Electrochemical characteristics of glucose oxidase adsorbed at carbon nanotubes modified electrode with ionic liquid as binder

Multiwall carbon nanotubes (CNTs)-modified electrode has been prepared by using ionic liquid (IL) as the binder. The as-prepared CNTs-IL composite modified electrode has good biocompatibility and is a suitable matrix to immobilize biomolecules. Glucose oxidase (GOx), containing flavin adenine dinucleotide as active site, stably adsorbed on modified electrode surface has resulted in the direct electron transfer. The electron transfer rate of 9.08 s(-1) obtained is much higher than that of GOx adsorbed on the CNTs papers (1.7 s(-1)), and the process is more reversible with small redox peak separation of 23 mV This may be due to the synergetic promotion of CNTs and IL to electron transfer of the protein, especially the IL as the binder, showing better electrochemical properties than that of chitosan and Nafion. Furthermore, GOx adsorbed at the modified electrode exhibits good stability and keeps good electrocatalytic activity to glucose with broad linear range up to 20 mM. Besides, the simple preparation procedure and easy renewability make the system a basis to investigate the electron transfer kinetics and biocatalytic performance of GOx and provide a promising platform for the development of biosensors.

Extraction kinetics of cerium(IV) from sulfuric acid medium by the primary amine N1923 using a constant interfacial area cell with laminar flow

BACKGROUND: Thermodynamic studies on Ce(IV) extraction with primary amine N1923 demonstrate that primary amine N1923 is an excellent extractant for separation of Ce(IV) from Re(III). In order to clarify the mechanism of extraction and to optimize the parameters in practical extraction systems used in the rare earth industry, the extraction kinetics was investigated using a constant interfacial area cell with laminar flow in the present work.RESULTS: The data indicate that the rate constant (k(ao).) becomes constant when stirring speed exceeds 250 rpm. The apparent forward extraction rate is calculated to be 10(-1.70). The activation energy (E.) was calculated to be 20.5 kJ/mol from the slope of log kao against 1000/T. The minimum bulk concentration of the extractant necessary to saturate the interface (C-min) is lower than 10(-5) mol L-1.CONCLUSION: Studies of interfacial tension and the effects of stirring rate and specific interfacial area on the extraction rate show that the extraction rate is kinetically controlled, and a mass transfer model has been proposed. The rate equation has been obtained as: -d[Ce(IV)]/dt = 10(-1.70)[Ce(IV)] [(RNH3)(2)SO4](1.376). The rate-controlling step has been evaluated from analysis of the experimental results.

Formation of ordered microphase-separated pattern during spin coating of ABC triblock copolymer

In this paper, the authors have systematically studied the microphase separation and crystallization during spin coating of an ABC triblock copolymer, polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO). The microphase separation of PS-b-P2VP-b-PEO and the crystallization of PEO blocks can be modulated by the types of the solvent and the substrate, the spinning speed, and the copolymer concentration. Ordered microphase-separated pattern, where PEO and P2VP blocks adsorbed to the substrate and PS blocks protrusions formed hexagonal dots above the P2VP domains, can only be obtained when PS-b-P2VP-b-PEO is dissolved in N,N-dimethylformamide and the films are spin coated onto the polar substrate, silicon wafers or mica. The mechanism of the formation of regular pattern by microphase separation is found to be mainly related to the inducement of the substrate (middle block P2VP wetting the polar substrate), the quick vanishment of the solvent during the early stage of the spin coating, and the slow evaporation of the remaining solvent during the subsequent stage. On the other hand, the probability of the crystallization of PEO blocks during spin coating decreases with the reduced film thickness. When the film thickness reaches a certain value (3.0 nm), the extensive crystallization of PEO is effectively prohibited and ordered microphase-separated pattern over large areas can be routinely prepared.

