Recent uclachemeng items

Antigen-presenting nanoparticles for in vivo CAR T cell engineering

Wed, 12 Aug 2026 00:00:00 +0000

In vivo cell engineering enables chimeric antigen receptor (CAR) production directly within the body. Most in vivo CAR approaches target broad T cell populations. However, antigen-presenting nanoparticles could be used to engineer specific T cell subsets, leveraging the phenotypic and functional properties of the cells for T cell therapy.

Propellane Alkaloid Biosynthesis and Total Synthesis via Interrupted Reaction Pathways

Sun, 9 Aug 2026 00:00:00 +0000

Interrupted reactions, in which an intermediate is redirected from its conventional mechanistic pathway, offer a unique approach to the assembly of complex natural products. This study details the biosynthesis of a newly discovered family of alkaloids named the subrubines alongside the total synthesis of the penultimate member, pensubrubine, featuring distinct interrupted reaction pathways. These natural products, identified using high-resolution genome mining of an active site mutation, represent the only reported microbial diaza[3.3.3]-propellane pyrrolidinoindolines. We demonstrate through complete pathway reconstitution that the putatively annotated ene-reductase SubF functions as the propellane synthase that directs an enolate intermediate toward an intramolecular Mannich cyclization. Concurrently, a concise 7-step total synthesis of pensubrubine was developed, employing a diastereoselective interrupted Fischer indolization reaction to rapidly construct the diaza[3.3.3]-propellane...

Synthetic Biology in Natural Product Biosynthesis

Sun, 9 Aug 2026 00:00:00 +0000

Synthetic biology has played an important role in the renaissance of natural products research during the post-genomics era. The development and integration of new tools have transformed the workflow of natural product discovery and engineering, generating multidisciplinary interest in the field. In this review, we summarize recent developments in natural product biosynthesis from three different aspects. First, advances in bioinformatics, experimental, and analytical tools to identify natural products associated with predicted biosynthetic gene clusters (BGCs) will be covered. This will be followed by an extensive review on the heterologous expression of natural products in bacterial, fungal and plant organisms. The native host-independent paradigm to natural product identification, pathway characterization, and enzyme discovery is where synthetic biology has played the most prominent role. Lastly, strategies to engineer biosynthetic pathways for structural diversification and...

Traces of Elements in the Electrochemical Reductive Amination of Acetone: Uncovering Bi as Substitute for Pb

Tue, 30 Jun 2026 00:00:00 +0000

Amines are broadly utilized as solvents, pharmaceuticals, herbicides, or materials. A benign synthesis route to produce amines from carbonylic substrates is the electrochemical reductive amination, whereby electrons combined with a green proton source like water serve as formal reducing agent. Surprisingly, investigating various p-block elements as mediator for the electrochemical conversion of acetone in presence of methylamine revealed that only elements of the sixth period show an activity. Building up on these findings and the general low toxicity of Bi compared to Tl or Pb, the electrochemical hydrogenation of N-methylpropan-2-imine was optimized by studying the effect of Bi concentration, reaction temperature, and cathode material. Thus, this work highlights Bi as innovative mediator for the electrochemical reductive amination, whereby in presence of a few ppm-amounts of Bi at ambient temperatures high amine yields are achievable.

Elementspuren in der elektrochemischen reduktiven Aminierung von Aceton: Enthüllung von Bi als Ersatz für Pb

Tue, 30 Jun 2026 00:00:00 +0000

ZUSAMMENFASSUNG Amine werden häufig als Lösungsmittel, Pharmazeutika, Herbizide oder Materialien verwendet. Eine umweltfreundliche Syntheseroute zur Herstellung von Aminen aus Carbonylverbindungen ist die elektrochemische reduktive Aminierung, bei der Elektronen in Kombination mit einer grünen Protonenquelle wie Wasser als formales Reduktionsmittel agieren. Die Untersuchung verschiedener Elemente des p‐Blocks als Mediator für die elektrochemische Umsetzung von Aceton in Gegenwart von Methylamin offenbarte überraschenderweise, dass nur Elemente der sechsten Periode eine Aktivität aufweisen. Aufbauend auf diesen Ergebnissen und der generell geringen Toxizität des Bi im Vergleich zu Tl oder Pb, wurde die elektrochemische Hydrierung von N ‐Methylpropan‐2‐imin durch Untersuchung des Einflusses der Bi‐Konzentration, der Reaktionstemperatur und des Kathodenmaterials optimiert. Diese Arbeit hebt somit Bi als innovativen Mediator für die elektrochemische reduktive Aminierung hervor, wobei...

