Study on the liquid membrane oscillation of water/oil/water system containing TTAB and picric acid

The liquid membrane oscillation of a novel water （aqueous tetradecyl trimethyl ammoniumbromide, TTAB and alcohol solution）/oil （picric acid in chloroform solution）/water （aqueous glucose solution） system was investigated. By using homemade device, the curves of various liquid membranes oscillation with different concentration of TTAB and picric acid, types of alcohol and other organic solvents at different temperature were measured. The results show that the water （aqueous 7 mmol/L of TTAB and 0.5 mol/L of n-propanol solution）/oil （0.5 mmol/L of picric acid in chloroform solution）/water （aqueous glucose solution） system performed sustained and stable oscillation at 30 ℃. And the novel system can recognise added amino acid.     

COMPARTMENTALIZATION OF ZINQII) TETRAPHENYLPORPHYRIN IN A HYDROPHOBIC MICRODOMAIN OF AN AMPHIPHILIC POLYELECTROLYTE: A PHYSICOCHEMICAL MODEL OF BIOLOGICAL METALLOPORPHYRIN SYSTEMS

Abstract— Small mole fractions of zinc(II) tetraphenylporphyrin (ZnTPP) moieties were covalently incorporated into amphiphilic polysulfonates having bulky hydrophobic groups such as lauryl, cyclododecyl, and (2-naphthyi)methyl (Np) groups in their side chains. The ZnTPP moieties are "compartmentalized" in the hydrophobic domains of these amphiphilic polyelectrolytes in aqueous solution. For comparison, the ZnTPP moieties were covalently incorporated into a polysulfonate without hydrophobic groups. The ZnTPP moieties in this reference polymer are exposed to water in aqueous solution. The compartmentalized ZnTPP systems in aqueous fluid solution emitted phosphorescence and thermally activated delayed fluorescence at room temperature. This is due to an extremely long-lived triplet excited state in the compartmentalized systems at room temperature in aqueous solution, e.g. 19 ms for ZnTPP compartmentalized in Np domains, compared with 3 ms for ZnTPP in the reference polymer. These remarkable compart-mentalization effects may be attributed to a restriction of motional freedom of the ZnTPP moiety isolated in a rigid and hydrophobic microenvironment provided by the amphiphilic polyelectrolytes in aqueous solution.     

N,O-羧甲基壳聚糖的合成和性质研究

采用多段升温法将壳聚糖改性,合成了取代度为1.84、平均分子量为3.08×105、等电点为7.28的N,O-羧甲基壳聚糖(CMC),分别用紫外光谱、红外光谱、荧光光谱对其结构进行了表征,并对其水溶液的Zeta电位、电导率、表面张力以及水分散体系中羧甲基壳聚糖微粒的粒径分布进行了研究.结果表明, N,O-羧甲基壳聚糖具有表面活性;介质的pH值和浓度对羧甲基壳聚糖溶液的稳定性有很大的影响.     

Self-assembly behavior of a stimuli-responsive water-soluble [60]fullerene-containing polymer

A novel pH- and temperature-responsive water-soluble [60]fullerene-containing poly[2-(dimethylamino)ethyl methacrylate] (C60-b-PDMAEMA) was synthesized by atom transfer radical polymerization. The pH and temperature dependence of the physical properties of the aqueous C60-b-PDMAEMA solution was studied by potentiometric and conductometric titrations, UV-vis transmittance, and laser light scattering techniques. At low pH and at temperatures ranging from 25 to 55 degrees C, in addition to C60-b-PDMAEMA unimers, micelle-like aggregates are produced in the aqueous solution containing C60 hydrophobic cores and protonated PDMAEMA shells. Only unimeric C60-b-PDMAEMAs are found to exist in solution at high pH and low temperature, where PDMAEMA segments form a charge-transfer complex with C60 molecules. However, C60-b-PDMAEMA precipitates from aqueous solution at temperatures exceeding the lower critical solution temperature of PDMAEMA of approximately 45 degrees C. The pH and temperature stimuli-responsive properties of the [60]fullerene-containing polymer in aqueous solution are completely reversible.     

