Immobilization and Activation of a Single‐Site Chromium Catalyst for Ethylene Polymerization using MgCl2/AlRn(OEt)3 − n Supports

Summary: The effective immobilization and activation of a single‐site chromium catalyst for ethylene polymerization has been achieved using MgCl₂/AlR_n(OEt)_{3 − n} supports, without the use of methylaluminoxane (MAO) or a borate activator. High catalyst activity and a spherical polyethylene‐particle morphology is obtained. Furthermore, the single‐site characteristics of the catalyst are retained, the narrow molecular weight distribution of the polymers obtained are apparent from gel permeation chromatography (GPC) and confirmed by rheological characterization.

Shear frequency dependence of the storage modulus of (♦ and ▴) polyethylene ( = 1.8–1.9) prepared using an immobilized Cr catalyst, compared to (▪) a reference polymer having = 4.1.     

Design Principles of Large Cation Incorporation in Halide Perovskites

Perovskites have stood out as excellent photoactive materials with high efficiencies and stabilities, achieved via cation mixing techniques. Overcoming challenges to the stabilization of Perovskite solar cells calls for the development of design principles of large cation incorporation in halide perovskite to accelerate the discovery of optimal stable compositions. Large fluorinated organic cations incorporation is an attractive method for enhancing the intrinsic stability of halide perovskites due to their high dipole moment and moisture-resistant nature. However, a fluorinated cation has a larger ionic size than its non-fluorinated counterpart, falling within the upper boundary of the mixed-cation incorporation. Here, we report on the intrinsic stability of mixed Methylammonium (MA) lead halides at different concentrations of large cation incorporation, namely, ehtylammonium (EA; [CH₃CH₂NH₃]⁺) and 2-fluoroethylammonium (FEA; [CH₂FCH₂NH₃]⁺). Density functional theory (DFT) calculations of the enthalpy of the mixing and analysis of the perovskite structural features enable us to narrow down the compositional search domain for EA and FEA cations around concentrations that preserve the perovskite structure while pointing towards the maximal stability. This work paves the way to developing design principles of a large cation mixture guided by data analysis of DFT data. Finally, we present the automated search of the minimum enthalpy of mixing by implementing Bayesian optimization over the compositional search domain. We introduce and validate an automated workflow designed to accelerate the compositional search, enabling researchers to cut down the computational expense and bias to search for optimal compositions.     

Monosaccharide-Directed Selective Internalization of Gold and Silver Nanoparticles in Hepatic Cancer Cells

The therapeutic success of nanomedicines requires nanomaterials to either adhere to the surface or internalize within the cytoplasm. The endocytosis phenomenon is controlled by the nanomaterial's shape, size, composition, charge, and capping molecules. The membrane potential-based non-specific internalization of therapeutic nanomedicines offers limited benefits than receptor-based specific delivery. Glut receptor-based internalization of glucose molecules is a well-known process in cancerous cells, which is one of the most exploited strategies to target cancer cells using nanoparticles. However, the internalization process of other structurally similar monosaccharides (D-Galactose, Mannose, and D-Fructose) conjugated nanoparticles remains to be unexplored. Herein, D-Glucose, D-Galactose, Mannose, and D-Fructose-coated AuNPs and AgNPs have been synthesized and studied the role of Glut receptors in their internalization in liver cancer cells, and compared them with non-cancerous cells. Results revealed that almost all monosaccharide-coated NPs exhibited high uptake in liver cancer cells than non-cancerous cells. Glut-1 receptor is observed to play a key role in the uptake and inhibition of Glut-1 receptors by genistein lead to a significant decrease in nanoparticle uptake. In conclusion, monosaccharide-conjugated nanoparticles can be used to direct the selective internalization of AuNPs and AgNPs in hepatic cancer cells to realize therapeutic and imaging applications.     

A Study on the ordering of intercalated solvents in poly-benzyl-l-glutamate; In-situ raman and X-ray scattering investigations

A polymer/solvent system can form a gel due to specific interactions between the polymer and the solvent. For poly-benzyl-L-glutamate/solvent systems, gelation can be based on carbonyl or phenyl ring interactions, depending on the solvent. The present paper describes X-ray scattering and Raman investigations on cast films of poly-benzyl-L-glutamate (PBLG) and benzylmethacrylate (BzMA). The studies indicate that in the cast samples separate zones of PBLG and BzMA are present. Upon heating, the system homogenises and the PBLG molecules pack in a pseudo hexagonal lattice. At approximately 150°C a new reflection at 11.4 Å in the WAXS pattern arises. This reflection is attributed to structural ordering of the solvent, due to intercalation of the solvent molecules within the helices of PBLG. The observed changes in the WAXS pattern upon heating are supported by Raman experiments.     

Synthesis of 1D β-MnO2 for high-performance supercapacitor application

Journal of Solid State Electrochemistry - Electrochemical supercapacitors (ESs) still need to overcome development obstacles in order to realize their full potential while being acknowledged as a...     