Solvent extraction of lanthanides and yttrium from nitrate medium with CYANEX 925 in heptane

The extraction behavior of lanthanides and yttrium usinsg CYANEX 925 (mixture of branched chain alkylated phosphine oxides) in n-heptane from nitrate medium has been studied. The effects of aqueous phase ionic strength, CYANEX 925 concentration in the organic phase, and temperature on Sm3+, Nd3+ and Y3+ extraction have been investigated. The extractability of the lanthanides and yttrium increases with increasing nitrate concentration, as well as with increasing CYANEX 925 concentration. An extraction mechanism is proposed based on slope analysis. Furthermore, the infra-red spectra of CYANEX 925 saturated with lanthanides are employed to provide evidence of the composition of the complex. The relationship between the logarithm of the distribution ratio and lanthanide atomic number is also discussed which indicates that yttrium can be separated from fight lanthanides. In addition separation of the light and heavy lanthanide groups is also possible using CYANEX 925. From the temperature dependence data, the thermodynamic parameters values (Delta H, Delta S and Delta G) are calculated.

Synthesis and characterization of electroactive and biodegradable ABA block copolymer of polylactide and aniline pentamer

A triblock copolymer PLA-b-AP-b-PLA (PAP) of polylactide (PLA) and aniline pentamer (AP) with the unique properties of being both electroactive and biodegradable is synthesized by coupling an electroactive carboxyl-capped AP with two biodegradable bihydroxyl-capped PLAs via a condensation reaction. Three different molecule weight PAP copolymers are prepared. The PAP copolymers exhibit excellent electroactivity similar to the AP and polyaniline, which may stimulate cell proliferation and differentiation. The electrical conductivity of the PAP2 copolymer film (similar to 5 x 10(-6) S/cm) is in the semiconducting region. Transmission electron microscopic results suggest that there is microphase separation of the two block segments in the copolymer, which might contribute to the observed conductivity. The biodegradation and biocompatibility experiments in vitro prove the copolymer is biodegradable and biocompatible. Moreover, these new block copolymer shows good solubility in common organic solvents, leading to the system with excellent processibility. These biodegradable PAP copolymers with electroactive function thus possess the properties that would be potentially used as scaffold materials for neuronal or cardiovascular tissue engineering.

Molecular weight effects on the phase morphology of PS/P4VP blend films on homogeneous SAM and heterogeneous SAM/Au substrates

The effects of the molecular weight of polystyrene (PS) component on the phase separation of PS/poly(4-vinylpyridine) (PS/P4VP) blend films on homogeneous alkanethiol self-assembled monolayer (SAM) and heterogeneous SAM/Au substrates have been investigated by means of atomic force microscopy (AFM). For the PS (22.4k)/P4VP (60k) system, owing to the molecular weight of PS component is relatively small, the well-aligned PS and P4VP stripes with good thermal stability are directed by the patterned SAM/Au surfaces. With the increase of the molecular weight of PS component (for the PS (582k)/P4VP (60k) system), the diffusion of P4VP is hindered by the high viscosity of PS during the fast spin-coating process. The phase separation behavior of PS/P4VP on the SAM/Au patterned substrates is similar to that on the homoueneous SAM and cannot be easily directed by the patterned SAM surfaces even though the characteristic length of the lateral domain morphology is commensurate with the stripe width.

Effect of annealing on the viscoelastic and viscoplastic responses of low-density polyethylene

Two series of tensile tests with constant crosshead speeds (ranging from 5 to 200 mm/min) and tensile relaxation tests (at strains from 0.03 to 0.09) were performed on low-density polyethylene in the subyield region of deformations at room temperature. Mechanical tests were carried out on nonannealed specimens and on samples annealed for 24 h at the temperatures T = 50, 60, 70, 80, and 100 degreesC. Constitutive equations were derived for the time-dependent response of semicrystalline polymers at isothermal deformations with small strains. A polymer is treated as an equivalent heterogeneous network of chains bridged by temporary junctions (entanglements, physical crosslinks, and lamellar blocks). The network is thought of as an ensemble of mesoregions linked with each other. The viscoelastic behavior of a polymer is modeled as a thermally induced rearrangement of strands (separation of active strands from temporary junctions and merging of dangling strands with the network). The viscoplastic response reflects sliding of junctions in the network with respect to their reference positions driven by macrostrains. Stress-strain relations involve five material constants that were found by fitting the observations.