Direct Electrochemical Reduction of Ammonium Carbamate on Transition Metal Surfaces: Finding Activity and Stability Descriptors beyond those for CO2 Reduction

Sun, 28 Jun 2026 00:00:00 +0000

Experiments and theory are combined to search for catalyst activity and stability descriptors for the direct reactive capture and conversion (RCC) of CO2 in ammonia capture solutions using Cu, Ag, Au, Sn and Ti electrodes. Two major phenomena emerge in RCC that are not predominant in the electrochemical CO2 reduction (CO2R) reaction, namely, the rapid corrosion and restructuring of the catalyst in the presence of the CO2-ammonia adducts, and the promotion of the competing hydrogen evolution reaction (HER). The prevalence of HER in RCC is correlated to the electrostatic attraction of the protonated amine and repulsion of the captured CO2 to the electrode, using the potential of zero charge (PZC). The stability of catalysts under RCC conditions is a function of the applied potential, and cannot be readily predicted using binding energy descriptors commonly used in the prediction of CO2R activity. Three different trends are experimentally observed under RCC testing: i) Cu, and Sn...

Structure Sensitivity and Catalyst Restructuring for CO2 Electro-reduction on Copper

Sun, 28 Jun 2026 00:00:00 +0000

Cu is the most promising metal catalyst for CO2 electroreduction (CO2RR) to multi-carbon products, but the structure sensitivity of the reaction and the stability versus restructuring of the catalyst surface under reaction conditions are still controversial. Here, atomic scale simulations of surface energies and reaction pathway kinetics supported by experimental evidence unveil that CO2RR does not take place on perfect planar Cu(111) and Cu(100) surfaces but rather on steps or kinks defects, and that these planar surfaces tend to restructure in reaction conditions to the active stepped surfaces. By combining basin hopping global sampling and grand canonical density functional theory, we show that the extremely low CO coverage on (111) and (100) surfaces, originating from sluggish CO2 conversion and unfavorable CO binding, limits the ability of these surfaces to reduce CO2 to multi-carbon products. Steps and kinks at surfaces, despite the lack of decrease in C-C coupling barriers...

H and CO Co-induced Adatom Formation on Cu in CO2 Electroreduction Conditions

Sun, 28 Jun 2026 00:00:00 +0000

Dynamic restructuring of Cu electrode has been observed under electrochemical conditions, and it has been hypothesized to underly the unique reactivity of Cu towards CO2 electroreduction. Surface roughening is one of the key surface phenomena to Cu activation, in which the surface forms numerous atomic vacancies and adatoms. However, the atomic structure of such surface motifs, in the presence of relevant adsorbates has remained elusive. Here, we explore the chemical space of Cu surface restructuring under coverage of CO and H in realistic electroreduction conditions, by a combination of grand canonical density functional theory and global optimization techniques, from which we construct a potential-dependent grand canonical ensemble representation of the surface. Significant vertical displacement of surface Cu atoms is observed in the regime of intermediate and mixed CO and H coverage. This regime, while predicted to be thermodynamically inaccessible, is kinetically controlled,...

