A Rapid LC-MS/MS-PRM Assay for Serologic Quantification of Sialylated O-HPX Glycoforms in Patients with Liver Fibrosis

Development of high throughput robust methods is a prerequisite for a successful clinical use of LC-MS/MS assays. In earlier studies, we reported that nLC-MS/MS measurement of the O-glycoforms of HPX is an indicator of liver fibrosis. In this study, we show that a microflow LC-MS/MS method using a single column setup for capture of the analytes, desalting, fast gradient elution, and on-line mass spectrometry measurements, is robust, substantially faster, and even more sensitive than our nLC setup. We demonstrate applicability of the workflow on the quantification of the O-HPX glycoforms in unfractionated serum samples of control and liver disease patients. The assay requires microliter volumes of serum samples, and the platform is amenable to one hundred sample injections per day, providing a valuable tool for biomarker validation and screening studies.     

Enhanced electrochemical performance of LiMnBO<Subscript>3</Subscript> with conductive glassy phase: a prospective cathode material for lithium-ion battery

LiMnBO₃ has been identified as a promising cathode material for next-generation lithium-ion batteries. In this study, LiMnBO₃ along with glassy lithium borate material (LiMnBO₃ (II)) is synthesized by sol-gel method. X-ray diffraction (XRD) analysis depicts the existence of LiBO₂ glassy phase along with m-LiMnBO₃ phase. Transmission electron microscopy (TEM) analysis confirms the presence of LiBO₂ glassy phase. An enhanced electrical conductivity of 3.64 × 10^?7 S/cm is observed for LiMnBO₃ (II). The LiBO₂ glassy phase is found to promote the Li reaction kinetics in LiMnBO₃ (II). The synthesized LiMnBO₃ (II) delivers a first discharge capacity of 310 mAh g^?1 within a potential window of 1.5–4.5 V at C/10 rate. Further, a discharge capacity of 186 mAh g^?1 at the 27th cycle shows a better cycle performance. The enhanced capacity is due to the presence of LiBO₂ glassy phase and more than one Li-ion transfer in the lithium-rich stoichiometry of LiMnBO₃ (II). Density functional theory calculation reveals the exact electronic structure of m-LiMnBO₃ with a band gap of 3.05 eV. A charge transfer mechanism is predicted for delithiation process of m-LiMnBO₃.     

Electric field gradient in transition metal: Scandium

Corrections to results of electric field gradient (EFG) already published [Pramana — J. Phys.41, 443 (1993)] are reported. The corrected net EFG is:q=−8.01×10¹³ esu/cm³ against the published valueq=16.06×10¹³ esu/cm³. The present result agrees reasonably well with the experimental result, |q _expt|=13×10¹³ esu/cm³. Recently, a computational error is detected, which modifies the results of EFG, we have already published [1]. The error was committed mainly in the part that evaluated thep-p contribution [1] to EFG by the conduction electrons. The corrected results are summarized in table 1 which must replace the table 1 of the published work [1]. In addition, the lattice parameters as well as the temperature were also misquoted in the previous work [1]. The right parameters are:a=6.25311 au andc=9.96509 au. The temperature at which EFG’s are calculated is 293 K instead of 11 K as reported before [1]. The discussions and conclusions made in the published work [1] remain almost unchanged except that they now refer to the corrected numbers. Although the corrected net EFG suffers a sign reversal from the one already published [1], the agreement with experiment is still considered reasonably good because the sign of experimental EFG is not determined. The computational error however does not affect the introduction and theory section of the published work [1].     

Micellar catalysis in the oxidation of acetophenones by Ce(IV)

Rate of oxidation of acetophenones by Ce(IV) in aqueous acetic acid 80:20 (v/v) either slows down or remains constant over a range of cetyltrimethyl ammonium bromide (CTAB) concentration exceeding the cmc value. The rate is then found to increase sharply as the surfactant concentration increases with no sign of reaching a maximum or constant value. From Fluorescence quenching, binding constant for p-nitro acetophenone has been evaluated. The rate data have been rationalized on the basis of a reaction between the acetophenones situated on the micelle surface and active Ce(IV) species in the bulk aqueous phase.     