Tube radial distribution phenomenon observed in an aqueous micellar solution of non-ionic surfactant fed into a microspace and an attempt of capillary chromatographic application

A new type of tube radial distribution phenomenon was observed in an aqueous micellar solution of non-ionic surfactant that was fed into a microspace. A homogeneous aqueous solution containing 2 wt % Triton X-100 and 2.0 M sodium chloride was fed into a microchannel (40 μm in depth and 200 μm in width) in a microchip at a flow rate of 4.0 μL/min, where the microchip was maintained at a temperature of 34°C. The homogeneous aqueous solution changed to a heterogeneous solution with two phases in the microchannel; the surfactant-rich phase was generated around the middle of the channel, while the aqueous phase containing little surfactant was formed near the wall. The radial distribution of the surfactant was observed through Rhodamine B dissolved in the aqueous micellar solution with a bright-field microscope — CCD camera system. An open-tubular capillary chromatographic system was also tried to develop using the fusedsilica capillary tube (75 μm inner diameter and 120 cm length) as a separation column and the aqueous micellar solution as a carrier.     

Redispersible and stable amorphous calcium phosphate nanoparticles functionalized by an organic bisphosphate

Although much effort has been focused on the preparation of stable amorphous calcium phosphate （ACP） nanoparticles in aqueous solution, the redispersibility and long-term stability of ACP nanoparticles in aqueous solution remains an unresolved problem. In this work, stable colloidal ACPs were prepared by using an organic bisphosphonate （BP） as a sterically hindered agent in aqueous solution. The harvested calcium phosphate nanoparticles were characterized by inductively coupled plasma atomic emission spectrometry （ICP-AES）, Fourier transform infrared （FTIR）, X-ray diffraction （XRD）, dynamic light scattering （DLS） and transmission electron microscopy （TEM）. ICP-AES, FTIR and XRD results suggested the particles were ACP. DLS and TEM results indicated that the size of the ACP nanoparticles were in the range of 60 nm with a spherical morphology. The resulting calcium phosphate nanoparticles retained its amorphous nature in aqueous solution for at least 6 months at room temperature due to the stabilizing effect of the organic bisphosphonate. Moreover, the surface of the ACP nanoparticles adsorbed with the organic bisphosphate used showed good redispersibility and high colloid stability both in organic and aqueous solutions.     

Synergism in the spreading of hydrocarbon-chain surfactants on polyethylene film-anionic and cationic mixtures by a two-step procedure

A study has been made of the adsorption, interaction, and spreading of mixtures of anionic and cationic surfactants at the aqueous solution/polyethylene (PE) interface. When a drop of an aqueous solution of an anionic or cationic hydrocarbon-chain surfactant is placed on a highly hydrophobic PE film (contact angle of water > 90 degrees ), it spreads to an area very little larger than that of a drop of water of the same volume. If the anionic and cationic hydrocarbon-chain surfactant solutions are mixed prior to being applied to PE film, synergism is small, if any, and the reproducibility of the experimental results is poor. However, when the cationic and anionic aqueous solutions are applied on the PE film in a sequential manner, a remarkable synergism in spreading is observed and the results are very reproducible. The area spread by an aqueous solution of the anionic-cationic mixture may be more than 400 times that of aqueous solutions of the same volume and surfactant concentration of the individual surfactant components. Previous work in this laboratory on surfactant systems showing synergism in spreading on PE film, but only weak interaction at the aqueous solution/air interface, showed that the synergy was due to changes at the aqueous solution/PE interface and not to the changes at the aqueous solution/air or PE/air interface. Investigation of the adsorption behavior at the aqueous solution/solid interface of two of the anionic-cationic mixtures studied here indicates the reason for differences in spreading behavior observed with different anionic-cationic mixtures. The more similar the adsorption tendencies at the solid/aqueous solution interface of the anionic and cationic surfactants, and the closer their adsorption to an equimolar monolayer there, the stronger their interaction there and the greater their enhancement of the spreading. A mechanism is proposed for the synergy in spreading observed, based upon the difference between the surface tension in the precursor film at the spreading interface and that at the top of the spreading drop.     

