Dynamic process of crystallization of Sb2Se3 from Sb50Se50 amorphous film

Dynamics of crystallization of amorphous antimony-selenium film deposited on carbon substrate have been studied by the high-resolution transmission electron microscopy. The amorphous film was suddenly crystallized at 200°C by heating in vacuum. By the electron beam irradiation crystallization occurred at the focused electron beam region in the amorphous film. The growth process of crystallization by electron beam irradiation was recorded on a video image at the atomic resolution mode. The growth front of crystallization showed nano-concave and -convex shapes. The recrystallization with the different orientation at the first grown crystal have been found, and discussed as the influence of remaining antimony crystallites at the first crystallized film region.     

List-mode coincidence data analysis for highly selective and low background detection of gamma-nuclides in activated samples

Highly selective and sensitive γ-ray detection was performed by coincidence and anticoincidence event analysis after list-mode data acquisition using an HPGe spectrometer equipped with NaI(Tl) and plastic scintillation detectors. In order to obtain the most suitable detection of specific nuclides, coincidence or anticoincidence spectra could be freely constructed by extracting events with particular time and energy correlations. Although the detector arrangement of this system was the same as that of a typical Compton suppression spectrometer, background counts were drastically reduced and γ-rays of particular nuclides could be selectively detected by using γ-γ, γ-X, γ-X-X, and γ-β⁺ coincidences.     

Comparative examination of titania nanocrystals synthesized by peroxo titanic acid approach from different precursors

Titanium dioxide nanocrystalline particles were synthesized by peroxo titanium acid (PTA) approach from titanium alkoxide and inorganic salt precursors, and their structural and surface properties, porosities, and photocatalytic activities were comparatively examined by XRD, TG/DTA, DRIFT, UV-vis, low temperature N(2) adsorption, and methyl orange (MO) degradation. It was found that nanoparticles with single anatase phase can be obtained from alkoxide precursor even near room temperature if synthesis conditions are appropriately controlled. PTA-derived anatase nanoparticles from titanium alkoxide precursor have smaller crystalline sizes and better porosities, and contain less amount of peroxo group and no organic impurities as compared to those from TiCl(4) precursor. The advantages in structural property, porosity, and surface properties (few deficiencies) lead to a much better photocatalytic activity for TiO(2) nanoparticles from titanium alkoxide precursor in comparison with those from TiCl(4) precursor.     

Sol–gel synthesis of a humic acid-silica gel composite material as low-cost adsorbent for thorium and uranium removal

In the present work, three neutral ^99mTc(CO)₃ complexes of nitroimidazole were synthesized and their potential to detect tumor hypoxia is evaluated in vivo. Triazole derivatives of 2-, 4- and 5-nitroimidazole were synthesized via ‘click chemistry’ route. The ligands synthesized were characterized and subsequently radiolabeled using [^99mTc(CO)₃(H₂O)₃]⁺ precursor complex to obtain corresponding neutral ^99mTc(CO)₃ complexes in >90 % radio chemical purity. The complexes were subsequently evaluated in Swiss mice bearing fibrosarcoma tumor and in vivo distribution observed was thoroughly analyzed. All complexes showed uptake in tumor, however, contrary to general expectations, the 5-nitroimidazole complex showed significantly higher tumor uptake (p < 0.05) at 30 min and 60 min p.i., compared to the 2-nitroimidazole counterpart. Though a conclusive explanation for this observation could not be obtained, present study underlined the significance of evaluating nitroimidazole radiotracers other than 2-nitroimidazole for detecting tissue hypoxia.     

Dissecting the proline effect: dissociations of proline radicals formed by electron transfer to protonated Pro-Gly and Gly-Pro dipeptides in the gas phase

We report a combined experimental and computational study of the proline effect in model dipeptides Pro-Gly and Gly-Pro. Gas-phase protonated peptide ions were discharged by glancing collisions with potassium or cesium atoms at 3 keV collision energies, and the peptide radical intermediates and their dissociation products were analyzed following collisional ionization to anions. The charge reversal (+CR-) mass spectra of (Pro-Gly + H)+(1a+) and (Gly-Pro + H)+ (2a+) showed dramatic differences and thus provided a sensitive probe of ion structure. Whereas 1a+ completely dissociated upon charge inversion, 2a+ gave a nondissociated anion as the most abundant product. Ab initio and density functional theory calculations provided structures and vertical recombination energies (REvert) for 1a+ and 2a+. The recombination energies, REvert = 3.07 and 3.36 eV for 1a+ and 2a+, respectively, were lower than the alkali metal ionization energies and indicated that the collisional electron transfer to the peptide ions was endoergic. Radical 1a* was found to exist in a very shallow local energy minimum, with transition state energies for loss and migration of H indicating very facile dissociation. In contrast, radical 2a* was calculated to spontaneously isomerize upon electron capture to a stable dihydroxycarbinyl isomer (2e*) that can undergo consecutive and competitive isomerizations by proline ring opening and intramolecular hydrogen atom transfers to yield stable radical isomers. Radical 2e* and its stable isomers were calculated to have substantial electron affinities and thus can form the stable anions that were observed in the +CR- mass spectra. The calculated TS energies and RRKM kinetic analysis indicated that peptide N-C alpha bond dissociations compete with pyrrolidine ring openings triggered by radical sites at both the N-terminal and C-terminal sides of the proline residue. Open-ring intermediates were found in which loss of an H atom was energetically preferred over backbone dissociations. This provided an explanation for the proline effect causing low incidence of electron capture dissociations of N-C alpha bonds adjacent to proline residues in tryptic peptides and also for some peculiar behavior of proline-containing protein cation-radicals.     

Control of stripelike and hexagonal self-assembly of gold nanoparticles by the tuning of interactions between triphenylene ligands

We describe the self-assembly of gold nanoparticles (Au NPs) protected with newly synthesized discotic liquid crystalline molecules of hexaalkoxy-substituted triphenylene (TP) in mixed toluene/methanol solvent. The stripelike (i.e., 2D consisting of linear 1D in stripe) self-assembly is realized successfully by the aid of pi-pi stacking of TP ligand on Au NPs. The smaller Au NPs with TP (AuTP) or the longer alkyl chain between TP and the gold core provide more free spaces among TP moieties. These spaces allow easy insertion of TP on adjacent AuTPs to lead an interparticle pi-pi interaction to form the stripelike arrangement. The solvent hydrophilicity can also serve as a controlled index to tune arrangement among stripelike, hexagonal close packed (hcp), or disorder. We have changed the solvent hydrophilicity by changing the ratio of methanol to toluene, which affects the balance of solution of AuTP (in toluene) and deposition (in methanol). The larger space between TPs and appropriate solvent hydrophilicity realize stripelike self-assembly caused by a strong pi-pi interaction between TPs, which was characterized by TEM, as well as fluorescence, dynamic light scattering, and 1H NMR spectra.     

Preparation of single-crystalline platinum nanowires with small diameters under mild conditions

We report a convenient method to synthesize single-crystalline platinum nanowires with high aspect ratio of ca. 2.0 nm diameter by sophisticated and precise control of Pt(0) nuclei and their growth.