Theoretical analysis of vibrational spectra and scaling‐factor of 2‐aryl‐1,3,4‐oxadiazole derivatives

In this study, the direct molecular structure implementations for calculating vibrational spectra and scaling factors, and infrared intensities at both the Hartree–Fock (HF) and density functional (B3LYP) levels of theory with 6‐31G(d), 6‐311G(d), 6‐31++G(d,p), and 6‐311++G(d,p) basis sets are presented. Also, vibrational frequencies have been investigated as dependence on the choice of method and basis set. The parameters of molecular geometry and vibrational frequencies values of 2‐aryl‐1,3,4‐oxadiazoles 5a–g in the ground state have been calculated. Theoretical determination of vibrational frequencies is quite useful both in understanding the relationship between the molecular structures and scaling factor. The data of 2‐aryl‐1,3,4‐oxadiazoles 5a–g display significant electronic properties provide the basis for future design of efficient materials having the oxadiazole core and theoretical IR studies. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Electrochemical Investigation of Gold Based Screen Printed Electrodes: An Application for a Seafood Toxin Detection

Although commercial screen-printed electrodes (SPEs) are used extensively for biosensor purposes nowadays, detailed studies on characterization are still limited. In this study, the surface of the gold-based screen-printed electrode (SPGE) was carefully modified with self-assembly-monolayer through an optimized immobilization procedure. The key physical and chemical properties with regeneration capacity of the developed biosensors were assessed by various characterization techniques. Then SPGE was used to determine its sensitivity, limit of detection (LOD) and limit of quantification (LOQ) for a toxin substance of domoic acid in seafood that has become more common and rising concern of marine wildlife and seawater pollution. LOD in phosphate buffered saline (PBS) and cell culture media were obtained as 2.93 ng mL⁻¹ and 4.28 ng mL⁻¹, respectively. The reduced sensitivity for antibody-based biosensors in the cell culture medium was probably due to interaction of nonspecific compounds with DA in the culture medium compared to the much less complex environment of PBS. In addition, the regeneration capacity has been found very limited due to inherent heterogeneity and low robustness. This study can be used for the main challenges with the design requirements of commercial SPE-based biosensors to provide a detailed perspective for further toxicity studies.     

Synthesis and photopolymerizations of first monomers with phosphonate and bisphosphonate or phosphonic and bisphosphonic acid functionalities for potential dental applications

The first monomers containing both phosphonate and bisphosphonate (M1) or phosphonic and bisphosphonic acid (M2) functionalities are synthesized, aiming to improve binding abilities of self-etching adhesive systems and composites: An amine having both phosphonate and bisphosphonate functionalities is prepared via Michael addition reaction between diethyl (6-aminohexyl)phosphonate and tetraethyl vinylidene bisphosphonate, its reaction with 2-isocyanatoethyl methacrylate gives M1 which is converted to M2 by selective dealkylation of the phosphonate/bisphosphonate ester groups. Their copolymerization with commercial dental monomers (bisphenol A glycidyl methacrylate, triethylene glycol dimethacrylate, and 2-hydroxyethyl methacrylate) investigated by photo-differential scanning calorimetry shows adequate photopolymerization rate and conversion. X-ray diffraction, Fourier transform infrared, and X-ray photoelectron spectroscopy analyses of M2-treated hydroxyapatite particles show formation of stable M2-calcium salts. These monomers are assessed to be not toxic according to MTT standards by in vitro cytotoxicity studies with NIH 3T3, U2OS, and Saos-2 cells. All these properties make these monomers potential candidates as biocompatible components for dental adhesives and composites. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2739–2751     

Numerical simulation of fluid-structure interaction problems by a coupled SPH-FEM approach

In scientific computing there is a great interest in numerical simulation of fluid-structure interaction (FSI) problems. Within this work a numerical approach to simulate fluid-structure interactions between elastic structures and weakly incompressible fluids is developed. For the fluid part and the solid part the Smoothed Particle Hydrodynamics method (SPH) and the Finite Element Method (FEM) are used, respectively. To transfer the resulting reaction forces from the fluid particles onto the structure's surface two methods are implemented, investigated and compared. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A semi-implicit multi-fluid SPH algorithm suitable for GPU

Multi-fluid flows are a common problem in process and naval engineering. In this paper an incompressible Smoothed Particle Hydrodynamics (SPH) algorithm is presented, to solve multi-fluid flows with high density ratios (≤ 1000). The results of the Rayleigh-Taylor instability and the rising bubble test case are compared with the results obtained by a weakly compressible SPH algorithm with respect to the results obtained by grid-based solvers. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A theoretical study on 1-(thiophen-2-yl-methyl)-2-(thiophen-2-yl)-1H-benzimidazole

The molecular geometry and vibrational frequencies of 1-(thiophen-2-yl-methyl)-2-(thiophen-2-yl)-1H-benzimidazole (C(16)H(12)N(2)S(2)) in the ground state has been calculated using the Hartree-Fock (HF) and density functional method (B3LYP) with 6-31G(d) basis set. The optimized geometric bond lengths and bond angles obtained by using HF and DFT (B3LYP) show the best agreement with the experimental data. Comparison of the observed fundamental vibrational frequencies of 1-(thiophen-2-yl-methyl)-2-(thiophen-2-yl)-1H-benzimidazole (C(16)H(12)N(2)S(2)) and calculated results by density functional B3LYP and Hartree-Fock methods indicate that B3LYP is superior to the scaled Hartree-Fock approach for molecular vibrational problems.     

