The β2-adrenergic receptor (β2AR) is a critical target for the treatment of airway diseases such as asthma or chronic obstructive pulmonary disease (COPD). To better understand its mechanism of action and study its dynamics, photoswitchable ligands provide a distinct advantage due to their ability to be activated with high spatiotemporal control. In this study, we developed a series of molecular tools featuring different combinations of pharmacophores, covalent warheads, and linker lengths. These compounds were characterized using highly specific assay protocols to evaluate their covalent binding capabilities, with the goal of identifying optimal covalently-bound photoswitches. Among these, the covalently-bound photoswitchable receptor agonist 6 exhibited a significant functional switch. To gain deeper insight into the binding thermodynamics and kinetics of this molecular tool, as well as the molecular determinants involved, we performed metadynamics (MetaD) simulations and analyzed their results using a Markov State Model (MSM) obtained by applying the Maximum Caliber (MaxCal) principle to the MetaD-derived free energies. These studies suggest that photoswitching of compound 6 occurs within the binding pocket of the β2AR. Consequently, compound 6 holds promise as a valuable tool for investigating β2AR activation kinetics and dynamics with high accuracy, thereby facilitating high-resolution biophysical studies.

Artificial liquid-repellent surfaces are highly desirable to combat pervasive biofouling and corrosion in biological environments. However, existing strategies often suffer from slow binding kinetics and harsh fabrication conditions, hindering the concurrent integration of liquid repellency, universal adhesion, and robust flexibility. Herein, we report that it is possible to engineer microbial biofilms as eco-friendly, cohesive, and flexible materials for omniphobic slippery coatings fulfilling all these requirements. Unlike conventional synthetic slippery coatings requiring laborious surface pretreatments, biofilm sheets formed on demand assemble a durable nanotextured framework on diverse substrates with multiple material categories and surface topologies, serving as hydrophobic lubricant reservoirs. Employing this renewable material enables the scalable and sustainable coating production. The resulting optically transparent and highly flexible coatings manifest exceptional self-cleaning properties, readily shedding both waterborne and oily liquids over a broad viscosity range. Notably, the synergy between the corrosion-protective extracellular matrix and non-stick slipping motion confers unprecedented anti-biofouling efficacy and corrosion resistance. This study offers a distinctive perspective on harnessing ubiquitous native biofilms as biomaterials for self-adaptive coatings, facilitating tailored functionality across broad applications.

Metal-organic cages (MOCs) are a class of self-assembled materials with promising applications in chemical purifications, sensing, and catalysis. Their potential is, however, hampered by challenges in the targeted design of MOCs with desirable properties. MOC discovery is thus often reliant on trial-and-error approaches and brute-force manual screening, which are time-consuming, costly and material-intensive. Translating the synthesis and property screening of MOCs to an automated workflow is therefore attractive, to both accelerate discovery and provide the datasets crucial for data-led approaches to accelerate MOC discovery and to realize their targeted properties for specific applications. Here, an automated workflow for the streamlined assembly and property screening of MOCs was developed, incorporating automated high-throughput screening of variables pertinent to MOC synthesis, data curation and automated analysis, and development of a host:guest assay to rapidly assess binding behavior. Computational modelling supplemented this automated experimental workflow for post priori rationalization of experimental outcomes. This study lays the groundwork for future large-scale MOC screening: from a relatively modest screen of 24 precursor combinations under one set of reaction conditions, 3 clean MOC species were identified, and subsequent screening of their host:guest behavior highlighted trends in binding and the identification of potential applications in molecular separations.

We describe herein an iridium-catalyzed highly diastereo- and enantioselective hydrogenation of 1,2-azaborines accessing δ-aminoboronic esters of potential biological importance. This method represents the first enantioselective hydrogenation of boron-containing heteroarene and features a diverse substitution pattern and wide scope. The synthetic utility of our method was demonstrated by the synthesis of (-)-Phenibut and the formal synthesis of (+)-3-PPP and Fluvirucinine A1.

