Potential energy surface of O2-(H2O) and factors controlling water-to-O2- binding motifs

The potential energy surface (PES) of O(2)(-)(H(2)O) is investigated by varying the interoxygen distance of O(2)(-) via ab initio calculations with a large basis set. Although two stationary points, C(s) and C(2v) conformers, are found along the interoxygen-distance coordinate, only the C(s) conformer is identified as a minimum-energy species. We find a critical distance, r(c), separating these two conformers in the PES. The C(s) conformer prevails at interoxygen distances of O(2)(-) that are less than r(c), while the C(2v) conformer dominates at the distances larger than r(c). The structural features of these two conformers are also discussed. Although the water deformation energy is shown to be the stabilization source responsible for the prevalence of the C(s) cluster conformer at the interoxygen distances of O(2)(-) less than r(c), the ionic hydrogen bonding is the major driving force for transformation of the water binding motif from C(s) to C(2v) when the interoxygen distance of O(2)(-) increases.     

Preparation and luminescence properties of Y2(WO4)3: Eu3+

A red-emitting Y₂(WO₄)₃: Eu³⁺ phosphor (orthorhombic high temperature phase, anhydride) is prepared by two different methods: the firing of mixtures of constituent oxides and that of precipitates from aqueous solutions. After optimizing preparation conditions, the cathodoluminescence brightness reaches 56% that of Y₂O₂S: Eu³⁺, a commercial red phosphor for color TV. Formation of a high temperature phase below the reported transition temperature is noted in the fired precipitates. This phase occurrence is shown to depend on the treatment of the precipitates to be fired. Reflection difference measurement of Eu-doped and undoped samples assigns an excitation band of about 245 nm to the Eu-O charge transfer band. Different by-products in the two preparation methods are identified by measuring emission spectra under selective excitation. Reversible hydration-dehydration of the phosphor is demonstrated by successively measuring photoluminescence first in vacuum and then in air at various temperatures. No deterioration of luminescence efficiency is observed after repeating this reversible structural change.     

1.3 m m InGaAsN/ GaAs Lasers Grown by MOCVD Using TBAs and DMHy Sources

We have demonstrated InGaAsN/ GaAs single quantum well (SQW) lasers grown by MOCVD using TBAs and DMHy sources. For un-buffer-strained InGaAsN/ GaAs system, our SQW lasers of 1.3 m m range is among the best in terms of transparency and threshold current density.     

Measurements of long-term changes in atmospheric OCS (carbonyl sulfide) from infrared solar observations

Multi-decade atmospheric OCS (carbonyl sulfide) infrared measurements have been analyzed with the goal of quantifying long-term changes and evaluating the consistency of the infrared atmospheric OCS remote-sensing measurement record. Solar-viewing grating spectrometer measurements recorded in April 1951 at the Jungfraujoch station (46.5°N latitude, 8.0°E longitude, 3.58 km altitude) show evidence for absorption by lines of the strong ν₃ band of OCS at 2062 cm⁻¹. The observation predates the earliest previously reported OCS atmosphere remote-sensing measurement by two decades. More recent infrared ground-based measurements of OCS have been obtained primarily with high-resolution solar-viewing Fourier transform spectrometers (FTSs). Long-term trends derived from this record span more than two decades and show OCS columns that have remained constant or have decreased slightly with time since the Mt. Pinatubo eruption, though retrievals assuming different versions of public spectroscopic databases have been impacted by OCS ν₃ band line intensity differences of ∼10%. The lower stratospheric OCS trend has been inferred assuming spectroscopic parameters from the high-resolution transmission (HITRAN) 2004 database. Volume mixing ratio (VMR) profiles measured near 30°N latitude with high-resolution solar-viewing FTSs operating in the solar occultation mode over a 22 years time span were combined. Atmospheric Trace MOlecucle Spectroscopy (ATMOS) version 3 FTS measurements in 1985 and 1994 were used with Atmospheric Chemistry Experiment (ACE) measurements during 2004-2007. Trends were calculated by referencing the measured OCS VMRs to those of the long-lived constituent N₂O to account for variations in the dynamic history of the sampled airmasses. Means and 1-sigma standard deviations of VMRs (in ppbv, or 10⁻⁹ per unit air volume) averaged over 30-100 hPa from measurements at 25-35°N latitude are 0.334±0.089 ppbv from 1985 (ATMOS Spacelab 3 measurements), 0.297±0.094 ppbv from 1994 ATLAS 3 measurements, 0.326±0.074 ppbv from ACE 2004 measurements, 0.305±0.096 ppbv from ACE 2005 measurements, 0.328±0.074 from ACE 2006 measurements, and 0.305±0.090 ppbv from ACE measurements through August 2007. Assuming these parameters, we conclude that there has been no statistically significant trend in lower stratospheric OCS over the measurement time span. We discuss past measurement sets, quantify the impact of changes in infrared spectroscopic parameters on atmospheric retrievals and trend measurements, and discuss OCS spectroscopic uncertainties of the current ν₃ band parameters in public atmospheric databases.     

Performance of a wavelength-tunable erbium-doped fiber laser using a Sagnac interferometer

We experimentally demonstrate a wavelength-tunable erbium-doped fiber laser that is composed of a ring cavity and a single-mode fiber Sagnac interferometer in a new and simple arrangement. We find that the fiber laser output wavelength is tunable by adjusting the filter effect of the Sagnac fiber loop through a fiber polarization controller set there. The quasi-single-wavelength continuously tunable laser outputs could be achieved within some wavelength range. The multi-wavelength laser outputs could also be observed under some appropriate settings of the polarization controller. A theoretical demonstration of the wavelength tunability about the transmission-type Sagnac loop filter has also been achieved using the Jones calculus theory.     