The viscoelastic and viscoplastic behavior of low-density polyethylene

Three series of tensile tests with constant cross-head speeds (ranging from 5 to 200 mm/min), tensile relaxation tests (at strains from 0.03 to 0.09) and tensile creep tests (at stresses from 2.0 to 6.0 MPa) are performed on low-density polyethylene at room temperature. Constitutive equations are derived for the time-dependent response of semicrystalline polymers at isothermal deformation with small strains. A polymer is treated as an equivalent heterogeneous network of chains bridged by temporary junctions (entanglements, physical cross-links and lamellar blocks). The network is thought of as an ensemble of meso-regions linked with each other. The viscoelastic behavior of a polymer is modelled as thermally-induced rearrangement of strands (separation of active strands from temporary junctions and merging of dangling strands with the network). The viscoplastic response reflects mutual displacement of meso-domains driven by macro-strains. Stress-strain relations for uniaxial deformation are developed by using the laws of thermodynamics. The governing equations involve five material constants that are found by fitting the observations. Fair agreement is demonstrated between the experimental data and the results of numerical simulation.

Partitioning behavior of amino acids in aqueous two-phase systems containing polyethylene glycol and phosphate buffer

The partitioning behavior of four amino acids, cysteine, phenylalanine, methionine, and lysine in 15 aqueous two-phase systems (ATPSs) with different polyethylene glycol (PEG) molecular weights and phosphate buffers has been studied in the present paper. The phase diagrams of the systems are investigated together with the effect of the PEG molecular weight and pH of the phosphate solutions. The composition of these systems and some parameters such as density and refractive index are determined. The influences of salts in ATPSs, side chain structure of the amino acids, pH of ATPSs, and the PEG molecular weight on the distribution ratios of the amino acids have been studied. This work is useful for the purification of amino acids and the separation of some proteins whose main surface exposed amino acid residues are these four amino acids, respectively.

Electrochemical characteristics of facile prepared carbon nanotubes-ionic liquid gel modified microelectrode and application in bioelectrochemistry

The carbon nanotubes (CNTs) based microelectrode (ME) by modifying CNTs-room temperature ionic liquid (IL) gel at carbon fiber microelectrode (CFME) is easily prepared, which exhibits the typical cyclic voltammogram of ME with sigmoid shape and possesses good stability, high conductivity and enlarged current response and tunable dimension. The direct electron transfer of glucose oxidase has been greatly promoted showing reversible electrochemical behavior even at high scan rate. In addition, the CNTs based ME also exhibits effectively electrocatalytic oxidized ability to biomolecules, e.g. dopamine (DA), ascorbic acid (AA) and dihydronicotinamide adenine dinucleotide. The obvious separation of oxidized peak potential for DA and AA makes it possible to selectively determine DA in presence of AA. These phenomena show that the CNTs based ME has promising potential to detect various species in vivo and in vitro.

Crystallization and phase behavior of crystalline syndiotactic 1,2-polybutadiene/isotactic polypropylene blends in solution-cast thin films

Crystallization and phase behavior in solution-cast thin films of crystalline syndiotactic 1,2-polybutadiene (s-1,2-PB) and isotactic polypropylene (i-PP) blends have been investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM) and field-emission scanning electron microscopy (FESEM) techniques. Thin films of pure s-1,2-PB consist of parallel lamellae with the c-axis perpendicular to the film plane and the lateral scale in micrometer size, while those of i-PP are composed of cross-hatched and single-crystal-like lamellae. For the blends, TEM and AFM observations show that with addition of i-PP, the s-1,2-PB long lamellae become bended and i-PP itself tends to form dispersed convex regions oil a continuous s-1,2-PB phase even when i-PP is the predominant component, which indicates a strong phase separation between the two polymers during film formation. FESEM micrographs of both lower and upper surfaces of the films reveal that the s-1,2-PB lamellae pass through i-PPconvex regions from the bottom, i.e. the dispersed i-PP regions lie on the continuous s-1,2-PB phase. The structural development is attributed to an interplay of crystallization and phase separation of the blends in the film forming process.

Characterization of triterpenoidic saponin mixture in crude extracts from leaves of Acanthopanax senticosus Harms by saponin structural correlation and mass spectrometry

Eighteen triterpenoidic saponins in crude extracts from leaves of Acanthopanax senticous Harms have been investigated by electrospray ionization multi-stage tandem mass spectrometry and high-resolution mass spectrometry. In ESI-MS spectra, predominant [M + Na](+) ions in the positive ion mode have been observed for molecular mass information. Meanwhile, specific structural correlations between these ions are firstly found. The 18 peaks (ions) can be classified into three groups (group D, E, and F with mass increase) with each group including six peaks. There is a mass difference of 132 Da between group D and E for each corresponding peak in turn (for example peak 1 to peak 7), indicating one more pentose residue was attached to saponins in group E than those corresponding in group D. The mass difference of 146 Da between group E and F implies one more deoxy-hexose attached to saponins in group F than those corresponding in group E. The structural correlations of the corresponding ions are confirmed by tandem mass spectrometry and high-re solution mass spectrometry. These structural features can not only facilitate the rapid characterization of the native known saponins in crude plant extracts, thus avoiding tedious derivation and separation of saponins, but also help find novel compounds of the same type in a specific medicinal plant.

