Arsenate Anion-π Interactions on Amine-Modified Polydivinylbenzene in Aqueous Systems: Experimental and Theoretical Investigation.

Anion-π interactions aiding in the adsorption of anions in the solution phase, though challenging to quantify, have attracted a lot of attention in supramolecular chemistry. We present the design of a polymer adsorbent that quantifies the adsorption of arsenate ions experimentally by optimizing anion-π interactions in a purely aqueous system and use density functional theory to compare these results with theoretical data. Arsenate anions are removed from water by amine-functionalized polydivinylbenzene using the comonomer 1-vinyl-1,2,4-triazole, which was cross-linked with divinylbenzene via radical polymerization in a hydrothermal procedure. The amine-functionalized polydivinylbenzene successfully removed arsenate anions from water with a capacity of 46 mg g-1, a 70% increase compared to the nonfunctionalized polydivinylbenzene (27 mg g-1) capacity under the same conditions. Adsorption is best described by the Sips isotherm model with a correlation coefficient R2 factor of 0.99, indicating that adsorption sites are homogeneous, and adsorption occurred by forming a monolayer. Kinetic studies indicated that adsorption is second order in the amine-functionalized polydivinylbenzene. Computational studies using density functional theory showed that the 1-vinyl-1,2,4-triazole comonomer improved the thermodynamic stability of the anionic-π interactions of polydivinylbenzene with arsenate anions. Electrostatic interactions dominate the mechanism of adsorption in polydivinylbenzene compared to the anion-induced interactions that dominate adsorption in amine-functionalized polydivinylbenzene.

Does COVID-19 increase the long-term relapsing-remitting multiple sclerosis clinical activity? A cohort study.

BACKGROUND: Some current evidence is pointing towards an association between COVID-19 and worsening of multiple sclerosis (MS), stressing the importance of preventing COVID-19 among people with MS (pwMS). However, population-based evidence regarding the long-term post-COVID-19 course of relapsing-remitting multiple sclerosis (RRMS) was limited when this study was initiated. OBJECTIVE: To detect possible changes in MS clinical disease activity after COVID-19. METHODS: We conducted an observational study from July 2020 until July 2021 in the Isfahan MS clinic, comparing the trends of probable disability progression (PDP) - defined as a three-month sustained increase in expanded disability status scale (EDSS) score - and relapses before and after probable/definitive COVID-19 diagnosis in a cohort of people with RRMS (pwRRMS). RESULTS: Ninety pwRRMS were identified with definitive COVID-19, 53 of which were included in the final analysis. The PDP rate was significantly (0.06 vs 0.19, P = 0.04), and the relapse rate was insignificantly (0.21 vs 0.30, P = 0.30) lower post-COVID-19, compared to the pre-COVID-19 period. The results were maintained after offsetting by follow-up period in the matched binary logistic model. Survival analysis did not indicate significant difference in PDP-free (Hazard Ratio [HR] [95% CI]: 0.46 [0.12, 1.73], P = 0.25) and relapse-free (HR [95% CI]: 0.69 [0.31, 1.53], P = 0.36) survivals between the pre- and post-COVID-19 periods. Sensitivity analysis resulted similar measurements, although statistical significance was not achieved. CONCLUSION: While subject to replication in future research settings, our results did not confirm any increase in the long-term clinical disease activity measures after COVID-19 contraction among pwRRMS.

Effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria: Soot-ceria contact and interfacial oxygen evolution.

Ceria is widely used as a catalyst for soot combustion, but effects of Zr substitution on the reaction mechanism is ambiguous. The present work elucidates effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria. The nanostructured CeO2, Ce0.92Zr0.08O2, and Ce0.84Zr0.16O2 composed of 5-6 nm crystallites display Tm-CO2 (the temperature at maximum CO2 yield) at 383, 355, and 375°C under 10 vol.% O2/N2, respectively. The size of agglomerate decreases from 165.5 to 51.9-57.3 nm, which is beneficial for the soot-ceria contact. Moreover, Zr increases the amount of surface oxygen vacancies, generating more active oxygen (O2- and O-) for soot oxidation. Thus, the activities of Ce0.92Zr0.08O2 and Ce0.84Zr0.16O2 in soot combustion are better than that of CeO2. Although oxygen vacancies promote the migration of lattice O2-, the enriched surface Zr also inhibits the mobility of lattice O2-. Therefore, the Tm-CO2 of Ce0.84Zr0.16O2 is higher than that of Ce0.92Zr0.08O2. Based on reaction kinetic study, soot in direct contact with ceria preferentially decomposes with low activation energy, while the oxidation of isolated soot occurs through diffusion with high activation energy. The obtained findings provide new understanding on the soot combustion over nanoceria.

