Preparation and characterization of cellulose and konjac glucomannan blend film from ionic liquid

Blend films from cellulose and konjac glucomannan (KGM) in room temperature ionic liquid 1‐allyl‐3‐methylimidazolium chloride were satisfactorily prepared by coagulating with water. The composition of the blend films was gravimetrically analyzed, and the compatibility of the two natural polymers was characterized by Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction. The results indicate good compatibility and strong interactions between cellulose and KGM, resulting in almost no loss of the water‐soluble KGM from the blend films even after the water coagulating and washing. However, microstructure analyses portrayed phase separations in the blend films, namely, egg‐like new phase particles were embedded in a continuous matrix base (MB). Phase diagram analysis and differential scanning calorimetry of the phase inversion coagulation process suggest that relative low molecular mass part of both cellulose and KGM formed the continuous MB, whereas the egg‐like new phase particles were super patterns of relative high molecular mass of both polymers, which played an important role in strengthening the blend material. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1686–1694, 2009     

AFM-based nanotribological and electrical characterization of ultrathin wear-resistant ionic liquid films

Ionic liquids (ILs) are considered as lubricants for micro/nanoelectromechanical systems (MEMS/NEMS) due to their excellent thermal and electrical conductivity. So far, only macroscale friction and wear tests have been conducted on these materials. Evaluating the nanoscale tribological performance of ILs when applied as a few nanometers-thick film on a substrate is a crucial step to understand how these novel materials can efficiently lubricate MEMS/NEMS devices. To this end, the adhesion, friction and wear properties of two ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) and 1-butyl-3-methylimidazolium octyl sulfate (BMIM-OctSO4), applied on Si(100), are investigated for the first time using atomic force microscopy (AFM). Data is compared to the perfluoropolyether lubricant Z-TETRAOL, which has high thermal stability and extremely low vapor pressure. Wear at ultralow loads was simulated and the lubricant removal mechanism was investigated using AFM-based surface potential and contact resistance techniques. Thermally treated coatings containing a mobile lubricant fraction (i.e., partially bonded) were better able to protect the Si substrate from wear compared to the fully bonded coatings, and this enhanced protection is attributed to lubricant replenishment.     

Nano-indentation of a room-temperature ionic liquid film on silica: a computational experiment

We investigate the structure of the [bmim][Tf(2)N]/silica interface by simulating the indentation of a thin (4 nm) [bmim][Tf(2)N] film by a hard nanometric tip. The ionic liquid/silica interface is represented in atomistic detail, while the tip is modelled by a spherical mesoscopic particle interacting via an effective short-range potential. Plots of the normal force (F(z)) on the tip as a function of its distance from the silica surface highlight the effect of weak layering in the ionic liquid structure, as well as the progressive loss of fluidity in approaching the silica surface. The simulation results for F(z) are in near-quantitative agreement with new AFM data measured on the same [bmim][Tf(2)N]/silica interface under comparable thermodynamic conditions.     

Preparation and micro-mechanical studies of polysiloxane-containing dual-layer film on Au surface

A novel polysiloxane-containing self-assembled dual-layer film was grafted onto Au surface with a simple three-step method. Firstly, (3-mercaptopropyl)trimethoxysilane (MPTMS) molecules were self-assembled on Au surfaces through S–Au bond followed by hydrolysis and condensation, then the octadecyltrichlorosilane molecules were attached to the resultant hydroxyl terminated surface via the Si–O–Si bonds. The structure and morphology of the film were characterized by means of contact angle measurement, ellipsometry, attenuated total reflectance Fourier transformed infrared spectra, and atomic force microscopy. The resistant ability of charge transfer in the film forming process was detected by electrochemical techniques. Using force–volume technique, we investigated how the different surface chemical groups influence the surface adhesion properties. The nano-friction properties of the as-prepared films were investigated by frictional force microscopy. The results indicated that the dual-layer film fabricated via the hydrolyzation of MPTMS underlayer had significantly less friction. Moreover, compared to the self-assembled monolayer of octadecane thiol, the resultant dual-layer film showed much less wear. This improvement was mainly ascribed to the existence of the network of lateral cross-linked polysiloxane layer within the film which can enhance the stability of the film.     

