Thermodynamic implications of the gravitationally induced particle creation scenario

A rigorous thermodynamic analysis has been done as regards the apparent horizon of a spatially flat Friedmann–Lemaitre–Robertson–Walker universe for the gravitationally induced particle creation scenario with constant specific entropy and an arbitrary particle creation rate \(\Gamma \). Assuming a perfect fluid equation of state \(p=(\gamma -1)\rho \) with \(\frac{2}{3} \le \gamma \le 2\), the first law, the generalized second law (GSL), and thermodynamic equilibrium have been studied, and an expression for the total entropy (i.e., horizon entropy plus fluid entropy) has been obtained which does not contain \(\Gamma \) explicitly. Moreover, a lower bound for the fluid temperature \(T_f\) has also been found which is given by \(T_f \ge 8\left( \frac{\frac{3\gamma }{2}-1}{\frac{2}{\gamma }-1}\right) H^2\). It has been shown that the GSL is satisfied for \(\frac{\Gamma }{3H} \le 1\). Further, when \(\Gamma \) is constant, thermodynamic equilibrium is always possible for \(\frac{1}{2}<\frac{\Gamma }{3H} < 1\), while for \(\frac{\Gamma }{3H} \le \text {min}\left\{ \frac{1}{2},\frac{2\gamma -2}{3\gamma -2} \right\} \) and \(\frac{\Gamma }{3H} \ge 1\), equilibrium can never be attained. Thermodynamic arguments also lead us to believe that during the radiation phase, \(\Gamma \le H\). When \(\Gamma \) is not a constant, thermodynamic equilibrium holds if \(\ddot{H} \ge \frac{27}{4}\gamma ^2 H^3 \left( 1-\frac{\Gamma }{3H}\right) ^2\), however, such a condition is by no means necessary for the attainment of equilibrium.     

Intramolecular Direct Dehydrohalide Coupling Promoted by KO(t)Bu: Total Synthesis of Amaryllidaceae Alkaloids Anhydrolycorinone and Oxoassoanine

A transition-metal-free intramolecular dehydrohalide coupling via intramolecular homolytic aromatic substitution (HAS) with aryl radicals has been developed in the presence of potassium tert-butoxide and an organic molecule as the catalyst. The methodology has been applied to a concise synthesis of Amaryllidaceae alkaloids viz. oxoassoanine (1b), anhydrolycorinone (1d), and other related structures. Interestingly, the method also works only in the presence of potassium tert-butoxide.     

Effect of Cr doping on the ac electrical properties of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles

Magnesium aluminate nanoparticles with different chromium concentration (0–12%) have been synthesized by a citrate–nitrate sol–gel route. X-ray diffraction studies confirmed the formation of single-phase cubic spinel structure excluding the presence of any secondary phase. Crystallite size of the synthesized nanoparticles was found to increase from 8.5 to 19.8 nm with the increase in Cr concentration. Fourier transformed infrared spectroscopic studies confirmed the presence of AlO₆ group which led to the formation of MgAl₂O₄ spinel structure. Surface morphology of the sintered pellets was investigated with the help of a field emission scanning electron microscope which revealed the existence of both grain and grain boundary along with their aggregates. The dielectric constant, dielectric loss and ac conductivity were studied as a function of frequency of the applied electric field for different composition and their nature of variation with frequency has been elucidated on the basis of Maxwell–Wagner interfacial model. Impedance spectroscopy technique has been used to study the effect of grain and grain boundary on the electrical properties of this spinel oxide. All the electrical parameters showed strong dependence on the nanostructural properties and were found to vary consistently with the increase of doping concentration.     

peri-Dimethylamino substituent effects on proton transfer at carbon in α-naphthylacetate esters: a model for mandelate racemase

The rate constants for exchange of hydrogen for deuterium at the α-CH(2) positions of 8-(N,N-dimethylaminonaphthalen-1-yl)acetic acid tert-butyl ester 1 and naphthalen-1-ylacetic acid tert-butyl ester 2 have been determined in potassium deuteroxide solutions in 1 : 1 D(2)O : CD(3)CN, in order to quantify the effect of the neighbouring peri-dimethylamino substituent on α-deprotonation. Intramolecular general base catalysis by the (weakly basic) neighbouring group was not detected. Second-order rate constants, k(DO), for the deuterium exchange reactions of esters 1 and 2 have been determined as 1.35 × 10(-4) M(-1) s(-1) and 3.95 × 10(-3) M(-1) s(-1), respectively. The unexpected 29-fold decrease in the k(DO) value upon the introduction of a peri-dimethylamino group is attributed to an unfavourable steric and/or electronic substituent effect on intermolecular deprotonation by deuteroxide ion. From the experimental k(DO) values, carbon acid pK(a) values of 26.8 and 23.1 have been calculated for esters 1 and 2.     