Modeling the free radical polymerization of acrylates

Acrylates have gained importance because of their ease of conversion to high‐molecular‐weight polymers and their broad industrial use. Methyl methacrylate (MMA) is a well‐known monomer for free radical polymerization, but its α‐methyl substituent restricts the chemical modification of the monomer and therefore the properties of the resulting polymer. The presence of a heteroatom in the methyl group is known to increase the polymerizability of MMA. Methyl α‐hydroxymethylacrylate (MHMA), methyl α‐methoxymethylacrylate (MC₁MA), methyl α‐acetoxymethylacrylate (MAcMA) show even better conversions to high‐molecular‐weight polymers than MMA. In contrast, the polymerization rate is known to decrease as the methyl group is replaced by ethyl in ethyl α‐hydroxymethylacrylate (EHMA) and t‐butyl in t‐butyl α‐hydroxymethylacrylate (TBHMA). In this study, quantum mechanical tools (B3LYP/6‐31G*) have been used in order to understand the mechanistic behavior of the free radical polymerization reactions of acrylates. The polymerization rates of MMA, MHMA, MC₁MA, MAcMA, EHMA, TBHMA, MC₁AN (α‐methoxymethyl acrylonitrile), and MC₁AA (α‐methoxymethyl acrylic acid) have been evaluated and rationalized. Simple monomers such as allyl alcohol (AA) and allyl chloride (AC) have also been modeled for comparative purposes. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Characterization of bidentate phosphoryl compounds on soil particulates using SIMS

The presence of organic compounds as surface contaminants on particles can provide valuable data about the particles environment, but identification can be analytically challenging. This is true particularly for compounds that have the potential for strong surface binding, such as compounds capable of multidentate attachment. Direct analysis using time‐of‐flight secondary ion mass spectrometry was evaluated for characterization of soil particles contaminated with low concentrations of two bidentate organophosphoryl compounds, diphenyl‐N,N‐di‐n‐butylcarbamoylmethylphosphine oxide and tetraphenylmethylene diphosphine dioxide. Molecular ions were formed by cationization with H⁺ and alkali elements Na⁺ and K⁺ that are indigenous to the particle surface chemistry. Spectra generated from a contaminated calcareous soil were dominated by K⁺‐containing ions, whereas spectra from a sandy loam had more abundant Na⁺‐species. Cation‐bound dimers were also formed which favored incorporation of K⁺, and a unique aluminosilicate‐phosphoryl conjugate cation was also formed when the diphosphoryl ligand was present on the surface. The phosphoryl ligands also underwent fragmentation reactions, the course of which varied depending on the cation that was bound. Minimum detectable surface concentrations were evaluated and were in the 0.04–0.2 monolayer range, depending on the compound and soil particle matrix they was bound to. The ion signature was detected on soil particle surfaces for time periods exceeding six months, suggesting that the characterization approach could be used for environmental exposure history at times well beyond initial exposure. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of deposition conditions on YBa2Cu3O7−δ thin films by inverted cylindrical magnetron sputtering and substrate effects

The dependence of YBCO thin film properties on the deposition conditions was studied for different substrates. The deposition conditions were optimized for the epitaxial growth of high quality YBCO thin films of 1500 Å thickness onto single crystal (100-oriented) SrTiO₃ (STO), MgO and LaAlO₃ (LAO) substrates by DC Inverted Cylindrical Magnetron Sputtering (ICMS). The samples were investigated in detail by means of X-ray diffraction analysis (XRD), EDX, AFM, ρ-T, magnetic susceptibility and current-voltage (I-V) characterizations. The samples show strong diamagnetic behavior and sharp transition temperatures of 89-91 K with ΔT<0.5 K. XRD of the samples exhibited highly c-axis orientation. The full width at half maximum (FWHM) values of the rocking curves were ranging typically from 0.22 to 0.28°. The samples have smooth surfaces as shown from AFM micrographs. The surface roughness, R_a, changed between 5-7 nm. I-V characteristics were obtained from the 20 μm-wide microbridges, which were patterned by a laser writing technique. The critical current densities (J_c, 1.06×10⁶ for LAO-based YBCO, 1.39×10⁶ for MgO-based YBCO, 1.67×10⁶ A/cm² for STO based YBCO) of the microbridges were evaluated from I-V curves at 77 K.