Preparation and characterization of polyoxometalate/protein ultrathin films grown on electrode surfaces using layer-by-layer assembly

We report a new electrostatic layer-by-layer assembly method for the controlled deposition of electrocatalytically active enzymes onto electrode surfaces using polyoxometalate as the counteranion. Cytochrome c (cyt c), a redox active protein, and P(2)W(18)O(62)(6-), a Dawson-type polyoxometalate, were deposited onto glassy carbon electrodes by two procedures: static dipping and electrochemical cycling. Cyclic voltammetry and UV-vis spectroscopy reveal that approximately 1.5 x 10(-10) mol/cm(2) of P(2)W(18)O(62)(6-) and 2.2 x 10(-11) mol/cm(2) of cytochrome c are deposited per cycle, which correspond to approximately one monolayer of each molecule. The thicknesses of the resulting films measured by atomic force microscopy also indicate that the films are formed in a layer-by-layer fashion. Experimental factors that affect electron-transfer rate in these films, such as scan rate and film thickness, were systematically analyzed. The use of {P(2)W(18)O(62)(6-)/cyt c}n films to catalyze hydrogen peroxide reduction was demonstrated.     

Preparation and characterization of inclusion complexes of beta-cyclodextrin with ionic liquid

The solubilities of beta-cyclodextrin (beta-CD), ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6), and their mixture in water were determined, and the conductivity of these aqueous solutions was measured. It was demonstrated that beta-CD and bmimPF6 could enhance the solubility of each other, and the solubility curves of each were linear with gradients of about 1. The conductivity decreased remarkably with increasing beta-CD concentration, and a discernible break in the conductivity curve could be observed when beta-CD and bmimPF6 were equimolar in the solution. The solubility and conductivity results indicated that inclusion complexes (ICs) of 1:1 stoichiometry were formed. The inclusion compounds were further characterized by using powder X-ray diffraction (XRD) analysis, 13C CP/MAS (cross-polarization magic-angle spinning) NMR and 1H NMR spectroscopy, and thermogravimetric analysis (TGA). The results showed that the ICs were a fine crystalline powder. The host-guest system exhibited a channel-type structure and each glucose unit of beta-CD was in a similar environment. The decomposition temperature of the ICs was lower than that of bmimPF6 and beta-CD individually.     

Preparation and characterization of helical carbon/silica nanofibers with lamellar mesopores on the surfaces

Helical 1,2-ethylene-silica nanofibers with lamellar mesopores on the surfaces and twisted rod-like mesopores inside were prepared according to literature procedures. After carbonization, helical carbon/ silica nanofibers with lamellar mesopores on the surfaces and twisted rod-like micropores inside were obtained. The morphologies and pore architectures of the carbon]silica nanofibers were characterized using transmission electron microscopy, field-emission scanning electron microscopy, powder X-ray diffraction and N2 sorptions. Although the mesopores inside shrank into micropores, the helical nanostructure remained. Moreover, several carbon/silica nanofibers with lamellar mesopores on the surfaces and concentric circular micropores inside were also obtained. After being calcined in air, helical silica nanofibers with lamellar mesopores on the surfaces and twisted rod-like micropores inside were produced as well.     

Synthesis of novel acidic ionic liquid immobilized on silica

A novel acidic ionic liquid immobilized on silica has been synthesized by hydrolyzing tetraethyl orthosilicate (TEOS) and the acidic ionic liquid derived from (3-aminopropyl) trimethoxysilane. The catalytic activities were evaluated in the acetalization and biodiesel synthesis. The results showed that the solid acid was a very efficient catalyst for the traditional acid-catalyzed reactions with the yield over 99.0%. A novel solid acid combined both the high activities inherent to the acidic ionic liquid and the feasibility of separation of the solid catalysts. High acidity, enhanced catalytic activities and improved stability were the key properties of the novel solid acid.     

Preparation and characterization of conductive chitosan–ionic liquid composite membranes

Anhydrous conductive membranes composing of a composite of chitosan (CS) and ionic liquids with symmetrical carboxyl groups were explored. Scanning electron microscope images revealed that porous composite membranes could be obtained by combining CS with different amounts of 1,4‐bis(3‐carboxymethyl‐imidazolium)‐1‐yl butane chloride ([CBIm]Cl). Fourier transform infrared and proton nuclear magnetic resonance confirmed that the formation of ammonium salts after CS was combined with [CBIm]Cl. The thermal property of CS–ionic liquid composite membranes was studied through thermogravimetric analysis. The anhydrous ionic conductivities of CS–[CBIm]X (X = Cl, Ac, BF₄, and I) composite membranes were measured using ac impedance spectroscopy at room temperature in N₂ atmosphere. The conductivities (0.4–0.7 × 10^?4 Scm^?1), found to be in the same range as semiconductors, were significantly higher than those of pure CS membrane (<10^?8 Scm^?1). In addition, the anhydrous conductivity of composite membrane based on CS–[CBIm]I at room temperature reached a level as high as 0.91 × 10^?2 Scm^?1 when iodine was doped. Copyright © 2011 John Wiley & Sons, Ltd.     