Bifaical solar cells hold great potential for achieving higher power output than conventional monofacial devices by harvesting solar irradiance from both their front and rear surfaces. However, almost all currently reported bifacial devices typically require a sputtered rear transparent conducting oxide electrode, which can damage the underlying layers due to plasma effects during the deposition process. Here we report a glue-bonding strategy that uses a high-viscosity photovoltaic absorber slurry-in the case of molten selenium (Se)-as the adhesive to bond two charge-transport layer-deposited commercial fluorine-doped tin oxide glasses, directly creating bifacial solar cells without the use of magnetron sputtering. We find that molten Se exhibits relatively high viscosity, high stability, and Newtonian fluid characteristics, facilitating film formation using this strategy. The resulting bifacial Se solar cells exhibit a bifaciality factor of 90.1%, surpassing all types of conventional thin-film solar cells. These cells achieve efficiencies of 8.61% under 1-sun illumination with an albedo of 0.3, and 26.17% under 1000-lux indoor illumination with an albedo of 0.8, with no efficiency loss after 1000 hours of ambient storage.

Reductive catalytic fractionation (RCF) is a promising technology that can selectively extract lignin in biomass and depolymerize it. Here, we prepared one low Ru loading catalyst (Ru0.8/C) for RCF of biomass to selectively produce different lignin oil (both monomers and oligomers) under different reaction atmospheres. The yield of phenolic monomers reached 46.0wt.% (rich in 4-propylguaiacol and 4-propylsyringol) in the RCF of birch wood under high H2 pressure and using methanol as solvent. But, under N2 atmosphere the dominant monomers shifted to 4-(prop-1-enyl)guaiacol and 4-(prop-1-enyl)syringol (79.6% selectivity) with 35.8wt.% yield of total monomers using the same catalyst. The developed catalyst can also transform native lignin in other biomasses such as pine and corn stover. Mechanistic investigation using different model compounds and deuteration indicates that removal of the Cγ-OH in methanol-extracted lignin fragments occurred before obtaining the monomeric lignin fragment, and the Cα-OH and β-O-4 bonds were then cleaved simultaneously to form 4-(prop-1-enyl) substituted monomers. The results are distinct from the reported mechanism that the precursors of the propyl and prop-1-enyl substituted monomers are monolignols with the removal of Cγ-OH at the monomeric level. Thus, this work provided novel insights into the reaction pathway of (native) lignin depolymerization.

γ-Lactams are privileged five-membered pharmaco-phores in numerous bioactive compounds, but access to these motifs typically rely on cycloaddition/substitution chemistry involving activated substrates or CO carbonylations under harsh conditions. Here, we report a new route to functionalized γ-lactams through formal carbonylation of azetidines under nonprecious metal catalysis. The method leverages a copper-stabilized difluorocarbene to promote site-selective insertion followed by in situ hydrolysis to unmask the lactam group. In contrast to most difluorocarbene reactions that cause ring cleavage of saturated heterocycles in the presence of heat, the present system operates at low temperature and retains the integrity of the cyclic structure. Synthesis of various drug-like lactams and a therapeutic agent for diabetes highlights utility.

The development of efficient electrocatalysts for CO2 reduction to CO is challenging due to competing hydrogen evolution and intermediate over-stabilization. In this study, a Cu-Co dual single-atom catalyst (CuCo-DSAC) anchored on carbon black was synthesized via scalable pyrolysis. The catalyst achieves 98.5% CO Faradaic efficiency at 500 mA cm⁻2, maintaining >95% selectivity across a 400 mV window with <6% decay over 48 hours, which is superior to the corresponding single-atom control samples. In situ spectroscopy and DFT calculations reveal a synergistic mechanism: Co sites activate CO2 and stabilize *COOH intermediates, while adjacent Cu sites facilitate CO desorption by lowering the energy barrier through charge redistribution. This dynamic buffer system mitigates active-site blocking and suppresses HER by weakening H adsorption. The electronic interplay between Cu and Co optimizes intermediate energetics, enabling industrial-level performance. This work demonstrates the potential of tailored dual-site architectures for complex electrocatalytic processes, offering a promising approach to overcoming traditional limitations.

