Zero-phonon transition of free electrons to bound holes in heavily gallium-doped silicon

A radiative zero-phonon transition of free electrons to bound holes has been observed in heavily gallium-doped silicon at various temperatures. This electronic transition competes with excitonic transitions, and dominates at high temperatures.     

Two-dimensional cross-spectral correlation analysis and its application to time-resolved Fourier transform emission spectra of transient radicals

A spectral analysis method, based on the generalized two-dimensional (2D) vibrational spectra correlation analysis, is developed for deciphering the correlation among the spectral peaks of two different spectra. This 2D cross-spectral correlation (2DCSC) analysis is aimed at revealing the vibrational features associated with a common species in two spectra, each obtained from a system containing multiple species with at least one common species. The cross-spectral correlation is based on the premise that the spectral features of the same species should have the same time and frequency responses toward similar perturbations. The effectiveness of the cross-spectral correlation analysis is first illustrated with model systems, with spectral peaks decaying linearly or exponentially with time, before being applied to analyzing time-resolved emission spectra obtained, by a Fourier transform IR spectrometer, for samples consisting of the vibrationally excited transient cyanooxomethyl radical (OCCN). 2DCSC among the three different sets of time-resolved spectra collected following the photodissociation of three different precursor molecules of OCCN, respectively, allows the identification of the CN and CO stretching modes of this radical.     

Role of ion pairing in anionic additive effects on the separation of cationic drugs in reversed-phase liquid chromatography

Mobile phase additives can significantly affect the separation of cationic drugs in reversed-phase liquid chromatography (RPLC). Although there are many applications for anionic additives in RPLC separations, the retention mechanism of basic drugs in the presence of inorganic and highly hydrophilic anionic species in the mobile phase is not at all well understood. Two major retention mechanisms by which anionic additives can influence the retention of cations are: (1) ion pair formation in the mobile phase with subsequent retention of the neutral ion pair; (2) pre-sorption of anionic additives on the stationary phase followed by "dynamic ion-exchange" or "electrostatic interaction" with the analytes. Because the use of ion pair chromatography in the separation of proteins, peptides, and basic drugs is rapidly increasing, understanding the retention mechanism involved is becoming more important, especially for the smaller commonly used hydrophilic anionic additives (e.g., formate HCOO, chloride Cl-, trifluoroacetate CF3COO-, perchlorate ClO4-, and hexafluorophosphate PF6-). In this work, we compared various anionic additives in light of their effects on the retention of basic drugs. As did many others we found that the addition of anionic additives (Cl-, CF3COO-, ClO4-, PF6-) profoundly influences the retention of basic drugs. In order to explain the data and differentiate the mechanisms by which the anionic additives perturb the chromatography, we used ion pair formation constants independently measured by capillary electrophoresis (CE) under the mobile phase conditions (pH, solvent composition) identical to those used in chromatography. Agreement between the predicted and experimental chromatographic data under various conditions was evaluated. Under specific circumstances (e.g., pH, stationary phase, and nature of anionic additive), we conclude that the ion pair mechanism is more important than the dynamic ion-exchange and at other conditions it remains a significant contribution.     

Facile, alternative synthesis of lanthanum phosphate nanocrystals by ultrasonication

Highly luminescent, rhabdophane (Ce(0.33)La(0.66))PO4.nH2O nanorods and nanoparticles were prepared in aqueous solutions by ultrasonication, at pH 1 and pH 12, respectively. Both nanorods (5 to 9 nm wide and several tens to several hundreds nm long) and nanoparticles (elongated, connected 5 nm particles) were as small and as uniform as products obtained from methods that utilize complexing agents or surfactants, only with no complexing agent. This method of synthesis by ultrasonication is a fast and simple method and it is expected to be applicable for the synthesis of other nanocrystalline lanthanide phosphates.     

