Click-and-Release Formation of Urea Bonds in Living Cells Enabled by Micelle Nanoreactors.

The development of innovative strategies enabling chemical reactions in living systems is of great interest for exploring and manipulating biological processes. Herein, we present a pioneering approach based on both bioorthogonal and confined chemistry for intracellular drug synthesis. Exploiting a click-to-release reaction, we engineered nanoparticles capable of synthesizing drugs within cellular environments through bioorthogonal reactions with cyclooctynes.

Unlocking Molecular Fingerprint of an Ombrotrophic Peat Bog: Advanced Characterization Through Hexamethyldisilazane Thermochemolysis and Principal Component Analysis.

This study examines a boreal peatland (the Sagnes peatland, Fanay, Limousin, France) with a depth of 1 m. This peatland is currently in the late stages of organic deposition, as evidenced by the growth of species, along with mosses, in the uppermost level. To gain molecular insights, we conducted an analysis of the lignin and polyphenolic counterparts using HMDS (hexamethyldisilazane) thermochemolysis, enabling the identification of lignin degradation proxies.

Advantages of Metabolomics-Based Multivariate Machine Learning to Predict Disease Severity: Example of COVID.

The COVID-19 outbreak caused saturations of hospitals, highlighting the importance of early patient triage to optimize resource prioritization. Herein, our objective was to test if high definition metabolomics, combined with ML, can improve prognostication and triage performance over standard clinical parameters using COVID infection as an example. Using high resolution mass spectrometry, we obtained metabolomics profiles of patients and combined them with clinical parameters to design machine learning (ML) algorithms predicting severity (herein determined as the need for mechanical ventilation during patient care).

An Open-Shell Functionalization of Inorganic Benzene.

A borazine derivative functionalized by nitroxide free radicals, ,',″-(tris(4-Bromophenyl))-,',″-tris((2,6-dimethyl-4-(--butyl--oxyamino)phenyl) borazine (), was synthesized as a milestone of open-shell inorganic benzene. The crystal structure determined from X-ray diffraction on a single crystal ascertains the grafting of three nitroxide radicals. The temperature dependence of the magnetic susceptibility evidences weak intramolecular antiferromagnetic interactions between the radicals with strong intermolecular antiferromagnetic interactions between two nitroxide moieties of two neighboring molecules.

Glycosylium Ions in Superacid Mimic the Transition State of Enzyme Reactions.

The hydrolysis of glycosides is a biochemical transformation that occurs in all living organisms, catalyzed by a broad group of enzymes, including glycoside hydrolases. These enzymes cleave the glycosidic bond via a transition state with substantial oxocarbenium ion character, resulting in short-lived oxocarbenium ion-like species. While such transient species have been inferred through theoretical studies and kinetic isotope effect measurements, their direct spectroscopic characterization remains challenging.

Superacid-Synthesized Fluorinated Diamines Act as Selective hCA IV Inhibitors.

Carbonic anhydrase (CA) IV is a membrane-bound enzyme involved in important physio-pathological processes, such as excitation-contraction coupling in heart muscle, central nervous system (CNS) extracellular buffering, and mediation of inflammatory response after stroke. Known since the mid-1980s, this isoform is still largely unexplored when compared to other isoforms, mostly for the current lack of inhibitors targeting selectively this isoform. The discovery of selective CA IV inhibitors is thus largely awaited.

Adsorption of methyl orange and methylene blue from aqueous solutions on pure bentonite: statistical physical modeling provides an analytical interpretation.

This study investigates the adsorption of methylene blue (MB) and methyl orange (MO) dyes from aqueous solutions using purified Moroccan bentonite, being mainly composed of silica and alumina, in the form of quartz and cristobalite. The temperature controls the adsorption capacity for the kinetics, increasing 5.08% (from 295.

A Zeolite-Templated Carbon Synthesized from Extralarge-Pore Zeolite ZEO-1.

A new member of the zeolite-templated carbon (ZTC) family with unprecedented properties has been developed using extralarge-pore zeolite ZEO-1 (JZO) as a template. The resulting ZTC-JZO exhibits strong X-ray diffraction long-range order, replicating three distinct zeolite planes with different lattice spacings. By harnessing the enhanced micropore void volume in the ZEO-1 template, we achieved the first ZTC with a bimodal micropore size distribution, resulting in superior skeleton density and thickness.

Enhancing the Catalytic Activity of Pd Nanocatalysts for Anion Exchange Membrane Direct Ethanol Fuel Cells by Functionalizing Vulcan XC-72 with Cu Organometallic Compounds.

The most widely used support in low-temperature fuel cell applications is the commercially available Vulcan XC-72. Herein, we report its functionalization with the home-obtained mesityl copper (Cu-mes) and Cu coordinate (Cu(dmpz)L2) organometallic compounds. Pd nanoparticles are anchored on the supports obtaining Pd/C, Pd/C, and Pd/C (on nonfunctionalized support).

Charge transfer interaction revisited by a Fermi-Dirac derived approach.

