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Engineered Biomimetic Nanoparticles With Targeted Delivery of Chlorothiazide for the Treatment of Inflammatory Bowel Disease

ABSTRACT While conventional treatment strategies for inflammatory bowel disease (IBD) focus primarily on suppressing overactive immunity, there is still a lack of definitive interventions targeting key pathological mechanisms, such as intestinal barrier dysfunction, dysbiosis of the gut microbiome, and disrupted mucosal immune regulation. Using a high‐throughput drug screening platform, the present study successfully identified chlorothiazide (Chl), a lead compound with anti‐inflammatory potential, from a library of 3152 natural compounds. To further increase the bioavailability of Chl and mitigate its potential toxicity, we constructed a biomimetic delivery system based on engineered bacterial membrane‐encapsulated reactive oxygen species (ROS)‐responsive biomimetic nanoparticles (CHM NPs). This delivery system achieved targeted accumulation in inflamed colonic tissue in a mouse model of acute colitis and effectively facilitated the restoration of epithelial barrier function. Moreover, CHM NPs significantly altered the gut microbiome, increasing overall microbial abundance and diversity while increasing the abundance of gut Lactobacillus , which plays a crucial role in maintaining gut microecological homeostasis. We systematically elucidated the multifaceted mechanisms by which CHM NPs regulate gut homeostasis, remodel the microbial composition, and modulate innate immunity. These findings provide novel theoretical foundations and potential intervention strategies for the treatment of IBD and other related inflammatory conditions.

Elliptical acoustic resonator-enabled synchronous acoustic excitation by multiple laser beams in quartz-enhanced photoacoustic spectroscopy

We report synchronous excitation of an acoustic mode in quartz-enhanced photoacoustic spectroscopy (QEPAS) enabled by an elliptical acoustic resonator under multi-beam illumination. In this configuration, multiple laser beams distributed within the prong gap of a quartz tuning fork (QTF) coherently excite the same acoustic mode, leading to efficient acoustic energy confinement and enhanced coupling to the QTF. Finite-element simulations based on distributed line acoustic sources reveal that, compared with the resonator-free case, a half-wavelength acoustic resonator enhances the effective acoustic excitation by a factor of approximately 4, while a three-quarter-wavelength resonator provides a higher enhancement of about 7. These predictions are experimentally validated using a multi-pass cell-based QEPAS system incorporating an elliptical acoustic resonator. The results demonstrate that resonator-enabled synchronous multi-beam excitation reshapes the acoustic coupling behavior in QEPAS and provides a practical route toward high-sensitivity photoacoustic sensing beyond optical field-limited enhancement.

Conformational Editing Drives Covalent Hybridization for Nonlinear Optical Crystals

ABSTRACT The covalent integration of planar organic molecules with inorganic tetrahedra into crystalline solids is fundamentally constrained by steric repulsion. Open‐chain organic moieties predominantly adopt thermodynamically stable trans ‐conformations, which spatially hinder close approach and covalent bond formation, often leading to centrosymmetric architectures. Here, we first report a solvent‐driven conformational editing strategy that overcomes this long‐standing synthetic challenge. By modulating HBF 4 concentration, we reprogram biuret from a sterically hindered trans ‐conformer into a spatially accessible cis ‐conformer. This in situ conformational switching, validated by interacting region indicator analysis and Raman spectroscopy, providing a general kinetic pathway for previously inaccessible bond formations. The resulting non‐centrosymmetric hybrid crystal, [C 2 O 2 N 3 H 5 BF 2 ][BF 4 ], features [C 2 O 2 N 3 H 5 BF 2 ] units that represent the first synthesis of a covalently linked biuret–[BO 2 F 2 ] hybrid. This compound achieves an outstanding combination of key properties for short‐wavelength ultraviolet nonlinear optical applications. Through this conformational editing approach, we further synthesized 14 additional compounds, establishing biuret as a versatile platform for hybrid assembly. Our work demonstrates solvent‐mediated conformational control as a general synthetic paradigm for overcoming steric hindrance and accessing previously inaccessible organic–inorganic architectures with tailored optical functionality.