Solvation structure of I- and Na+ on the surface of NaI aqueous solution studied by photodetachment spectroscopy in combination with mass spectrometry

We investigated solvation structures of I(-) and Na(+) on an aqueous solution surface by photodetachment spectroscopy and mass spectrometry. An aqueous solution of NaI was introduced into the vacuum as a continuous liquid flow (liquid beam), and the liquid beam was irradiated with a UV laser pulse. The abundance of electrons emitted by the laser excitation was measured as a function of wavelength (photodetachment spectroscopy). For a concentrated aqueous solution of NaI, we observe an absorption peak at longer wavelengths than the charge-transfer-to-solvent band of I(-) in solution. This feature is assigned to the photoabsorption of I(-) at the surface. This finding indicates that when the concentration of NaI is high (>1.0 M), I(-) exists on the solution surface. The identity of the ion clusters ejected from the liquid beam following selective laser excitation of I(-) on the surface or I(-) inside the solution was revealed by mass spectrometry. The mass spectra show that Na rich clusters are formed when I(-) inside the solution is excited, whereas Na rich clusters are hardly formed by the excitation of surface I(-). These findings lead us to conclude that Na(+) does not exist on the surface of the NaI aqueous solution.     

电场条件下高分子共混物组分浓度梯度化的研究

研究了聚乙烯醇/聚丙烯酸高分子共混物水溶液中,共混物各组分在电场诱导条件下沿电场方向的浓度梯度分布情况.通过测定不同时刻PVA/PAA高分子共混物水溶液在电场的不同区域内的pH值,研究了电场诱导下共混物各组分沿电场方向的迁移过程.结果表明,PAAn-向电场正极迁移,同时由于浓差梯度,PVA向负极迁移,并形成浓度梯度分布.随时间的延长,高分子共混物的组分梯度程度逐渐加大.     

Photoluminescence of 2-(2′-hydroxy-5′-methylbenzoyl)-1,5-diphenylpyrrole in aqueous and β-cyclodextrin environments: manifestation of open and closed conformers

Steady-state fluorometric studies have been performed on 2-(2′-hydroxy-5′-methylbenzoyl)-1,5-diphenylpyrrole (HMBDPP) in aqueous and aqueous β-cyclodextrin (β-CD) environments at ambient temperature. The fluorophore mostly shows a single emission in aqueous solution. Addition of β-CD to the aqueous solution of the fluorophore results in the development of another emission band at higher energy. The difference in the fluorometric behaviour is assigned to a remarkable change in the polarity of the microenvironment within the supramolecular structural environment compared to that of the bulk aqueous phase. Semi-empirical calculation (AM1-SCI) rules out the possibility of intramolecular proton transfer reaction in any of the S₀, S₁ and T₁ states of the fluorophore. It is proposed that HMBDPP exists mostly in the intermolecularly hydrogen-bonded form (open conformer) in aqueous solution while within β-CD environment, it is the intramolecularly hydrogen-bonded form (closed conformer) that predominates.     

Non-linear vibrational sum frequency spectroscopy of atmospherically relevant molecules at aqueous solution surfaces

Surface vibrational sum frequency spectroscopy has been shown to be a powerful surface probe of molecules adsorbed at solid and liquid surfaces. Studies described herein apply this method to studying heterogeneous air/aqueous solution interfaces to understand surface adsorption and structure of several solute molecules adsorbed at aqueous surfaces. The molecules examined at aqueous solution surfaces include Dimethyl sulfoxide (DMSO), methane sulfonic acid (MSA) and acetone. These results reveal that small soluble molecules such as these organize in different ways at the surface of aqueous solutions. This surface organization has implications for atmospheric chemical processes since adsorption at the surface of atmospheric aerosols affects bulk chemical concentrations.     

