Metal–Sulfur Linkages Achieved by Organic Tethering of Ruthenium Nanocrystals for Enhanced Electrochemical Nitrogen Reduction

Inspired by the metal–sulfur (M-S) linkages in the nitrogenase enzyme, here we show a surface modification strategy to modulate the electronic structure and improve the N₂ availability on a catalytic surface, which suppresses the hydrogen evolution reaction (HER) and improves the rate of NH₃ production. Ruthenium nanocrystals anchored on reduced graphene oxide (Ru/rGO) are modified with different aliphatic thiols to achieve M-S linkages. A high faradaic efficiency (11 %) with an improved NH₃ yield (50 μg h⁻¹ mg⁻¹) is achieved at −0.1 V vs. RHE in acidic conditions by using dodecanethiol. DFT calculations reveal intermediate N₂ adsorption and desorption of the product is achieved by electronic structure modification along with the suppression of the HER by surface modification. The modified catalyst shows excellent stability and recyclability for NH₃ production, as confirmed by rigorous control experiments including ¹⁵N isotope labeling experiments.     

Accretion of Phantom Energy and Generalized Second Law of Thermodynamics for Einstein-Maxwell-Gauss-Bonnet Black Hole

We have investigated the accretion of phantom energy onto a 5-dimensional extreme Einstein-Maxwell-Gauss-Bonnet (EMGB) black hole. It is shown that the evolution of the EMGB black hole mass due to phantom energy accretion depends only on the pressure and density of the phantom energy and not on the black hole mass. Further we study the generalized second law of thermodynamics (GSL) at the event horizon and obtain a lower bound on the pressure of the phantom energy.     

Phase Transitions of Ruthenium-Doped Iron Oxide Studied by 57Fe Mössbauer Spectroscopy at Elevated Temperatures

Hyperfine Interactions - The 57Fe Mössbauer spectra recorded in situ from 5% ruthenium-doped maghemite show parameters typical for maghemite up to 600 K and a hyperfine field distribution...     

Enhancing dielectric and mechanical behaviors of hybrid polymer nanocomposites based on polystyrene,polyaniline and carbon nanotubes coated with polyaniline

The dielectric and mechanical properties of hybrid polymer nanocomposites of polystyrene/polyaniline/carbon nanotubes coated with polyaniline(PCNTs) have been investigated using impedance analyzer and extensometer. The blends of PS/PANI formed the heterogeneous phase separated morphology in which PCNTs are dispersed uniformly. The incorporation of a small amount of PCNTs into the blend of PS/PANI has remarkably increased the dielectric properties. Similarly, the AC conductivity of PS/PANI is also increased five orders of magnitude from 1.6 × 10~(-10) to 2.0 × 10~(-5) S·cm~(-1) in the hybrid nanocomposites. Such behavior of hybrid nanocomposites is owing to the interfacial polarization occurring due to the presence of multicomponent domains with varying conductivity character of the phases from insulative PS to poor conductor PANI to highly conductive CNTs. Meanwhile, the tensile modulus and tensile strength are also enhanced significantly up to 55% and 160%, respectively, without much loss of ductility for three phase hybrid nanocomposites as compared to the neat PS. Thereby, the hybrid nanocomposites of PS/PANI/_P CNTs become stiffer, stronger and tougher as compared to the neat systems.     

Effect of dark energy models on the energy content of charged and rotating black holes

The energy content of the charged-Kerr(CK)spacetime surrounded by dark energy(DE)is investigated using approximate Lie symmetry methods for the differential equations.For this,we consider three different DE scenarios:cosmological constant with an equation of state parameter$ω_q=-2/3,quintessence DE with an equation of state parameterω_c=-1,and a frustrated network of cosmic strings with an equation of state parameterω_n=-1/3.To study the gravitational energy of the CK black hole surrounded by the DE,we explore the symmetries of the 2nd-order perturbed geodesic equations.It is noticed,for all the values ofω,the exact symmetries are recovered as 2nd-order approximate trivial symmetries.These trivial approximate symmetries give the rescaling of arc length parameter s in this spacetime which indicates that the energy in the underlying spacetime has to be rescaled by a factor that depends on the black hole parameters and the DE parameter.This rescaling factor is compared with the factor of the CK spacetime found in[Hussain et al.Gen.Relativ.Gravit.(2009)]and the effects of the DE on it are discussed.It is observed that for all the three values of the equation of state parameterω,the effect of DE results in decreased energy content of the black hole spacetime,regardless of values of the charge Q,spin a and the DE parameterα.This reduction in the energy content due to the involvement of the DE favours the idea of mass reduction of black holes by accretion of DE given by[Babichev et al.Phys.Rev.Lett.(2004)].     