基于室温离子液体的有序多孔金膜葡萄糖传感器

将1-丁基-3-甲基咪唑四氟硼酸盐（[BMIm][BF4]）、N,N-二甲基甲酰胺（DMF）与葡萄糖氧化酶（GOD）的混合物修饰于三维有序大孔（3DOM）金膜电极上,构建了一种新型的葡萄糖传感器．固定的GOD在pH7．0的磷酸缓冲液（PBS）中展现出一对可逆性好的氧化还原峰,这归因于GOD的活性中心黄素腺嘌呤二核苷酸（FAD）的直接电化学行为．研究表明,离子液体（IL）、DMF以及3DOM金膜对GOD的直接电化学都起到了重要的作用．3DOM金膜修饰电极作为基底提高了酶的负载量,加速了GOD与电极表面的电子传递;IL的应用增加了固定GOD的电化学活性;DMF与IL、GOD的协同作用更好地保持了GOD的生物活性．固定在电极表面的GOD对葡萄糖显示出良好的催化性能,其检测线性范围为10～125nmol／L,检测限为3．3nmol／L（S／N=3）,酶催化反应的表观米氏常数Km为0．018mmol／L．     

Preparation and characterization of nonfouling polymer brushes on poly(ethylene terephthalate) film surfaces

In this study, a surface grafting of nonfouling poly(ethylene glycol) methyl ether acrylate (PEGMA) on poly(ethylene terephthalate) (PET) was carried out via surface-initiated atom-transfer radical polymerization (SI-ATRP) to improve hemocompatibility of polymer based biomaterials. To do this, the coupling agent with hydroxyl groups for the ATRP initiator was first anchored on the surface of PET films using photochemical method, and then these hydroxyl groups were esterified by bromoisobutyryl bromide, from which PET with various main chain lengths of PEGMA was prepared. The structures and properties of modified PET surfaces were investigated using water contact angle (WAC), ATR-FTIR, X-ray photoelectron spectroscopy (XPS) and Atomic force microscopy (AFM). The molecular weights of the free polymer from solution were determined by gel permeation chromatography (GPC). These results indicated that grafting of PEGMA on PET film is a simple way to change its surface properties. The protein adsorption resistance on the surfaces of PET was primarily evaluated by an enzyme-linked immunosorbent assay (ELISA). The result demonstrated that the protein adsorption could be well suppressed by poly(PEGMA) brush structure on the surface of PET. This work provides a new approach for polymers to enhance their biocompatibility.     

Preparation and characterization of functionalized precipitated silica SYLOID® 244 using ionic liquids as modifiers

Studies were performed on the chemical modification of SYLOID^® 244 (Grace) precipitated silica using ionic liquids. The unmodified and ionic‐liquid‐functionalized silica were subjected to a comprehensive physicochemical and dispersive evaluation. Particle size, polydispersity and specific surface area (BET) and porous structure were examined. Moreover, stability of the colloids obtained was evaluated by estimation of isoelectric points. The extent of modification and its type were defined using fourier transform infrared spectroscopy and ²⁹Si‐cross‐polarization/magic angle spinning/nuclear magnetic resonance techniques. The modification was not observed to deteriorate the dispersive properties of the silica. The silicas obtained exhibited a restricted tendency to form larger accumulations of particles, i.e. aggregates and agglomerates. Moreover, application of ionic liquids with a heptyloxymethyl or octyloxymethyl substituent resulted in complete hydrophobization of the silica surface. Tested powders manifested the highest stability within a pH range of 10–12. Copyright © 2004 John Wiley & Sons, Ltd.     

Preparation of the glucose sensor based on three-dimensional ordered macroporous gold film and room temperature ionic liquid

A novel type of glucose sensor was fabricated based on a glucose oxidase (GOD)-N,N-dimethtylformamide (DMF)-[BMIm][BF₄] composites modified three-dimensional ordered macroporous (3DOM) gold film electrode. The immobilized GOD exhibits a pair of well-defined reversible peaks in 50 mM pH 7.0 phosphate buffer solutions (PBS), which could be attributed to the redox of flavin adenine dinucleotide (FAD) in GOD. The research results show that ionic liquid ([BMIm][BF₄]), DMF and 3DOM gold film are crucial for GOD to exhibit a pair of stable and reversible peaks. It is believed that the large active area of 3DOM gold film can increase the amount of immobilized GOD. Simultaneously, the application of IL enhances the stability of GOD and facilitates the electron transfer between GOD and the electrode. The synergetic effect of DMF can help the GOD to maintain its bioactivity better. GOD immobilized on the electrode exhibits the favorable electrocatalytic property to glucose, and the prepared sensor has a linear range from 10 to 125 nM with a detection limit of 3.3 nM at a signal-to-noise ratio of 3σ. The apparent K _m (Michaelis- Menten constant) for the enzymatic reaction is 0.018 mM.     

