Ru-O Site-Mediated Product Selectivity Switch for Overall Photocatalytic CO Reduction.

The photocatalytic reduction of carbon dioxide (CO) to methane (CH) represents a sustainable route for directly converting greenhouse gases into chemicals but poses a significant challenge in achieving high selectivity due to thermodynamic and kinetic limitations during the reaction process. This work establishes Ru-O active sites on the surface of TiO by anchoring coordination unsaturated Ru single-atoms, which stabilize crucial reaction intermediates and facilitate local mass transfer to achieve dual optimization of the thermodynamics and kinetics of the overall photocatalytic CO reduction. Combining operando spectroscopy with density functional theory (DFT) calculations indicates that oxygen vacancies (O) inhibits the desorption of *CO, whereas Ru facilitates proton extraction.

Engineering Metal-MOF Interfaces for Selective CO₂ Hydrogenation to Methanol.

The hydrogenation of CO₂ to methanol is a promising pathway toward sustainable fuel production and carbon recycling. A key factor in the efficiency of this process lies in the interaction between the metal catalyst and its support. Metal-Organic Frameworks (MOFs) have emerged as highly effective platforms due to their tunable structures, large surface areas, and ability to form stable interfaces with single-atom metals or metal nanoparticles.

Balancing Surface Chemistry and Flake Size of MXene-Based Electrodes for Bioelectrochemical Reactors.

MXenes have excellent properties as electrode materials in energy storage devices or fuel cells. In bioelectrochemical systems (for wastewater treatment and energy harvesting), MXenes can have antimicrobial characteristics in some conditions. Here, different intercalation and delamination approaches to obtain TiCT MXene flakes with different terminal groups and lateral dimensions are comprehensively investigated.

Highly Dispersed Pd@ZIF-8 for Photo-Assisted Cross-Couplings and CO to Methanol: Activity and Selectivity Insights.

Our study unveils a pioneering methodology that effectively distributes Pd species within a zeolitic imidazolate framework-8 (ZIF-8). We demonstrate that Pd can be encapsulated within ZIF-8 as atomically dispersed Pd species that function as an excited-state transition metal catalyst for promoting carbon-carbon (C-C) cross-couplings at room temperature using visible light as the driving force. Furthermore, the same material can be reduced at 250 °C, forming Pd metal nanoparticles encapsulated in ZIF-8.

Mechanistic Insight into Heteroatom Removal from Vacuum Gas Oil Blended with PMMA or PET Waste.

This work analyzes vacuum gas oil (VGO) and hydrocracking products of this feed blended with polymethylmethacrylate (PMMA) or polyethylene terephthalate (PET) to clarify the oxygen, nitrogen, and sulfur removal pathways in these complex mixtures. Hydrocracking reactions are conducted in a semi-batch reactor with a Pt-Pd/HY bifunctional catalyst at 400 °C and 80 bar for 300 min with 10 wt % waste plastic using 0.1 catalyst/feed weight ratio.

Copper nanoparticles encapsulated in zeolitic imidazolate framework-8 as a stable and selective CO hydrogenation catalyst.

Metal-organic frameworks have drawn attention as potential catalysts owing to their unique tunable surface chemistry and accessibility. However, their application in thermal catalysis has been limited because of their instability under harsh temperatures and pressures, such as the hydrogenation of CO to methanol. Herein, we use a controlled two-step method to synthesize finely dispersed Cu on a zeolitic imidazolate framework-8 (ZIF-8).

Highly Efficient and Stable Methane Dry Reforming Enabled by a Single-Site Cationic Ni Catalyst.

Zeolite-supported nickel (Ni) catalysts have been extensively studied for the dry reforming of methane (DRM). It is generally believed that prior to or during the reaction, Ni is reduced to a metallic state to act as the catalytic site. Here, we employed a ligand-protected synthesis method to achieve a high degree of Ni incorporation into the framework of the MFI zeolite.

Thermochemical CO Reduction Catalyzed by Homometallic and Heterometallic Nanoparticles Generated from the Thermolysis of Supramolecularly Assembled Porous Metal-Adenine Precursors.

