Characterization of the Mixing Layer Resulting from the Detonation of Heterogeneous Explosive Charges

A dense, two-phase numerical methodology is used to study the mixing layer developing behind the detonation of a heterogeneous explosive charge, i.e., a charge comprising of a high explosive with metal particles. The filtered Navier–Stokes equations are solved in addition to a sub-grid kinetic energy equation, along with a recently developed Eulerian–Lagrangian formulation to handle dense flow-fields. The mixing layer resulting from the post-detonation phase of the explosion of a nitromethane charge consisting of inert steel particles is of interest in this study. Significant mixing and turbulence effects are observed in the mixing layer, and the rms of the radial velocity component is found to be about 25% higher than that of the azimuthal and zenith velocity components due to the flow being primarily radial. The mean concentration profiles are self-similar in shape at different times, based on a scaling procedure used in the past for a homogeneous explosive charge. The peak rms of concentration profiles are 23–30% in intensity and decrease in magnitude with time. The behavior of concentration gradients in the mixing layer is investigated, and stretching along the radial direction is observed to decrease the concentration gradients along the azimuth and zenith directions faster than the radial direction. The mixing and turbulence effects in the mixing layer subsequent to the detonation of the heterogeneous explosive charge are superior to that of a homogeneous explosive charge containing the same amount of the high explosive, exemplifying the role played by the particles in perturbing the flow-field. The non-linear growth of the mixing layer width starts early for the heterogeneous explosive charge, and the rate is reduced during the implosion phase in comparison with the homogeneous charge. The turbulence intensities in the mixing layer for the heterogeneous explosive charge are found to be nearly independent of the particle size for two different sizes considered in the initial charge. Overall, this study has provided some useful insights on the mixing layer characteristics subsequent to the detonation of heterogeneous explosives, and has also demonstrated the efficacy of the dense, multiphase formulation for such applications.     

Surface-Mediated Synthesis of O-Alkyl 2-Methoxyethyl Alkylphosphonates Under Solvent Free Conditions: Potential Marker of Nerve Agents

This article describes rapid and efficient surface mediated synthesis of O-alkyl 2-methoxyethyl alkylphosphonates from alkylphosphonic acids and alcohols using dicyclohexyl carbodiimide (DCC)-Celite as a solid support. These compounds are markers of nerve agents. 2-Methoxyethyl methylphosphonic acids (2a–d) were reacted with various alcohols to yield O-alkyl 2-methoxyethyl alkylphosphonates (AMEAPs, 3a–m). This synthetic method has advantages over other methods in terms of selectivity, shorter reaction time, high yield, and easy work-up.     

Short New Route to the Chiral Spiro‐Tetrahydrofuran Subunit Common to Some Terpenoids

Synthetic strategy based on a stereoselective iodoetherification reaction of a carvone‐derived hydroxyalkene unit has been developed for the asymmetric synthesis of the key spiro‐tetrahydrofuran subunit common to some naturally occurring terpenoids.     

Highly efficient dialkylphosphate-mediated syntheses of hydantoins and a bicyclohydantoin under solvent-free conditions

Diversely substituted hydantoins have been synthesized by new strategy from cyanamide based precursor, that is, methyl N-cyano-N-alkyl/arylaminoacetate. Dialkylphosphates were employed as the mild reagent to hydrolyze and cyclize the substrate in one step to give quantitative yields of the desired products. Syntheses of multivalent hydantoins viz bis-hydantoin, bicyclohydantoin have potentially widened the scope and applicability of the present method. Solvent-free conditions and very easy work-up procedure make the reaction convenient and eco-friendly. Single crystal structures of some of the representative compounds are also reported.     

Multiresidue pesticide analysis in ginseng and spinach by nontargeted and targeted screening procedures

Five different mass spectrometers interfaced to GC or LC were evaluated for their application to targeted and nontargeted screening of pesticides in two foods, spinach and ginseng. The five MS systems were capillary GC/MS/MS, GC-high resolution time-of-flight (GC/HR-TOF)-MS, TOF-MS interfaced with a comprehensive multidimensional GC (GCxGC/TOF-MS), an MS/MS ion trap hybrid mass (qTrap) system interfaced with an ultra-performance liquid chromatograph (UPLC-qTrap), and UPLC interfaced to an orbital trap high resolution mass spectrometer (UPLC/Orbitrap HR-MS). Each MS system was tested with spinach and ginseng extracts prepared through a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure. Each matrix was fortified at 10 and 50 ng/g for spinach or 25 and 100 ng/g for ginseng with subsets of 486 pesticides, isomers, and metabolites representing most pesticide classes. HR-TOF-MS was effective in a targeted search for characteristic accurate mass ions and identified 97% of 170 pesticides in ginseng at 25 ng/g. A targeted screen of either ginseng or spinach found 94-95% of pesticides fortified for analysis at 10 ng/g with GC/MS/MS or LC/MS/MS using multiple reaction monitoring (MRM) procedures. Orbitrap-MS successfully found 89% of 177 fortified pesticides in spinach at 25 ng/g using a targeted search of accurate mass pseudomolecular ions in the positive electrospray ionization mode. A comprehensive GCxGC/TOF-MS system provided separation and identification of 342 pesticides and metabolites in a single 32 min acquisition with standards. Only 67 or 81% of the pesticides were identified in ginseng and spinach matrixes at 25 ng/g or 10 ng/g, respectively. MS/MS or qTrap-MS operated in the MRM mode produced the lowest false-negative rates, at 10 ng/g. Improvements to instrumentation, methods, and software are needed for efficient use of nontargeted screens in parallel with triple quadrupole MS.     

