Controlled-rate thermal analysis

Controlled-rate thermal analysis (CRTA) and differential scanning calorimetry (DSC) were used to investigate the adsorbed water layers and the surface properties of different commercial activated carbons. A simple method is proposed to obtain information on the properties of the adsorbed water film and the surface heterogeneity of the materials studied. This method utilizes TG mass loss and the first derivative of the DTG mass loss curves with respect to temperature and time, obtained during programmed liquid thermodesorption. The obtained TG mass loss curves, which reflect the energetic heterogeneity, consisted of steps and inflections which were associated with the mechanism of wetting of the solid surfaces. The heights of these steps and inflections depend on the adsorption capacity, the adsorption potential and the nature and number of the active centers of the carbon samples studied. The values of the total porosity and the surface phase capacity obtained by this method are in good agreement with those estimated on the basis of independent methods. The behaviour of water/carbon samples was studied by means of DSC at subambient and elevated temperatures. The experimental results provided novel data on the structural heterogeneity, the thermal stability of the water/carbon interface and its phase and structural transitions.Support from the Research Council of Kent State University (Ohio, USA) is acknowledged. The author is pleased to thank Drs M. Jaroniec, R. K. Gilpin, J. Choma and R. Dobrowolski for fruitful discussions and the active carbon samples.     

Development and validation of a hydrophilic interaction chromatography–tandem mass spectrometry for quantification of nicotine and its metabolites in human maternal and cord sera

A selective and sensitive HILIC‐MS/MS method for the simultaneous quantification of nicotine and its metabolites in human maternal and cord sera was developed and validated. After solid‐phase extraction, LC separation was achieved on a hydrophilic interaction chromatography. The validated method is capable of selective identification as well as accurate and sensitive quantification. Analyte recovery ranged from 86.2 to 107.7% and intra‐ and inter‐day assay precision were less than 15% relative standard deviation. This sensitive HILIC‐MS/MS method can be used to determine nicotine and its metabolic profile in smokers. This validated method is useful for the determination of nicotine and its metabolites in human serum in future studies of the effects of nicotine exposure on neonatal outcome. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of Oligo(thienylfuran)s with Thiophene Rings at Both Ends and Their Structural,Electronic, and Field‐Effect Properties

Oligo(thienylfuran)s with thiophene rings at both ends ( SOSOSOS , DE‐SOSOS , DH‐SOSOS , DE‐SOSOSOS , and DH‐SOSOSOS ; S and O denote thiophene and furan rings, respectively, DE and DH denote diethyl‐ and dihexyl‐substituted, respectively) were newly synthesized by repetitive Stille coupling reactions. The UV/Vis maximum absorptions of the oligomers, SO , SOSO , SOSOS , SOSOSO , and SOSOSOS , exhibited a clear bathochromic shift with increasing number of heterocycles. The value of the oxidation peak potential (E_pa¹) determined by cyclic voltammetry decreased with an increase in the number of heterocycles by 0.06–0.08 V per heterocycle. The crystal‐packing structures of DE‐SOSOS and DH‐SOSOS determined by X‐ray crystallography have a herringbone motif and are denser than the reported structures of pentacene and α‐sexithiophene. The morphologies of thin films prepared by vacuum deposition and spin coating were investigated by atomic force microscopy and X‐ray diffraction. Among these films, those of DE‐SOSOS and DH‐SOSOS exhibited highly ordered arrangements. The devices based on vacuum‐deposited and spin‐coated films of DE‐SOSOS and DH‐SOSOS displayed the highest FET mobilities of 10^?2–10^?3 cm² V^?1 s^?1 among the oligomers reported in this study.     

