Laser Desorption Ionization of As<Subscript>2</Subscript>Ch<Subscript>3</Subscript> (Ch = S,Se, and Te) Chalcogenides Using Quadrupole Ion Trap Time-of-Flight Mass Spectrometry: A Comparative Study

Laser desorption ionization using time-of-flight mass spectrometer afforded with quadrupole ion trap was used to study As₂Ch₃ (Ch = S, Se, and Te) bulk chalcogenide materials. The main goal of the study is the identification of species present in the plasma originating from the interaction of laser pulses with solid state material. The generated clusters in both positive and negative ion mode are identified as 10 unary (S _p ^+/– and As _m ^+/– ) and 34 binary (As _m S _p ^+/– ) species for As₂S₃ glass, 2 unary (Se _q ^+/– ) and 26 binary (As _m Se _q ^+/– ) species for As₂Se₃ glass, 7 unary (Te _r ^+/– ) and 23 binary (As _m Te _r ^+/– ) species for As₂Te₃ material. The fragmentation of chalcogenide materials was diminished using some polymers and in this way 45 new, higher mass clusters have been detected. This novel approach opens a new possibility for laser desorption ionization mass spectrometry analysis of chalcogenides as well as other materials.

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A systematic study of the hydration and drying process of silica xerogels using Cu(II) EPR spectroscopy

Journal of Sol-Gel Science and Technology - The influence of the hydration and drying process on the line shape and signal intensity of the electron paramagnetic resonance spectra recorded from...     

Unifying pricing formula for several stochastic volatility models with jumps

In this paper, we introduce a unifying approach to option pricing under continuous‐time stochastic volatility models with jumps. For European style options, a new semi‐closed pricing formula is derived using the generalized complex Fourier transform of the corresponding partial integro‐differential equation. This approach is successfully applied to models with different volatility diffusion and jump processes. We also discuss how to price options with different payoff functions in a similar way. In particular, we focus on a log‐normal and a log‐uniform jump diffusion stochastic volatility model, originally introduced by Bates and Yan and Hanson, respectively. The comparison of existing and newly proposed option pricing formulas with respect to time efficiency and precision is discussed. We also derive a representation of an option price under a new approximative fractional jump diffusion model that differs from the aforementioned models, especially for the out‐of‐the money contracts. Copyright © 2017 John Wiley & Sons, Ltd.     

Steady motion of a rigid disk of finite thickness on a horizontal plane

The article discusses the steady motion of a rigid disk of finite thickness rolling on its edge on a horizontal plane under the influence of gravity. The governing equations are presented and two cases allowing for a steady-state solution are considered: rolling on consistently rough ground and rolling on perfectly smooth ground. The conditions of steady motion are derived for both kinds of ground and it is shown that the possible steady motion of a disk is either on a straight line or in a circle. Oscillations about steady state are discussed and conditions for stable motion established. The bifurcations of steady motions on a smooth surface are also considered.     

Hydrogen‐Bond‐Based Magnetic Exchange Between μ‐Diethylnicotinamide(aqua)bis(X‐salicylato)copper(II) Polymeric Chains

Polymeric salicylatocopper(II) complexes of unusual composition [C u(X‐ sal)₂( μ‐denia)(H₂O)]_n [denia = diethylnicotinamide, and X‐sal = 5‐methylsalicylate ( 1 ), 3‐methylsalicylate ( 2 ), 4‐methoxysalicylate ( 3 ), 3,5‐dichlorosalicylate ( 4 ) and 3,5‐dibromosalicylate ( 5 )] were synthesized and characterized. Magnetic measurements were performed in the temperature range 1.8–300 K. The structural unit of all complexes consists of a Cu^II atom, which is monodentately coordinated by the pair of X‐salicylate anions in trans positions. Water and the diethylnicotinamide ligand occupy the other two basal plane positions of the tetragonal pyramid. The axial positions are occupied by a diethylnicotinamide oxygen atom of neighboring structural units, thus forming a spiral polymeric structure parallel to b axis. Magnetic measurements showed that all complexes 1 – 5 exhibit a susceptibility maximum at about 6–8 K. The obtained data fit to Bleaney–Bowers equation gave singlet‐triplet energy gaps 2J = –8.60 cm^–1 for 1 , 2J = –6.57 cm^–1 for 2 , 2J = –8.57 cm^–1 for 3 , 2J = –6.82 cm^–1 for 4 , and 2J = –6.45 cm^–1 for 5 . The supramolecular structure based on hydrogen bonds [described by supramolecular synthons R₂²(10) and R₂²(12)] is the pathway for antiferromagnetic interactions of the magnetically coupled pairs of copper atoms of neighboring chains within the 2D supramolecular layers. The results of the magnetic measurements suggest involvement of the COO groups in the magnetic interaction pathway for all five complexes.     

Disulfide bond decay during matrix-assisted laser desorption/ionization time-of-flight mass spectrometry experiments

In our laboratory, we have been studying the reductive processes that occur during matrix-assisted laser desorption/ionization (MALDI) experiments. Recently, we have finished an analysis of the DHB matrix effect on the azo group in cyclic peptides. However, deep understanding of disulfide bond behaviour during a mass spectrometry (MS) experiment is much more important in proteomics as its reduction can cause serious errors in protein spectra interpretation. Therefore, we have focused on intra- and intermolecular disulfide bonds as well as disulfide bonds connecting cysteine and 2-thio-5-nitrobenzoic acid (TNB, Ellman's reagent modification) in model peptides during MALDI MS measurements. While the reduction was not observed for intra- and intermolecular cysteine-cysteine disulfide bonds, the disulfide connection between cysteine and TNB was always affected. It was proved that TNB and Ellman's reagent can act as a matrix itself. The results obtained enabled us to propose a reaction mechanism model which is able to describe the phenomena observed during the desorption/ionization process of disulfide-containing molecules.     

Additive-free clicking for polymer functionalization and coupling by tetrazine-norbornene chemistry

Herein we report the use of a tetrazine-norbornene inverse electron demand Diels-Alder conjugation applied to polymer end-functionalization and polymer-polymer coupling. The reaction was found to be applicable to polymer-polymer coupling, as judged by SEC, DOSY NMR, and LCxSEC analyses, giving diblock copolymers by merely mixing the constituent homopolymers together under ambient conditions, using no catalyst, additive, or external stimulus.     

Fast motion in molecular solids at low temperatures: evidence from a pulsed electron paramagnetic resonance study of nitroxyl radical relaxation

We have investigated the electron phase-memory relaxation time of the nitroxyl radical 2,2,6,6-tetramethylpiperidine-1-oxyl at temperatures between 5 and 80 K in crystalline and glassy states of ethanol using pulsed X-band electron paramagnetic resonance spectroscopy. The results indicate that the transition from the slow to fast motion regimes of the paramagnetic center occurs upon further cooling of the sample below ～20 K. We provide experimental evidence that this phenomenon cannot be ascribed to the impact of hyperfine interactions with methyl protons in the system, but it can be instead a signature of the coupling of the electron spin with the boson peak excitations of the lattice.