Post-Synthetic Modification of Zr-based Metal-Organic Frameworks with Imidazole: Variable Optical Behavior and Sensing

UiO-66-NH₂-IM, a fluorescent metal-organic framework (MOF), was synthesized by post-synthetic modification of UiO-66-NH₂ with 2-imidazole carboxaldehyde via a Schiff base reaction. It was examined using various characterization techniques (PXRD, FTIR, NMR, SEM, TGA, UV-Vis DRS, and photoluminescence spectroscopy). The emissive feature of UiO-66-NH₂-IM was utilized to detect volatile organic compounds (VOCs), metal ions, and anions, such as acetone, Fe³⁺, and carbonate (CO₃²⁻). Acetone turns off the high luminescence of UiO-66-NH₂-IM in DMSO, with the limit of detection (LOD) being 3.6 ppm. Similarly, Fe³⁺ in an aqueous medium is detected at LOD=0.67 μM (0.04 ppm) via quenching. On the contrary, CO₃²⁻ in an aqueous medium significantly enhances the luminescence of UiO-66-NH₂-IM, which is detected with extremely high sensitivity (LOD=1.16 μM, i. e., 0.07 ppm). Large Stern-Volmer constant, K_sv, and low LOD values indicate excellent sensitivity of the post-synthetic MOF. Experimental data supported by density functional theory (DFT) calculations discern photo-induced electron transfer (PET), resonance energy transfer (RET), inner filter effect (IFE), or proton abstraction as putative sensing mechanisms. NMR and computational studies propose a proton abstraction mechanism for luminescence enhancement with CO₃²⁻. Moreover, the optical behavior of the post-synthetic material toward analytes is recyclable.     

A pharmacokinetic study to correlate the hypoglycemic effect of phlorizin in rats: Identification of metabolites as inhibitors of sodium/glucose cotransporters

Phlorizin (PRZ) is a natural product that belongs to a class of dihydrochalcones. The unique pharmacological property of PRZ is to block glucose absorption or reabsorption through specific and competitive inhibitors of the sodium/glucose cotransporters (SGLTs) in the intestine (SGLT1) and kidney (SGLT2). This results in glycosuria by inhibiting renal reabsorption of glucose and can be used as an adjuvant treatment for type 2 diabetes. The pharmacokinetic profile, metabolites of the PRZ, and efficacy of metabolites towards SGLTs are unknown. Therefore, the present study on the characterization of hitherto unknown in vivo metabolites of PRZ and pharmacokinetic profiling using liquid chromatography-electrospray ionization tandem mass spectrometry (LC/ESI/MS/MS) and accurate mass measurements is undertaken. Plasma, urine, and feces samples were collected after oral administration of PRZ to Sprague–Dawley rats to identify in vivo metabolites. Furthermore, in silico efficacy of the identified metabolites was evaluated by docking study. PRZ at an intraperitoneal dose of 400 mg/kg showed maximum concentration in the blood to 439.32 ± 8.84 ng/mL at 1 h, while phloretin showed 14.38 ± 0.33 ng/mL at 6 h. The pharmacokinetic profile of PRZ showed that the maximum concentration lies between 1 and 2 h after dosing. Decreased blood glucose levels and maximum excretion of glucose in the urine were observed when the PRZ and metabolites were observed in plasma. The identification and characterization of PRZ metabolites by LC/ESI/MS/MS further revealed that the phase I metabolites of PRZ are hydroxy (mono-, di-, and tri-) and reduction. Phase II metabolites are O-methylated, O-acetylated, O-sulfated, and glucuronide metabolites of PRZ. Further docking study revealed that the metabolites diglucuronide metabolite of mono-hydroxylated PRZ and mono-glucuronidation of PRZ could be considered novel inhibitors of SGLT1 and SGLT2, respectively, which show better binding affinities than their parent compound PRZ and the known inhibitors.     

Normal- and reversed-phase high-performance thin-layer chromatography methods for the simultaneous determination of remogliflozin etabonate and metformin hydrochloride antidiabetic drugs in bulk and tablet formulation

JPC – Journal of Planar Chromatography – Modern TLC - Two new, simple, fast, and sensitive methods, normal- and reversed-phase high-performance thin-layer chromatography (NP-HPTLC and...     

Passivation techniques for InAs/GaSb strained layer superlattice detectors

InAs/(In,Ga)Sb Strained Layer Superlattices (SLSs) have made significant progress since they were first proposed as an infrared (IR) sensing material more than three decades ago. The basic material properties of SLS provide a prospective benefit in the realization of IR imagers with suppressed interband tunneling and Auger recombination processes, as well as high quantum efficiency and responsivity. With scaling of single pixel dimensions, the performance of focal plane arrays is strongly dependent on surface effects due to the large pixels’ surface/volume ratio. This article discusses the cause of surface leakage currents and various approaches of their reduction including dielectric passivation, passivation with organic materials (polyimide or various photoresists), passivation by overgrowth of wider bandgap material, and chalcogenide passivation. Performance of SLS detectors passivated by different techniques and operating in various regions of infrared spectrum has been compared.