Structural, textural, and electronic properties of a nanosized mesoporous ZnxTi1-xO2-) solid solution prepared by a supercritical drying route

Mesoporous nanosized TiO2 and Zn(x)Ti(1-x)O(2-x) solid solution having a Zn content below 10 mol % with a particles size between 13 and 17 nm are prepared by a template-free sol-gel method followed by high-temperature supercritical drying in 2-propanol. The structural, textural, and electronic properties of the obtained nanomaterials are methodically investigated by using XRD, SEM, TEM, ED, HREM, EDX, ICP-OES, N(2) adsorption-desorption, Raman spectroscopy, and diffuse reflectance UV-vis spectroscopy. It is shown that the proposed synthesis technique leads to the formation of a Zn(x)Ti(1-x)O(2-x) solid solution based on the anatase crystal structure rather than a two-phase sample. High-resolution electron microscopy and electron diffraction indicate that the distribution of zinc atoms over the anatase structure does not lead to a considerable deformation of the crystal structure.     

Recoverable solution reaction of HiPco carbon nanotubes with hydrogen peroxide

There is increasing interest in developing single-walled carbon nanotubes (SWNTs)-based optical biosensors for remote or in vitro and in vivo sensing because the near-IR optical properties of SWNTs are very sensitive to surrounding environmental changes. Many enzyme-catalyzed reactions yield hydrogen peroxide (H(2)O(2)) as a product. To our knowledge, there is no report on the interaction of H(2)O(2) with SWNTs from the optical sensing point of view. Here, we study the reaction of H(2)O(2) with an aqueous suspension of water-soluble (ws) HiPco SWNTs encased in the surfactant sodium dodecyl sulfate (SDS). The SWNTs are optically sensitive to hydrogen peroxide in pH 6.0 buffer solutions through suppression of the near-IR absorption band intensity. Interestingly, the suppressed spectral intensity of the nanotubes recovers by increasing the pH, by decomposing the H(2)O(2) into H(2)O and O(2) with the enzyme catalase, and by dialytically removing H(2)O(2). Preliminary studies on the mechanisms suggest that H(2)O(2) withdraws electrons from the SWNT valence band by charge transfer, which suppresses the nanotube spectral intensity. The findings suggest possible enzyme-assisted molecular recognition applications by selective optical detection of biological species whose enzyme-catalyzed products include hydrogen peroxide.     

A density functional study on a biomimetic non-heme iron catalyst: insights into alkane hydroxylation by a formally HO-FeV=O oxidant

The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane.     

Superporous agarose beads as a hydrophobic interaction chromatography support

Superporous agarose beads were used as a support for hydrophobic interaction chromatography. These beads have large connecting flow pores in addition to their normal diffusion pores. The flow pores, which are approximately one fifth of the overall diameter of the superporous agarose beads, were earlier shown to give the beads improved mass transfer properties relative to homogeneous agarose beads (Gustavsson and Larsson, J. Chromatogr. A, 734 (1996) 231–240). Superporous agarose beads and homogeneous agarose beads of the same particle size range (106–180 μm) were derivatized with phenyl groups. The properties of the superporous beads were then compared with the homogeneous beads in the separation of a mixture of three model proteins (ribonuclease A, lysozyme and bovine serum albumin) at various superficial flow velocities from 30 to 600 cm/h. The superporous beads gave satisfactory separation at flow velocities five times higher than was possible for homogeneous beads. The performance of the two types of beads was also compared in the purification of lactate dehydrogenase from a beef heart extract at a superficial flow velocity of 150 cm/h. The superporous beads performed considerably better, leading to twice the purification factor and twice the concentration of the desired product. The results were interpreted using the theoretical treatment given by Carta and Rodrigues (Carta and Rodrigues, Chem. Eng. Sci., 48 (1993) 3927).     

Remodeling of ordered membrane domains by GPI-anchored intestinal alkaline phosphatase

Glycosylphosphatidyl-inositol (GPI)-anchored proteins preferentially localize in the most ordered regions of the cell plasma membrane. Acyl and alkyl chain composition of GPI anchors influence the association with the ordered domains. This suggests that, conversely, changes in the fluid and in the ordered domains lipid composition affect the interaction of GPI-anchored proteins with membrane microdomains. Validity of this hypothesis was examined by investigating the spontaneous insertion of the GPI-anchored intestinal alkaline phophatase (BIAP) into the solid (gel) phase domains of preformed supported membranes made of dioleoylphosphatidylcholine/dipalmitoylphosphatidylcholine (DOPC/DPPC), DOPC/sphingomyelin (DOPC/SM), and palmitoyloleoylphosphatidylcholine/SM (POPC/SM). Atomic force microscopy (AFM) showed that BIAP inserted in the gel phases of the three mixtures. However, changes in the lipid composition of membranes had a marked effect on the protein containing bilayer topography. Moreover, BIAP insertion was associated with a net transfer of phospholipids from the fluid to the gel (DOPC/DPPC) or from the gel to the fluid (POPC/SM) phases. For DOPC/SM bilayers, transfer of lipids was dependent on the homogeneity of the gel SM phase. The data strongly suggest that BIAP interacts with the most ordered lipid species present in the gel phases of phase-separated membranes. They also suggest that GPI-anchored proteins might contribute to the selection of their own microdomain environment.     

煤中砷,铅,铍,铬等元素的存在状态

煤是由有机物和无机物组成的混合物。无机物按其在煤中的浓度大小可分为三类:(1)常量元素,在煤中浓度大于0.5%,如Si,Al,Fe,Ca等。(2)次要元素,约占煤的0.02%—.5%,包括K,Mg,Na,Ti,有时还有P,Ba等。(3)微量元素,在煤中浓度<0.02%,这类元素目前已测出60种左右。60年代以来,基于能源需求的增加,国内外煤炭消耗量都很大,考虑到有害的微量元素对环境的污染,国外进行了大量的煤     

Temporary threshold shifts and recovery following noise exposure in the Atlantic bottlenosed dolphin (Tursiops truncatus)

Behaviorally determined hearing thresholds for a 7.5-kHz tone for an Atlantic bottlenosed dolphin (Tursiops truncatus) were obtained following exposure to fatiguing low-frequency octave band noise. The fatiguing stimulus ranged from 4 to 11 kHz and was gradually increased in intensity to 179 dB re 1 microPa and in duration to 55 min. Exposures occurred no more frequently than once per week. Measured temporary threshold shifts averaged 11 dB. Threshold determination took at least 20 min. Recovery was examined 360, 180, 90, and 45 min following exposure and was essentially complete within 45 min.     

Enhanced fusion-evaporation cross sections in neutron-rich 132Sn on 64Ni

Evaporation residue cross sections have been measured with neutron-rich radioactive 132Sn beams on 64Ni in the vicinity of the Coulomb barrier. The average beam intensity was 2 x 10(4) particles per second and the smallest cross section measured was less than 5 mb. Large sub-barrier fusion enhancement was observed. Coupled-channel calculations taking into account inelastic excitation significantly underpredict the measured cross sections below the barrier. The presence of several neutron transfer channels with large positive Q values suggests that multinucleon transfer may play an important role in enhancing the fusion of 132Sn and 64Ni.