Implementing photoactivation into chemical reaction networks (CRNs) offers opportunities for on-demand and remote activation, fuel storage, and creating autonomous materials and systems with precise spatial activation. However, examples in this domain remain limited. Here, we introduce a cascaded redox-based enzymatic reaction network (ERN) capable of photoinitiation and refueling, centered around dissipative aromatic disulfide bond formation. To achieve photoinitiation, we integrate an upstream enzymatic module (EM) into the ERN, where the substrate of the EM can be photouncaged using blue light irradiation. A downstream regeneration system enhances the robustness of the reducing environment for repeated fueling. This cascaded ERN operates in solution, allowing for controlled dissipative disulfide formation while avoiding short-circuit reactions (SCR) between the oxidative and reductive halves of the reaction cycle. To showcase the utility of this photoactivated ERN, we couple it with aromatic thiol-terminated star polymers (sPEG-ArSH) to enable spatiotemporally controlled dissipative hydrogel formation using lithographic masks.

Rare-earth-based all-inorganic glass-ceramics have exhibited an important role in the field of optoelectronics. However, the research of organo-inorganic hybrid rare-earth halide glass which can be produced at low temperatures is still in the blank stage. In this paper, we report for the first time on novel amorphous organic-inorganic hybrid rare-earth-based halide luminescent glasses, Bzmim3LnCl6 (Bzmim = 1-benzyl-3-methylimidazolium; Ln3+ = Tb3+, Eu3+), and realize tunable multicolor photoluminescence emission. By adjusting the ratio of Tb3+: Eu3+ within the Bzmim3LnCl6 glass, we have successfully induced controllable radioluminescence properties ranging from green to red under X-ray irradiation. Notably, these amorphous organic-inorganic hybrid rare-earth glasses exhibit remarkable sensitivity to variations in X-ray dose, suggesting promising applications in the field of passive color visualization radiation detection. Furthermore, the Bzmim3TbCl6 glass demonstrates exceptional light transmittance greater than 85% across the 480-800 nm range, which results in superior spatial resolution in X-ray imaging (>25 lp mm-1). These findings not only provide a good example for the design and development of hybrid rare-earth-based halide glasses, but also hold great potential for applications in detection, sensing, illumination, and display technologies.

Developing photocatalysts that can efficiently utilize the full solar spectrum is a crucial step toward transforming sustainable energy solutions. Due to their light absorption limitations, most photo-responsive metal-organic frameworks (MOFs) are constrained to the ultraviolet (UV) and blue light regions. Expanding their absorp-tion to encompass the entire solar spectrum would unlock their full potential, greatly enhancing efficiency and applicability. Here, we report the design and synthesis of a series of highly stable boron-dipyrromethene (bodipy) based MOFs (BMOFs) by reacting dicar-boxyl-functionalized bodipy ligands with Zr-oxo clusters. Leveraging the acidity of the methyl groups on the bodipy backbone, we ex-panded the conjugation system through a solid-state condensation reaction with various aldehydes, achieving full-color absorption, thereby extending the band edge into the near-infrared (NIR) and infrared (IR) regions. These BMOFs demonstrated exceptional reac-tivity and recyclability in heterogeneous photocatalytic activities, including C-H bond activation of saturated aza-heterocycles and C-N bond cleavage of N,N-dimethylanilines to produce amides under visible light. Our findings highlight the transformative potential of BMOFs in photocatalysis, marking a significant leap forward in the design of advanced photocatalytic materials with tunable prop-erties.

Functionalized ionogels have attracted significant attention in chemical design of new materials and versatile applications, which are formed by polymer network as a matrix with introducing ionic liquids containing characteristic units as a dispersion medium. Here, we present an universal scheme to rapidly synthesize luminescent ionogels through the in-situ formation of zero-dimensional (0D) hybrid metal halides during the polymerization of monomer. In particular, Mn(II)-based hybrid halide ionogels (Mn-IG) were formed by incorporating [C20H20P]+ cations and [MnBr4]2- anions into the polymer network structure. Thanks to the amorphous nature of Mn-IG and the homogeneous distribution of self-trapped [MnBr4]2- light-emitting units with [C20H20P]+ cations, Mn-IG exhibits high transparency (nearly 90% transmittance at 550 nm-1100 nm) and homogeneous highly-efficient emission. Taking advantage of its processability, we fabricate an 18 cm × 12 cm scintillation film and successfully realize large-area and high-resolution X-ray imaging. The straightforward and rapid synthesis method on such ionogels paves the way for the low-process-demand preparation of large-area scintillators, and also opens up new routes for the in-situ construction of uniform 0D metal halide polymer composites.