Reinforcing CsPbI3 all-inorganic perovskite grain boundaries through bilateral cyano-based molecular cross-linking for efficient and stable solar cells

CsPbI3 all-inorganic perovskite solar cells (PSCs) are highly promising for photovoltaics owing to their excellent thermal stability and suitable bandgap. However, their performance and operational stability are often compromised by weak grain boundaries accompanied by a high density of defects. To overcome this limitation, we introduce succinonitrile (SN) as a multifunctional additive. SN features a flexible carbon chain terminated with cyano (–C≡N) groups at both ends, enabling it to coordinate strongly with Pb2+ via Lewis acid–base interactions and thereby act as a molecular cross-linker between adjacent grains. This bilateral coordination facilitates controlled crystallization, improves film morphology, passivates grain-boundary defects, and increases moisture resistance. As a result, the power conversion efficiency of SN-modified CsPbI3 PSCs increases from 14.52% to 16.17%, accompanied by significantly improved environmental stability. This work provides useful guidance for the design of efficient additives toward high-performance and stable all-inorganic CsPbI3 PSCs.

Engineering Amino Acid Functionalized Chiral Carbon‐Organic Frameworks for Enhanced Photocatalytic Hydrogen Production

ABSTRACT The spin‐dependent recombination behavior of photogenerated charges has long been overlooked in the study of photocatalytic hydrogen (H 2 ) evolution over covalent organic frameworks (COFs). Moreover, correlating the structure of COFs with the spin states of photogenerated charges to enhance photocatalytic H 2 evolution performance remains a significant challenge. Herein, we present a chiral amino acid functionalization strategy to engineer chiral TpPa‐1 COF for boosted photocatalytic H 2 evolution. Following systematic optimization, the chiral TpPa‐1 COFs showcased a ∼5‐fold enhancement in photocatalytic performance, achieving a record TOF of 9867 h −1 , alongside the second‐highest reported AQY of 66% at 475 nm and HER of 2.54 mmol h −1 among the reported state‐of‐the‐art COF‐based photocatalysts for H 2 evolution. Mechanism studies revealed that the synergistic effect between the chirality and the directional charge transfer allows efficient photo‐generated charge separation. Furthermore, Chiral TpPa‐1 assembled with polymeric carbon nitride (g‐C 3 N 4 ) in an S‐scheme heterojunction can overcome the bottleneck in photocatalytic overall water splitting on g‐C 3 N 4 without oxygen evolution co‐catalysts. In this work, we present a universal design strategy from a charge spin perspective to synthesize chiral photocatalysts for efficient photocatalytic performance.

Anomalous in-plane thermal conductivity suppression and dominant optical phonon transport in SnSe2/SnTe2 superlattice

Superlattice engineering is a well-established strategy for reducing lattice thermal conductivity (κL), typically achieving stronger suppression perpendicular to the interfaces. In this study, we employ density functional theory and the phonon Boltzmann transport equation to investigate thermal transport in bulk SnSe2 and SnSe2/SnM2 (M = S, Te) superlattices. Counterintuitively, our results reveal that the SnSe2/SnTe2 superlattice exhibits a more pronounced in-plane κL reduction (83.68%) than that in the out-of-plane direction (77.3%), reversing the conventional out-of-plane-dominated κL suppression phenomenon. Furthermore, optical phonons rather than acoustic ones dominate the thermal transport in SnSe2/SnTe2 superlattice, contributing up to 73.5% and 64.1% to κL along the in-plane and out-of-plane directions, respectively. These anomalous behaviors are attributed to additional phonon scattering channels arising from an in-plane avoided-crossing point in the phonon dispersion, as well as the marked enhancement of in-plane acoustic phonon anharmonicity. This work not only advances the understanding of phonon transport mechanisms in superlattices but also provides a novel perspective to effectively suppress in-plane lattice thermal conductivity in layered materials.