Synergistic extraction of rare earths by mixture of bis(2,4,4-trimethylpentyl)phosphinic acid and Sec-nonylphenoxy acetic acid

Synergistic extraction of trivalent rare earths (RE=Sc, Y, La, Gd, Yb) from hydrochloride medium using mixture of bis(2,4,4-trimethylpentyl)phosphinic acid (HL, Cyanex272) and Sec-nonylphenoxy acetic acid (HA, CA-100) in n-heptane has been studied. The synergistic enhancement coefficients were observed for La (1.30), Gd (1.97), Y (3.59), Yb (8.21) and Sc (14.41). The results indicated yttrium was extracted into n-heptane as YH(5)A(4)L(4) mixed species instead of Y(HL2)(3), Y(OH)(2)A(HA)(3) which were extracted by Cyanex272 and CA-100, respectively. A cation exchange mechanism was proposed and further clarified by IR spectra. The equilibrium constants, formation constants and thermodynamic functions such as Delta G, Delta H and Delta S were determined. The Cyanex272 + CA-100 system not only enhanced the extraction efficiency of RE but also improved the selectivities significantly. The mutual separation factors of these ions suggested the mixture system would be of practical value in extraction and separation of rare earths.

Preparation and properties of ternary polyimide/SiO2/polydiphenyisiloxane composite films

A series of novel ternary polyimide/SiO2/polydiphenylsiloxane (PI/SiO2/PDPhS) composite films were prepared through co-hydrolysis and condensation between tetramethoxysilane, diphenyldimethoxysilane (DDS) and aminopropyltriethoxysilane-terminated polyamic acid, using an in situ sol-gel method. The composite films exhibited good optical transparency up to 30 wt% of total content of DDS and SiO2. SEM analysis showed that the PDPhS and SiO2 were well dispersed in the PI matrix without macroscopic separation of the composite films. TGA analysis indicated that the introduction of SiO2 could improve the thermal stability of the composite films. Dynamic mechanical thermal analysis showed that the composite films with low DDS content (5 wt%) had a higher glass transition temperature (T-g) than pure PI matrix. When the content of DDS was above 10 wt%, the T-g of the composite decreased slightly due to the plasticizing effect of flexible PDPhS linkages on the rigid PI chains. The composite films with high SiO2 content exhibited higher values of storage modulus. Tensile measurements also showed that the modulus and tensile strength of the composite films increased with increasing SiO2 content, and the composite films still retained a high elongation at break due the introduction of DDS.

Rheological properties in blends of poly(aryl ether ether ketone) and liquid crystalline poly(aryl ether ketone)

Rheological properties of the blends of poly(aryl ether ether ketone) (PEEK) with liquid crystalline poly(aryl ether ketone) containing substituted 3-trifluoro-methylbenzene side group (F-PAEK), prepared by solution precipitation, have been investigated by rheometer. Dynamic rheological behaviors of the blends under the oscillatory shear mode are strongly dependent on blend composition. For PEEK-rich blends, the systems show flow curves similar to those of the pure PEEK, i.e., dynamic storage modulus G' is larger than dynamic loss modulus G", showing the feature of elastic fluid. For F-PAEK-rich systems, the rheological behavior of the blends has a resemblance to pure F-PAEK, i.e., G" is greater than G', showing the characteristic of viscous fluid. When the PEEK content is in the range of 50-70%, the blends exhibit an unusual rheological behavior, which is the result of phase inversion between the two components. Moreover, as a whole, the complex viscosity values of the blends are between those of two pure polymers and decrease with increasing F-PAEK content. However, at 50% weight fraction of PEEK, the viscosity-composition curves exhibit a local maximum, which may be mainly attributed to the phase separation of two components at such a composition.