The aggregation behavior of O-carboxymethylchitosan in dilute aqueous solution

O-Carboxymethylchitosan (OCMCS) is a kind of biocompatible derivatives of chitosan whose water solubility is strongly dependent on the degree of carboxymethylation. The OCMCS with 100 carboxymethyl groups and 75 amino groups per 100 anhydroglucosamine units of OCMCS was synthesized by the reaction of chitosan and monochloroacetic. When OCMCS was dissolved in water, its solution was neutral and OCMCS behaved like a weak polyanionic polyeclectrolyte because most of carboxylic groups were not dissociated in neutral aqueous solution. The aggregation behavior of OCMCS in aqueous solution was studied by surface tensiometry, steady-state fluorescence spectroscopy and viscometry. The critical aggregation concentration (cac) of OCMCS was determined to be between 0.042 mg/ml and 0.050 mg/ml. The possible aggregation mechanism of OCMCS in water was elucidated.     

DNA-directed self-assembling of carbon nanotubes

Multicomponent structures were constructed by DNA-directed self-assembling of multiple carbon nanotubes and gold nanoparticles. The work presented here represents an important advance in constructing many multicomponent nanotube structures for multifunctional material and device applications.     

Pyrolysis of mesoporous silica-immobilized 1,3-diphenylpropane. Impact of pore confinement and size

Mesoporous silicas such as SBA-15 and MCM-41 are being actively investigated for potential applications in catalysis, separations, and synthesis of nanostructured materials. A new method for functionalizing these mesoporous silicas with aromatic phenols is described. The resulting novel hybrid materials possess silyl aryl ether linkages to the silica surface that are thermally stable to ca. 550 degrees C, but can be easily cleaved at room temperature with aqueous base for quantitative recovery of the organic moieties. The materials have been characterized by nitrogen physisorption, FTIR, NMR, and quantitative analysis of surface coverages. The maximum densities of 1,3-diphenylpropane (DPP) molecules that could be grafted to the surface were less than those measured on a nonporous, fumed silica (Cabosil) and were also found to decrease as a function of decreasing pore size (5.6-1.7 nm). This is a consequence of steric congestion in the pores that is magnified at the smaller pore sizes, consistent with parallel studies conducted using a conventional silylating reagent, 1,1,3,3-tetramethyldisilazane. Pyrolysis of the silica-immobilized DPP revealed that pore confinement leads to enhanced rates and altered product selectivity for this free-radical reaction compared with the nonporous silica, and the rates and selectivities also depended on pore size. The influence of confinement is discussed in terms of enhanced encounter frequencies for bimolecular reaction steps and pore surface curvature that alters the accessibility and resultant selectivity for hydrogen transfer steps.     

Preparation and characterization of a novel adsorbent for removing lipophilic organic from water

The initial twelve persistent organic pollutants (POPs) in Stockholm Convention on Persistent Or-ganic Pollutions include many organochlorinated pes-ticides (OCPs) and some industrial by-products from manufacture processes, most of which are lipophilic or…     

A unique microwave effect on the microstructural modification of Cu/ZnO/Al2O3 catalysts for steam reforming of methanol

A short time (3-10 min) of microwave irradiation on the CuO/ZnO/Al2O3 oxide precursor can result in a unique tailored microstructural modification on the catalyst, leading to a significantly enhanced performance for H2 production from steam reforming of methanol.     

Intense blue up-conversion luminescence in Tm3+/Yb3+ codoped oxyfluoride glass-ceramics containing beta-PbF2 nanocrystals

Up-conversion luminescence properties of a Tm3+/Yb3+ codoped oxyfluoride glass-ceramics under 980 nm excitation are investigated. Intense blue emission centered at 476 nm, corresponding to 1G4-->3H6 transitions of Tm3+ was simultaneously observed in the transparent oxyfluoride glass ceramics at room temperature. The intensity of the blue up-conversion luminescence in a 1 mol% YbF3-containing glass-ceramic was found to be about 40 times stronger than that in the precursor oxyfluoride glass. The reason for the intense Tm3+ up-conversion luminescence in the oxyfluoride glass-ceramics is discussed. The dependence of up-conversion intensities on excitation power and possible up-conversion mechanism are also evaluated.