Crystal Structure of Bis[hydrobis(3-phenylpyrazolyl)(5-phenylpyrazolyl)borato]-zinc(II)

Abstract  

The X-ray crystal structure of (C₅₄ H₄₂ B₂ N₁₂ Zn)*2(C H Cl₃) is reported. The title compound is a chloroform-solvated neutral complex crystallizing in the Triclinic space group, P − 1, with two half complexes (each located on a crystallographic center of inversion) and two full chloroform molecules appearing in the asymmetric unit. The capping ligands are related by symmetry and together form, essentially, an octahedral coordination sphere. Strain is apparent in the complex as indicated by asymmetric bond distances and angles. Final statistical data: R = 4.60% with I > 2σ(I), a = 11.2912(8) ?, b = 14.7912(11) ?, c = 17.0047(13) ?, α = 72.3560(10)°, β = 89.8950(10)°, γ = 88.1010(10)°, Z = 2.     

Building an Iron Chromophore Incorporating Prussian Blue Analogue for Photoelectrochemical Water Oxidation

The replacement of traditional ruthenium-based photosensitizers with low-cost and abundant iron analogs is a key step for the advancement of scalable and sustainable dye-sensitized water splitting cells. In this proof-of-concept study, a pyridinium ligand coordinated pentacyanoferrate(II) chromophore is used to construct a cyanide-based CoFe extended bulk framework, in which the iron photosensitizer units are connected to cobalt water oxidation catalytic sites through cyanide linkers. The iron-sensitized photoanode exhibits exceptional stability for at least 5 h at pH 7 and features its photosensitizing ability with an incident photon-to-current conversion capacity up to 500 nm with nanosecond scale excited state lifetime. Ultrafast transient absorption and computational studies reveal that iron and cobalt sites mutually support each other for charge separation via short bridging cyanide groups and for injection to the semiconductor in our proof-of-concept photoelectrochemical device. The reorganization of the excited states due to the mixing of electronic states of metal-based orbitals subsequently tailor the electron transfer cascade during the photoelectrochemical process. This breakthrough in chromophore-catalyst assemblies will spark interest in dye-sensitization with robust bulk systems for photoconversion applications.     

Oxidation of Dimethyl Sulfide in Air Using Electron-Beam Irradiation,and Enhancement of its Oxidation Via an MnO<Subscript>2</Subscript> Catalyst

The decomposition of dimethyl sulfide (DMS) at initial concentrations of 4.5–18.0 ppmv in air was studied under electron-beam (EB) irradiation. Doses to decompose 90% of input DMS were 2.5 kGy for 4.5 ppmv, 3.4 kGy for 10.6 ppmv, and 3.9 kGy for 18.0 ppmv. HCOOH, (CH₃)₂SO, and trace CH₃OH and (CH₃)₂SO₂ were produced as irradiation products in addition to CO₂ and CO. Application of an O₃ decomposition catalyst to an irradiated sample gas led to an enhancement in the oxidation of DMS and its products into CO₂ and the decomposition of O₃. For 10.6 ppmv DMS/air, the mineralization ratio increased from 41% via only EB irradiation to 100% via the combination treatment at 6.3 kGy. The yield of CO₂ to CO_x increased from 5.3 to 87.6% by combination with catalytic oxidation. This combination treatment enables the irradiation energy used to deodorize gas streams containing DMS to be reduced.     

Efficient shooting method for solving two point boundary value problems

We present an efficient shooting method for solving two point boundary value problems. The Adomian decomposition method will be utilized to obtain a series solution of the initial value problems involved. Numerical examples and comparison of the work of others will also be done.     

Generation of Coherent Extreme Ultraviolet Radiation in an Air Gas Cell with a High Power Femtosecond Laser System

Optics and Spectroscopy - High harmonic generation (HHG) in air medium is experimentally produced by using a state-of-the-art high power laser system. The harmonic orders up to 35th harmonic are...     

Effect of quantization and positron concentration on shielding potentials in electron-positron-ion plasma

The kinetic theory of plasma has been employed to compute the test-charge potential distributions accounting for quantization effects in magnetized electron-positron-ion (EPI) plasmas. In this regard, the degenerate positrons and electrons are assumed to follow the Fermi-Dirac distribution, while inertial ions are modelled by Maxwellian velocity distribution. By solving the Fourier-transformed Vlasov–Poisson equations, a modified dielectric function and electrostatic potential is obtained. By imposing various constraints on the test-charge speed, the potential profile has been analysed in terms of Debye–Hückel (DH), far-field (FF), and wake-field (WF) potentials. It has been found that the amplitude of DH and FF potentials increases by the inclusion of quantization effects, and it becomes the opposite for the WF potential profile. Furthermore, the variation of positron concentration significantly affects the DH, FF, and WF potentials. The present findings are important to understand the shielding phenomenon in degenerate multi-species plasmas.     

