyether. It was known that L64 (EO₁₃PO₃₀EO₁₃) and F68 (EO₈₀PO₃₀EO₈₀) had the same size PPO block but different content of PEO. We concluded that the size of the ZnO products obtained in F68 was larger due to its longer PEO chain.     

Semidifferential Electroanalysis of Aqueous Triton X—100／Toluene／H2O Microemulsion

Semidifferential electroanalysis is used as an effective method for investigating microstructure and structural transition of Triton X-100 microemulsions.     

The Aqueous Dispersions of Bicontinuous Cubic Phases Formed by Precursor Method

The morphologies and the microstructures of the dispersed particles of the cubic phase, which were formed by precursor method, were studied. The freeze-fracture TEM clearly showed that the aqueous dispersed particles have irregular cubic shapes. X-ray diffraction technique has been utilized to study the microstructure of the particles and it was found that these particles still retained the cubic character. The sizes of the particles were measured by dynamic light scattering, and the results showed that the sizes of the dispersed particles were between 200～400 nm under different conditions.     

Study on Dynamic Interfacial Tension of 3‐Dodecyloxy‐2‐hydroxypropyl Trimethyl Ammonium Chloride at n‐Decane/Water Interface

Dynamic interfacial tension (DIT) and interface adsorption kinetics at the n‐decane/water interface of 3‐dodecyloxy‐2‐hydroxypropyl trimethyl ammonium chloride (R₁₂TAC) were measured using spinning drop method. The effects of R_nTAC concentration and temperature on DIT have been investigated, the reason of the change of DIT with time has been discussed. The effective diffusion coefficient, D _a, and the adsorption barrier, ?_a, have been obtained with extended Word‐Tordai equation. The results show that the higher the concentration of surfactants is, and the smaller will be the DIT and the lower will be the curve of the DIT, and the R₁₂TAC solutions follow a mixed diffusion‐activation adsorption mechanism in this investigation. With increase of concentration in bulk solution of R₁₂TAC from 8×10^?4 mol · dm^?3 to 4×10^?3 mol · dm^?3, D _a decreases from 2.02×10^?10 m^?2 · s^?1 to 1.4×10^?11 m^?2 · s^?1 and ? _a increases from 2.60 kJ · mol^?1 to 9.32 kJ · mol^?1, while with increase of temperature from 30°C to 50°C, D _a increases from 2.02×10^?10 m^?2 · s^?1 to 5.86×10^?10 m^?2 · s^?1 and ε_a decreases from 2.60 kJ · mol^?1 to 0.73 kJ · mol^?1. This indicates that the diffusion tendency becomes weak with increase strength of the interaction between surfactant molecules and that the thermo‐motion of molecules favors interface adsorption.     

Temperature Effect on the Phase Behavior of the Systems Water/Sucrose Laurate/Ethoxylated‐mono‐di‐glyceride/Oil

The phase behavior of the systems water/sucrose laurate/ethoxylated mono‐di‐glyceride/oil was investigated as function of temperature and the weight ratio of EMDG in the mixed surfactants. The oils were R (+)‐limonene, isopropylmyristate, and caprylic‐capric triglyceride. This study demonstrates that the phase inversion temperature (PIT) decreases and the efficiency of the mixed surfactants (γ¯) increase as the weight ratio of the EMDG in the mixed surfactants increases. R (+)‐limonene gave lower phase inversion temperatures and higher efficiencies compared to isopropylmyristate, and caprylic‐capric triglyceride. The solubilization capacity of the system water/sucrose laurate/oil increased upon the addition of ethoxylated mono‐di‐ glyceride which stabilize the surfactant layer and increase the interfacial area.     

Salt Effects on Aqueous Cationic/Anionic Surfactant Two‐Phase Regions

The influence of added salts (KCl, NaF, NaCl, NaBr, Na₂SO₄, Na₃PO₄) on aqueous cetyltrimethylammonium bromide (CTAB)/sodium dodecyl sulfonate (AS) two‐phase regions were studied. For KCl, the concentration dependence of salt effect on aqueous two‐phase regions was investigated. When brine substitutes pure water as a solvent, the positions of aqueous two‐phase regions in the phase diagram change. The results indicate that for aqueous two‐phase systems with excess anionic surfactant (ATPS‐A), the salt effect was mainly dependent on the cationic inorganic counterions, whereas for aqueous two‐phase systems with excess cationic surfactant (ATPS‐C), the salt effect was mainly dependent on the anionic inorganic counterions. The shift of aqueous two‐phase region is strengthened following the Hofmeister series. All the experiments were performed at 318.15 K.     

Lyotropic Liquid Crystals Formed by Brij 97/PEO‐PPO‐PEO Mixtures

The phase diagrams of Brij 97/(PEO)_m(PPO)_n(PEO)_m/water/IPM quaternary systems (A L‐64: m=13, n=30; A L‐62: m=7, n=32; A L‐61: m=3.5, n=31) were determined at 25°C. The liquid crystalline phases (lamellar L_αand hexagonal H₁) were investigated by means of small angle x‐ray scattering (SAXS) and rheological techniques, with comparison of composition and component effects. The lamellar phases formed in Brij 97/A L‐64 and Brij 97/A L‐62 systems array more orderly than that of Brij 97/A L‐61 system, indicated by the stronger intensity of the second reflection peak in the SAXS patterns and the higher moduli (G′ and G″) in the dynamic rheograms. In Brij 97/A L‐64/water/IPM system, all L_α phases exhibit elastic rheograms, moreover the viscous property get increased with increase in water content. On the other hand, with this change, the H₁ phases show Maxwell and gel‐like rheograms in order, in which the latter shows mechanical and relaxation spectra typical of highly structured materials.     

