The influence of crystal structures on the performance of CoMoO battery-type supercapacitor electrodes.

CoMoO is a promising battery-type supercapacitor electrode material that can offer relatively high storage capacity and cycle stability. In this work, we investigate the role of the crystalline phase of CoMoO in determining these performance parameters. The hydrate phase of CoMoO was synthesized on a nickel foam substrate hydrothermal reaction with subsequent annealing under an inert atmosphere leading to the formation of the β-phase CoMoO.

Electrochemical Polarization of Disparate Catalytic Sites Drives Thermochemical Rate Enhancement.

Supported bimetallic catalysts commonly exhibit higher rates of reaction compared to their monometallic counterparts, but the origin of these enhancements is often poorly defined. The recent discovery that cooperative redox enhancement effects in Au-Pd systems promote bimetallic catalysis in thermochemical oxidation is an important development in this field. This effect aligns two important research fields, thermo- and electrocatalysis, but questions relating to the generality and origin of the effect remain.

Bioinspired, Non-Enzymatic, Aqueous Synthesis of Size-Tunable CdS Quantum Dots for Sustainable Optoelectronic Applications.

The enzymatic production of hydrogen sulfide (HS) from cysteine in various metabolic processes has been exploited as an intrinsically "green" and sustainable mode for the aqueous biomineralization of functional metal sulfide quantum dots (QDs). Yet, the reliance on proteinaceous enzymes tends to limit the efficacy of the synthesis to physiological temperature and pH, with implications for QD functionality, stability, and tunability (, particle size and composition). Inspired by a secondary non-enzymatic biochemical cycle that is responsible for basal HS production in mammalian systems, we establish how iron(III)- and vitamin B (pyridoxal phosphate, PLP)-catalyzed decomposition of cysteine can be harnessed for the aqueous synthesis of size-tunable QDs, demonstrated here for CdS, within an expanded temperature, pH, and compositional space.

Insights into the Effect of Metal Ratio on Cooperative Redox Enhancement Effects over Au- and Pd-Mediated Alcohol Oxidation.

The aerobic oxidation of alcohols and aldehydes over supported heterogeneous catalysts can be considered as comprising two complementary and linked processes: dehydrogenation and oxygen reduction. Significant rate enhancements can be observed when these processes are catalyzed by independent active sites, coupled by electron transport between the two catalysts. This effect, termed cooperative redox enhancement (CORE), could significantly influence how researchers approach catalyst design, but a greater understanding of the factors which influence it is required.

Uncovering Structure-Activity Relationships in Pt/CeO Catalysts for Hydrogen-Borrowing Amination.

The hydrogen-borrowing amination of alcohols is a promising route to produce amines. In this study, experimental parameters involved in the preparation of Pt/CeO catalysts were varied to assess how physicochemical properties influence their performance in such reactions. An amination reaction between cyclopentanol and cyclopentylamine was used as the model reaction for this study.

Methane Oxidation to Methanol.

The direct transformation of methane to methanol remains a significant challenge for operation at a larger scale. Central to this challenge is the low reactivity of methane at conditions that can facilitate product recovery. This review discusses the issue through examination of several promising routes to methanol and an evaluation of performance targets that are required to develop the process at scale.

Distinct pretreatment innate immune landscape and posttreatment T cell responses underlie immunotherapy-induced colitis.

Immune-related adverse events represent a major hurdle to the success of immunotherapy. The immunological mechanisms underlying their development and relation to antitumor responses are poorly understood. By examining both systemic and tissue-specific immune changes induced by combination anti-CTLA-4 and anti-PD-1 immunotherapy, we found distinct repertoire changes in patients who developed moderate-severe colitis, irrespective of their antitumor response to therapy.

Sequential, low-temperature aqueous synthesis of Ag-In-S/Zn quantum dots staged cation exchange under biomineralization conditions.

The development of high quality, non-toxic (, heavy-metal-free), and functional quantum dots (QDs) 'green' and scalable synthesis routes is critical for realizing truly sustainable QD-based solutions to diverse technological challenges. Herein, we demonstrate the low-temperature all-aqueous-phase synthesis of silver indium sulfide/zinc (AIS/Zn) QDs with a process initiated by the biomineralization of highly crystalline indium sulfide nanocrystals, and followed by the sequential staging of Ag cation exchange and Zn addition directly within the biomineralization media without any intermediate product purification. Therein, we exploit solution phase cation concentration, the duration of incubation in the presence of InS precursor nanocrystals, and the subsequent addition of Zn as facile handles under biomineralization conditions for controlling QD composition, tuning optical properties, and improving the photoluminescence quantum yield of the AIS/Zn product.