Zwitterionic Engineering of Vinylene‐Linked Covalent Organic Frameworks for Superior Protonic Electrolytes

ABSTRACT Solid protonic electrolytes are a promising avenue for advanced solid‐state proton batteries, offering enhanced safety, long‐term cycling stability, and high energy density. However, achieving high proton conductivity under ambient conditions remains a formidable challenge. In this study, we demonstrate a highly robust zwitterionic vinylene‐linked covalent organic framework (COF) engineered with sulfobetaine functionalities that promote efficient proton dissociation and migration, enabling superior proton conduction under ambient conditions and setting a new benchmark in the COF field. The solid protonic electrolyte comprising phosphoric acid‐modified zwitterionic COFs achieved the highest proton conductivity (5.34 × 10 −2 S cm −1 ) under ambient conditions among all reported COF‐based protonic electrolytes, along with incredible long‐term stability. Furthermore, solid‐state proton batteries assembled using the solid electrolyte delivered a record‐high specific capacity (108.5 mAh g −1 at 1.0 A g −1 ), good cycling durability (90% capacity retention after 2000 charge‐discharge cycles at 1.0 A g −1 ), and excellent rate capability. This study presents a viable and effective strategy for constructing high‐performance COF‐based protonic electrolytes tailored for advanced solid‐state proton battery technologies.

Tailored Pyridine Enables Diverse Electrochemical Benzylic C–H Functionalization

ABSTRACT C─H diversification strategies that enable access to various C─X (X = heteroatom) and C─C bonds are of central importance in synthetic chemistry. Here we present a benzylic C─H diversification protocol that merges electrochemical C─H pyridination with subsequent aminolysis or substitution to access unprotected benzylamines and a wide range of benzylic products. The electrochemical transformation proceeds in an undivided flow cell under oxidant‐ and transition‐metal‐free conditions and shows broad generality across electron‐rich, electron‐deficient, and halogenated alkylarenes. A key element is the use of a tailored pyridine with appropriate electronic properties, which suppresses undesired aromatic substitution while facilitating aminolysis and nucleophilic substitution of the pyridinium intermediate. The practicality of this method is underscored by a continuous operation in parallel microreactors, which furnished more than 100 g of benzylamine product.

Enantioselective Synthesis of Axially Chiral Anthracenes via [4+2] Cycloaddition and Cycloreversion of Cyclopentadienones

ABSTRACT The sequential inverse‐electron‐demand [4+2] cycloaddition and cycloreversion of cyclopentadienones with alkynes or alkenes represent one of the most important approaches for the synthesis of polycyclic aromatic hydrocarbons. However, catalytic asymmetric variants of these transformations have not yet been realized. Herein, we report a Cu(II)‐catalyzed enantioselective inverse‐electron‐demand Diels–Alder reaction between cyclopentadienones and strained oxabenzonorbornadiene derivatives. Subsequent aromatization via Brønsted acid‐promoted dehydrative aromatization, followed by spontaneous cheletropic retro‐[4+1] extrusion of carbon monoxide, efficiently delivered anthracene products. Using this ring‐extension strategy, a broad range of axially chiral anthracenes are obtained in good yields and with high enantioselectivities from readily accessible prochiral cyclopentadienones. The synthetic utility of this method is further demonstrated through versatile downstream transformations of the anthracene products. DFT calculations reveal that the inverse‐electron‐demand Diels–Alder reaction proceeds in a concert manner via a dynamic kinetic resolution pathway, and elucidates the mechanism of the aromatization step.

Dynamic Decoupling of Pt─H Intermediates Formation From Water Dissociation for Efficient Alkaline Hydrogen Evolution

ABSTRACT The formation of metal–hydrogen intermediates (M─H*) is critical for the alkaline hydrogen evolution reaction (HER), but is kinetically hindered by the energy‐intensive water dissociation. Here, we report a distinct pathway in the model catalyst of Pt nanoparticles loaded on TiH 1.924 (Pt/TiH 1.924 ), which directly generates Pt─H* by transferring lattice hydrogen from TiH 1.924 to Pt catalytic sites, while the lattice hydrogen can be dynamically replenished by the electrolyte spontaneously. This pathway decouples Pt─H* formation from water dissociation at a significantly lower energy barrier, as evidenced by operando differential electrochemical mass spectrometry and in situ Raman spectroscopy. The continuous hydrogen supply from the hydride support enables the Pt/TiH 1.924 catalyst to achieve a 35.6‐fold higher mass activity than Pt/C at 100 mV overpotential. Moreover, in an anion exchange membrane water electrolyzer with Pt/TiH 1.924 as the cathode, the cell voltage only requires 1.76 V at a current density of 1 A cm −2 , and the device can operate stably for over 1000  h under this current density. This work proposes a lattice hydrogen‐mediated mechanism to boost alkaline HER and other electrochemical processes constrained by slow M─H* formation, by decoupling Pt─H* production from water dissociation using metal hydride supports.