Staged Development of Modified Silicon Dioxide Films

The hydrolytic generation of SiO₂ films from chlorosilanes or alkoxysilanes is interrupted by incorporating labile organic groups which stop SiO₂ formation at a processable prepolymer stage. The monomers for the prepolymer have electron withdrawing substituents in the -position. The organic groups are removed from the prepolymer at low temperature, extruding ethylene. The formation of SiO₂ proceeds by intramolecular condensation of the electronegative substituents which are now in a hydrolytically unstable bond with silicon and hydroxyl groups or ambient moisture. Films of the prepolymer spun onto silicon wafers are converted into uniform SiO₂-rich films at temperatures between 150–400°C.     

Structure and Reactivity of Iron(0)-Phenyltellurolate [PPN][PhTeFe(CO)4]

Anionic iron(0) tetracarbonyl with terminal phenyltellurolate ligand PhTe^?, [PhTeFe(CO)₄]^?, has been synthesized and characterized. The title compound was obtained by addition of (PhTe)₂ to [PPN][HFe(CO)₄] THF solution dropwise. [PPN][PhTeFe(CO)₄] crystallizes in the monoclinic space group C c, with a = 16.119(4) Å, b = 13.141(3) Å, c = 19.880(8) Å, β = 93.04(3)°, V = 4205(2) ų, and Z = 4. The [PhTeFe(CO)₄]^? anion is a trigonal-bipyramidal complex in which the phenyltellurolate ligand occupies an axial position with Fe-Te bond length 2.630(5) Å and the Fe-Te-C(Ph) angle is 103.4(5)°. The neutral iron(0)-telluroether compound, (PhTeMe)Fe(CO)₄, was prepared by alkylation of the [PhTeFe(CO)₄]^?. Protonation of [PhTeFe(CO)₄]^?and reaction of H₂Fe(CO)₄ and PhTe)₂ ultimately lead to formation of the known dimer Fe₂(μ-TePh)₂(CO)₆ and H₂.     

A novel titanium dioxide-polydimethylsiloxane plate for phosphopeptide enrichment and mass spectrometry analysis

The phosphorylation of proteins is a major post-translational modification that is required for the regulation of many cellular processes and activities. Mass spectrometry signals of low-abundance phosphorylated peptides are commonly suppressed by the presence of abundant non-phosphorylated peptides. Therefore, one of the major challenges in the detection of low-abundance phosphopeptides is their enrichment from complex peptide mixtures. Titanium dioxide (TiO₂) has been proven to be a highly efficient approach for phosphopeptide enrichment and is widely applied. In this study, a novel TiO₂ plate was developed by coating TiO₂ particles onto polydimethylsiloxane (PDMS)-coated MALDI plates, glass, or plastic substrates. The TiO₂-PDMS plate (TP plate) could be used for on-target MALDI-TOF analysis, or as a purification plate on which phosphopeptides were eluted out and subjected to MALDI-TOF or nanoLC-MS/MS analysis. The detection limit of the TP plate was ∼10-folds lower than that of a TiO₂-packed tip approach. The capacity of the ∼2.5 mm diameter TiO₂ spots was estimated to be ∼10 μg of β-casein. Following TiO₂ plate enrichment of SCC4 cell lysate digests and nanoLC-MS/MS analysis, ∼82% of the detected proteins were phosphorylated, illustrating the sensitivity and effectiveness of the TP plate for phosphoproteomic study.     

Dirhodium-catalyzed phenol and aniline oxidations with T-HYDRO. Substrate scope and mechanism of oxidation

Dirhodium caprolactamate, Rh(2)(cap)(4), is a very efficient catalyst for the generation of the tert-butylperoxy radical from tert-butyl hydroperoxide, and the tert-butylperoxy radical is a highly effective oxidant for phenols and anilines. These reactions are performed with 70% aqueous tert-butyl hydroperoxide using dirhodium caprolactamate in amounts as low as 0.01 mol % to oxidize para-substituted phenols to 4-(tert-butyldioxy)cyclohexadienones. Although these transformations have normally been performed in halocarbon solvents, there is a significant rate enhancement when Rh(2)(cap)(4)-catalyzed phenol oxidations are performed in toluene or chlorobenzene. Electron-rich and electron-poor phenolic substrates undergo selective oxidation in good to excellent yields, but steric influences from bulky para substituents force oxidation onto the ortho position resulting in ortho-quinones. Comparative results with RuCl(2)(PPh(3))(3) and CuI are provided, and mechanistic comparisons are made between these catalysts that are based on diastereoselectivity (reactions with estrone), regioselectivity (reactions with p-tert-butylphenol), and chemoselectivity in the formation of 4-(tert-butyldioxy)cyclohexadienones. The data obtained are consistent with hydrogen atom abstraction by the tert-butylperoxy radical followed by radical combination between the phenoxy radical and the tert-butylperoxy radical. Under similar reaction conditions, para-substituted anilines are oxidized to nitroarenes in good yield, presumably through the corresponding nitrosoarene, and primary amines are oxidized to carbonyl compounds by TBHP in the presence of catalytic amounts of Rh(2)(cap)(4).     

High-speed droplet generation on demand driven by pulse laser-induced cavitation

We report on a pulse laser-driven droplet generation (PLDG) mechanism that enables on-demand droplet generation at rates up to 10,000 droplets per second in a single-layer PDMS-based microfluidic device. Injected droplet volumes can be continuously tuned between 1 pL and 150 pL with less than 1% volume variation.