Effect of pressure on the low-temperature reaction of ethylene with N2O4

Calorimetric monitoring of the autoclave reaction N₂O₄ + C₂H₄ at –85 to +10 °C under argon pressure 10–30 bar revealed that the exothermic chemical reaction started at temperatures above –52 °C at 10 bar, whereas an intensive exothermic reaction started at –85 °C and pressure of 30 bar. IR study showed that oligo/polynitroethylene was formed at 30 bar, while carbonyl and hydroxy compound as well as nitrate R–ONO₂ formation occurred upon processing at 10 bar.     

Application of microcrystalline cellulose as an efficient and cheap sorbent for the extraction of metoprolol from plasma and wastewater before HPLC–MS/MS determination

A dispersive solid-phase extraction method based on a new sorbent has been performed on plasma and wastewater samples to determine metoprolol by high-performance liquid chromatography–tandem mass spectrometry. In this study, the analyte was adsorbed from the samples onto microcrystalline cellulose as a green and efficient sorbent and then eluted for use in the determination step. In the mass spectrometer, the analyte was detected in the positive mode and selectivity of the analysis was increased by sequential mass analysis through multiple reaction monitoring. All of the effective parameters in the extraction of metoprolol from plasma and wastewater were optimized. Under optimal conditions the method was linear in the ranges of 1–1,000 and 0.1–1,000 ng/ml in plasma and wastewater samples, respectively. The detection limits of the method were 0.30 and 0.03 ng/ml in plasma and wastewater samples, respectively. The data showed that the method provides low detection limit, wide linear range, good precision and high extraction recovery. Finally several plasma and wastewater samples were successfully analyzed using the method. The use of a small amount of a green and inexpensive sorbent and a low volume of plasma without the need for further pretreatment steps are the main advantages of the method.     

Dark Energy with Phantom Crossing and the H0 Tension

We investigate the possibility of phantom crossing in the dark energy sector and the solution for the Hubble tension between early and late universe observations. We use robust combinations of different cosmological observations, namely the Cosmic Microwave Background (CMB), local measurement of Hubble constant (H0), Baryon Acoustic Oscillation (BAO) and SnIa for this purpose. For a combination of CMB+BAO data that is related to early universe physics, phantom crossing in the dark energy sector was confirmed at a 95% confidence level and we obtained the constraint H0=71.0−3.8+2.9 km/s/Mpc at a 68% confidence level, which is in perfect agreement with the local measurement by Riess et al. We show that constraints from different combinations of data are consistent with each other and all of them are consistent with phantom crossing in the dark energy sector. For the combination of all data considered, we obtained the constraint H0=70.25±0.78 km/s/Mpc at a 68% confidence level and the phantom crossing happening at the scale factor am=0.851−0.031+0.048 at a 68% confidence level.     

Ultrahigh Loading Copper Single Atom Catalyst for Palladium-free Wacker Oxidation

Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by ¹⁸O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.     

Developing Flexible Quinacridone-Derivatives-Based Photothermal Evaporaters for Solar Steam and Thermoelectric Power Generation

Solar-driven interfacial vaporization by localizing solar-thermal energy conversion to the air−water interface has attracted tremendous attention. In the process of converting solar energy into heat energy, photothermal materials play an essential role. Herein, a flexible solar-thermal material di-cyan substituted 5,12-dibutylquinacridone (DCN−4CQA)@Paper was developed by coating photothermal quinacridone derivatives on the cellulose paper. The DCN−4CQA@Paper combines desired chemical and physical properties, broadband light-absorbing, and shape-conforming abilities that render efficient photothermic vaporization. Notably, synergetic coupling of solar-steam and solar-electricity technologies by integrating DCN−4CQA@Paper and the thermoelectric devices is realized without trade-offs, highlighting the practical consideration toward more impactful solar heat exploitation. Such solar distillation and low-grade heat-to-electricity generation functions can provide potential opportunities for fresh water and electricity supply in off-grid or remote areas.     

Anti-fibrosis attributes: UHPLC-MS/MS-based pharmacokinetics profiling of a novel autotaxin inhibitor with excellent in vivo efficacy in rat

3,4-Difluorobenzyl(1-ethyl-5-(4-((4-hydroxypiperidin-1-yl)-methyl)thiazol-2-yl)-1H-indol-3-yl)carbamate (NAI59), a small molecule with outstanding therapeutic effectiveness to anti-pulmonary fibrosis, was developed as an autotaxin inhibitor candidate compound. To evaluate the pharmacokinetics and plasma protein binding of NAI59, a UPLC–MS/MS method was developed to quantify NAI59 in plasma and phosphate-buffered saline. The calibration curve linearity ranged from 9.95 to 1990.00 ng/mL in plasma. The accuracy was −6.8 to 5.9%, and the intra- and inter-day precision was within 15%. The matrix effect and recovery, as well as dilution integrity, were within the criteria. The chromatographic and mass spectrometric conditions were also feasible to determine phosphate-buffered saline samples, and it has been proved that this method exhibits good precision and accuracy in the range of 9.95–497.50 ng/mL in phosphate-buffered saline. This study is the first to determine the pharmacokinetics, absolute bioavailability, and plasma protein binding of NAI59 in rats using this established method. Therefore, the pharmacokinetic profiles of NAI59 showed a dose-dependent relationship after oral administration, and the absolute bioavailability in rats was 6.3%. In addition, the results of protein binding showed that the combining capacity of NAI59 with plasma protein attained 90% and increased with the increase in drug concentration.     

Influence of Polarity and Activation Energy in Microwave–Assisted Organic Synthesis (MAOS)

The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol⁻¹ and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation.     

Pd0‐Catalyzed Intramolecular α‐Arylation of Sulfones: Domino Reactions in the Synthesis of Functionalized Tetrahydroisoquinolines

A new strategy for the synthesis of tetrahydroisoquinolines based on the Pd⁰‐catalyzed intramolecular α‐arylation of sulfones is reported. The combination of this Pd‐catalyzed reaction with intermolecular Michael and aza‐Michael reactions allows the development of two‐ and three‐step domino processes to synthesize diversely functionalized scaffolds from readily available starting materials.