Preparation and characterization of silica aquasols

Aquasols containing silica nanoparticles with diameters of 75 to 95 nm were obtained directly by hydrolysis of 2 wt.% tetraethoxysilane (TEOS) in water in the presence of a non-ionic surfactant. The reaction was catalyzed by hydrochloric acid, ammonia, or sodium hydroxide. The particle size, which mainly depends on the concentration of TEOS in water, was determined by dynamic light scattering (DLS). Whereas the catalysts have almost no influence on the particle size, they very strongly affect the morphology of the silica particles formed. The dried SiO(2) particles obtained via the HCl-catalyzed reaction have film-forming properties and show no measurable BET surface area. SiO(2) particles prepared with ammonia as catalyst form nanoporous films on glass, and the BET surface area of the freeze-dried particles is 540 m(2)/g. Using sodium hydroxide as catalyst results in some agglomeration of uniform spherical particles with a BET surface area of 237 m(2)/g. (29)Si MAS NMR investigations of the freeze-dried particles provide information about the degree of condensation and the ratio of "free" hydroxyl groups. The silica aquasols described have a surprisingly high hydrophilizing effect on hydrophobic fibers (PP, PET). Silica nanoparticles of comparable diameters, prepared by the "St?ber method", dispersed in alcohol do not show any hydrophilizing properties worth to mention.     

Vibrational spectroscopy of dimethylchlorooctadecylsilane covalently bonded to ultrathin silica films immobilized on Ag surfaces

FTIR and Raman spectroscopies have been used to characterize the structure and conformational order of dimethylchlorooctadecylsilane (DOS) covalently bonded to ultrathin silica films supported on Ag substrates. Ultrathin silica films of ca. 30 A thickness prepared from sol-gel methods are immobilized on Ag surfaces modified with a self-assembled monolayer of (3-mercaptopropyl)trimethoxysilane (3MPT). This layered structure provides a unique opportunity for acquiring complementary spectral data from both FTIR and Raman spectroscopies, which are useful in elucidating alkylsilane conformation pertaining to stationary phases for reversed-phase liquid chromatography (RPLC). Characterization of octadecyltrichlorosilane (OTS) layers on thin silica films of ca. 800 A thickness on 3MPT-modified Ag surfaces has been reported previously. Differences between the ultrathin silica films used in this study and the thin silica films used in this previous study are considered. The results from both FTIR and Raman spectroscopy presented here suggest that bonded DOS alkyl chains are in a disordered, liquid-like state with close to monolayer surface coverage.     

Vibrational spectroscopy of dimethylchlorooctadecylsilane covalently bonded to ultrathin silica films immobilized on Ag surfaces

FTIR and Raman spectroscopies have been used to characterize the structure and conformational order of dimethylchlorooctadecylsilane (DOS) covalently bonded to ultrathin silica films supported on Ag substrates. Ultrathin silica films of ca. 30 Å thickness prepared from sol-gel methods are immobilized on Ag surfaces modified with a self-assembled monolayer of (3-mercaptopropyl)trimethoxysilane (3MPT). This layered structure provides a unique opportunity for acquiring complementary spectral data from both FTIR and Raman spectroscopies, which are useful in elucidating alkylsilane conformation pertaining to stationary phases for reversed-phase liquid chromatography (RPLC). Characterization of octadecyltrichlorosilane (OTS) layers on thin silica films of ca. 800 Å thickness on 3MPT-modified Ag surfaces has been reported previously. Differences between the ultrathin silica films used in this study and the thin silica films used in this previous study are considered. The results from both FTIR and Raman spectroscopy presented here suggest that bonded DOS alkyl chains are in a disordered, liquid-like state with close to monolayer surface coverage.     