Bioisosteric replacement is an important strategy in drug discovery and is commonly practiced in medicinal chemistry, however, the incorporation of bioisosteres typically requires laborious multistep de novo synthesis. The direct conversion of a functional group into its corresponding bioisostere is of particular significance in evaluating structure-property relationships. Herein, we report a functional-group-exchange strategy that enables the direct conversion of aromatic lactones, a prevalent motif in bioactive molecules, into their corresponding cyclic hemiboronic acid bioisosteres. Scope evaluation and product derivatization experiments demonstrate the synthetic value and broad functional-group compatibility of this strategy, while the application of this methodology to the rapid remodeling of chromenone cores in bioactive molecules highlights its utility.

Inverted flexible perovskite solar cells (f-PSCs) are promising candidates for mechanical photovoltaic applications due to their ease of preparation, lightweight, and portability. However, the weak interface connections, residual strain and the nonradiative recombination loss among adjacent layers are critical challenges that restrict f-PSCs development. To address these issues, a functionalized molecule with multiple hydrogen bond acceptors, 4-Carboxyphenylboronic acid (4-BBA), is designed in the perovskite precursor for modulating perovskite crystallization, which achieves uniform and stress-relaxation perovskite film and forms a robust bridging structure anchored at the buried interface. Theoretical calculation and experimental results show that the C=O group passivates Pb2+ with I- vacancy defect through Lewis acid-base interactions, reducing trap-assisted recombination. Furthermore, the designed 4-BBA is preferentially deposited at the buried layer interface between the perovskite and substrate, forming hydrogen bonds with the self-assembled monolayer via B-OH bonds, creating a mechanically stable bridge between the layers. As a result, the power conversion efficiency of the champion f-PSC reached 25.30% (25.13% certified). And the f-PSC open-circuit voltage set a record of 1.21V. Importantly, the unencapsulated f-PSC using 4-BBA retains 95.3% of its original performance after 5000 cycles at a bending radius of 10 mm, demonstrating extraordinary bending stability.

Heating the readily available trinuclear Ti dinitrogen complex [{TiCp*(μ-Cl)}3(μ3-η1: η2: η2-N2)] 1(Cp* = η5-C5Me5), originally reported by C. Yélamos and J. Jover, in benzene at 80 °C leads to the cleavage of N≡N bond, forming a tetranuclear titanium nitride cluster [{TiCp*}4Cl(μ-Cl)3(μ3-N)2] 2. The structure of 2 was confirmed by single-crystal X-ray diffraction analysis. Kinetics study and DFT calculations indicate that the energy barrier for the NN bond cleavage in the transformation from 1 to 2 is about 26 kcal/mol. Complex 2 exhibits reactivity toward various electrophiles, producing a range of nitrogen-containing compounds in the presence of air, while concurrently regenerating Ti(IV) salts. Furthermore, complex 2 reacts with pinacolborane, leading to the formation of N-B bond derivatives [{TiCp*(μ-NBPin)Cl}2] 3. When complex 2-15N is treated with pyridine or 4-dimethylaminopyridine (DMAP), it dissociates to form a bent trinuclear Ti nitrido complex [{TiCp*}3Cl3(L)2(μ-15N)2] 4-L (L = py or DMAP).

A new kind of supramolecular thio-naphthalene diimide (SNDI) which can be immediately reduced as supramolecular radical anion by bacteria is reported. The introduction of thiocarbonyl effectively elevates the reduction potential of SNDI, largely increasing the bacteria-response speed in hypoxia. It selectively distinguishes the bacteria with high and low reduction ability in real time. The host-guest complexation of SNDI and cucurbit[7]uril can enhance radical anion quantum yield, ensuring intense NIR-II absorption and realizing high photothermal conversion. The real-time NIR-II photothermal anti-bacteria is successfully carried out. This development will enrich the design of bio-responsive agent with promising future towards actual application.