Electrocatalytic hydrogen evolution at full atomic utilization over ITO-supported sub-nano Ptn clusters: High, size-dependent activity controlled by fluxional Pt hydride species

Sun, 28 Jun 2026 00:00:00 +0000

A combination of density functional theory (DFT) and experiments with atomically size-selected Ptn clusters deposited on indium-tin oxide (ITO) electrodes was used to examine the effects of applied potential and Ptn size on the electrocatalytic activity of Ptn (n = 1, 4, 7, 8) for the hydrogen evolution reaction (HER). Activity is found to be negligible for isolated Pt atoms on ITO, increasing rapidly with Ptn size, such that Pt7/ITO and Pt8/ITO have roughly double the activity per Pt atom compared atoms in the surface layer of polycrystalline Pt. Both DFT and experiment find that hydrogen under-potential deposition (Hupd) results in Ptn/ITO (n = 4, 7, 8) adsorbing ~2 H atoms/Pt atom at the HER threshold potential, equal to ca. double the Hupd observed for bulk Pt or Pt nanoparticles. The cluster catalysts under electrocatalytic conditions are hence best described as a Pt hydride compound, significantly departing from a metallic Pt cluster. The exception is Pt1/ITO, where H adsorption...

Solution and Active Site Speciation Drive Selectivity for Electrocatalytic Reactive Carbon Capture in Diethanolamine over Ni–N–C Catalysts

Sun, 28 Jun 2026 00:00:00 +0000

Direct conversion of captured forms of carbon, or reactive carbon capture (RCC), presents an opportunity to reduce the energy intensity and cost of direct CO₂ utilization from dilute sources. While amine-based sorbents effectively capture CO₂, their use for RCC presents numerous challenges with typical pure metal catalysts used for electrochemical CO₂ reduction (CO₂R). Here, using both theory and experiments, we find that Ni-N-C single atom catalysts are effective for RCC conversion to CO using a diethanolamine sorbent, in contrast to pure metal catalysts. Computational analysis reveals that RCC can proceed directly through direct reduction of the sorbent-CO₂ adduct or indirectly by C-N bond breaking facilitating CO₂ adsorption and subsequent reduction. We find that the latter mechanism is most prevalent at low overpotentials where we experimentally observe RCC selectivity. We also find experimentally that the rate...

Cu-supported ZnO in Conditions of CO2 Reduction to Methanol: Why 0.2 ML Coverage?

Sun, 28 Jun 2026 00:00:00 +0000

By hydrogenating carbon dioxide to value-added products such as methanol, heterogenous catalysts can lower greenhouse gas emissions and generate alternative, liquid fuels. The most common commercial catalyst for CO2 reduction to methanol is Cu/ZnO/Al2O3, where ZnO improves conversion and selectivity toward methanol. The structure of this catalyst is thought to be Zn oxy(hydroxyl) overlayers at the nanometer scale on Cu. In the presence of CO2 and H2 under reaction conditions, the Cu substrate itself can be restructured and/or partially oxidized at its interface with ZnO, or the Zn might be reduced, possibly completely to a CuZn alloy, making the exact structure and stoichiometry of the active site a topic of active debate. In this study, we examine Zn3 clusters on Cu(100) and Cu(111), as a sub-nano model of the catalyst. We use a grand canonical genetic algorithm to sample the system structure and stoichiometry under catalytic conditions: T = 550 K, initial partial pressures of...

Corrosion and Enhanced Hydrogen Evolution in Electrochemical Reduction of Ammonium Carbamate on Transition Metal Surfaces

Sun, 28 Jun 2026 00:00:00 +0000

Experiments and theory are combined to search for catalyst activity and stability descriptors for the direct reactive capture and conversion (RCC) of CO2 in ammonia capture solutions using Cu, Ag, Au, Sn and Ti electrodes. Two major phenomena emerge in RCC that are not predominant in the electrochemical CO2 reduction (CO2R) reaction, namely, the rapid corrosion and restructuring of the catalyst in the presence of the CO2-ammonia adducts, and the promotion of the competing hydrogen evolution reaction (HER). The prevalence of HER in RCC is correlated to the electrostatic attraction of the protonated amine to the electrode and the repulsion of the captured CO2, using the potential of zero charge (PZC). The stability of catalysts under RCC conditions is a function of the applied potential and cannot be readily predicted using binding energy descriptors commonly used in the prediction of CO2R activity. Three different trends are experimentally observed under RCC testing: i) Cu, and...

