Efficient monooleoyl glycerol synthesis employing hybrid ultrasonic-infrared-wave promoted reactor: Concurrent catalytic and noncatalytic esterification kinetics

For the first time, intensification of monooleoyl glycerol (MOG) synthesis has been investigated in an ultrasonic-infrared-wave (USIRW) promoted batch reactor. Esterification of octadecanoic acid (ODA) with glycerol (Gl) has been conducted [using Amberlyst 36 wet catalyst] in three different reactors, namely traditional batch reactor (TBR), infrared wave promoted batch reactor (IRWPBR), and USIRW-promoted batch reactor (USIRWPBR) to assess the relative efficacy. The energy-efficient USIRWPBR remarkably intensifies the ODA-Gl esterification as manifested through superior ODA conversion (92.5 ± 1.25%) compared to that achieved in IRWPBR (79.8 ± 1.2%) and TBR (36.39 ± 1.25%). The most favorable reaction condition for optimum ODA conversion and maximum MOG yield was identified through statistical optimization over a selected parametric range, namely 3-5 Gl/ODA mole ratio, 0.004-0.006 g/mL Amberlyst 36 catalyst concentration, 300-700 rpm impeller speed, and 333-353 K reaction temperature. The present study also reports the formulation and validation of an innovative reaction kinetics, that is, concurrent noncatalytic and heterogeneously catalyzed (CNCHC) reaction mechanism in addition to the conventional heterogeneous kinetic models (LH and Eley-Rideal mechanisms). Under combined USIRW, the CNCHC esterification mechanism could best describe ODA-Gl esterification (R² = 0.98) compared to LH (R² = 0.97) and Eley-Rideal (R² = 0.88) mechanisms. The optimal product (MOG) was characterized by differential scanning calorimetry and thermogravimetric analysis to assess its crystallization property and thermal stability for possible application as plasticizer/fuel additives.     

Synthesis of gemini surfactants with twelve symmetric fluorine atoms and one singlet F MR signal as novel F MRI agents

A family of fluorinated gemini surfactants derived from perfluoropinacol has been synthesized as novel ¹⁹F magnetic resonance imaging (¹⁹F MRI) agents. These fluorinated surfactants with 12 symmetric fluorine atoms and one singlet ¹⁹F MR peak can be conveniently prepared from perfluoropinacol and oligo(ethylene glycols) on multi-gram scales. Solubility, hydrophilicity (log P), and critical micelle concentration (CMC) measurements of these fluorinated surfactants indicated that high aqueous solubility can be achieved by introducing oligo(ethylene glycols) with appropriate length into perfluoropinacol, i.e., manipulating the fluorine content (F%). One of these fluorinated surfactants with high aqueous solubility and excellent ¹⁹F MR properties has been identified by ¹⁹F MRI phantom experiments as a promising ¹⁹F MRI agent.     

Effect of soil properties on radioactivity concentrations and dose assessment

This study evaluated the correlation between radioactivity concentrations and soil properties, and determined the total annual effective dose near an underground geologic repository for transuranic wastes. Soil samples were collected from two historical monitoring areas (Near Field and Cactus Flats). Alpha-particle spectrometry was used for the analysis of ²⁴¹Am, ^239+240Pu and ²³⁸U, while ¹³⁷Cs, ⁴⁰K, ²³²Th and ²²⁶Ra were detected by gamma ray spectrometry. Higher radioactivity concentrations and stronger positive correlations between radioactivity concentrations and soil properties were obtained in Cactus Flats compared to Near Field. The total annual effective dose was lower than the recommended limit of 1 mSv y^??1.

     

Rules of Boron–Nitrogen Doping in Defect Graphene Sheets: A First‐Principles Investigation of Band‐Gap Tuning and Oxygen Reduction Reaction Catalysis Capabilities

Introduction of defects and nitrogen doping are two of the most pursued methods to tailor the properties of graphene for better suitability to applications such as catalysis and energy conversion. Doping nitrogen atoms at defect sites of graphene and codoping them along with boron atoms can further increase the efficiency of such systems due to better stability of nitrogen at defect sites and stabilization provided by B?N bonding. Systematic exploration of the possible doping/codoping configurations reflecting defect regions of graphene presents a prevalent doping site for nitrogen‐rich BN clusters and they are also highly suitable for modulating (0.2–0.9 eV) the band gap of defect graphene. Such codoped systems perform significantly better than the platinum surface, undoped defect graphene, and the single nitrogen or boron atom doped defect graphene system for dioxygen adsorption. Significant stretching of the O?O bond indicates a lowering of the bond breakage barrier, which is advantageous for applications in the oxygen reduction reaction.     

Bandgap widening in highly conducting CdO thin film by Ti incorporation through radio frequency magnetron sputtering technique

Transparent and highly conducting thin films of cadmium oxide (CdO) with titanium doping were synthesized by using radio frequency magnetron sputtering technique. The thin films were deposited on glass and silicon substrates with different percentages of titanium at a fixed substrate temperature 473 K and a fixed pressure of 0.1 mbar in Ar atmosphere. The deposited films were characterized by studying their crystallographic structure, optical and electrical properties. X-ray diffractometer, atomic force microscope, UV–Vis–NIR spectrophotometer, and X-ray photoelectron spectrophotometer were used for different characterizations. All the films have a rock-salt structure. A systematic increase in the optical bandgap was found for the CdO thin films with Ti doping, so that it can be considered as a candidate material for different optoelectronic device applications. Electrical conductivity was also found to increase with Ti doping concentration.     