Oxidation of amino acids by peroxomonophosphoric acid—a kinetic study

Aliphatic amino acids are smoothly oxidized by peroxomonophosphoric acid (PMPA) in the pH region 6–10. Kinetic studies reveal second order dependence in the amino acid not observed hitherto in any of the PMPA oxidations. Dependence in PMPA is unity. Rate-pH profile yields a maximum around pH 8. The reaction path includes oxidation steps due to H₂PO₅^? and HPO₅^2?. Second order dependence in the amino acid has been attributed to participation of two Zwitter-ionic molecules of the amino acid to form a nucleophile.     

Kinetics and mechanism of oxidation of S2O 32? by potassium bis (tellurato) cuprate(III)

The kinetics of oxidation of sodium thiosulphate by potassiumbis(tellurato) cuprate(III) in an alkaline medium has been reported. The reaction is first order in [S₂O ₃ ²⁻ ] but zero order in copper(III). Hydroxide ions are found to retard the oxidation rate. A rate expression rationalising the kinetic data has been derived. Sodium tetrathionate has been found to be the product of oxidation.     

Synergistic fluorescence enhancement of Tb with aromatic monocarboxylic acids and TOPO-Triton X-100: role of Triton X-100 in synergism

Fluorescence enhancement of Tb3+ has been studied, using substituted benzoic acids as ligands. These ligands enhance the fluorescence of Tb3+ by about three orders of magnitude. The enhancement is observed due to ligand sensitized fluorescence. The fluorescence of Tb3+ in these complexes is synergistically enhanced by the addition of trioctylphosphine oxide (TOPO) in Triton X-100. The synergism displayed by TOPO was observed only when Triton X-100 micellar medium was used. TOPO dissolved in SDS/DTAB micellar medium did not result in synergistic fluorescence enhancement of Tb3+. These observations are discussed in detail and the synergism displayed by TOPO is rationalized on the basis of the structure of the surfactants.     

Blue luminescence of Au nanoclusters embedded in silica matrix

Photoluminescence study using the 325 nm He-Cd excitation is reported for the Au nanoclusters embedded in SiO(2) matrix. Au clusters are grown by ion beam mixing with 100 KeV Ar(+) irradiation on Au [40 nm]/SiO(2) at various fluences and subsequent annealing at high temperature. The blue bands above approximately 3 eV match closely with reported values for colloidal Au nanoclusters and supported Au nanoislands. Radiative recombination of sp electrons above Fermi level to occupied d-band holes are assigned for observed luminescence peaks. Peaks at 3.1 and 3.4 eV are correlated to energy gaps at the X- and L-symmetry points, respectively, with possible involvement of relaxation mechanism. The blueshift of peak positions at 3.4 eV with decreasing cluster size is reported to be due to the compressive strain in small clusters. A first principle calculation based on density functional theory using the full potential linear augmented plane wave plus local orbitals formalism with generalized gradient approximation for the exchange correlation energy is used to estimate the band gaps at the X- and L-symmetry points by calculating the band structures and joint density of states for different strain values in order to explain the blueshift of approximately 0.1 eV with decreasing cluster size around L-symmetry point.     

Evolution,migration and clustering of helium-vacancy complexes in RAFM steel- depth resolved positron annihilation Doppler broadening study

Indian Reduced Activation Ferritic Martensitic steel is implanted with 130 keV helium ions to a fluence of 5 × 10¹⁴ and 1 × 10¹⁶ ions/cm² and investigated using positron annihilation spectroscopy. The samples were characterised by defect sensitive S and W-parameters using depth resolved slow positron beam. A dose dependency is observed in the nucleation and growth of helium bubbles with annealing temperature. An experimental evidence for the migration of smaller helium-vacancy complexes is observed via the variation in thickness/width of irradiated layer with temperature. The S–W plot clearly shows the regions corresponding to defect annealing, bubble nucleation and growth.