Beyond Boltzmann: thermalization of cluster catalyst ensembles can extend beyond reaction timescales

Sun, 28 Jun 2026 00:00:00 +0000

The fluxionality of subnanocluster catalysts is essential for understanding their be- havior at an atomistic level. Up until now, when it is at all considered, fluxionality has been treated primarily thermodynamically, representing relevant isomer populations as their Boltzmann populations. Previous work supported this, suggesting that the Pt7/Al2O3 ensemble should be kinetically accessible within ns, based on the barrier heights for isomerization. In the current work, we explore the isomerization kinetics of gas-phase and surface-supported Pt4Hx clusters, using kMC to explore the evolution of isomer populations with time as a function of temperature. We additionally revisit the previously-obtained Pt7/Al2O3 network. This allows us to determine the temperature- dependent timescales at which the ensembles of these subnanoclusters reach thermal equilibirum. Gas-phase clusters readily thermalize by 350 K, while surface-supported clusters require temperatures between 500-700 K. These...

Mechanism of Stoichiometrically Governed Titanium Oxide Brownian Tree Formation on Stepped Au(111)

Sun, 28 Jun 2026 00:00:00 +0000

Previously observed formation of sub-stoichiometric titanium oxide dendritic structures across terraces of Au(111) are computationally studied and shown to follow the classical fractal formation mechanism of diffusion limited aggregation (DLA). Globally optimized gas-phase oxide cluster structures were sampled in a variety of landing formations on gold surfaces and shown to favor isomers driving polymerization to Brownian tree fractal structures. Mobility of Ti3O5 monomers is shown to be extremely high, with diffusion barriers of 0.21 eV or less. Through bonding stabilization, polymerization of these monomers is energetically favorable and irreversible on the 111 terrace, but geometrically impossible to propagate along the step edge. Simulated STM images show strong similarity to experiment. By contrast, observation of Ti3O6 aggregating as wires along step edges is explained by affinity of oxygen to step edges and statistical arguments for aggregation entropy at the step, in addition...

Hybrid catalysis-reactive sorption mechanism for 2-CEES and sulfur mustard dehydrochlorination on single metal atoms on anatase–TiO 2

Fri, 26 Jun 2026 00:00:00 +0000

The threat posed by chemical warfare agents (CWAs) in the modern era necessitates increased innovation in understanding new mechanisms to neutralize their lethality. By identifying novel materials and chemical reaction pathways, better protection can be offered. Single metal atoms supported on TiO₂ represent a promising avenue of exploration in designing systems which can effectively capture and degrade the sulfur mustard agent. By modelling sulfur mustard and its simulant, 2-chloroethyl-ethylsulfide (2-CEES), this work provides a proof of concept for the facile decomposition pathways of sulfur-containing vesicant agents over Pt, Pd, and Ir single atoms on the anatase TiO₂(101) surface with and without the presence of water. Under ambient conditions, 2-CEES will favorably be transformed into ethyl-vinylsulfide (EVS) through a dehydrochlorination reaction involving C-H and C-Cl bond cleavages. Notably, the single atom cleaves the α-C-H bond with a low calculated...

Electrochemical Amination of Acetone using Ag as Cathode: Mechanism and Role of Pb Impurities for Hydrogen Transfer

Fri, 26 Jun 2026 00:00:00 +0000

Electrochemical reductive amination of acetone using Ag electrodes is strongly enhanced by 1 ppm Pb in the solution but the underlying mechanisms and the nature of the Pb species remain poorly understood. Electrochemical reductive amination of acetone using Ag electrodes is strongly enhanced by 1 ppm Pb in the solution but the underlying mechanisms and the nature of the Pb species remain poorly understood. To understand how trace elements alter reaction pathways and enhance catalytic performance, the catalytic behavior of Pb traces in electrochemical hydrogenation was theoretically investigated. Using computational modeling, we examined the formation of Pb hydrides (PbH 2 and PbH 4 ) on the electrified silver surface at the highly reducing potential used experimentally and their reactivity either at the polarized surface or in the solution in proximity of the electrode, including for hydrogen transfer towards the imine intermediate in the electrocatalytic amination of acetone...

