The poor solubility and permeability of Biopharmaceutics Classification System (BCS) Class IV drugs pose major challenges to achieving sufficient oral bioavailability and therapeutic efficacy. Improving drug dissolution is a key strategy to enhance bioavailability, which in turn can enable more effective targeting of drugs to their site of action. To address this, we formulated cefdinir, a model BCS Class IV compound, using three amorphisation strategies; solid dispersions, mesoporous silica dispersions, and co-amorphous systems to assess the impact of formulation on stability and dissolution. Formulations were prepared via spray drying and solvent immersion using different drug-to-polymer ratios, with miscibility predicted using Flory-Huggins theory. The amorphous nature of each system was confirmed using differential scanning calorimetry (DSC), polarised light microscopy (PLM), and powder X-ray diffraction (PXRD). Dissolution studies revealed significantly enhanced drug release from all formulations compared to crystalline cefdinir. Among them, solid dispersion and co-amorphous systems exhibited the greatest improvement in dissolution rates, attributed to their ability to maintain supersaturation and inhibit crystallisation via kinetic stabilisation. These systems also showed better physical stability under non-sink aqueous conditions. However, mesoporous silica dispersions demonstrated superior long-term stability, retaining over 95% drug content and preserving their amorphous structure across three storage conditions (25°C/0% RH, 40°C/0% RH, and 40°C/75% RH) for 6months. This was attributed to the confinement of the drug within silica pores and the absence of hygroscopic excipients. Overall, this study highlights the distinct advantages of each approach, emphasising the importance of balancing dissolution enhancement with solid-state stability, and supports the use of theoretical modelling to guide rational formulation design for poorly soluble drugs to improve oral bioavailability and enable more targeted therapeutic outcomes.

Copper barrier immunity to corrosion in groundwater conditions is a significant concern for nuclear waste isolation in deep geological repositories (DGR). Ongoing discussion surrounding the use of copper as a corrosion-resistant barrier highlights the need for further investigation, particularly through computational thermodynamic modeling, to refine our understanding of its immunity behavior. Here we re-examine the thermodynamic feasibility of copper oxidation in oxygen-free aqueous environments using updated thermodynamic data derived from density functional theory (DFT). Thermodynamic immunity is revisited in the context of possible deep geological repository (DGR) conditions, contrasting it with the potential for spontaneous copper oxidation. To this end, we map aqueous electrochemical conditions encountered by the copper surface of nuclear waste disposal containers, including O2 free anoxic environments, surface effects, and chloride- and sulfide-containing electrolyte solutions. We utilize predominance diagrams, generated using state-of-the-art DFT and the revised Helgeson–Kirkham–Flowers method, to probe the sensitivity of copper’s immunity to these various environmental parameters. We show that copper oxidation is thermodynamically favored over certain elevated temperatures and pressures─conditions that copper-lined nuclear waste disposal containers might be subjected to. Moreover, copper immunity is not assumed under all possible DGR conditions, strongly suggesting the use of multibarrier systems for long-term repositories that utilize copper as one corrosion resistance layer.

Ferrate (Fe(VI))-coated sand was developed as a heterogeneous Fe(VI) medium with potential for oxidation, coagulation, disinfection, and filtration processes during (waste)water treatment. However, its reactivity under complex aqueous conditions is still unknown. Herein, we investigated the effect of representative effluent organic matter (EfOM) components─octanoic acid (OA), bovine serum albumin (BSA), alginate (ALG), and humic acid (HA)─on Fe(VI)-coated sand treatment of acetaminophen (ACM), phenol (PHE), sulfamethoxazole (SMX), copper (Cu), lead (Pb), and zinc (Zn) in a synthetic wastewater effluent matrix. While EfOM composition influenced the oxidation of SMX and PHE, there was no observed effect on ACM oxidation. In the presence of HA, 80% PHE degradation was observed within 15 min of reaction by the Fe(VI)-coated sand compared to only 60% in the presence of BSA. Additionally, BSA decreased Fe(VI)-coated sand reactivity toward SMX and PHE. Removal of Cu, Pb, and Zn was nearly complete in the presence of OA within 15 min of reaction but varied (between 59–100%) in the presence of BSA, HA, and ALG, indicating that EfOM composition also affects Fe(VI)-coated sand reactivity toward metals. This study expands our knowledge of Fe(VI)-coated sand functionality for more nuanced water treatment applications.