Surface Dynamic Redox Modulation of CuFe Achieving Near‐Unity Selectivity in Solar‐Integrated Nitrate‐to‐Ammonia Conversion

ABSTRACT Electrocatalytic nitrate reduction (NO 3 − RR) provides a sustainable pathway for NH 3 production under ambient conditions. Although operation in neutral media is more practically relevant, the reaction generally suffers from sluggish kinetics and unfavorable hydrogenation steps, which collectively limit NH 3 selectivity. Here, we develop a graphene‐encapsulated CuFe alloy catalyst (CuFe‐G) that enables highly efficient NO 3 − RR via a dynamically generated CuFe δ+ surface active layer. The synergistic alloy interface drives the spontaneous conversion of NO 3 − to NO 2 − , while in Situ surface redox dynamics create an active CuFe δ+ layer that optimizes *NO adsorption and accelerates hydrogenation kinetics. In parallel, encapsulation of the dynamic CuFe δ+ species within multilayer graphene constructs a mechanically robust and highly conductive interface that stabilizes the active sites and facilitates rapid charge transport. As a result, CuFe‐G delivers a peak NH 3 Faradaic efficiency of 99.63% at −1.0 V vs. RHE, together with an NH 3 yield rate of 8.03 mg h −1 mg cat −1 . When integrated into a CuFe‐G‖RuO 2 electrolyzer, the system further achieves a current density of 400 mA cm −2 at 2.6 V and maintains a solar‐to‐ammonia efficiency of 4.1% under fluctuating illumination. This work therefore establishes a dynamically redox‐regulated catalytic platform for sustainable, solar‐driven nitrate‐to‐ammonia conversion.

A Real‐Time Antifouling Multivalent Aptamer Platform for Wash‐Free Electrochemical Detection of Low‐Abundance Biomarkers in Human Plasma

ABSTRACT Sensitive and specific detection of low‐abundance proteins in complex biofluids is essential for early disease diagnosis and real‐time health monitoring. Electrochemical aptamer‐based biosensors offer rapid, point‐of‐care potential, but their clinical translation has been limited by biofouling, matrix variability, and signal instability in samples such as human plasma. Here, we introduce the Real‐Time Magnetic Multivalent Aptamer (RT‐MagMAp) assay, a one‐pot, wash‐free electrochemical platform that detects the low‐abundance biomarker VEGF 165 directly in diluted human plasma. The RT‐MagMAp system integrates three enabling chemical designs: (i) a hierarchical multivalent aptamer architecture combining bead‐immobilized monomeric aptamers with electrode‐bound trimeric aptamers to form highly stable electroactive sandwich assemblies; (ii) antifouling zwitterionic polymer coatings that house trimeric aptamers while suppressing nonspecific adsorption; and (iii) a dynamic internal calibration mechanism using nonfunctional mutant aptamers to correct for plasma‐dependent variability. Together, these elements enable femtomolar VEGF 165 detection (32–354 fM, depending on calibration method) and quantitative performance across 124 blinded plasma samples, achieving a Pearson correlation coefficient of 1.00 and a concordance correlation coefficient of 0.996 relative to a commercial ELISA. Together, these results establish RT‐MagMAp as a robust, clinically relevant electrochemical platform capable of quantitative, wash‐free protein detection directly in complex biological fluids.

Highly Active Nodules on Concave–Convex Channel Walls of Covalent Organic Frameworks for Photocatalytic Hydroperoxide Production

ABSTRACT Covalent organic frameworks (COFs) are promising photocatalysts for hydrogen peroxide (H 2 O 2 ) production. However, the smooth channels of traditional COFs exhibit weak charge density gradients and lack highly electron‐localized sites for O 2 adsorption, thereby showing unsatisfactory photocatalytic performances. Herein, we present a channel wall engineering strategy to introduce nodules with high electron localization into COF channels by topological regulation. In contrast with the smooth channel walls within the traditional COFs, the nodules on the concave–convex channel walls of COFs served as active sites with an electron‐rich structure and enhanced charge separation ability for the photocatalytic H 2 O 2 production. Grafting polar carboxylic groups to the nodules further resulted in a strong built‐in electric field and hydrogen bond network inside the channels, accelerating the transport of electrons and protons. The carboxylic group‐grafted COF (DFH‐COF) achieved a H 2 O 2 production rate of 6075 µmol h −1 g −1 in pure water and an apparent quantum yield as high as 14.6% at 475 nm. This study provides a powerful strategy of channel wall engineering of COFs to enhance the photocatalytic performances.

