十二烷基磺基甜菜碱与铂电极支撑的磷脂双层膜作用的电化学研究

以铂电极支撑的磷脂双层膜(Supported Bilayer Lipid Membrane,s-BLM)作为生物膜的模型,以Fe(CN)36-和Fe(CN)64-为探针分子,利用循环伏安法(CV)和交流阻抗谱(EIS)研究两性表面活性剂十二烷基磺基甜菜碱(Dodecyl Sulfobetaine,DSB)对s-BLM相互作用。结果显示,DSB可以嵌入到s-BLM的疏水区,容易使其表面分子的排列发生变化,产生缺陷或孔洞,探针分子Fe(CN)63-和Fe(CN)64-可以通过这些微孔接近电极,产生氧化还原响应。并且作用时间、DSB的浓度以及胆固醇的存在与否对二者的相互作用有直接影响。此外作用后的双层膜在0.1mol/LKCl溶液中能够自我修复,这表明DSB与s-BLM的相互作用是可逆的。     

Breakthrough and future: nanoscale controls of compositions,morphologies, and mesochannel orientations toward advanced mesoporous materials

Currently, ordered mesoporous materials prepared through the self‐assembly of surfactants have attracted growing interests owing to their special properties, including uniform mesopores and a high specific surface area. Here we focus on fine controls of compositions, morphologies, mesochannel orientations which are important factors for design of mesoporous materials with new functionalities. This Review describes our recent progress toward advanced mesoporous materials. Mesoporous materials now include a variety of inorganic‐based materials, for example, transition‐metal oxides, carbons, inorganic‐organic hybrid materials, polymers, and even metals. Mesoporous metals with metallic frameworks can be produced by using surfactant‐based synthesis with electrochemical methods. Owing to their metallic frameworks, mesoporous metals with high electroconductivity and high surface areas hold promise for a wide range of potential applications, such as electronic devices, magnetic recording media, and metal catalysts. Fabrication of mesoporous materials with controllable morphologies is also one of the main subjects in this rapidly developing research field. Mesoporous materials in the form of films, spheres, fibers, and tubes have been obtained by various synthetic processes such as evaporation‐mediated direct templating (EDIT), spray‐dried techniques, and collaboration with hard‐templates such as porous anodic alumina and polymer membranes. Furthermore, we have developed several approaches for orientation controls of 1D mesochannels. The macroscopic‐scale controls of mesochannels are important for innovative applications such as molecular‐scale devices and electrodes with enhanced diffusions of guest species. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 321–339; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900022     

Comblike poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers as anti-infection surface modifying agents

A series of structurally well-defined poly(ethylene oxide)/hydrophobic C₆ branched chitosan surfactant polymers that undergo surface induced self assembly on hydrophobic biomaterial surfaces were synthesized and characterized. The surfactant polymers consist of low molecular weight (M_w) chitosan backbone with hydrophilic poly(ethylene oxide) (PEO) and hydrophobic hexyl pendant groups. Chitosan was depolymerized by nitrous acid deaminative cleavage. Hexanal and aldehyde-terminated PEO chains were simultaneously attached to low M_w chitosan hydrochloride via reductive amination. The surfactant polymers were prepared with various ratios of the two side chains. The molecular composition of the surfactant polymers was determined by FT-IR and ¹H NMR. Surface active properties at the air–water interface were determined by Langmuir film balance measurements. The surfactant polymers with PEO/hexyl ratios of 1:3.0 and 1:14.4 were used as surface modifying agents to investigate their anti-infection properties. E. coli adhesion on Silastic^® surface was decreased significantly by the surfactant polymer with PEO/hexyl 1:3.0. Surface growth of adherent E. coli was effectively suppressed by both tested surfactant polymers.     

Influence of the presence of surfactants and humic acid in waters on the indophenol-type reaction method for ammonium determination

This work has evaluated the influence of humic acid and/or surfactants in the quantification of ammonium in waters with the indophenol-type reaction method. Thymol has been employed with the colorimetric method for sample ammonium concentrations between 0.25 and 1 mg L⁻¹. In addition, SPE/diffuse reflectance method has been used for quantification of ammonium at low concentrations (between 0.025 and 0.25 mg L⁻¹). Matrix effect owing to humic substances were observed with the colorimetric method when the concentration was equal or higher than 25 mg L⁻¹. Lower concentrations of humic compounds produced matrix effects with the more sensitive SPE/diffuse reflectance method. Generalized H-point standard addition method (GHPSAM) was employed for evaluating the effect of humic acids and for eliminating the bias error produced by humic acids. Real water samples of different types were analyzed and accurate results for ammonium concentration were obtained with both procedures in presence or absence of humic acids. Cationic and anionic surfactants inhibited the derivatization reaction at percentages up to 0.001% and 0.5%, respectively, and non-ionic surfactants at percentages of 5.5%     

Electrochemical polymerization of 3,4-ethylenedioxythiophene in aqueous solution containing N-dodecyl-β-d-maltoside

Poly(3,4-ethylenedioxythiophene) (PEDOT) films were synthesized electrochemically by direct anodic oxidation of 3,4-ethylenedioxythiophene (EDOT) at relatively low monomer concentration (0.005-0.01 mol L⁻¹) in aqueous solution containing green nonionic sugar-based surfactant N-dodecyl-β-d-maltoside (DM), which has good biocompatibility and biodegradability. The moderate interaction between DM through the hydroxy groups and EDOT monomer led to the decrease of monomer oxidation onset. Different surfactants, such as anionic sodium dodecylbenzenesulfate (SDBS), nonionic triton X-100 (TX100), were also tested for comparison. As-formed PEDOT films were characterized electrochemically and spectroscopically using FTIR and UV-visible techniques. PEDOT nano-materials with good thermal stability and conductivity of 26.2 S cm⁻¹ can be synthesized in water-DM micellar solution, which can be proved by the results of scanning electron microscopy (SEM). PEDOT prepared from water-DM media with good biocompatibility can be a good candidate for application in biosensors.     