A family of unprecedented supramolecularly assembled porous metal-organic compounds (SMOFs), based on [CuM(μ-adeninato)(μ-OH)(μ-HO)] cations (M: Cu, Co, Ni, and Zn) and different dicarboxylate anions (fumarate, benzoate, and naphthalene-2,6-dicarboxylate), have been employed as precursors of catalysts for the thermocatalytic reduction of CO. The selected metal-organic cation allows us to tune the composition of the SMOFs and, therefore, the features and performance of the final homometallic and bimetallic catalysts. These catalysts were obtained by thermolysis at 600 °C under a N atmosphere and consist of big metal particles (10-20 μm) placed on the surface of the carbonaceous matrix and very tiny metal aggregates (<10 nm) within this carbonaceous matrix.

Is cavitation a truly sensible choice for intensifying photocatalytic oxidation processes? - Implications on phenol degradation using ZnO photocatalysts.

Phenols are recalcitrant compounds that constitute the majority of organic contaminants in industrial wastewaters. Their removal at large scales require a combination of various processes to reach the desired discharge quality. An extensive body of work has already been published in the area of phenol removal from wastewater, however none of them have focussed on a truly 'sensible' approach for coupling advanced oxidation processes (AOPs).

Leaching in Specific Facets of ZIF-67 and ZIF-L Zeolitic Imidazolate Frameworks During the CO Cycloaddition with Epichlorohydrin.

Zeolitic imidazolate frameworks (ZIFs) have been profusely used as catalysts for inserting CO into organic epoxides (i.e., epichlorohydrin) through cycloaddition.

Effects of Physical Exercise on Gross Motor Skills in Children with Autism Spectrum Disorder.

Research shows many positive effects from physical exercise. The present study examined the impact of a structured physical exercise program compared to treatment as usual on the gross motor skills of children diagnosed with autism spectrum disorder (ASD). Participants included 20 children, from 4 to 7 years old, who were assigned to two groups; an experimental group (n = 10) who received a structured physical exercise program for 60-min sessions, three times a week for eight weeks, and a control group (n = 10) who received conventional physiotherapy.

Post-Synthetic Surface Modification of Metal-Organic Frameworks and Their Potential Applications.

Metal-organic frameworks (MOFs) are porous hybrid materials with countless potential applications. Most of these rely on their porous structure, tunable composition, and the possibility of incorporating and expanding their functions. Although functionalization of the inner surface of MOF crystals has received considerable attention in recent years, methods to functionalize selectively the outer crystal surface of MOFs are developed to a lesser extent, despite their importance.

Maximizing Active Fe Species in ZSM-5 Zeolite Using Organic-Template-Free Synthesis for Efficient Selective Methane Oxidation.

The selective oxidation of CH in the aqueous phase to produce valuable chemicals has attracted considerable attention due to its mild reaction conditions and simple process. As the most widely studied catalyst for this reaction, Fe-ZSM-5 demonstrates high intrinsic activity and selectivity; however, Fe-ZSM-5 prepared using conventional methods has a limited number of active Fe sites, resulting in low CH conversion per unit mass of the catalyst. This study reports a facile organic-template-free synthesis strategy that enables the incorporation of more Fe into the zeolite framework with a higher dispersion degree compared to conventional synthesis methods.

Neuroleptic malignant syndrome associated with acute organophosphate poisoning: Case report.

Neuroleptic malignant syndrome is a rare and potentially fatal clinical condition frequently associated with the use of antipsychotics. In the literature, there is only one case report associated with the intake of organophosphates. We present the case of a patient who presented with a clinical picture compatible with neuroleptic malignant syndrome, after the ingestion of an organophosphate (chlorpyrifos).

Continuation rates of two different-sized copper intrauterine devices among nulliparous women: Interim 12-month results of a single-blind, randomised, multicentre trial.

Background: The most widely used copper intrauterine device (IUD) in the world (the TCu380A), and the only product available in many countries, causes side effects and early removals for many users. These problems are exacerbated in nulliparous women, who have smaller uterine cavities compared to parous women. We compared first-year continuation rates and reasons/probabilities for early removal of the TCu380A versus a smaller Belgian copper IUD among nulliparous users.

Vascular smooth muscle cell phenotype is modulated by ligands of the lymphotoxin β receptor and the tumor necrosis factor receptor.