Quantifying Hydroxyl Adsorption on Copper with Electrochemical-Aware Random Phase Approximation

Fri, 26 Jun 2026 00:00:00 +0000

Accurate adsorption thermodynamics of reactive intermediates at electrified metal interfaces are central to predictive surface science, heterogeneous catalysis, and electrochemical modeling, yet remain challenging for standard density functional approximations and difficult to benchmark experimentally. Here we apply electrochemical-aware random phase approximation (RPA) methods that incorporate solvent dielectric screening and grand-canonical constant-potential control to establish a reference-quality description of hydroxyl (*OH) adsorption on Cu(100) in electrocatalytic conditions. At the potential of zero charge (pzc), we quantify the site dependence of *OH binding across terrace sites and representative defective motifs. Under applied potential, electrochemical-aware RPA reproduces the experimentally inferred *OH desorption fingerprint, predicting an *OH desorption potential of -0.54 V vs SHE, in excellent agreement with experimental value -0.56 V vs SHE at pH = 7, whereas...

Early transition metal Cu-based single-atom alloys for selective propane dehydrogenation to propylene

Fri, 26 Jun 2026 00:00:00 +0000

Propane dehydrogenation is a major reaction in industry, as it transforms the abundant propane into propylene, which is a vital raw material for higher-value products. Although Pt-based catalysts have been extensively used for this process, challenges such as over-dehydrogenation and coking often pose obstacles to their effectiveness. Here, we show from first-principles calculations that single-atom alloys formed by dispersing more electropositive, earlier transition metals into Cu(111) could potentially enhance the reactivity and selectivity for propylene formation. Density functional theory (DFT) calculations show that CuIr1 possesses reactivity comparable to pure Pt and that it does not lead to over-dehydrogenation beyond propylene. An even higher propylene production rate, surpassing Pt(111) by 10-fold, is predicted using earlier Hf with CuHf1. This study demonstrates the depletion of anti-bonding orbitals and, hence, the stronger interaction between the rate-limiting transition...

Time-dependent surface polarization breaks static scaling relationship for selective acetylene hydrogenation

Fri, 26 Jun 2026 00:00:00 +0000

Controlling the surface-adsorbates interactions is critical to advancing numerous chemical processes. Static scaling correlations between adsorption energies of chemically related surface species impose limits on selectivity in chemical processes, as exemplified by constraints in heterogeneous catalysis. Here we demonstrate that dynamic surface polarization under oscillating electric potentials can overcome this limitation in Pd-catalysed acetylene semi-hydrogenation. Unlike static polarization, which only imparts a minor improvement to ethylene selectivity, dynamic polarization drastically enhances selectivity without further sacrificing conversion, yielding a high ethylene productivity. Mechanistic insights from hydrogenation kinetics, in situ diffuse reflectance infrared Fourier transform spectroscopy, X-ray absorption spectroscopy and density functional theory reveal that time-dependent polarization dynamically modulates the Pd’s electronic structure and adsorption energetics....

Mechanistic Insights into the Selectivity of Catalytic CO2 Hydrogenation to High-Value Chemicals over Fe–Co Bimetallic Catalysts

Fri, 26 Jun 2026 00:00:00 +0000

Carbon dioxide hydrogenation has captured significant attention as a key reaction in CO2 valorization. This reaction has proved valuable as it is considered as both a mitigating solution to harmful greenhouse gas emissions and a production method of high-value chemicals and fuels. Due to the thermal stability of CO2, an intermediate C1 building block is required to initiate the formation of valuable C2+ hydrocarbon products. As such, considerable previous research has sought to identify possible precursor-mediated pathways for the formation of C2+ products, revealing two as the most prominent: (1) methanol-synthesis route, where methanol is the C1 precursor, and (2) Fischer–Tropsch synthesis (FTS) route, which utilizes CO as the C1 precursor. For the FTS route, Fe and Co catalysts have proven to be the most promising. However, the wide range of products formed with such catalysts imposes a challenge on understanding the underlying mechanism of FTS, and thus selectivity control...