Highly efficient catalytic production of oximes from ketones using in situ-generated HO.

The ammoximation of cyclohexanone using preformed hydrogen peroxide (HO) is currently applied commercially to produce cyclohexanone oxime, an important feedstock in nylon-6 production. We demonstrate that by using supported gold-palladium (AuPd) alloyed nanoparticles in conjunction with a titanium silicate-1 (TS-1) catalyst, HO can be generated in situ as needed, producing cyclohexanone oxime with >95% selectivity, comparable to the current industrial route. The ammoximation of several additional simple ketones is also demonstrated.

Au-Pd separation enhances bimetallic catalysis of alcohol oxidation.

In oxidation reactions catalysed by supported metal nanoparticles with oxygen as the terminal oxidant, the rate of the oxygen reduction can be a limiting factor. This is exemplified by the oxidative dehydrogenation of alcohols, an important class of reactions with modern commercial applications. Supported gold nanoparticles are highly active for the dehydrogenation of the alcohol to an aldehyde but are less effective for oxygen reduction.

Two microbiota subtypes identified in irritable bowel syndrome with distinct responses to the low FODMAP diet.

Objective: Reducing FODMAPs (fermentable oligosaccharides, disaccharides, monosaccharides and polyols) can be clinically beneficial in IBS but the mechanism is incompletely understood. We aimed to detect microbial signatures that might predict response to the low FODMAP diet and assess whether microbiota compositional and functional shifts could provide insights into its mode of action.

Design: We used metagenomics to determine high-resolution taxonomic and functional profiles of the stool microbiota from IBS cases and household controls (n=56 pairs) on their usual diet.

Calcineurin inhibitors in steroid and anti-TNF-alpha refractory immune checkpoint inhibitor colitis.

Background And Aim: Immune checkpoint inhibitor (ICI) colitis is an increasingly common problem encountered as the use of checkpoint inhibitors (CPIs) grows in the management of cancers. Corticosteroids and tumour necrosis factor (TNF)-alpha inhibitors are widely recommended in the management of ICI colitis; however, the experience is limited when patients are refractory. Different authors have reported success with vedolizumab, mycophenolate, and cyclosporine.

Methane Oxidation to Methanol in Water.

Methane represents one of the most abundant carbon sources for fuel or chemical production. However, remote geographical locations and high transportation costs result in a substantial proportion being flared at the source. The selective oxidation of methane to methanol remains a grand challenge for catalytic chemistry due to the large energy barrier for the initial C-H activation and prevention of overoxidation to CO.

Sulfur Promotion in Au/C Catalyzed Acetylene Hydrochlorination.

The formation of highly active and stable acetylene hydrochlorination catalysts is of great industrial importance. The successful replacement of the highly toxic mercuric chloride catalyst with gold has led to a flurry of research in this area. One key aspect, which led to the commercialization of the gold catalyst is the use of thiosulphate as a stabilizing ligand.

Clinicopathological characteristics and management of colitis with anti-PD1 immunotherapy alone or in combination with ipilimumab.

Background: Colitis is one of the common immune-related adverse events that leads to morbidity and treatment discontinuation of immunotherapy. The clinical presentation, endoscopic and histopathological features and best management of this toxicity are not well defined.

Patients And Methods: Patients with metastatic melanoma who received immunotherapy (programmed cell death protein 1 (PD1) antibodies, alone or in combination with a cytotoxic T-lymphocyte-associated protein 4 (CTLA-4) antibody (PD1 +CTLA-4)) and who developed clinically significant colitis (requiring systemic corticosteroids) were identified retrospectively from two academic centers.

Tailored Coupling of Biomineralized CdS Quantum Dots to rGO to Realize Ambient Aqueous Synthesis of a High-Performance Hydrogen Evolution Photocatalyst.

Nanocomposite photocatalysts offer a promising route to efficient and clean hydrogen production. However, the multistep, high-temperature, solvent-based syntheses typically utilized to prepare these photocatalysts can limit their scalability and sustainability. Biosynthetic routes to produce functional nanomaterials occur at room temperature and in aqueous conditions, but typically do not produce high-performance materials.

Facile synthesis of precious-metal single-site catalysts using organic solvents.