Reduction of MnFe2O4 without and with carbon

We succeeded in studying the mechanism of hydrogen added carbothermic reduction process of iron-manganese oxide by means of the new technique, simultaneous measurement of evolved gas analysis (EGA) and humidity sensor (HS). Water vapor evolved by the reduction with hydrogen can be detected by HS. Other gas was detected by TCD. Without carbon, the hydrogen reduction process was followed to the formation of the intermediate product between MnO and FeO and finally reduction to the mixture of MnO and Fe. With carbon, the intermediate products between MnO and FeO was formed at about 780 K. The methane was formed in higher temperature than 1073 K and the reduction with carbon proceeded mainly. At higher temperatures, methane decomposed to yield nascent carbon that tended to result in the acceleration of the reduction rate with carbon. The study is concerned with the mechanism of the hydrogen reduction of MnFe₂O₄ and the effect of without and with carbon on this reduction by means of combining EGA and HS. This revised version was published online in August 2006 with corrections to the Cover Date.     

General route to 2-alkyl-2-butenolactones via the retro-Diels-Alder reaction

Various 2-alkyl-2-butenolactones were simply prepared from cyclopentadiene-maleic anhydride adducts through the retro-Diels-Alder reaction. The procedure was applied for the synthesis of dehydrolappaol A dimethyl ether.     

Synthesis of TiO2 nanocoral structures in ever-changing aqueous reaction systems

A far-from-equilibrium strategy is developed to synthesize coral-like nanostructures of TiO(2) on a variety of surfaces. TiO(2) nanocoral structures consist of anatase base film and rutile nanowire layers, and they are continuously formed on substrates immersed in aqueous TiOSO(4)-H(2)O(2). The sequential deposition of TiO(2) starts with hydrolysis and condensation reactions of titanium peroxocomplexes in the aqueous phase, resulting in deposition of amorphous film. The film serves as adhesive interface on which succeeding growth of rutile nanowires to occur. This initial deposition reaction is accompanied by shift in pH of the reaction media, which is favorable condition for the growth of rutile nanocrystals. During the growth of rutile nanocoral layers, the amorphous base films are transformed to anatase phase. These sequential deposition reactions occur at temperatures as low as 80 °C, and the mild synthetic condition allows the use of a wide range of substrates such as ITO (indium tin oxide), glass, and even organic polymer films. The thickness of nanocoral layer is controllable by repeating the growth reaction of rutile nanocorals. TiO(2) nanocorals show photocatalytic activity as demonstrated by site-specific reduction of Ag(I) ions, which proceeds preferentially on the rutile nanowire layer. The rutile nanowire layer also shows photocatalytic decomposition of acetaldehyde, which is promoted upon increase of the thickness of the nanowire layer. The use of temporally transforming reaction media allows the formation of biphasic TiO(2) nanocoral structures, and the concept of nonequilibrium synthetic approach would be widely applicable to developing structurally graded inorganic nanointerfaces.     

Aqueous dispersion behavior of drug particles by addition of surfactant and polymer

The effect of surfactant and polymer on dispersion stability of aqueous suspensions of 5-(3-ethoxy-4-pentyloxyphenyl)-2,4-thiazolidinedione (CT112) was investigated by measuring the adsorbed amount of surfactant and polymer, zeta potential, particle size, and sedimentation rate of CT112. The addition of celluloses rather than sodium dodecyl sulfate (SDS) provided a high stable suspension of CT112. In addition, mixed systems of celluloses and SDS enhanced CT112 dispersion more effectively. The mechanism of dispersion stability of CT112 by addition of SDS and celluloses is discussed.     

Polystyrene-based blend nanorods with gradient composition distribution

The polystyrene-based polymer blends, partially miscible poly(bisphenol A carbonate)/polystyrene (PC/PS) and completely miscible poly(2,6-dimethylphenylene oxide)/polystyrene (PPO/PS), in nanorods with gradient composition distribution were discussed. The polymer blend nanorods were prepared by infiltrating the polymer blends into nanopores of anodic aluminum oxide (AAO) templates via capillary action. Their morphology was investigated by micro-Fourier transform infrared spectroscopy (micro-FTIR) and nano-thermal analysis (nano-TA) with spatial resolution. The composition gradient of polymer blends in the nanopores is governed by the difference of viscosity and miscibility between the two polymers in the blends and the pore diameter. The capillary wetting of porous AAO templates by polymer blends offers a unique method to fabricate functional nanostructured materials with gradient composition distribution for the potential application to nanodevices.