Ensemble of Active Acid Sites on Amorphous Silica–Alumina Surfaces for Catalytic Cracking

Fri, 26 Jun 2026 00:00:00 +0000

Amorphous silica-alumina are critical materials in catalysis, particularly for fluid catalytic cracking (FCC). However, the atomic scale understanding of the active sites has been challenging, because of the nonuniform atomic distribution and the material's amorphous nature. Here, we use density functional theory (DFT), machine learning potentials and sampling methods to investigate the relationship between structure and acidity in silica-modified alumina. Under FCC conditions, we predict an ensemble of acid sites with diverse local structures and a spectrum of acid strengths, including zeolite-like bridging Brønsted acid sites (BAS) and pseudo-bridging silanol BAS. This distribution is influenced by surface structure, Si coverage, and extent of hydroxylation, shaped by synthesis methods and reaction conditions. Experiments using a model Si-stabilized alumina catalyst confirm that Brønsted acidity increases with Si content, peaking at an optimal value before declining. These insights...

High‐Performance Cu6Sn5 Alloy Electrocatalysts for Formaldehyde Oxidative Dehydrogenation and Bipolar Hydrogen Production

Fri, 26 Jun 2026 00:00:00 +0000

Aldehyde-assisted water electrolysis offers an attractive pathway for energy-saving bipolar hydrogen production with combined faradaic efficiency (FE) of 200% while converting formaldehyde into value-added formate. Herein we report the design and synthesis of noble metal-free Cu₆Sn₅ alloy as a highly effective electrocatalyst for formaldehyde electro-oxidative dehydrogenation, demonstrating a geometric current density of 915 ± 46 mA cm^-2 at 0.4 V versus reversible hydrogen electrode, outperforming many noble metal electrocatalysts reported previously. The formaldehyde-assisted water electrolyzer delivers 100 mA cm^-2 at a low cell voltage of 0.124 V, and a current density of 486 ± 20 mA cm^-2 at a cell voltage of 0.6 V without any iR compensation and exhibits nearly 200% faradaic efficiency for bipolar hydrogen production at 100 mA cm^-2 in 88 h long-term...

Modeling CO2 Hydrogenation to Methanol on an Ensemble of Inverse ZrO2 on Cu Catalytic Sites: Mechanism, Reactivity, and Deactivation

Fri, 26 Jun 2026 00:00:00 +0000

ABSTRACT Inverse ZrO 2 /Cu catalysts, where Zr oxide is deposited on Cu particles, show a high catalytic performance converting CO 2 to methanol. We employ density functional theory (DFT) calculations to investigate the CO 2 hydrogenation reaction mechanisms on a model of highly dispersed Zr oxide clusters on Cu (111). The exploration is not performed on a single active site configuration but across an ensemble of 83 formate configurations accessible under reaction conditions. Detailed reaction‐pathway analysis reveals that structural sensitivity is pronounced, and only 10 of the catalyst configurations are significantly active across the full pathway. The turnover frequency of the studied inverse structures is largely determined by reaction steps after methoxy formation, rather than the formate hydrogenation steps, and the energy of the methoxy intermediate is a key reactivity descriptor. Two hypotheses are presented for the ensemble average activity: where the probabilities...

Modeling CO2 Hydrogenation to Methanol on an Ensemble of Inverse ZrO2 on Cu Catalytic Sites: Mechanism, Reactivity, and Deactivation

Fri, 26 Jun 2026 00:00:00 +0000

Inverse ZrO₂/Cu catalysts, where Zr oxide is deposited on Cu particles, show a high catalytic performance converting CO₂ to methanol. We employ density functional theory (DFT) calculations to investigate the CO₂ hydrogenation reaction mechanisms on a model of highly dispersed Zr oxide clusters on Cu (111). The exploration is not performed on a single active site configuration but across an ensemble of 83 formate configurations accessible under reaction conditions. Detailed reaction-pathway analysis reveals that structural sensitivity is pronounced, and only 10 of the catalyst configurations are significantly active across the full pathway. The turnover frequency of the studied inverse structures is largely determined by reaction steps after methoxy formation, rather than the formate hydrogenation steps, and the energy of the methoxy intermediate is a key reactivity descriptor. Two hypotheses are presented for the ensemble average activity: where...

Structural Evolution of Pt Nanoclusters Driven by CO Reactant Pressure and Catalyst Temperature.