Vibrational Raman optical activity characterization of poly(l-proline) II helix in alanine oligopeptides

A vibrational Raman optical activity (ROA) study of a series of alanine peptides in aqueous solution is presented. The seven-alanine peptide Acetyl-OOAAAAAAAOO-Amide (OAO), recently shown by NMR and UVCD to adopt a predominantly poly(l-proline II) (PPII) helical conformation in aqueous solution, gave an ROA spectrum very similar to that of disordered poly(l-glutamic acid) which has long been considered to adopt the PPII conformation, both being dominated by a strong positive extended amide III ROA band at approximately 1319 cm-1 together with weak positive amide I ROA intensity at approximately 1675 cm-1. A series of alanine peptides Ala2-Ala6 studied in their cationic states in aqueous solution at low pH displayed ROA spectra which steadily evolved toward that of OAO with increasing chain length. As well as confirming that alanine peptides can support the PPII conformation in aqueous solution, our results also confirm the previous ROA band assignments for PPII structure, thereby reinforcing the foundation for ongoing ROA studies of unfolded and partially folded proteins.     

A new method for the determination of the critical micelle concentration of Triton X-100 in the absence and presence of beta-cyclodextrin by resonance Rayleigh scattering technology

A new method for the determination of the critical micelle concentration (CMC) of Triton X-100 in aqueous solution and beta-cyclodextrin solution by resonance Rayleigh scattering (RRS) has been developed. The method is based on the measurement of the RRS intensity of different concentration of Triton X-100 in aqueous solution and beta-cyclodextrin solution (6.0 x 10(-4) mol l(-1)). When the RRS intensities were plotted against the concentration of Triton X-100, an inflection point appeared at the Triton X-100 concentration of 5.0 x 10(-4) mol l(-1) in aqueous solution and 1.1 x 10(-3) mol l(-1) in beta-cyclodextrin solution, respectively. These values of concentration corresponded to the CMC of Triton X-100 in aqueous solution and beta-cyclodextrin solution, which also agreed closely with the results reported by surface tension and UV-Vis absorption spectrophotometry. Therefore, the present RRS method is very convenient, rapid and accurate and can be used as a new technology for the determination of CMC values of surfactants without any probe. The relationship between the RRS intensity and the concentration, aggregate state and the aggregate molecular size of Triton X-100 has been primarily discussed.     

The radiation-induced peroxidation of poly(N-vinylpyrrolidone) in an aqueous solution

The radiation-induced peroxidation of poly(N-vinylpyrrolidone) (PVP) in its aqueous solution is reported. The amount of peroxides formed in PVP aqueous solution increased with radiation dose. The peroxides decomposed slowly at a low temperature. The molecular weight of PVP decreased with absorbed dose. The peroxidized PVP can function as initiators and crosslinkers for the syntheses of tough hydrogels.     

Simultaneous assay of four stereoisomers of diltiazem hydrochloride. Application to in vitro chiral inversion studies

Summary The simultaneous stereospecific assay of four stereoisomers of diltiazem hydrochloride in bulk drug and aqueous solution was developed using HPLC on a Chiralcel OF column. The four isomers were quantitated with good precision by the internal standard method. The chiral inversion of (+)-cis-diltiazem hydrochloride in vitro, stability of its (2S, 3S) configuration in the solid and aqueous states was examined by HPLC. Chiral inversion of (+)-cis-diltiazem hydrochloride was not observed in the solid state, and its (2S, 3S) configuration was stable to heat, humidity and light. Chiral inversion of (+)-cis-diltiazem hydrochloride (2S, 3S) was observed in aqueous solution under UV, but not in aqueous solution stored at 80°C for 5 h nor under visible light for 10 h. The (+)-cis-diltiazem hydrochloride (2S, 3S) epimerized to (+)-trans-diltiazem hydrochloride (2R, 3S) with a half-life of 5 h in aqueous solution under UV but the reverse chiral inversion of (+)-trans-diltiazem hydrochloride (2R, 3S) to (+)-cis-diltiazem hydrochloride (2S, 3S) was not observed.     