The persistence of water-soluble plastics such as poly(vinyl alcohol) (PVA) in aquatic systems poses a growing environmental challenge due to their poor biodegradability and structural recalcitrance. Current technologies struggle to efficiently mineralize PVA at a low cost. Here, we present an immersed biotic-abiotic hybrid system that spatially couples a visible-light-active CTO photocatalyst with microbial biofilms on a porous scaffold. This dual-function platform enables rapid polymer chain scission via photoinduced superoxide radicals, followed by substantial microbial mineralization under ambient aqueous conditions. The system achieves 99.1% PVA removal and over 80% mineralization within 330 min, significantly outperforming standalone photocatalytic or biological processes, and maintains high degradation efficiency over multiple cycles. This work provides a scalable and ecologically adaptive strategy for polymer pollutant treatment by integrating light-driven catalysis with microbial metabolism.

ABSTRACT The selective conversion of cellulose into ethylene glycol (EG) under aqueous conditions is an attractive yet challenging route for sustainable biomass valorization. Herein, a multifunctional Pd/WMoAlNiSiO x catalyst was developed through a polyvinylpyrrolidone (PVP)‐assisted sol‐gel strategy, where Pd nanoparticles and PdNi alloy domains were uniformly embedded within an entropy‐stabilized high‐entropy oxide (HEO) matrix. The high configurational entropy promoted the generation of abundant oxygen vacancies and stabilized Pd‐O(H)‐M (M = W, Mo, Al, Ni, and Si) interfacial linkages, creating a robust bifunctional interface with cooperative hydrogenation and Lewis acid sites. Under mild hydrothermal conditions (245°C, 4.5 MPa H 2 ), the catalyst achieved complete cellulose conversion and 68.3% EG selectivity, outperforming conventional Pd/WO 3 systems. Characterization and kinetic studies confirmed that the enhanced performance originated from synergistic interactions between PdNi alloy domains and oxygen‐deficient HEO interfaces, which facilitate tandem hydrolysis, retro‐aldol cleavage, and hydrogenation. The catalyst also exhibited excellent structural stability and minimal Pd leaching after multiple recycling cycles. This study demonstrates a sustainable catalyst design concept based on entropy‐stabilized oxide–metal interfaces, providing a promising approach for efficient biomass conversion in aqueous‐phase environments.

We present a methionine-selective, nonreversible bioconjugation strategy that employs activated allylic bromides under mild, aqueous reaction conditions compatible with various peptides and proteins. Compared with conventional allylic bromides, our method improves conjugate stability and suppresses nonspecific reactivity under the examined reaction conditions. This method enables methionine-preferred labeling of peptides and proteins, and provides proof-of-concept applications in covalent inhibitor design and protein functionalization. As a complementary addition to existing methionine bioconjugation strategies, this chemistry expands the toolkit available for protein modification and chemical biology research.

We expanded our previous mapping of the peptide condensation reaction mechanism from the linear dipeptide formation to the cyclization reaction that results in diketopiperazines. The overarching theme of our computational investigations is a reaction network that connects all intermediates via proton-transfer pathways. We conducted the simulations designed to be predictive in a range of environments, such as the gas phase, hydrothermal aqueous conditions, deliquescent salts, and bulk water. While the free-energy profiles are similar to the linear peptide, the presence of the cis amide bond leading to a pre-arranged vicinity of the two reacting groups and the role of explicit solvent molecules revealed new mechanistic insights that differentiate the linear versus cyclic peptide formation/hydrolysis reactions. The rate-determining step corresponds to the final water-elimination reaction using the most realistic computational models with both implicit and explicit water solvation models at neutral pH. At high pH, the highest barrier corresponds to the C-N bond formation at a significantly lower free energy, while at low pH, the water elimination step's barrier increases by close to 30%; thus, effectively shutting down the reaction in agreement with experiments. Due to the central role of proton transfer, we studied the impact of nuclear wave functions on all active H-centers. By utilizing two quantum protons, we document up to 0.1 Å impact on H positions, ca. 20 kJ mol-1 tunneling effects, and a significant change in the shape of the potential energy surface in comparison with the classical DFT calculations. The calculated reaction rates well reproduce the experimentally determined values under hydrothermal conditions.