Fri, 26 Jun 2026 00:00:00 +0000

The atomic-scale structure of a metal catalyst surface controls its catalytic performance. Through a combination of high-pressure scanning tunneling microscopy (HP-STM), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), and machine learning-accelerated computational studies, we uncovered that Pt nanoclusters, formed by restructuring of hex-Pt(100) under reaction conditions involving CO, experience major structural evolution when exposed to increasing CO pressure in the range of 2 × 10^-8-750 Torr. Atom-resolved images and simulations demonstrate that CO binds strongly on these nanoclusters, leading to a CO coverage of one molecule per Pt atom, while the lateral CO-CO repulsion is released by tilting CO molecules outward at the nanocluster edge. Metal nanoclusters break down along as CO pressure is increased from 2 × 10^-8 to 1 Torr with the average size decreasing from 3.2 ± 1.5 to 2.3 ± 1.0 nm, consistent with Pt 4f_7/2 photoemission feature...

In Situ Formed Pt–Ga Hetero Duo-Atomic Catalyst for Efficient Hydrogen Storage in N‑Heterocycles

Fri, 26 Jun 2026 00:00:00 +0000

Efficient catalysts for the dehydrogenation and hydrogenation of liquid organic hydrogen carriers (LOHCs) are essential for advancing hydrogen storage and transportation. Conventional nanoparticle catalysts suffer from low metal utilization, while single-atom catalysts (SAC) are limited by isolated active sites. Here, we present a hetero duo-atomic catalyst, Pt₁-Ga₁/CeO₂ DAC, which exhibits exceptional activity, selectivity, stability, and recyclability for N-heterocycle hydrogen storage. Ga plays a critical role in C-H bond activation, acting as a mediator in catalytic bond-breaking and formation. Compared with Pt₁/CeO₂ SAC, Pt₁-Ga₁/CeO₂ DAC enhances metal utilization while overcoming SAC limitations for large substrates. This work establishes a promising strategy for designing highly efficient catalysts for LOHC applications.

Sarin Decomposition on a Pt Cluster Supported on Anatase-TiO2 in Ambient Conditions

Fri, 26 Jun 2026 00:00:00 +0000

Organophosphorus chemical warfare agents (CWAs) such as sarin are highly toxic and inhalation hazards for personnel at risk to exposure to such compounds are typically mitigated using metal-impregnated activated carbon in gas mask filters. In this work we considered anatase (a-) TiO₂ and a Pt cluster supported on a-TiO₂ as potential active filtration materials. Density functional theory (DFT) calculations combined with Fourier transform infrared (FTIR) spectroscopy were used to probe sarin adsorption and decomposition mechanisms. Using the grand canonical basin hopping (GCBH) technique, the structural stability and reactivity of Pt₆O_x clusters supported on a-TiO₂(101) were examined under ambient oxidative conditions, identifying the global minimum and thermodynamically accessible metastable configurations. The Pt₆ cluster is partially oxidized to Pt₆O₁₀ on a-TiO₂ in ambient...

Metabolite biomarkers in lung cancer: unlocking the potential of body fluid analysis for early detection and prognosis-a narrative review.

Thu, 21 May 2026 00:00:00 +0000

Background and objective

Lung cancer is a leading cause of cancer-related mortality, due to delayed diagnosis and the complexity of selecting the optimal treatment method, given the genetic diversity and heterogeneity of the disease. Traditional invasive techniques, such as tissue biopsy, carry risks of severe complications and are often costly. Therefore, there is increasing interest in non-invasive alternatives, particularly liquid biopsy. This review aims to propose promising circulating metabolite biomarkers for lung cancer and their clinical applications.

Methods

A PubMed search [2014-2024] was conducted, focusing on fluid-based, non-invasive samples such as blood, urine, pleural effusion, and bronchoalveolar lavage fluid. Only English-language articles relevant to lung cancer metabolomics were included.

Key content and findings

Analysis of altered metabolites in lung cancer patients revealed significant metabolic pathway enrichments. Upregulated pathways...

Atomistic Landscape of Pt Nanoparticles via Machine Learning: How Size Effect and Hydrogen Adsorption Govern Structural Ensembles and Catalytic Activity