Effect of Triton‐X‐100 Solvent in the Micellar Catalysis of the Aquation of Tris(2‐nitroso‐1‐naphtholate) Ferrate (II)

The effect of triton‐X‐100 micelles on the aquation of Fe(C₁₀H₆N₂O)₃ ²⁺ has been investigated with triton‐X‐100 as solvent. In liquid triton‐X‐100, over a range of [H₂O] _T (0.0–3 M), significant rate enhancement factors of 50–150 are observe. Acid inhibits the rate of aquation at fixed [H₂O] _T . A mechanism based on effective solvent participation in a chemical environment similar to that in reversed micelles is proposed in liquid triton‐X‐100 with dispersed water pockets. This mechanism predicts direct H₂O substitution into the coordination sphere of Fe(C₁₀H₆N₂O)₃ ²⁺ in the highly polar water pockets or cavities where the Fe (II) complex molecules are solubilized. Changes in the tumbling rate, structure, and activity of water are suggested to account for the observed changes in the rate of aquation as a function OH [H₂O] _T . All k _ψ–[H₂O] _T profiles are structured and exhibit maxima with k _ψ(max) shifted to progressively higher [H₂O] _T as the fixed concentration [H⁺] _T is increased.     

Three‐Component One‐Pot Synthesis of 1,4‐Dihydropyrano[2,3‐c]pyrazole Derivatives in Aqueous Media

Abstract

6‐Amino‐5‐cyano‐4‐aryl‐1,4‐dihydropyrano[2,3‐c]pyrazoles were synthesized by three‐component reaction of aromatic aldehydes, malononitrile, and 3‐methyl‐1‐phenyl‐2‐pyrazolin‐5‐one using triethylbenzylammonium chloride (TEBA) as catalyst in aqueous media. The reaction has the advantages of good yield, less pollution, ease of separation, and of being environment friendly.     

One‐Step Synthesis of Tolunitriles by Heterogeneously Catalyzed Liquid‐Phase Ammoxidation

Tolunitriles have been efficiently synthesized by selective ammoxidation of corresponding xylene over silica‐supported Co‐Mn‐Mg‐Ni catalysts, without solvent for the first time in a one‐pot procedure. The selectivity for mono‐nitriles is almost 100%.     

Three‐Component,One‐Pot Synthesis of Pyrazolo[3,4‐b]pyridine Derivatives in Aqueous Media

6‐Amino‐4‐aryl‐5‐cyanopyrazolo[3,4‐b]pyridines were synthesized by a three‐component reaction of aromatic aldehydes, malononitrile, and 5‐amino‐3‐methyl‐1‐phenylpyrazole using sodium 1‐dodecanesulfonic (SDS) as catalyst in aqueous media. The reaction has the advantages of good yields, less pollution, ease of separation, and environmental friendliness.     

Influences of Triton X-100 on Hemoglobin Behaviors in Hemoglobin/Acyclovir/Triton X-100/H2O System

The influences of Triton X-100 on hemoglobin （Hb） behaviors were studied by the methods of UV-Vis spectrum, fluorescence spectrum, HPLC, conductivity, zeta potential and negative-staining transmission electron microscope in Hb/acyclovir/Triton X-100/H2O system. With the increase of Triton X-100 concentration in the system, the percentage of the free acyclovir increased from 58%--63% to 90%--94%. The static quenching constant and the association number of acyclovir to Hb decreased. The fluorescence spectrum, conductivity, zeta potential, fluorescence polarization and negative-staining morphology of Hb tended to recover to those of the original state of Hb in the same concentration of Hb. The interaction between Triton X-100 and Hb is stronger than that between acyclovir and Hb. Most Triton-X-100 was associated with Hb at low Triton X-100 concentration. But the interaction of Triton X-100 with Hb was apparently dominant in high Triton X-100 concentration. The Hb structure was unfolded and finally denatured.     

Liquid‐Phase Synthesis of Methyl (E)‐2‐Nitromethyl‐2‐alkenoates Based on PEG‐Supported α‐Phenylselenopropionate

The reaction of the lithio derivative of novel polyethylene glycol (PEG)‐supported α‐phenylselenopropionate with aldehydes, followed by oxidation–elimination with 30% hydrogen peroxide and then treatment with sodium nitrite, formed PEG‐bound 2‐nitromethyl‐2‐alkenoates. Subsequent cleavage from the PEG efficiently afforded methyl (E)‐2‐nitromethyl‐2‐alkenoates in good yields and high purities.     

Solid‐Phase Synthesis of N‐Aryl‐N′‐Carboalkoxy Guanidines by the Mitsunobu Reaction of Fmoc‐Guanidines

Abstract

A new method for the solid‐phase synthesis of N‐aryl‐N′‐carboalkoxy guanidines is described. Aromatic amines were reacted with Fmoc‐isothiocyanate to provide Fmoc‐thioureas, which were coupled with Rink amide resin to provide the corresponding resin‐bound Fmoc‐guanidines. Subsequent Mitsunobu alkylation with a variety of alcohols delivered N‐aryl‐N′ carboalkoxy guanidines in good to high purity after resin cleavage.