Mössbauer effect studies on thermal decomposition of iron(III) hydroxy- and amino-benzoates

The thermal decomposition of iron(III) aminobenzoates (o-, m-, p-) and iron(III) hydroxybenzoates (p-, m-, p-) have been investigated from ambient temperature to 873 K in air using derivatography DTG-DTA-TG, Mössbauer, IR spectroscopy and XRD. The importance of Mössbauer spectra recorded at various stages of heating, without separating the product mixture, in studying the mode of decomposition is highlighted. The intermediates (e.g., Fe(II)-species) were confirmed. The nature of water of hydration and the order of stability (p->m->o-) have been investigated from decomposition temperatures. The kinetic model and parameters have been investigated for dehydration.P.U. and G.K.B. thank to Guru Nanak Dev. University, Amritsar for financial assistance.     

Optical and electrical properties of p-type transparent conducting CuAlO2 thin film synthesized by reactive radio frequency magnetron sputtering technique

Thin films of p-type transparent conducting CuAlO₂ have been synthesized through reactive radio frequency magnetron sputtering on silicon and glass substrates at substrate temperature 300°C. Reactive sputtering of a target fabricated from Cu and Al powder (1:1.5) was performed in Ar+O₂ atmosphere. The deposition parameters were optimized to obtain phase pure, good quality CuAlO₂ thin films. The films were characterized by studying their structural, morphological, optical and electrical properties.     

Effect of monovalent ion binding on molecular dynamics of the S100-family calcium-binding protein calbindin D9k

Calbindin D_9k is a member of the S100 subfamily of EF-hand calcium binding proteins, and has served as an important model system for biophysical studies. The fast timescale dynamics of the calcium-free (apo) state is characterized using molecular dynamics simulations. Order parameters for the backbone NH bond vectors are determined from the simulations and compared with experimentally derived values, with a focus on the dynamics of calcium-binding site I. There is a significant discrepancy between simulated and experimental order parameters for site I residues in the case of no ion bound in site I. However, it was found in the simulations that a Na⁺ ion can bind in site I, and the resulting order parameters determined from the simulations are in excellent agreement with experiment. Comparisons are made to X-ray structures of other S100 family members in which Na⁺ ions were observed or suggested to be bound in site I. © 2019 Wiley Periodicals, Inc.     

Photoluminescence, cathodoluminescence, and reflectance study of AlN layers and AlN single crystals

Strained AlN layers grown by MOVPE on sapphire and nominally unstrained AlN single crystals were studied employing photoluminescence, cathodoluminescence, and reflectance spectroscopy in the near-band edge range. The data allow one to determine fundamental optical parameters such as the band edge energy with its crystal field splitting and strain dependence which are still under discussion. Reflection measurements performed on crystal facets with different orientations and subjected to varying selection rules serve to assign the observed transitions to valence band states with specific symmetries.Near-band edge excitonic luminescence at around 6 eV was recorded as a function of temperature (). Fits to the data using standard models from the literature yield the temperature dependence E_g(T) of the band gap.     

Triangular CdS nanostructure: effect of Mn doping on photoluminescence,electron spin resonance,and magneto-optical properties

In this paper, we report synthesis and study of magneto-optic Faraday effect for dilute magnetic semiconductor nanostructure. The colloidal CdS nanocrystals were prepared via hot injection method and successfully doped with Mn²⁺ cations. The synthesized nanoparticles were characterized by using UV–Vis spectroscopy, X-ray diffraction, photoluminescence spectroscopy, transmission electron microscopy, and electron spin resonance spectroscopy. Systematic studies on effect of Mn²⁺ doping on photoluminescence, electron spin resonance, and magneto-optical properties are carried out. UV–Vis spectral analysis confirms blue shift in bandgap of CdS nanoparticles due to quantum confinement effect. The X-ray diffraction study confirms hexagonal wurtzite phase formation of CdS nanoparticles without any impurity phases. TEM analysis confirms uniform particle size, having particle size distribution around 5 nm. As-synthesized undoped CdS shows triangular-shaped nanocrystals with hexagonal structure; however, triangular shape of CdS nanoparticles is not conserved after Mn²⁺ doping. The photoluminescence characteristic spectra of Mn²⁺-doped CdS nanocrystals showed emission band at 660 nm and its intensity was found to increase with increasing Mn²⁺ concentration. Electron spin resonance signal, with six-line hyperfine structure splitting, confirmed doping of Mn²⁺ ions in CdS lattice. Magneto-optic measurements showed linear variation of Faraday rotation with respect to applied magnetic field, indicating paramagnetic behavior of Mn-doped CdS. The highest Verdet constant 24.81 deg/T cm was observed for 2% Mn-doped CdS nanocrystals, which further decreases with increasing Mn²⁺ concentration.

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Graphical abstract Illustration of Magneto-optic Faraday effect using dilute magnetic semiconductors (TEM image of triangular CdS nanoparticles)