Photocatalytic Cross‐Coupling of Phenols and Heteroaryl Halides With Machine Learning‐Guided Reaction Prediction

ABSTRACT Developing sustainable methods for C(sp 2 )─C(sp 2 ) bond formation that avoid transition‐metals and prefunctionalized substrates remains a central goal in synthetic chemistry. Phenols and N ‐heteroarenes (azines) are abundantly available, yet their cross‐coupling is hindered by mismatched redox properties and chemoselectivity issues. Herein, we report a photochemical strategy that couples phenols with heteroaryl halides under redox‐neutral conditions using an organic dye photocatalyst and base. Concurrent oxidation of the phenol component and reduction of the azine component generates complementary radicals that cross‐couple efficiently, delivering moderate to high yields (up to 91%) with high functional group tolerance. Mechanistic experiments and density functional theory (DFT) studies elucidate the radical reaction pathways, while substrate clustering, high‐throughput experimentation (HTE), and machine learning (ML) enable prediction of C–C versus S N Ar reactivity across broad chemical space.

Electronic‐Effect‐Guided Bifunctional Iron Catalyst for the Copolymerization of Epoxides and Anhydrides: Enabling the Synthesis of High Molecular Weight Polyesters

ABSTRACT Ring‐opening copolymerization (ROCOP) of epoxides and anhydrides using metal‐based catalysts is a promising route to synthesize polyesters. However, conventional catalysts suffered from inadequate activity and tolerance to impurities that are essential for synthesizing high‐performance polyesters. Herein, a new electronic‐effect‐guided design principle was adopted to develop a novel bifunctional (salen)Fe(III) catalyst with outstanding efficiency. The electron‐withdrawing effect of the cocatalyst decreased the electron density at the iron center, which enhanced the catalytic activity of the (salen)Fe(III) catalyst. In contrast to conventional systems that required mol% catalyst loadings, the bifunctional (salen)Fe(III) catalyst maintained activity at an extremely low loading of 0.005 mol% and achieved an unprecedented turnover number of 19,000. Notably, the bifunctional (salen)Fe(III) catalyst emerged as the first example of organometallic complexes to synthesize polyesters with high molecular weights up to 254 kDa and high polyester selectivity over 98%. The high molecular weight polyesters showed remarkable thermal stability and high tensile strength comparable to commodity plastics. Moreover, the catalyst exhibited robust tolerance to impurities. This feature enabled the ROCOP of epoxides and anhydrides to proceed in air using commercial monomers without further purification, which was not accessible by previous catalysts.

Direct Oxidation of Methane to Formaldehyde With Molecular Oxygen Catalyzed by Gold‐Tungsten Oxide Cluster Cations

ABSTRACT Catalytic direct oxidation of methane with molecular oxygen can be highly exothermic in thermodynamics. It offers a promising green method for production of value‐added chemicals such as formaldehyde (CH 2 O), an indispensable feedstock in industry, under mild conditions. However, it faces a long‐standing grand challenge due to the intrinsic kinetic inertness of methane. Herein, an active gold‐tungsten oxide cluster catalyst, AuWO 2 + , being able to spontaneously catalyze CH 4 + O 2  → CH 2 O + H 2 O at room temperature has been successfully identified by mass spectrometry, which is distinctly different from the related condensed phase catalysis wherein the photo‐excitation of catalysts in the presence of H 2 O or H 2 was prerequisite to initiate catalytic reactions. The previously unrecognized mechanisms of direct methane oxidation have been unveiled: the interfacial Au−metal centers can undergo thermal reaction with O 2 to spontaneously generate the active (O···O) −• hole that subsequently works together with Au atom in a relay‐manner to easily cleave two C−H bonds of methane directional for CH 2 O and H 2 O production. This finding lays a solid foundation for future design of better‐performing catalysts for direct oxidation of methane (or other molecules) with O 2 without the need of any external energy or co‐feeding with alien molecules.