Samples collected from the carbonaceous near-Earth asteroid Bennu and delivered to Earth by NASA's OSIRIS-REx mission contain organic molecules relevant to prebiotic chemistry. Stable isotopic measurements of extraterrestrial soluble organic matter provide critical insights into the formation pathways and alteration histories of such molecules, which hold significance for understanding the origins of life. We leverage state-of-the-art techniques for picomolar-scale isotopic analyses of amino acids in samples of Bennu and, for comparison, the carbonaceous meteorite Murchison. We report intramolecular δ13C values for glycine, which have not previously been measured in extraterrestrial materials; molecular-averaged δ13C values for amino acids, aldehydes, and ketones; and δ15N values for glycine, β-alanine, and D/L-glutamic acid. Intramolecular carbon isotope patterns of glycine in Bennu contrast with those in Murchison, suggesting distinct formation pathways. We explore several formation mechanisms and hypothesize that the observed glycine in Murchison formed dominantly by a Strecker-like synthesis under aqueous conditions, whereas the glycine currently found in Bennu may have formed mainly by modified radical-radical reactions in primordial ices at the cold, outer reaches of the early Solar System and retained its isotopic values throughout accretion and multiple episodes of aqueous alteration. This hypothesis is supported by the highly 15N-enriched δ15N values in Bennu amino acids (+170 to 277‰). Differences in the δ15N values of D- and L-glutamic acid (Δ = 87‰) in Bennu affirm published reports of enantiomeric differences in meteoritic amino acids and challenge the assumption of isotopic uniformity between amino acid chiral pairs.

In addition to well-known traditional synthetic illicit drugs like cocaine, amphetamines, and heroin, an increasing number of new psychoactive substances (NPS) are appearing on the global drug market. Among them, cathinones represent a prominent class. These amphetamine-like compounds contain a stereogenic center, resulting in the possible presence of two enantiomers. Pure enantiomers of cathinone derivatives are not commonly available, and their production is cost-intensive. Thus, there is very little knowledge about the possible distinct effects of single enantiomers of cathinones. The objective of this study was to evaluate the stability of a set of eight cathinone derivatives, namely 3-methylethcathinone, 3-methylmethcathinone, 4-methylethcathinone, 4-methylmethcathinone, ethylone, 3,4-trimethylene-α-ethylaminovalerophenone, 3,4-tetramethylene-α-pyrrolidinovalerophenone, and 3,4-trimethylene-α-pyrrolidinobutiophenone, over a six-month period. Any racemization that may have occurred under different storage and solution conditions was monitored and compared. Pure enantiomeric fractions were collected on a multi-milligram scale using semi-preparative HPLC under isocratic normal-phase conditions. A Phenomenex Lux® i-Cellulose-5, 5 μm 250 × 10 mm column containing cellulose tris(3,5-dichlorophenylcarbamate) served as the chiral selector. The tests showed that aqueous conditions, pH, temperature, chemical structure, sunlight, and oxygen influence compound stability. The long-term storage of cathinone derivative enantiomers was found to be optimal as solids under deep-freezing conditions or in a slightly acidified solvent where they are protected from air and light.

In this study, chlorogenic acid (CGA) was isolated from the methanolic extract of Prangos serpentinica, a plant adapted to serpentine soils known for their unique phytochemical profiles. Using preparative HPLC, 9.85 µg of CGA was obtained per milligram of extract. The isolated CGA was then utilized to synthesize a bio-inspired copper(0) nanocomposite (CGA-Cu(0)) through complexation with Cu(II) ions followed by chemical reduction using sodium borohydride. The resulting nanostructures were characterized by FT-IR, XRD, EDX, SEM, and TEM analyses, confirming the formation of metallic copper nanoparticles within the CGA matrix, with sizes ranging from 20 to 50 nm. The CGA-Cu(0) nanocomposite was then evaluated as a heterogeneous catalyst in the Henry reaction under aqueous conditions. Systematic optimization revealed that 3 mol% of the catalyst in water at 70°C provided β-nitroalcohols in high yields. Control experiments indicated the superior catalytic performance of CGA-Cu(0) compared to its unreduced form and bulk copper. The developed system presents an eco-friendly, cost-effective, and plant-based alternative to conventional metal catalysts in C-C bond-forming reactions. This study reports the first usage of CGA-metal complex as a catalyst in organic reactions.

Dynamic polymer networks (DPN) leverage transient cross-linking to yield macroscopic materials that exhibit self-healing and environmentally responsive behaviors. Despite the broad scope of chemical interactions available for cross-linking, imbuing those transient interactions into biologically compatible materials is difficult because many chemistries are incompatible with aqueous conditions, and it is difficult to tune preexisting biological interactions that have evolved over millions of years for specificity. To enable the assembly of chemically tunable and biologically compatible DPNs, we have developed a set of bifunctional, heteroaffinity cross-linkers (HAX) where the reactive moieties have different binding affinities to the same binding sites of an oligomeric protein. The use of cross-linking moieties with vastly different dissociation rates enables purification of protein modules with monodisperse HAX valencies. Assembly of DPNs from stoichiometrically identical pairs of protein modules then yields unique, metastable, nonequilibrium network topologies. Here, we demonstrate these concepts using the well-studied avidin-biotin interaction chemistry. We also develop a pH-sensitive HAX that yields DPNs with robust pH-responsive assembly dynamics, and demonstrate how this DPN can be made into a magnetically responsive, molecular delivery system to low-pH regions, such as tumor microenvironments.