Effect of Li2CO3 on formation temperature of hBN by modified O'Connor model

This study is interested in the effect of lithium carbonate on the formation of hexagonal boron nitride (hBN) by means of the available experimental methods including TGA, XRD, FTIR, SEM and HR‐TEM. hBN samples were synthesized at the 1450 °C with different molar ratios of lithium carbonate by modified O'Connor routine. The crystalline hBN formation tended to improve with the increment of the Li₂CO₃ concentration level (especially after more 20 %). The dopant quantity decreased the residual stresses due to the presence of possible relaxation mechanisms along with the nanocrystal structure, even favored by XRD experimental findings regarding the enhancement of crystal plane alignments, crystallite sizes and lattice parameters. As for the FTIR surveys, the Li₂CO₃ foreign impurities strengthened more and more the covalent bonds between boron and nitrogen atoms. At the same time, the samples with 40 % lithium carbonate were annealed at the varied temperatures of 1000, 1150, 1300 and 1450 °C to determine the optimum annealing temperature. The XRD+FTIR investigations indicated that the degree of hexagonality improved with the increased annealing temperature. Similarly, the surface morphology confirmed not only the formation of regularity and flaky hexagonal BN structures, but also the strengthening of covalent bonds between the atoms.     

Thio acid-mediated conversion of azides to amides – Exploratory studies en route to oroidin alkaloids

The utility of the thio acid-azide coupling reaction to afford amides is explored in imidazole-containing substrates for application in the total synthesis of examples of oroidin alkaloids. Good yields of the expected amides are obtained in both monomeric and dimeric substrates. Bis azides react preferentially at the 2-azido position but hydrosulfenylation and reduction interfere. 2-Thiophenyl and 2-oxo groups were evaluated as 2-amino surrogates, the thioether delivered the expected amide, whereas 2-imidazolone gave a mixture of the expected amide and the hydrosulfenylation product.     

Asymmetric total synthesis of ent-cyclooroidin

An enantiospecific total synthesis of the pyrrole-imidazole natural product cyclooroidin from histidine is described. The key N1-C9 bond is constructed through an intramolecular SN2-type of reaction of a chloro ester. Subsequent imidazole azidation at the 2-position, pyrrole bromination, azide reduction, and deprotection leads to the completion of the synthesis.     

Multifunctional core–shell nanoparticles: superparamagnetic,mesoporous, and thermosensitive

Multifunctional core–shell composite nanoparticles (NPs) have been developed by the combination of three functionalities into one entity, which is composed of a single Fe₃O₄ NP as the magnetic core, mesoporous silica (mSiO₂) with cavities as the sandwiched layer, and thermosensitive poly(N-isopropylacrylamide-co-acrylamide) (P(NIPAAm-co-AAm)) copolymer as the outer shell. The mSiO₂-coated Fe₃O₄ NPs (Fe₃O₄@mSiO₂) are monodisperse and the particle sizes were varied from 25 to 95 nm by precisely controlling the thickness of mSiO₂-coating layer. The P(NIPAAm-co-AAm) were then grown onto surface-initiator-modified Fe₃O₄@mSiO₂ NPs through free radical polymerization. These core–shell composite NPs (designated as Fe₃O₄@mSiO₂@P(NIPAAm-co-AAm)) were found to be superparamagnetic with high r ₂ relaxivity. To manipulate the phase transition behavior of these thermosensitive polymer-coated NPs for future in vivo applications, the characteristic lower critical solution temperature (LCST) was subtly tuned by adjusting the composition of the monomers to be around the human body temperature (i.e. 37 °C), from ca. 34 to ca. 42 °C. The thermal response of the core–shell composite NPs to the external magnetic field was also demonstrated. Owing to their multiple functionality characteristics, these porous superparamagnetic and thermosensitive NPs may prove valuable for simultaneous magnetic resonance imaging (MRI), temperature-controlled drug release, and temperature-programed magnetic targeting and separation applications.