Water‐Soluble Pd ₈ L ₄ Barrel for Binding of Versatile Hydrophobic Dyes and Visible‐Light Promoted Catalysis in Aqueous Medium

ABSTRACT Achieving efficient supramolecular recognition of hydrophobic dyes and their use as photosensitizers in water remain a major challenge because of their inherent insolubility and loss of activity in aqueous medium. We address this issue by designing a metal‐organic barrel ( M ) that combines water solubility with a spacious hydrophobic cavity. This barrel functions as a versatile host capable of binding a broad range of polyaromatic guests, from small hydrocarbons to fullerenes. Interestingly, the barrel protects fragile fluorophores such as benzothiadiazole, benzoselenadiazole, quinoxaline, and BODIPY dyes from aggregation‐caused quenching (ACQ), thereby preserving their excited‐state integrity in water. Binding of the hydrophobic benzothiadiazole‐dithiophene (BDT) photosensitizer within the barrel transforms it into an efficient photocatalyst in water, enabling C─H functionalization of indole derivatives with malonate. Overall, this work demonstrates a water‐soluble barrel that serves as a powerful host capable of solubilizing hydrophobic dyes and enabling interesting catalytic reactivity directly in water.

A Convenient, Safe, and Atom‐Economical Route to a Large Portfolio of Grubbs‐Type Catalysts for Olefin Metathesis via Four‐Coordinate Ruthenium Alkylidynes

ABSTRACT p ‐Tolyl(trimethylsilyl)diazomethane is a readily accessible and easy‐to‐handle net carbyne donor reagent. It reacts with [( p ‐cymene)RuCl 2 ] 2 in MeCN to give the phosphine‐free chloride‐bridged dinuclear complex [(MeCN) 2 RuCl 2 ( = C( p ‐tolyl)(SiMe 3 ))] 2 ( 2 ) carrying a silyl group on each of the carbene ligands. Treatment of 2 with either PCy 3 or an N‐heterocyclic carbene (NHC) causes elimination of TMSCl with formation of the corresponding four‐coordinate ruthenium alkylidynes. The non‐bonding electron lone pair of significant d z2 character at their Ru center is prone to protonation; in this way, the alkylidyne unit is converted into a carbene ligand under very mild conditions. The sequence of alkylidyne formation/protonation opens a novel entry into all relevant “generations” of Grubbs and Grubbs‐Hoveyda type catalysts, which is distinguished by a superior ligand‐ and atom economy, a good safety profile, and high overall yields. Moreover, the method is inherently flexible and arguably suitable for parallel screening and reaction optimization purposes.

Nanotwinning of the Nickel Nitride Nanosheets for Robust Hydrogen Oxidation Electrocatalysis

ABSTRACT Nanotwinning of heterogeneous electrocatalysts represents an attractive tool to reconfigure the interfacial microenvironments with refined delivery and adsorption behaviors of reactants for high‐performance electrocatalysis. Here, we describe a facile iridium‐mediated‐nanotwinning strategy to synthesize nanotwinned Ir‐atom‐substituted Ni 3 N nanosheets with compatibly promoted hydroxyl delivery and adsorption as robust electrocatalysts for alkaline hydrogen oxidation reaction (HOR). These nanotwinned architecture can weaken the interfacial electric field with improved connectivity of hydrogen‐bond network for enhanced hydroxyl delivery, and also stimulate the valence‐electron delocalization with strengthened Ni 3 d ‐O 2 p valence‐electron‐orbital interaction for enhanced hydroxyl adsorption, together with elevated electrical conductivity. Accordingly, the mass activity of the nanotwinned Ir‐atom‐substituted Ni 3 N nanosheets was five times higher than that of commercial Pt/C toward alkaline HOR. This strategy sheds light on the rational design of high‐performance electrocatalysts with controllable delivery and adsorption behaviors of reactants by nanotwinning.

Electronic band and core-shell structure engineering enables ultrahigh energy storage in high-entropy ceramics