Preparation of ultrathin coating layers using surface modified silica nanoparticles

Silica nanoparticles are used in various applications including catalysts, paints and coatings. To reach an optimal performance via stability and functionality, in most cases, the surface properties of the particles are altered using complex procedures. Here we describe a simple method for surface modification of silica nanoparticles (SNP) using sequential adsorption of oppositely charged components. First, the SNPs were made cationic by adsorption of a cationic polyelectrolyte. Poly(allylamine hydrochloride) (PAH) and polyethyleneimine (PEI) were chosen as polycations to investigate the difference between a linear and a branched polyelectrolyte. Next, the dispersion of cationic SNPs was combined with an anionic alkyl ketene dimer (AKD) emulsion. Using this approach cationic, hydrophobic silica particle dispersions were produced. Dynamic light scattering, contact angle measurements and atomic force microscopy (AFM) were used for analyzing the particle and coating layer properties. The chosen polyelectrolyte affected the structure of the dispersion. The layer build-up was studied in detail using a quartz crystal microbalance with dissipation monitoring (QCM-D). The adsorption and layer properties of the cationic polyelectrolytes adsorbed on silica as well as the affinity of AKD to this layer were explored. The application possibilities of the modified particle dispersions were demonstrated by preparing paper and silica surfaces with tailored properties, such as elevated surface hydrophobicity, using an ultrathin coating layer.     

Direct electrochemistry and electrocatalysis of myoglobin based on silica-coated gold nanorods/room temperature ionic liquid/silica sol-gel composite film

A novel biosensor based on the silica-coated gold nanorods (GNRs@SiO₂) and hydrophilic room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium tetrafluroborate ([bmim][BF₄]) was fabricated for the determination of hydrogen peroxide (H₂O₂) and nitrite. GNRs@SiO₂ can not only act as a binder to hinder [bmim][BF₄] (RTIL) leaking from the electrode surface, but also provide a favorable microenvironment for direct electrochemistry of myoglobin (Mb). A pair of well-defined and quasi-reversible redox peaks of Mb was obtained at the GNRs@SiO₂-Mb/RTIL-sol-gel composite film modified GCE (GNRs@SiO₂-Mb/RTIL-sol-gel/GCE) through direct electron transfer between Mb and the underlying electrode. This biosensor showed an excellent electrocatalytic activity towards hydrogen peroxide and nitrite. The linear range for the determination of H₂O₂ was from 0.2 to 180 μM with a detection limit of 0.12 μM based on the signal-to-noise ratio of 3. In addition, the biosensor also exhibited high selectivity, good reproducibility, and long-term stability. Therefore, this kind of composite film can provide an ideal matrix for protein immobilization and biosensor fabrication.     

Formation and tribological properties of two‐component ultrathin ionic liquid films on Si

Several single‐component and two‐component imidazolium ionic liquids (ILs) ultrathin films were formed on Si substrates by a dip‐coating and heat treatment process. The formation and surface properties of the films were analyzed by means of ellipsometric thickness measurement, X‐ray photoelectron spectra and atomic force microscope. The adhesive and nanotribological behaviors of the films were evaluated by a homemade colloidal probe. A ball‐on‐plate tribometer was used to test the microtribological performances of these films. As a result, the two‐component ILs ultrathin film containing 80% solid‐like ILs phase shows more homogenous surface morphologies and optimal micro/nano‐tribological properties as compared to single‐component ILs films, which is ascribed to a synergic effect between the steady solid‐like ILs phase as the backbone and the proper amount of flowable liquid‐like ILs phase. By studying the influence of various solid/liquid ILs ratios on tribological properties of the two‐component ILs films, we might find the way to design ILs films with excellent comprehensive tribological properties. Copyright © 2010 John Wiley & Sons, Ltd.     

Interfacial rheology of an ultrathin nanocrystalline film formed at the liquid/liquid interface

We report the interfacial properties of monolayers of Ag nanoparticles 10-50 nm in diameter formed at the toluene-water interface under steady as well as oscillatory shear. Strain amplitude sweep measurements carried out on the film reveal a shear thickening peak in the loss moduli (G") at large amplitudes followed by a power law decay of the storage (G') and loss moduli with exponents in the ratio 2:1. In the frequency sweep measurements at low frequencies, the storage modulus remains nearly independent of the angular frequency, whereas G" reveals a power law dependence with a negative slope, a behavior reminiscent of soft glassy systems. Under steady shear, a finite yield stress is observed in the limit of shear rate .gamma going to zero. However, for .gamma > 1 s-1, the shear stress increases gradually. In addition, a significant deviation from the Cox-Merz rule confirms that the monolayer of Ag nanoparticles at the toluene-water interface forms a soft two-dimensional colloidal glass.