Rapid Quantification of 25-Hydroxyvitamin D<Subscript>3</Subscript> in Human Serum by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

LC-MS/MS is widely utilized today for quantification of vitamin D in biological fluids. Mass spectrometric assays for vitamin D require very careful method optimization for precise and interference-free, accurate analyses however. Here, we explore chemical derivatization and matrix-assisted laser desorption/ionization (MALDI) as a rapid alternative for quantitative measurement of 25-hydroxyvitamin D₃ in human serum, and compare it to results from LC-MS/MS. The method implemented an automated imaging step of each MALDI spot, to locate areas of high intensity, avoid sweet spot phenomena, and thus improve precision. There was no statistically significant difference in vitamin D quantification between the MALDI-MS/MS and LC-MS/MS: mean ± standard deviation for MALDI-MS—29.4?±?10.3 ng/mL—versus LC-MS/MS—30.3?±?11.2 ng/mL (P?=?0.128)—for the sum of the 25-hydroxyvitamin D epimers. The MALDI-based assay avoided time-consuming chromatographic separation steps and was thus much faster than the LC-MS/MS assay. It also consumed less sample, required no organic solvents, and was readily automated. In this proof-of-concept study, MALDI-MS readily demonstrated its potential for mass spectrometric quantification of vitamin D compounds in biological fluids.

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Demonstration of an integrated capillary electrophoresis-laser-induced fluorescence fiber-optic sensor

A unique integrated separation-based fiber-optic sensor for remote analysis, that incorporates capillary electrophoresis (CE) directly at the fiber sensing terminus is described for the first time. Based on laser-induced fluorescence detection, the sensor offers the potential for high sensitivity. Although the broad-band nature of fluorescence spectra limits selectivity, the high separation power of CE provides a unique dimension of selectivity, while permitting a design of diminutive size. Previously reported fluorescence-based sensors that utilize a chemical reagent phase to impart selectivity tend to be inflexible (not readily adaptable to the detection of different species) and "one-measurement-only" sensors. Conversely, the CE-based fiber-optic sensor described here is both versatile and reusable. The analysis speed and the potential for remote control are further attributes which make the system amenable to remote sensing. A "single-fiber" optical detection arrangement and a "single-reservoir" CE system with the fiber-optic probing the outlet of the separation capillary are employed. A preliminary evaluation of the separation characteristics of this CE-based sensor is presented. Highlights include an observed separation efficiency of up to 3000 theoretical plates (8 cm separation capillary) and migration time reproducibility of less than 10% for frontal mode CE separations. The potential utility of the sensor for remote analysis is demonstrated with separations involving the CE analysis of charged fluorescent dyes, CE analysis of metal complexes based on in situ complexation and micellar electrokinetic capillary chromatographic analysis of neutral fluorescent compounds.     

Broadband Noise in Orthorhombic TaS3

We report experimental results on the broadband noise in sliding charge density wave conductor orthorhombic TaSn. The experimental results are in excellent agreement with a phenomenological model based on fluctuations in threshold field due to deformations of the sliding condensate.     

How to generalise demonic composition

Semigroup Forum - Demonic composition is defined on the set of binary relations over the non-empty set X, $$Rel_X$$ , and is a variant of standard or “angelic” composition. It arises...     

The Casimir effect for fields with arbitrary spin

The Casimir force arises when a quantum field is confined between objects that apply boundary conditions to it. In a recent paper we used the two-spinor calculus to derive boundary conditions applicable to fields with arbitrary spin in the presence of perfectly reflecting surfaces. Here we use these general boundary conditions to investigate the Casimir force between two parallel perfectly reflecting plates for fields up to spin-2. We use the two-spinor calculus formalism to present a unified calculation of well-known results for spin-1/2 (Dirac) and spin-1 (Maxwell) fields. We then use our unified framework to derive new results for the spin-3/2 and spin-2 fields, which turn out to be the same as those for spin-1/2 and spin-1. This is part of a broader conclusion that there are only two different Casimir forces for perfectly reflecting plates—one associated with fermions and the other with bosons.     

Effects of Rh on the thermoelectric performance of the p-type Zr0.5Hf0.5Co1−xRhxSb0.99Sn0.01 half-Heusler alloys

We show that Rh substitution at the Co site in Zr_0.5Hf_0.5Co_1−xRh_xSb_0.99Sn_0.01 (0≤x≤1) half-Heusler alloys strongly reduces the thermal conductivity with a simultaneous, significant improvement of the power factor of the materials. Thermoelectric properties of hot-pressed pellets of several compositions with various Rh concentrations were investigated in the temperature range from 300 to 775 K. The Rh “free” composition shows n-type conduction, while Rh substitution at the Co site drives the system to p-type semiconducting behavior. The lattice thermal conductivity of Zr_0.5Hf_0.5Co_1−xRh_xSb_0.99Sn_0.01 alloys rapidly decreased with increasing Rh concentration and lattice thermal conductivity as low as 3.7 W/m*K was obtained at 300 K for Zr_0.5Hf_0.5RhSb_0.99Sn_0.01. The drastic reduction of the lattice thermal conductivity is attributed to mass fluctuation induced by the Rh substitution at the Co site, as well as enhanced phonon scattering at grain boundaries due to the small grain size of the synthesized materials.     

The crystallization kinetics and morphology of nitric acid trihydrate

Crystallization kinetics of stable and metastable nitric acid trihydrate (NAT) were investigated by time dependent X-ray powder diffraction (XRD) measurements. Kinetic conversion curves were evaluated adopting the Avrami model. The growth and morphology of the respective crystallites were monitored in situ on the cryo-stage of an environmental scanning electron microscope (ESEM) under a partial pressure of nitrogen gas (0.3 Torr, 40 Pa). The results show a close relationship between the presence of ice in the sample and the crystallization mechanism of NAT, which results in different shapes and sizes of NAT crystal particles.     

Morphology control of the produced Ag nanoparticles by soft-template technique

The morphology of the produced Ag nanoparticle is controlled successfully by UV irradiating the reaction solution of AgAc/ethyl alcohol/1-octadeconal/1-dodecanethiol. With use of a novel solution such as soft template, Ag nanorods with different sizes and different ratios of length to diameter can be obtained by adjusting the concentrations of the solution compositions.     

Organic peroxide assisted transition metal hydrosilylation catalysis

Summary The catalytic activity of rhodium complexes for the hydrosilylation of substrates such as alkenes, 1,3-dienes, 1-alkynes, or ketones, is enhanced by the addition of organic oxidizing agents, such ast-butyl hydroperoxide, hydrogen peroxide, orm-chloroperbenzoic acid. Similar enhancement is found for the Group VIA hexacarbonyls in the hydrosilylation of 1,3-dienes.