Multiresidue analysis of plant growth regulators in grapes by triple quadrupole and quadrupole-time of flight-based liquid chromatography/mass spectrometry

A selective and sensitive LC-MS/MS method is presented for simultaneous determination of 12 plant growth regulators, viz., indol-3-acetic acid, indol-3-butyric acid, kinetin, zeatin, 6-benzyl aminopurine, gibberellic acid, abscisic acid, chlormequat chloride, forchlorfenuron, paclobutrazole, daminozide, and 2,4-dichlorophenoxy acetic acid, in bud sprouts and grape berries. The sample preparation method involved extraction of homogenized sample (5 g) with 40 mL methanol (80%), and final determination was by LC-MS/MS in the multiple reaction monitoring (MRM) mode with time segmentation for quantification supported by complementary analysis by quadrupole-time of flight (Q-TOF) MS with targeted high-resolution MS/MS scanning for confirmatory identification based on accurate mass measurements. The recovery of the test compounds ranged within 90-107% with precision RSD less than 5% (n = 6). The method could be successfully applied in analyzing incurred residue samples, and the strength of accurate mass analysis could be utilized in identifying the compounds in cases where the qualifier MRM ions were absent or at an S/N less than 3:1 due to low concentrations.     

Traceless synthesis of diketopiperazine fused tetrahydro-β-carbolines on soluble polymer support

Abstract  

The Pictet–Spengler reaction, using polyethylene glycol immobilized tryptophan ester with a variety of ketones, was achieved by refluxing condition in acidic chloroform. The linear as well as cyclic ketones were employed. All the ketones were reacted within 6–8 h to furnish soluble polymer-supported tetrahydro-β-carboline in good yields. Further expansion at N-terminus of tetrahydro-β-carbolines was achieved through a reaction with chloroacetyl chloride. Finally, the 2,5-diketopiperazine skeleton was constructed over a β-carboline by amination of the resulting N-chloroacetamides and subsequent intramolecular cyclization leading to cleavage of the polymer; constitutes a traceless synthesis of tetracyclic molecular architecture. Significantly, this strategy affords a straightforward and efficient approach for the construction of biological promising molecules with high purity and good yields.     

Simple analytical model of a thermal diode

Recently there is a lot of attention given to manipulation of heat by constructing thermal devices such as thermal diodes, transistors and logic gates. Many of the models proposed have an asymmetry which leads to the desired effect. Presence of non-linear interactions among the particles is also essential. But, such models lack analytical understanding. Here we propose a simple, analytically solvable model of a thermal diode. Our model consists of classical spins in contact with multiple heat baths and constant external magnetic fields. Interestingly the magnetic field is the only parameter required to get the effect of heat rectification.     

Synergic effect of Type II ZnO/BiVO4 magnetic heterostructures for visible light-driven degradation of bisphenol A and methyl violet

Construction of an effective heterojunction for unimpeded flow of photogenerated charges and their prolonged separation is imperative for environmental photocatalysis. Herein, we have designed an efficient magnetic ZnO/BiVO₄ type-II heterostructure, which was employed for proficient degradation of persistent methyl violet dye with an efficiency of 97.6% in 90 min and a hazardous organic pollutant, namely, bisphenol A. UV-DRS and photoluminescence studies demonstrated that the fabricated nanocomposite exhibited effective light absorption and prolonged charge separation, thereby resulting in high photocatalytic efficacy under visible light irradiation. The efficacy of developed magnetic ZnO/BiVO₄ was also compared with pristine BiVO₄ and undoped magnetic ZnO, which indicated that the constructed heterostructure displayed approximately threefold and sixfold activity in contrast with bare BiVO₄ and undoped magnetic ZnO nanoparticles, respectively. Radical trapping studies, ESR analysis along with GC-MS analysis were conducted to elucidate the mechanistic pathway during the photodegradation process. This work provides a rational technical approach and research ideas for photocatalytic degradation of harmful organic pollutants in an environment-friendly manner by employing energy-efficient LEDs. Besides, good recyclability of catalyst makes it a promising candidate for large-scale applications.