Zwitterionically modified hydroxypropylcellulose for biomedical applications

Novel polyelectrolytes have been synthesized by grafting sulfobetaine side chains onto hydroxypropylcellulose backbone. Polymers with various degrees of grafting have been obtained. The polymers do not interact with model anionic, cationic and zwitterionic surfactants as found in fluorescence studies using pyrene as a molecular probe. Dynamic light scattering (DLS) studies indicated that in the graft polymer solution two types of polymers are present. The films were formed from the grafted polymers. Using atomic force microscopy (AFM) technique it was found that they are resistant to the adhesion of proteins and can be used for the preparation of antiadhesive surfaces which may find biomedical applications.     

Impacts of ultrasonication time and surfactants on stability and optical properties of CuO,Fe3O4, and CNTs/water nanofluids for spectrum selective applications

The prime objective of the present experimental work is to evaluate the impact of ultrasonication time and surfactants on the optical characteristics (transmittance and absorbance) and stability of CuO/water, CNTs/water, and Fe₃O₄/water nanofluids to be used in spectrum selective applications. Two-step method with various ultrasonication times (30 min, 60 min, and 90 min) was employed to prepare nanofluids (having volume fractions of 0.004 % and 0.0004 %). Furthermore, various surfactants (anionic, cationic, and polymer) were added to the base fluid. The study results revealed that surfactants have a significant effect on the stability of nanofluids over ultrasonication time. The nanofluids prepared using sodium dodecylbenzene sulfonate (SDBS) have the highest zeta potential values than other surfactants used in the experimentation. The increase in transmittance of nanofluid was more prominent for lower concentration (0.0004 %) after one week of preparation. The concentration of nanoparticles, ultrasonication time, temperature, and surfactants influenced the optical characteristics of nanofluids. The most stabled CNTs nanofluid with 0.004 % concentration and 90 min of ultrasonication obtained an average of 67.6 % and 74.6 % higher absorbance than stabled CuO and Fe₃O₄ nanofluids, respectively. The irradiance transmitted through nanofluid was strongly dependent on the concentration and type of nanoparticles.     

RP‐HPLC enantioseparation of β‐adrenolytics using micellar mobile phase without organic solvents

Enantioseparation of a few commonly administered racemic β‐adrenolytics (namely, carvedilol, betaxolol, salbutamol and bisoprolol) has been achieved using a water micellar mobile phase containing surfactants (sodium dodecyl sulphate and Brij‐35) without organic solvents as a new approach in RP‐HPLC. Two chiral derivatizing reagents based on enantiomerically pure (S )‐(−)‐levofloxacin were synthesized using N ‐hydroxysuccinimide and N ‐hydroxybenzotriazole as the activation auxiliaries. Diastereomeric derivatives of the chosen β‐adrenolytics were synthesized under microwave irradiation in a very short reaction time. The (S )‐(−)‐levofloxacin moiety enhanced molar absorbance of the diastereomeric derivatives resulting in very low limit of detection (1.618 and 4.902 ng/mL, respectively, for diastereomeric derivatives of (RS )‐betaxolol and better resolution with lower retention times (for all the analytes), in comparison to literature reports. There was 15–20 times less consumption of mobile phase because of lower retention time.     

Analysis of alcohol ethoxylates and alkylamine ethoxylates in agricultural soils using pressurised liquid extraction and liquid chromatography–mass spectrometry

Nonionic surfactants e.g. alcohol ethoxylates (AEOs) and alkylamine ethoxylates (ANEOs) are commonly utilised as adjuvants in pesticide formulations to enhance their effectiveness. In this study, analytical methods for AEO and ANEO determination in soil samples using pressurised liquid extraction (PLE) were developed and used in connection with LC–MS. The recovery of the method, which was highly dependent on the soil properties, varied in the range 47–106% for AEO and 27–109% for ANEO. Detection limits (LOD) were 7–13 µg kg^–1 for AEO and 24–43 µg kg^–1 for ANEO. The developed method has been applied to determine AEOs and ANEOs in surface soil samples from fields sprayed with glyphosate herbicides. Tallowalkylamine ethoxylates (an ANEO) were detected in the soil before and after pesticide application, with increasing concentrations after treatment. The highest concentration in the soil samples was observed for the ANEO homologues with the longest ethoxy chains; in the clay soil the concentration decreased with the length of the ethoxy chain. ANEOs added to pesticide formulations as a technical mixture will, as demonstrated in this study, behave as individual homologues, which is reflected in their behaviour in the environment.Abbreviations AEO Alcohol ethoxylates - ANEO Alkylamine ethoxylates - APEO Alkylphenol ethoxylates - APCI Atmospheric pressure chemical ionisation - ASE Accelerated solvent extraction - CEC Cationic exchange capacity - LC–MS Liquid chromatography–mass spectrometry - LOD Limit of detection - MAE Microwave-assisted extraction - PLE Pressurised liquid extraction - SD Standard deviation - SIM Selected-ion monitoring - SPE Solid-phase extraction - TEA Triethylamine