可光交联的共聚物肉桂酰化的聚(N-乙烯基吡咯烷酮-丙烯酸-2-羟基乙酯)的合成及其水溶液的温敏性

可光交联的共聚物肉桂酰化的聚(N-乙烯基吡咯烷酮-丙烯酸-2-羟基乙酯)的合成及其水溶液的温敏性     

Simultaneous assay of four stereoisomers of diltiazem hydrochloride. Application to in vitro chiral inversion studies

Summary The simultaneous stereospecific assay of four stereoisomers of diltiazem hydrochloride in bulk drug and aqueous solution was developed using HPLC on a Chiralcel OF column. The four isomers were quantitated with good precision by the internal standard method. The chiral inversion of (+)-cis-diltiazem hydrochloride in vitro, stability of its (2S, 3S) configuration in the solid and aqueous states was examined by HPLC. Chiral inversion of (+)-cis-diltiazem hydrochloride was not observed in the solid state, and its (2S, 3S) configuration was stable to heat, humidity and light. Chiral inversion of (+)-cis-diltiazem hydrochloride (2S, 3S) was observed in aqueous solution under UV, but not in aqueous solution stored at 80°C for 5h nor under visible light for 10 h. The (+)-cis-diltiazem hydrochloride (2S, 3S) epimerized to (+)-trans-diltiazem hydrochloride (2R, 3S) with a half-life of 5h in aqueous solution under UV but the reverse chiral inversion of (+)-trans-diltiazem hydrochloride (2R, 3S) to (+)-cis-diltiazem hydrochloride (2S, 3S) was not observed.     

Photooxidation of poly(N-vinylpyrrolidone) (PVP) in the solid state and in aqueous solution

The photooxidation of poly(N-vinylpyrrolidone) (PVP) in the solid state and in an aqueous solution has been studied under irradiation at long wavelengths (at λ ≥ 300 nm) and in the presence of oxygen, as these conditions of irradiation are those of natural outdoor aging. Infrared spectroscopy was used to follow the photochemical evolution of the polymer either for solid films of PVP or for PVP irradiated in an aqueous solution. Chemical treatments (NH₃, SF₄) were carried out on the photooxidized samples, and aqueous solutions of PVP were characterized by viscometry and size exclusion chromatography (SEC). Based on photooxidation results obtained in both the solid state and in an aqueous solution, a general mechanism that accounts for the main routes of oxidation is proposed. It was shown that the rates of oxidation and the stoichiometries of the reactions were strongly influenced by the physical state of the polymer (solid state or aqueous solution).     

快速响应的温敏性聚(N-异丙基丙烯酰胺)水凝胶的合成及表征

快速响应的温敏性聚(N-异丙基丙烯酰胺)水凝胶的合成及表征;N-异丙基丙烯酰胺;水凝胶;温敏性;快速响应     

Synthesis of Calcium Silicate Hydrate from Coal Gangue for Cr(VI) and Cu(II) Removal from Aqueous Solution

Both the accumulation of coal gangue and potentially toxic elements in aqueous solution have caused biological damage to the surrounding ecosystem of the Huainan coal mining field. In this study, coal gangue was used to synthesize calcium silicate hydrate (C-S-H) to remove Cr(VI) and Cu(II)from aqueous solutions and aqueous solution. The optimum parameters for C-S-H synthesis were 700 °C for 1 h and a Ca/Si molar ratio of 1.0. Quantitative sorption analysis was done at variable temperature, C-S-H dosages, solution pH, initial concentrations of metals, and reaction time. The solution pH was precisely controlled by a pH meter. The adsorption temperature was controlled by a thermostatic gas bath oscillator. The error of solution temperature was controlled at ± 0.3, compared with the adsorption temperature. For Cr(VI) and Cu(II), the optimum initial concentration, temperature, and reaction time were 200 mg/L, 40 °C and 90 min, pH 2 and 0.1 g C-S-H for Cr(VI), pH 6 and 0.07 g C-S-H for Cu(II), respectively. The maximum adsorption capacities of Cr(VI) and Cu(II) were 68.03 and 70.42 mg·g⁻¹, respectively. Furthermore, the concentrations of Cu(II) and Cr(VI) in aqueous solution could meet the surface water quality standards in China. The adsorption mechanism of Cu(II) and Cr(VI) onto C-S-H were reduction, electrostatic interaction, chelation interaction, and surface complexation. It was found that C-S-H is an environmentally friendly adsorbent for effective removal of metals from aqueous solution through different mechanisms.