Context: In this article, we adapt a recent proposition to use a Fermi-Dirac-type population scheme on Kohn-Sham molecular orbitals to the case of an interaction with a thermalised electrode. This allows to derive a fundamental non-linear equation linking the chemical potential of the electrode and the amount of charge transferred to the system under study, hence allows to quantify the propensity to charge transfer (philicity). This methodology is applied to a large set of common electrophiles and nucleophiles, showing decent relation with more standard philicity descriptors.

Potential of Sorghum Seeds in Alleviating Hyperglycemia, Oxidative Stress, and Glycation Damage.

Diabetes mellitus, characterized by dysregulated glucose metabolism, oxidative stress, and the formation of advanced glycation end products, poses a significant global health burden. In this study, we explored the potential of sorghum () seeds, known for their abundant phytochemical composition, as a natural remedy for diabetes and its associated damage. High-performance liquid chromatography/high-resolution mass spectrometry analysis revealed a remarkable phenolic richness in sorghum grains, including gallic acid, quercetin, and the predominant procyanidin B-1, with ecotype-specific variations in flavonoid distribution.

Automated exploration of the conformational degrees of freedom along reaction profiles - driving a FASTCAR.

This publication aims at presenting a Python-based workflow designed to enable a fully automatised and exhaustive exploration of the conformational degrees of freedom within the calculation of reaction paths in molecular systems. The proposed strategy focuses on effectively representing the lowest energy conformers for intricate, highly rotatable, and non-intuitive transition states, reagents and products, using existing computational tools. The article presents a workflow that is demonstrated through the application of five chemical reactions, chosen to be representative of the diversity and complexity of actual experimental studies, and which often prove to be challenging to study "by hand".

Theoretical study of the catalytic hydrodeoxygenation of furan, methylfuran and benzofurane on MoS.

Herein, we have studied the direct deoxygenation (DDO) (without prior hydrogenation) of furan, 2-methylfuran and benzofuran on the metal edge of MoS with a vacancy created under pressure of dihydrogen. For the three molecules, we found that the desorption of the water molecule for the regeneration of the vacancy is the most endothermic. Based on the thermodynamic and kinetic aspects, the reactivity order of the oxygenated compounds is furan ≈ 2-methylfuran > benzofuran, which is in agreement with literature.

SBA-15 Supported Ni-Cu Catalysts for Hydrodeoxygenation of m-cresol to Toluene.

Amidst concerns over fossil fuel dependency and environmental sustainability, the utilization of biomass-derived aromatic compounds emerges as a viable solution across diverse industries. In this scheme, the conversion of biomass involves pyrolysis, followed by a hydrodeoxygenation (HDO) step to reduce the oxygen content of pyrolysis oils and stabilize the end products including aromatics. In this study, we explored the properties of size controlled NiCu bimetallic catalysts supported on ordered mesoporous silica (SBA-15) for the catalytic gas-phase HDO of m-cresol, a lignin model compound.

An Enzyme-Responsive Self-Immolative Recognition Marker for Manipulating Cell-Cell Interactions.

The development of innovative strategies for cell membranes engineering is of prime interest to explore and manipulate cell-cell interactions. Herein, an enzyme-sensitive recognition marker that can be introduced on cell surface via bioorthogonal chemistry is designed. Once functionalized in this fashion, the cells gain the ability to assemble with cell partners coated with the complementary marker through non-covalent click chemistry.

Formation of extraterrestrial peptides and their derivatives.

The formation of protein precursors, due to the condensation of atomic carbon under the low-temperature conditions of the molecular phases of the interstellar medium, opens alternative pathways for the origin of life. We perform peptide synthesis under conditions prevailing in space and provide a comprehensive analytic characterization of its products. The application of C allowed us to confirm the suggested pathway of peptide formation that proceeds due to the polymerization of aminoketene molecules that are formed in the C + CO + NH reaction.

Determination of the Hammett Acidity of HF/Base Reagents.

Harnessing the acidity of HF/base reagents is of paramount importance to improve the efficiency and selectivity of fluorination reactions. Yet, no general method has been reported to evaluate their acidic properties, and experimental designs are still relying on a trial-and-error approach. We report a new method based on F NMR spectroscopy which allows highly sensitive measures and short-time analyses.

Insights into adsorbable organic halogen analysis: Two overlooked factors impacting water quality assessment.

Adsorbable organic halogen (AOX) represents the total amount of halogenated organics that can be adsorbed on activated carbon (AC) from samples. Measuring AOX is crucial for assessing water quality, and any erroneous estimation of AOX risks misleading decision-makers. This study demonstrated two overlooked factors that may introduce biases to AOX measurement.

Accumulation, Characterization and Reactivity of Chiral Ammonium-Carboxonium Dications in Superacid.

The accumulation of chiral ammonium-oxocarbenium dications in superacid is evidenced by low-temperature NMR spectroscopy, X-ray diffraction analysis and confirmed by DFT calculations. Its potential for the diastereoselective remote hydrofunctionalization of non-activated alkene is also explored.

Role of zeolite content on the sorption properties of analcime-rich rocks from the Abinky Formation (Niger).

The Abinky formation, composed of analcimolites (i.e., rocks with <70 wt% analcime), underlies Tchirezrine II, which hosts the Imouraren (Niger) uranium deposit.