Efficacious and sustained release of an anticancer drug mitoxantrone from new covalent organic frameworks using protein corona

Solid porous and crystalline covalent organic frameworks (COFs) are characterized by their higher specific BET surface areas and functional pore walls, which allow the adsorption of various bioactive molecules inside the porous lattices. We have introduced a perylene-based COF, PER@PDA-COF-1, which acts as an effective porous volumetric reservoir for an anticancer drug, mitoxantrone (MXT). The drug-loaded COF (MXT–PER@PDA-COF-1) exhibited zero cellular release of MXT towards cancer cells, which can be attributed to the strong intercalation between the anthracene-dione motif of the drug and the perylene-based COF backbone. Here, we have introduced a strategy involving the serum-albumin-triggered intracellular release of mitoxantrone from MXT–PER@PDA-COF-1. The serum albumin acts as an exfoliating agent and as a colloidal stabilizer in PBS medium (pH = 7.4), rapidly forming a protein corona around the exfoliated COF crystallites and inducing the sustained release of MXT from the COF into tumorigenic cells.

Solid porous and crystalline covalent organic frameworks (COFs) are characterized by their higher specific BET surface areas and functional pore walls, which allow the adsorption of various bioactive molecules inside the porous lattices.     

Tailoring a robust Al-MOF for trapping C2H6 and C2H2 towards efficient C2H4 purification from quaternary mixtures

Light hydrocarbon separation is considered one of the most industrially challenging and desired chemical separation processes and is highly essential in polymer and chemical industries. Among them, separating ethylene (C₂H₄) from C2 hydrocarbon mixtures such as ethane (C₂H₆), acetylene (C₂H₂), and other natural gas elements (CO₂, CH₄) is of paramount importance and poses significant difficulty. We demonstrate such separations using an Al-MOF synthesised earlier as a non-porous material, but herein endowed with hierarchical porosity created under microwave conditions in an equimolar water/ethanol solution. The material possessing a large surface area (793 m² g⁻¹) exhibits an excellent uptake capacity for major industrial hydrocarbons in the order of C₂H₂ > C₂H₆ > CO₂ > C₂H₄ > CH₄ under ambient conditions. It shows an outstanding dynamic breakthrough separation of ethylene (C₂H₄) not only for a binary mixture (C₂H₆/C₂H₄) but also for a quaternary combination (C₂H₄/C₂H₆/C₂H₂/CO₂ and C₂H₄/C₂H₆/C₂H₂/CH₄) of varying concentrations. The detailed separation/purification mechanism was unveiled by gas adsorption isotherms, mixed-gas adsorption calculations, selectivity estimations, advanced computer simulations such as density functional theory (DFT), grand canonical Monte Carlo (GCMC) and ab initio molecular dynamics (AIMD), and stepwise multicomponent dynamic breakthrough experiments.

Industrially important C₂H₄ purification from multi-component hydrocarbon mixtures.     

Non-Equilibrium Polymerization of Cross-β Amyloid Peptides for Temporal Control of Electronic Properties

Hydrophobic collapse plays crucial roles in protein functions, from accessing the complex three-dimensional structures of native enzymes to the dynamic polymerization of non-equilibrium microtubules. However, hydrophobic collapse can also lead to the thermodynamically downhill aggregation of aberrant proteins, which has interestingly led to the development of a unique class of soft nanomaterials. There remain critical gaps in the understanding of the mechanisms of how hydrophobic collapse can regulate such aggregation. Demonstrated herein is a methodology for non-equilibrium amyloid polymerization through mutations of the core sequence of Aβ peptides by a thermodynamically activated moiety. An out of equilibrium state is realized because of the negative feedback from the transiently formed cross-β amyloid networks. Such non-equilibrium amyloid nanostructures were utilized to access temporal control over its electronic properties.     

Pd/C-catalyzed one-pot Suzuki-Miyaura cross-coupling/hydrogenation of pyridine derivatives

Using bromopyridines and methoxyphenyl boronic acid as starting materials, consecutive Suzuki-Miyaura cross-coupling and hydrogenation reactions were undertaken using a heterogeneous Pd/C catalyst in one-pot manner under mild conditions (balloon-pressure at room temperature for hydrogenation) with excellent yield. To counter Pd leaching as well as catalyst poisoning, addition of an appropriate amount of H₂O was crucial to achieving successful AcOH-promoted hydrogenation, which ensured a selective reduction of the pyridine rings to the corresponding piperidines.     

Highly effective peroxidic epoxidation of olefins using hexathiocyanatorhenate(IV) as catalyst and bicarbonate as co-catalyst

In the presence of bicarbonate as co-catalyst hexathiocyanatorhenate(IV) functions as an extremely effective catalyst in the epoxidation of olefins using aqueous hydrogen peroxide as the terminal oxidant.