Weak deflection angle and shadow cast by the charged-Kiselev black hole with cloud of strings in plasma

In this study, the gravitational deflection angle of photons in the weak field limit (or the weak deflection angle) and shadow cast by the electrically charged and spherically symmetric static Kiselev black hole (BH) in the string cloud background are investigated. The influences of the BH charge Q, quintessence parameter γ, and string cloud parameter a on the weak deflection angle are studied using the Gauss-Bonnet theorem, in addition to studying the influences on the radius of photon spheres and size of the BH shadow in the spacetime geometry of the charged-Kiselev BH in string clouds. Moreover, we study the effects of plasma (uniform and non-uniform) on the weak deflection angle and shadow cast by the charged-Kiselev BH surrounded by the clouds of strings. In the presence of a uniform/nonuniform plasma medium, an increase in the string cloud parameter a increases the deflection angle α. In contrast, a decrease in the BH charge Q decreases the deflection angle. Further, we observe that an increase in the BH charge Q causes a decrease in the size of the shadow of the BH. We notice that, with an increase in the values of the parameters γ and a, the size of the BH shadow increases, and therefore, the intensity of the gravitational field around the charged-Kiselev BH in string clouds increases. Thus, the gravitational field of the charged-Kiselev BH in the string cloud background is stronger than the field produced by the pure Reissner-Nordstrom BH. Moreover, we use the data released by the Event Horizon Telescope (EHT) collaboration, for the supermassive BHs M87* and Sgr A*, to obtain constraints on the values of the parameters γ and a.     

New N‐(Aryl)‐5‐((quinolin‐8‐yloxy)methyl)‐1,3,4‐oxa/Thiadiazol‐2‐amines and 4‐Aryl‐5‐((quinolin‐8‐yloxy)methyl)‐2H‐1,2,4‐triazole‐3(4H)‐thiones,Synthesis and Characterization

In this study, methyl 2‐(quinolin‐8‐yloxy) acetate ( 2 ) obtained by reaction of 8‐hydroxyquinoline ( 1 ) with methyl chloroacetate was condensed with hydrazine hydrate to afford the carbohydrazide ( 3 ). Thio/semicarbazide derivatives ( 4a , 4b , 4c , 4d , 4e , 4f , 4g ) were obtained by treatment of the 3 with substituted phenyl iso/thioisocyanates. The 4a , 4b , 4c , 4d , 4e , 4f , 4g on acidic and basic intramolecular cyclization led to N‐(aryl)‐5‐((quinolin‐8‐yloxy)methyl)‐1,3,4‐oxa/thiadiazol‐2‐amines ( 5a , 5b , 5c , 5d , 5e , 5f , 5g ) and 4‐aryl‐5‐((quinolin‐8‐yloxy)methyl)‐2H‐1,2,4‐triazole‐3(4H)‐thiones ( 6a , 6b , 6c , 6d , 6e , 6f , 6g ), respectively. All the synthesized compounds were characterized by spectroscopic techniques and elemental analyses. The thiosemicarbazide ( 4c ) was also confirmed by X‐ray crystallography.     

Synthesis of dibenzo[b,d]pyran-6-ones based on [3 + 3] cyclizations of 1,3-bis(silyl enol ethers) with 3-silyloxy-2-en-1-ones

Functionalized dibenzo[b,d]pyran-6-ones were prepared by formal [3 + 3] cyclization of 1,3-bis(silyl enol ethers) with 3-silyloxy-2-en-1-ones or 1,1-diacetylcyclopropane to give functionalized salicylates, Suzuki cross-coupling reactions of the corresponding triflates, and subsequent BBr3-mediated lactonization. A second approach to dibenzo[b,d]pyran-6-ones relies on the [3 + 3] cyclization of 1,3-bis(silyl enol ethers) with 1-(2-methoxyphenyl)-1-(trimethylsilyloxy)alk-1-en-3-ones and subsequent BBr3-mediated lactonization.     

Hybrid Quinoline-Thiosemicarbazone Therapeutics as a New Treatment Opportunity for Alzheimer’s Disease‒Synthesis,In Vitro Cholinesterase Inhibitory Potential and Computational Modeling Analysis

Alzheimer’s disease (AD) is a progressive neurodegenerative disorder and the leading cause of dementia worldwide. The limited pharmacological approaches based on cholinesterase inhibitors only provide symptomatic relief to AD patients. Moreover, the adverse side effects such as nausea, vomiting, loss of appetite, muscle cramps, and headaches associated with these drugs and numerous clinical trial failures present substantial limitations on the use of medications and call for a detailed insight of disease heterogeneity and development of preventive and multifactorial therapeutic strategies on urgent basis. In this context, we herein report a series of quinoline-thiosemicarbazone hybrid therapeutics as selective and potent inhibitors of cholinesterases. A facile multistep synthetic approach was utilized to generate target structures bearing multiple sites for chemical modifications and establishing drug-receptor interactions. The structures of all the synthesized compounds were fully established using readily available spectroscopic techniques (FTIR, ¹H- and ¹³C-NMR). In vitro inhibitory results revealed compound 5b as a promising and lead inhibitor with an IC₅₀ value of 0.12 ± 0.02 μM, a 5-fold higher potency than standard drug (galantamine; IC₅₀ = 0.62 ± 0.01 μM). The synergistic effect of electron-rich (methoxy) group and ethylmorpholine moiety in quinoline-thiosemicarbazone conjugates contributes significantly in improving the inhibition level. Molecular docking analysis revealed various vital interactions of potent compounds with amino acid residues and reinforced the in vitro results. Kinetics experiments revealed the competitive mode of inhibition while ADME properties favored the translation of identified inhibitors into safe and promising drug candidates for pre-clinical testing. Collectively, inhibitory activity data and results from key physicochemical properties merit further research to ensure the design and development of safe and high-quality drug candidates for Alzheimer’s disease.