$(p,q)$-Analogue of Mittag-Leffler Function with $(p,q)$-Laplace Transform

The aim of this paper is to define $(p, q)$-analogue of Mittag-Leffler Function, by using $(p, q)$-Gamma function. Some transformation formulae are also derived by using the $(p, q)$-derivative. The $(p, q)$-analogue for this function provides elegant generalization of $q$-analogue of Mittag-Leffler function in connection with $q$-calculus. Moreover, the $(p, q)$-Laplace Transform of the Mittag-Leffler function has been obtained. Some special cases have also been discussed.     

Simultaneous quantification of (E) and (Z) isomers of rilpivirine and four degradation products in bulk and tablets by reversed-phase ultra-high-performance liquid chromatography and confirmation of all by molecular weight

The (E)-isomer of rilpivirine is an approved antiretroviral drug used to treat human immunodeficiency virus. A simple, fast, accurate, and precise analytical method is required to confirm the quality, purity, efficacy, and safety of drug substances and drug products containing rilpivirine. This research article offers a comprehensive ultra-high performance liquid chromatography method for the simultaneous separation and quantification of (E) and (Z) isomers of rilpivirine, including two amide impurities, one nitrile impurity, and one dimer impurity, in both bulk and tablet forms. After complete validation, the proposed reversed-phase ultra-high-performance liquid chromatography method has proven to be simple, fast, linear, accurate, and precise, with a lower limit of quantification and detection of 0.05 and 0.03 μg/ml, respectively, for all six analytes. Separation was achieved on a Waters Acquity ethylene bridged hybrid Shield RP18 (150 × 2.1 mm, 1.7 μm) column maintained at 35.0°C using a gradient elution of acetonitrile and 0.05% formic acid in 10 mM ammonium formate at a flow rate of 0.30 ml/min. A systematic forced degradation study on the undissolved rilpivirine revealed the formation of acid-base hydrolyzed amide impurities (Impurity-A and Impurity-B), oxidative nitrile impurities (Impurity-C), and Z-isomer and dimer impurities of rilpivirine (Impurity-D and Impurity-E) due to alkaline hydrolysis and photodegradation. The proposed method is primarily appropriate for applications requiring the precise determination of desired and undesired isomers of rilpivirine and its degradation products, such as those involving the safety, efficacy, and quality roles of rilpivirine in bulk and tablet forms. Additionally, the proposed ultra-high-performance liquid chromatography method in combination with a mass spectrometer and photo-diode array detector is helpful for the confirmation and correct identification of all analytes.     

Modified-Hydroxyapatite-Chitosan Hybrid Composite Interfacial Coating on 3D Polymeric Scaffolds for Bone Tissue Engineering

Three dimensional (3D) scaffolds have huge limitations due to their low porosity, mechanical strength, and lack of direct cell-bioactive drug contact. Whereas bisphosphonate drug has the ability to stimulate osteogenesis in osteoblasts and bone marrow mesenchymal stem cells (hMSC) which attracted its therapeutic use. However it is hard administration low bioavailability, and lack of site-specificity, limiting its usage. The proposed scaffold architecture allows cells to access the bioactive surface at their apex by interacting at the scaffold's interfacial layer. The interface of 3D polycaprolactone (PCL) scaffolds has been coated with alendronate-modified hydroxyapatite (MALD) enclosed in a chitosan matrix, to mimic the native environment and stupulate the through interaction of cells to bioactive layer. Where the mechanical strength will be provided by the skeleton of PCL. In the MALD composite's hydroxyapatite (HAP) component will govern alendronate (ALD) release behavior, and HAP presence will drive the increase in local calcium ion concentration increases hMSC proliferation and differentiation. In results, MALD show release of 86.28 ± 0.22. XPS and SEM investigation of the scaffold structure, shows inspiring particle deposition with chitosan over the interface. All scaffolds enhanced cell adhesion, proliferation, and osteocyte differentiation for over a week without in vitro cell toxicity with 3.03 ± 0.2 kPa mechanical strength.     

A palladium catalyzed atom-efficient cross-coupling reactivity of triarylbismuths with α,β-unsaturated acyl chlorides

An atom-efficient cross-coupling reactivity of triarylbismuths (1 equiv) was demonstrated by cross-coupling reaction with 3 equiv of α,β-unsaturated acyl chlorides under palladium catalysis in the synthesis of a series of functionalized α, β-unsaturated ketones in high isolated yields.     

RhCl3-assisted C-H and C-S bond scissions: isomeric self-association of organorhodium(iii) thiolato complex. synthesis, structure, and electrochemistry