ABSTRACT Dynamic polymer networks (DPN) leverage transient cross‐linking to yield macroscopic materials that exhibit self‐healing and environmentally responsive behaviors. Despite the broad scope of chemical interactions available for cross‐linking, imbuing those transient interactions into biologically compatible materials is difficult because many chemistries are incompatible with aqueous conditions, and it is difficult to tune preexisting biological interactions that have evolved over millions of years for specificity. To enable the assembly of chemically tunable and biologically compatible DPNs, we have developed a set of bifunctional, heteroaffinity cross‐linkers (HAX) where the reactive moieties have different binding affinities to the same binding sites of an oligomeric protein. The use of cross‐linking moieties with vastly different dissociation rates enables purification of protein modules with monodisperse HAX valencies. Assembly of DPNs from stoichiometrically identical pairs of protein modules then yields unique, metastable, nonequilibrium network topologies. Here, we demonstrate these concepts using the well‐studied avidin‐biotin interaction chemistry. We also develop a pH‐sensitive HAX that yields DPNs with robust pH‐responsive assembly dynamics, and demonstrate how this DPN can be made into a magnetically responsive, molecular delivery system to low‐pH regions, such as tumor microenvironments.

Catalytic hydrodeoxygenation (HDO) is critical for bio-oil upgrading, yet the selective cleavage of stable C(sp2)-OH bonds in lignin-derived substrates under aqueous conditions remains a challenge. Here, we report a heteroatomic zeolite catalyst, RuFA/SAPO-34-Nb, featuring few-atom Ru clusters on a Nb(V)-modified SAPO-34 framework, which achieves highly efficient HDO of lignin-derived creosol (2-methoxy-4-methylphenol) in water. Under mild conditions (250 °C, 7 bar H2, 24 h), this catalyst delivers quantitative conversion of creosol to toluene (99.2% conversion, 99.6% selectivity), fully preserving the aromaticity of lignin-derived feedstocks─a key requirement for sustainable production of chemicals. Synchrotron X-ray diffraction, X-ray absorption spectroscopy, and inelastic neutron scattering, combined with theoretical modeling, elucidate the cooperative mechanism: the Nb(V) sites selectively cleave the strong C-O bonds, while the few-atom Ru cluster generates hydrogen species with an exceptionally low rotational barrier of 65 cm-1. This synergistic interaction enables the direct and selective HDO of C(sp2)-O bonds without saturation of the aromatic ring. This work establishes a promissing strategy for aqueous-phase HDO catalysis and provides a general approach for designing bimetallic zeolite catalysts to convert lignin-derived compounds to value-added aromatic chemicals, advancing sustainable biorefinery processes.

Nerve agents pose severe risks to human health, underscoring the need for efficient decontamination strategies. This study explores metal-organic frameworks (MOFs) as catalytic platforms owing to their structural tunability, redox-active metal centers, and abundance of Lewis acidic sites. Single- and bimetallic UiO-series MOFs incorporating Ce(IV) and Zr(IV) (confirmed by inductively coupled plasma mass spectrometry) were synthesized using different approaches, including ligand exchange and controlled crystal growth, with four ligands: BDC, BDC-NH2, BDC-NO2, and BDC-(OH)2. These frameworks were systematically evaluated for the hydrolysis of p-nitrophenyl phosphate (PNPP), a simulant for G- and V-type nerve agents (e.g., sarin, VX). The design strategy leverages the redox activity and cooperativity of Ce/Zr nodes, alongside the caging effect of the MOF architecture, to enhance catalytic efficacy. Density functional theory (DFT) calculations provided mechanistic insights into sarin degradation, revealing how metal composition and linker functionality govern substrate binding and activation. Experimental results demonstrated that bimetallic Ce/Zr-MOFs with electron-withdrawing functional groups exhibit significantly accelerated hydrolysis under basic aqueous conditions. Notably, a Ce/Zr-MOF with -NO2 functionality achieved the shortest half-life of 1.16min. These findings highlight Ce/Zr-UiO frameworks as promising candidates for real-world nerve agent decontamination technologies.