Single-site catalysts can demonstrate high activity and selectivity in many catalytic reactions. The synthesis of these materials by impregnation from strongly oxidizing aqueous solutions or pH-controlled deposition often leads to low metal loadings or a range of metal species. Here, we demonstrate that simple impregnation of the metal precursors onto activated carbon from a low-boiling-point, low-polarity solvent, such as acetone, results in catalysts with an atomic dispersion of cationic metal species.

Role of the Support in Gold-Containing Nanoparticles as Heterogeneous Catalysts.

In this review, we discuss selected examples from recent literature on the role of the support on directing the nanostructures of Au-based monometallic and bimetallic nanoparticles. The role of support is then discussed in relation to the catalytic properties of Au-based monometallic and bimetallic nanoparticles using different gas phase and liquid phase reactions. The reactions discussed include CO oxidation, aerobic oxidation of monohydric and polyhydric alcohols, selective hydrogenation of alkynes, hydrogenation of nitroaromatics, CO hydrogenation, C-C coupling, and methane oxidation.

In Situ Biomineralization of CuZnSnS Nanocrystals within TiO-Based Quantum Dot Sensitized Solar Cell Anodes.

CuZnSnS (CZTS) quantum dots (QDs) have potential application in quantum dot sensitized solar cells (QDSSCs); however, traditional synthesis approaches typically require elevated temperatures, expensive precursors, and organic solvents that can hinder large-scale application. Herein we develop and utilize an enzymatic, aqueous-phase, ambient temperature route to prepare CZTS nanocrystals with good compositional control. Nanoparticle synthesis occurs in a minimal buffered solution containing only the enzyme, metal chloride and acetate salts, and l-cysteine as a capping agent and sulfur source.

Benzyl alcohol oxidation with Pd-Zn/TiO: computational and experimental studies.

Pd-Zn/TiO catalysts containing 1 wt% total metal loading, but with different Pd to Zn ratios, were prepared using a modified impregnation method and tested in the solvent-free aerobic oxidation of benzyl alcohol. The catalyst with the higher Pd content exhibited an enhanced activity for benzyl alcohol oxidation. However, the selectivity to benzaldehyde was significantly improved with increasing presence of Zn.

Synthesis of highly uniform and composition-controlled gold-palladium supported nanoparticles in continuous flow.

The synthesis of supported bimetallic nanoparticles with well-defined size and compositional parameters has long been a challenge. Although batch colloidal methods are commonly used to pre-form metal nanoparticles with the desired size-range in solution, inhomogeneous mixing of the reactant solutions often leads to variations in size, structure and composition from batch-to-batch and even particle-to-particle. Here we describe a millifluidic approach for the production of oxide supported monometallic Au and bimetallic AuPd nanoparticles in a continuous fashion.

Hydrated Electron Generation by Excitation of Copper Localized Surface Plasmon Resonance.

Hydrated electrons are important in radiation chemistry and charge-transfer reactions, with applications that include chemical damage of DNA, catalysis, and signaling. Conventionally, hydrated electrons are produced by pulsed radiolysis, sonolysis, two-ultraviolet-photon laser excitation of liquid water, or photodetachment of suitable electron donors. Here we report a method for the generation of hydrated electrons via single-visible-photon excitation of localized surface plasmon resonances (LSPRs) of supported sub-3 nm copper nanoparticles in contact with water.

Low temperature aqueous synthesis of size-controlled nanocrystals through size focusing: a quantum dot biomineralization case study.

Traditional quantum dot synthesis techniques rely on the separation of nucleation and growth to control nanocrystal size. However, the same goal can be achieved through slow and continuous introduction of reactive precursors to keep the growth mechanism in the size focusing regime throughout synthesis. In this work, we demonstrate the efficacy of this approach within the framework of functional material biomineralization where, despite simultaneous nucleation and growth of particles, this growth mechanism enables size-controlled nanocrystal synthesis.

The microbiome of Crohn's disease aphthous ulcers.

Background: Reduced intestinal microbial diversity and bacterial imbalance (dysbiosis) are seen in studies of Crohn's disease. As it is difficult to obtain biopsy samples before disease presentation, the earliest mucosal lesions in Crohn's disease, aphthous ulcers, present the best chance at assessing microbial communities at the onset of disease or a new flare. The aim of our study was to compare the microbial communities of aphthous ulcers and adjacent normal mucosa from patients with Crohn's disease with normal mucosa from controls.