The ligating properties of alkyl 2-(phenylazo)phenyl thioether 1 (HL(R); R = Me, CH(2)Ph) toward Rh(III) have been examined. A novel hexacoordinated orthometalated rhodium(III) thiolato complex trans-[Rh(L)Cl(PPh3)2] 5 has been synthesized from 1 and RhCl(3).3H(2)O in the presence of excess PPh(3) via in situ C(sp(2))-H and C(sp(3))-S bond scissions, which is the first example for a coordination compound of [L](2-). We were also able to isolate the intermediate organothioether rhodium(III) compound trans-[Rh(L(R))Cl(2)(PPh(3))] 6 with 1 equiv of PPh(3) relative to both 1 and RhCl(3).3H2O in the course of the synthesis of the S-dealkylated product. PPh(3) plays a crucial role in the C(sp(3))-S cleavage process. A plausible mechanistic pathway is presented for C-S bond cleavage, and reductive cleavage by single-electron transfer mechanism is likely to be operative. The electronically and coordinatively saturated thiolato complex 5, indefinitely stable in the solid state, undergoes spontaneous self-dimerization in solution via dissociation of one coordinated PPh3 molecule to afford edge-shared bioctahedral anti-[Rh(L)Cl(PPh(3))]2 7 and syn-[Rh(L)Cl(PPh(3))]2 8 isomers. All the synthesized organosulfur rhodium(III) compounds were isolated as both air- and moisture-stable solids and spectroscopically characterized in both solution and solid states. In addition, all the representative members have been authenticated by single-crystal X-ray structure analyses. Availability of the isomeric dimers provides an opportunity to recognize the presence of noncovalent intramolecular "metallochelate-metallochelate" interaction in the sterically encumbered syn isomer. Unlike other organosulfur rhodium complexes, the monomeric thiolato complex 5 exhibits a fully reversible oxidative wave at 0.82 V vs Ag/AgCl, which is supposed to be primarily centered on the thiolato sulfur atom, and such perception is consistent with the DFT study. Formation of rhodium-bound thiyl radical cation 5(*+) by electrochemical oxidation was scrutinized by EPR spectroscopy.     

Binuclear copper(II) complexes with N4O3 coordinating heptadentate ligand: synthesis, structure, magnetic properties, density-functional theory study, and catecholase activity

The N4O3 coordinating heptadentate ligand afforded binuclear complex [Cu 2(H 2L)(mu-OH)](ClO4)2 (1) and [Cu2(L)(H2O)2]PF6 (2). In complex 1, two copper ions are held together by mu-phenoxo and mu-hydroxo bridges, whereas in complex 2, the copper centers are connected only by a mu-phenoxo bridge. In 1, both the Cu(II) centers have square pyramidal geometry (tau=0.01-0.205), whereas in the case of 2, one Cu(II) center has square pyramidal (tau=0.2517) and other one has square based pyramidal distorted trigonal bipyramidal (tau=0.54) geometry. Complexes 1 and 2 show an strong intramolecular and very weak antiferromagnetic interaction, respectively. Density-functional theory calculations were performed to establish the magneto structural correlation between the two paramagnetic copper(II) centers. Both of the complexes display a couple of one-electron reductive responses near -0.80 and -1.10 V. The complexes show significant catalytic activity at pH 8.5 on the oxidation of 3,5-di- tert-butylcatechol (3,5-DTBC) to 3,5-di- tert-butylquinone (3,5-DTBQ), and the activity measured in terms of kcat=29-37 h(-1).     

Molecular dynamics simulations of carbon nanotube/silicon interfacial thermal conductance

Using molecular dynamics simulations with Tersoff reactive many-body potential for Si-Si, Si-C, and C-C interactions, we have calculated the thermal conductance at the interfaces between carbon nanotube (CNT) and silicon at different applied pressures. The interfaces are formed by axially compressing and indenting capped or uncapped CNTs against 2 x 1 reconstructed Si surfaces. The results show an increase in the interfacial thermal conductance with applied pressure for interfaces with both capped and uncapped CNTs. At low applied pressure, the thermal conductance at interface with uncapped CNTs is found to be much higher than that at interface with capped CNTs. Our results demonstrate that the contact area or the number of bonds formed between the CNT and Si substrate is key to the interfacial thermal conductance, which can be increased by either applying pressure or by opening the CNT caps that usually form in the synthesis process. The temperature and size dependences of interfacial thermal conductance are also simulated. These findings have important technological implications for the application of vertically aligned CNTs as thermal interface materials.     

2‐[(E)‐(4‐Hydroxy‐3‐methoxybenzylidene)amino]‐N‐(2‐methylphenyl)‐4,5,6,7‐tetrahydro‐1‐benzothiophene‐3‐carboxamide

The title compound, C₂₄H₂₄N₂O₃S, exhibits antifungal and antibacterial properties. The compound crystallizes with two molecules in the asymmetric unit, with one molecule exhibiting `orientational disorder' in the crystal structure with respect to the cyclohexene ring. The o‐toluidine groups in both molecules are noncoplanar with the respective cyclohexene‐fused thiophene ring. In both molecules, there is an intramolecular N—H...N hydrogen bond forming a pseudo‐six‐membered ring which locks the molecular conformation and eliminates conformational flexibility. The crystal structure is stabilized by O—H...O hydrogen bonds; both molecules in the asymmetric unit form independent chains, each such chain consisting of alternating `ordered' and `disordered' molecules in the crystal lattice.     

Analyses of the complex proton NMR spectra: determination of anisotropic proton chemical shifts of oriented molecules by a two dimensional experiment

NMR spectra of molecules oriented in the liquid crystalline media provide information on the molecular structure and order parameter. However, the numerical iterative analysis of the proton spectra of strongly coupled spins is difficult and time consuming. Such analysis is simplified if nearly accurate starting parameters are available. One such parameter is the chemical shift which in the oriented media is very different from the isotropic values due to anisotropic contributions. In this study, we have explored the possibility of obtaining chemical shifts in the oriented phase to aid the analysis of the spectra. A two dimensional experiment in which FSLG decoupling employed during the t1 period eliminates the homonuclear dipolar couplings and retains only the chemical shifts has been implemented. Experiments on the molecule cis,cis-mucononitrile demonstrate that the chemical shifts obtained by this procedure are nearly the same as the chemical shifts derived by iterative analysis of the one dimensional spectrum of the molecule following the standard procedure. The method has also been used to analyse the spectrum of 1-iodopropane using the chemical shifts obtained from the proposed experiment as the starting parameters.