Objective: Vascular smooth muscle cells (VSMCs) undergo a phenotypic-switching process during the generation of unstable atheroma plaques. In this investigation, the potential implication of the tumor necrosis factor superfamily (TNFSF) ligands, in the gene expression signature associated with VSMC plasticity was studied.

Material And Methods: Human aortic (ha)VSMCs were obtained commercially and treated with the cytokine TNFSF14, also called LIGHT, the lymphotoxin alpha (LTα), the heterotrimer LTαβ or with vehicle for 72h.

Dynamic genome-wide gene expression and immune cell composition in the developing human placenta.

Despite the central role of the placenta in supporting a pregnancy, relatively little is known about transcriptomic and immune-cell changes that occur across gestation. To generate a reference gene expression map of first (T1), second (T2) and third (T3) trimester human placenta, and assess differences in transcriptome in maternal versus fetal side tissues sections of full-term placenta, we performed RNA-Seq analysis on 64 biopsy samples from 18 placentas across all three gestations. We identified 1120 differentially expressed genes in placenta tissues from T1 and T3 samples using a generalized linear model within DESeq2.

Type 2 Marine-Lenhart Syndrome: An Uncommon Cause of Thyrotoxicosis.

Marine-Lenhart syndrome (MLS) is an uncommon cause of primary hyperthyroidism, which can occur in the context of diffuse goiter due to Graves disease (GD) or autonomic nodular disease (Plummer disease (PD)). The coexistence of these two conditions is the hallmark of the MLS. Patients with MLS have a lower remission rate with oral antithyroid drugs, requiring definitive management therapies with radioactive iodine or surgery.

Female permanent contraception trends and updates.

Permanent contraception remains one of the most popular methods of contraception worldwide. This article has reviewed recent literature related to demographic characteristics of users, prevalence of use and trends over time, surgical techniques, and barriers to obtain the procedure. We have emphasized the patient's perspective as a key element of choosing permanent contraception.

Designing a Multifunctional Catalyst for the Direct Production of Gasoline-Range Isoparaffins from CO.

The production of carbon-neutral fuels from CO presents an avenue for causing an appreciable effect in terms of volume toward the mitigation of global carbon emissions. To that end, the production of isoparaffin-rich fuels is highly desirable. Here, we demonstrate the potential of a multifunctional catalyst combination, consisting of a methanol producer (InCo) and a Zn-modified zeolite beta, which produces a mostly isoparaffinic hydrocarbon mixture from CO (up to ∼85% isoparaffin selectivity among hydrocarbons) at a CO conversion of >15%.

From Value to Valuation: Pragmatist and Hermeneutic Orientations for Assessing Science on the International Space Station.

Based on a study of the International Space Station (ISS), this paper argues that - as a set of orientations for sociological inquiry - pragmatism and hermeneutics are confluent frameworks to examine valuation as a social process. This confluence is grounded on their common attunement to valuing as a problematic and relational process, their equally common updates with theories of institutions, and a further conceptual development regarding the temporalities of valuation. I advance the argument in four steps.

Unraveling the reaction mechanism of selective C9 monomeric phenols formation from lignin using Pd-AlO-activated biochar catalyst.

The conversion of biomass-derived lignin to valuable monomeric phenols at high selectivity is of paramount importance for sustainable biorefineries. In this study, a novel Pd-AlO supported on activated biochar catalyst is developed for lignin hydrogenolysis. The catalyst characterization revealed that the (111) planes of both of Pd and AlO were exposed to the surface.

Detailed nature of tire pyrolysis oil blended with light cycle oil and its hydroprocessed products using a NiW/HY catalyst.

The pyrolysis of scrap tires is a very attractive strategy to valorize chemically these end-of-life wastes. The products of this step and any additional one, such as hydrotreating, are relatively complex in nature entangling the understanding and limiting the viability. In this work, we have investigated in detail the composition of a tire pyrolysis oil blended with light cycle oil (from a refinery) and its hydrotreated products using a bifunctional NiW/HY catalyst at 320-400 °C.

Subfascial-located contraceptive devices requiring surgical removal.

Background: Subdermal etonogestrel implants are highly effective contraceptive methods. Despite standardization of insertion technique by the manufacturer, some implants are inadvertently placed too deeply within or below the plane of the biceps brachii fascia. Placement of these implants in a deep tissue plane results in more difficult removal, which is not always possible in the office setting.