Syntheses of ZnO with Different Morphologies: Catalytic Activity toward Coumarin Synthesis via the Knoevenagel Condensation Reaction.

Heterogeneous catalysts are preferred in fine chemical industries due to their easy recovery and reusability. Here, we report an easily scalable method of ZnO catalysts for coumarin synthesis. Nanocrystalline ZnO particles with diverse morphologies and crystallite sizes were prepared using different solvents. The change in morphology results in changes in band gaps, defects, basicity, and textural properties (surface areas, pore volumes, and pore sizes). The catalytic performances of the synthesized ZnO materials were tested using coumarin synthesis via the Knoevenagel condensation. The catalyst synthesized using methanol shows the highest activity and selectivity (conversion of 74%, selectivity of 94%) with a turnover number of 14.69. The increased activity of the ZnO synthesized in methanol is attributed to the combined effects of moderate basicity and relatively high textural properties of the sample.

Synthesis of Large Mesoporous-Macroporous and High Pore Volume, Mixed Crystallographic Phase Manganese Oxide, Mn2O3/Mn3O4 Sponge.

The controlled synthesis of mixed crystallographic phase Mn2O3/Mn3O4 sponge material by varying heating rates and isothermal segments provides valuable information about the morphological and physical properties of the obtained sample. The well-characterized Mn2O3/Mn3O4 sponge and applicability of difference in reactivity of H2 and CO2 desorbed during the synthesis provide new developments in the synthesis of metal oxide materials with unique morphological and surface properties. We report the preparation of a Mn2O3/Mn3O4 sponge using a metal nitrate salt, water, and Dextran, a biopolymer consisting of glucose monomers. The Mn2O3/Mn3O4 sponge prepared at 1 °C·min-1 heating rate to 500 °C and held isothermally for 1 h consisted of large mesopores-macropores (25.5 nm, pore diameter) and a pore volume of 0.413 mL/g. Furthermore, the prepared Mn2O3/Mn3O4 and 5 mol %-Fe-Mn2O3/Mn3O4 sponges provide potential avenues in the development of solid-state catalyst materials for alcohol and amine oxidation reactions.

Synthesis and Electrocatalytic Activity of Ammonium Nickel Phosphate, [NH4]NiPO4·6H2O, and ß-Nickel Pyrophosphate, ß-Ni2P2O7: Catalysts for Electrocatalytic Decomposition of Urea.

Electrocatalytic decomposition of urea for the production of hydrogen, H2, for clean energy applications, such as in fuel cells, has several potential advantages such as reducing carbon emissions in the energy sector and environmental applications to remove urea from animal and human waste facilities. The study and development of new catalyst materials containing nickel metal, the active site for urea decomposition, is a critical aspect of research in inorganic and materials chemistry. We report the synthesis and application of [NH4]NiPO4·6H2O and ß-Ni2P2O7 using in situ prepared [NH4]2HPO4. The [NH4]NiPO4·6H2O is calcined at varying temperatures and tested for electrocatalytic decomposition of urea. Our results indicate that [NH4]NiPO4·6H2O calcined at 300 °C with an amorphous crystal structure and, for the first time applied for urea electrocatalytic decomposition, had the greatest reported electroactive surface area (ESA) of 142 cm2/mg and an onset potential of 0.33 V (SCE) and was stable over a 24-h test period.

Photocatalytic Water Splitting-The Untamed Dream: A Review of Recent Advances.

Photocatalytic water splitting using sunlight is a promising technology capable of providing high energy yield without pollutant byproducts. Herein, we review various aspects of this technology including chemical reactions, physiochemical conditions and photocatalyst types such as metal oxides, sulfides, nitrides, nanocomposites, and doped materials followed by recent advances in computational modeling of photoactive materials. As the best-known catalyst for photocatalytic hydrogen and oxygen evolution, TiO2 is discussed in a separate section, along with its challenges such as the wide band gap, large overpotential for hydrogen evolution, and rapid recombination of produced electron-hole pairs. Various approaches are addressed to overcome these shortcomings, such as doping with different elements, heterojunction catalysts, noble metal deposition, and surface modification. Development of a photocatalytic corrosion resistant, visible light absorbing, defect-tuned material with small particle size is the key to complete the sunlight to hydrogen cycle efficiently. Computational studies have opened new avenues to understand and predict the electronic density of states and band structure of advanced materials and could pave the way for the rational design of efficient photocatalysts for water splitting. Future directions are focused on developing innovative junction architectures, novel synthesis methods and optimizing the existing active materials to enhance charge transfer, visible light absorption, reducing the gas evolution overpotential and maintaining chemical and physical stability.