Indigo dyes are historically significant and possess a unique π-conjugated core, making them valuable for both traditional pigments and emerging applications in organic electronics. A fundamental challenge is understanding how subtle molecular modifications, particularly substituent effects, quantitatively influence their conjugation extent and resulting color properties. This study systematically investigates the parent indigo and three N, N'-substituted derivatives (phenyl, ethyl, and vinyl) to elucidate the precise relationship between molecular structure, electronic properties, and visible light absorption. Density functional theory (DFT) and Time-dependent DFT (TD-DFT) calculations reveal how substituents modulate the HOMO-LUMO gap and intramolecular interactions, directly correlating with calculated absorption wavelengths (628 to 807nm) and predicted colors (medium blue to green-cyan) via complementary color theory. These findings provide a quantitative framework for designing indigo-based dyes with targeted optical properties, including near-infrared absorption. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed. Ground-state geometry optimizations and frequency calculations were carried out using the B3LYP-D3(BJ) functional with the def2TZVP basis set. Excited-state calculations employed the CAM-B3LYP-D3(BJ)/def2TZVP level, with the IEFPCM solvation model simulating aqueous conditions. The Multiwfn 3.8 and VMD 1.9.3 software packages were used for interaction region indicator (IRI) analysis, electrostatic potential (ESP) mapping, electron density difference (EDD) analysis, hole-electron analysis, and color prediction based on absorption spectra.

The development of oxidation-resistant and regenerable materials remains a major challenge for mercury removal from contaminated waters and industrial effluents. In this study, a zwitterionic mesoporous silica gel functionalized with L-cysteine (SG-3PS-Cys) was synthesized, where the thiol group is covalently anchored to the silica framework, preventing oxidative degradation while preserving -NH3+ and -COO- groups for Hg(II) coordination. Spectroscopic analyses (FTIR, XPS, and 13C NMR) confirmed the formation of a stable, thiol-free binding environment in which mercury interacts through carboxylate oxygen atoms, electrostatically stabilized by neighboring ammonium groups. The material exhibited a high surface area (134 m2 g-1) and uniform mesoporosity (9.8 nm), achieving a maximum Hg(II) uptake of 82.7 mg g-1 at pH 3 with rapid kinetics and cooperative S-type isotherms. The adsorbent retained 72% of its capacity after five regeneration cycles and maintained 38.7% selectivity toward Hg(II) in multicomponent solutions. DFT-based surface energy distribution analysis supported the zwitterionic coordination mechanism, revealing energetically homogeneous and high-affinity binding domains. Beyond its chemical stability, the material introduces a sustainable route for mercury remediation, linking surface energy, electrostatic effects, and porosity to achieve durable performance under acidic and complex aqueous conditions. These findings provide a mechanistic and design framework for the next generation of non-thiol adsorbents capable of selective and reusable Hg(II) removal in environmentally relevant scenarios.

Aqueous LC-MS/MS quantification of α-/β-nicotinamide mononucleotide in dietary supplements using a pentabromophenyl column.

The efficient removal of toxic organic dyes from wastewater is of great significance in water pollution remediation. In this work, an azo-functionalized Zr-MOF (UiO-67-BCDC) was successfully designed and synthesized. The successful modification of azo groups enables the formation of broader π-conjugated electron systems, thereby strengthening the π-π interactions between the MOF and dye molecules consisting of π-rich conjugated aromatic systems. UiO-67-BCDC achieves over 90% removal efficiency for small molecule dyes within 10 min. Under aqueous conditions at 313K and pH = 7, optimal adsorption performance was achieved at an adsorbent dosage of 0.50g/L, resulting in an adsorption capacity of 710.27mg/g for Basic Blue 3 (BB-3). The maximum adsorption capacity of UiO-67-BCDC toward BB-3 is 621.68mg/g at 303 K, approximately 1.2 times that of UiO-67. To prevent agglomeration and loss of powdery MOFs, the UiO-67-BCDC@SA membrane was made with sodium alginate (SA), achieving a BB-3 adsorption capacity of 507.04mg/g. This study demonstrates an effective strategy for dye removal by azo functionalization and membranization, producing a high-capacity adsorbent with exceptional performance.

β-Cyclodextrin-nickel biomacromolecular host system for sustainable ligand-free aqueous CC and CN cross-couplings of aryl chlorides: Toward donor-π-acceptor distyrylbenzene chromophores.

Interaction of plant genomic DNA with arsenic and cadmium: Double trouble or protective pair.