Predictive power of the eTBI score for 30 day outcome in elderly patients with traumatic brain Injury.

Traumatic brain injury (TBI) is a common problem in elderly individuals, with significant morbidity and mortality. The elderly Traumatic Brain Injury (eTBI) score, a novel tool for predicting outcomes in elderly patients with TBI, has shown promising results in previous studies. This study aimed to validate the eTBI score in a larger cohort of elderly patients with TBI in the Middle East. We conducted a retrospective study on 337 TBI patients with a mean age of 73.04 ± 8.73, admitted to a tertiary care hospital between March 2021 and November 2022. Within 30 days of admission, the patients' conditions, including mortality and entering a vegetative state, were evaluated. The study population was split into three groups based on eTBI score: low, medium, and high risk; then patients were divided into two subgroups based on their Glasgow Outcome Scale (GOS ≤ 2, GOS > 2) in 30 days from hospital admission. Poor outcomes (mortality and entering a vegetative state) occurred in 24.3% of the study population. Within 30 days of hospital admission, 88% of low-risk patients experienced some degree of improvement, while 100% of high-risk patients died or fell into a vegetative state. In the medium-risk group, there was a significant correlation between unresponsive pupil (P = 0.006), initial GCS score (P = 0.003), need for a ventilator device (P = 0.015), need for surgical treatment (P = 0.031) and poor outcomes. Despite having a low sensitivity (21% vs. 57%), the eTBI score performed well in terms of accuracy (81% vs. 88%), specificity (100 vs. 98%), positive predictive value (100% vs. 90%), and negative predictive value (80% vs. 88%) for both eTBI ≤ 0 and eTBI ≤ 3 thresholds. The eTBI score is a reliable tool for predicting outcomes in elderly patients with TBI. This scoring system has a positive predictive value of 100% in the eTBI ≤ 0 group, which shows that 100% of the patients who are predicted by the eTBI score to have a poor outcome will indeed have a poor outcome. Patients in the high-risk group should be closely monitored and provided with intensive care, while those in the low-risk group can be reassured about their prognosis. The eTBI score can also be used in conjunction with other clinical factors to inform treatment decisions for patients in the medium-risk group.

Cycling-Induced Capacity Increase of Bulk and Artificially Layered LiTaO3 Anodes in Lithium-Ion Batteries.

Tantalum-based oxide electrodes have recently drawn much attention as promising anode materials owing to their hybrid Li+ storage mechanism. However, the utilization of LiTaO3 electrode materials that can deliver a high theoretical capacity of 568 mAh g-1 has been neglected. Herein, we prepare a layered LiTaO3 electrode formed artificially by restacking LiTaO3 nanosheets using a facile synthesis method and investigate the Li+ storage performance of this electrode compared with its bulk counterpart. The designed artificially layered anode reaches specific capacities of 474, 290, and 201 mAh g-1, respectively, at 56 (>500 cycles), 280 (>1000 cycles), and 1120 mAg-1 (>2000 cycles) current densities. We also determine that the Li+ storage capacity of the layered LiTaO3 demonstrates a cycling-induced capacity increase after a certain number of cycles. Adopting various characterization techniques on LiTaO3 electrodes before and after electrochemical cycling, we attribute the origin of the cycling-induced improvement of the Li+ storage capacity in these electrodes to the amorphization of the electrode after cycling, formation of metallic tantalum during the partially irreversible conversion mechanism, lower activation overpotential of electrodes due to the formation of Li-rich species by the lithium insertion mechanism, and finally the intrinsic piezoelectric behavior of LiTaO3 that can regulate Li+ diffusion kinetics.

Mesoporous Crystalline Niobium Oxide with a High Surface Area: A Solid Acid Catalyst for Alkyne Hydration.

A mesoporous crystalline niobium oxide with tunable pore sizes was synthesized via the sol-gel-based inverse micelle method. The material shows a surface area of 127 m2/g, which is the highest surface area reported so far for crystalline niobium oxide synthesized by soft template methods. The material also has a monomodal pore size distribution with an average pore diameter of 5.6 nm. A comprehensive characterization of niobium oxide was performed using powder X-ray diffraction, Brunauer-Emmett-Teller, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, UV-vis, and X-ray photoelectron spectroscopy. The material acts as an environmentally friendly, solid acid catalyst toward hydration of alkynes under with excellent catalytic activity (99% conversion, 99% selectivity, and 4.39 h-1 TOF). Brønsted acid sites present in the catalyst were found to be responsible for the high catalytic activity. The catalyst was reusable up to five cycles without a significant loss of the activity.