We have designed and successfully synthesized N-(acyldithio)saccharin for the first time, which is a highly electrophilic, bench-stable, and user-friendly disulfurating reagent. This reagent can undergo reactions with diverse N-, S-, and C-nucleophiles at room temperature. In most cases, no additional catalyst is required, and the desired disulfides were readily obtained in moderate to excellent yields. With this reagent, late-stage disulfuration of pharmaceuticals and biomolecules was readily accomplished. For the first time, catalytic enantioselective disulfuration/amination of unactivated alkenes was achieved using this reagent. A series of chiral disulfides were obtained with high enantioselectivities and yields. The chiral disulfide products can be readily further transformed into chiral sulfonyl fluoride, chiral thiol, and structurally diverse disulfide products. Furthermore, we have evaluated the electrophilic reactivity of a series of disulfurating reagents based on density functional theory calculations, verifying the high reactivity of N-(acyldithio)saccharin both experimentally and theoretically.

DNA damage repair mechanisms, such as base excision repair (BER), safeguard cells against genotoxic agents that cause genetic instability and diseases, including cancer. In eukaryotic nuclei, DNA within nucleosome arrays is less accessible to repair factors than naked DNA due to chromatin's structural constraints. Histone acetylation is crucial for loosening chromatin structure and facilitating access to damaged DNA, yet its effects-particularly in histone globular domains-on BER in nucleosome arrays remain unexplored. Here, we employ an Abiotic/Enzymatic Hybrid Catalyst System (ABEHCS) and a Plug-and-Play strategy to regioselectively introduce histone acetylation and deoxycytidine-to-deoxyuridine DNA damage. This approach enables the construction of nucleosome arrays with diverse spatial configurations of histone acetylation and DNA lesions, similar to those found in living organisms. Our findings reveal that H3K56 acetylation in the histone globular domain enhances BER efficiency mediated by UDG and APE1 in nucleosome arrays, contingent upon the spatial relationship between H3K56Ac and the DNA damage site.

Developing highly-efficient and robust bifunctional electrocatalyst for overall water splitting (OWS) is desirable, but it confronts long-term challenge in the local structural reconstruction of catalyst during the hydrogen and oxygen evolution reaction (HER and OER). As inspired by the stable acid-base buffer system in human life, here we construct an electron buffer system to well address the key issue of structural reconstruction, in which the charge-buffered fullerene renders the Ru-based active species to be reversibly shuttled between Ru and RuO2 during HER and OER. Consequently, the as-prepared Ru-RuO2/C60-x catalyst exhibits overpotentials of merely 7 and 194 mV at 10 mA cm-2 for HER and OER in alkaline conditions, respectively. The photovoltaic-driven OWS device with a solar-to-hydrogen (STH) efficiency of 18.9% and an anion exchange membrane water electrolysis (AEMWE) system with good robustness was fabricated based on Ru-RuO2/C60-x. It was unraveled by in-situ/operando spectroscopy and theoretical calculation that the significantly promoted performance of water electrolysis benefits from the fullerene-based electron shuttle effect on inhibition of structural reconstruction and electronic structural modulation of active sites as well as adsorption energy of the reaction intermediates. Our work may open an avenue to develop efficient and robust bifunctional electrocatalyst for promising industrial water electrolysis.

The study of G-quadruplex (G4) structures that form in DNA and RNA is a rapidly growing field, which has evolved from in vitro studies of isolated G4 sequences to genome-wide detection of G4s in a cellular context. This work has revealed the tangible and significant effects that G4s may have on biological regulation. This minireview describes recent progress in the design of photoluminescent intensity-independent optical probes for G4s. We discuss the design and use of probes based on fluorescence or phosphorescence lifetime, rather than intensity-based detection; spectral ratiometric probes; and fluorescent probes for single-molecule G4-detection. We argue that each of these modalities improve unbiased G4 detection in cellular experiments, overcoming problems associated with unknown cellular uptake of probes or their organelle concentration. We discuss the improvements offered by these types of probes, as well as limitations and future research directions needed to facilitate more robust research into G4 biology.

Octalenobisterphenylene 1 (also known as terphenylene dimer) was synthesized from 3,3',5,5'-tetraaryl-substituted biaryl by tert-butyllithium-mediated cyclization followed by oxidative coupling. This one-pot two-step protocol facilitated the successive formation of four four-membered and two eight-membered rings. Treatment of 1 with sodium metal, followed by crystallization from THF, yielded the remarkable diradical dianion [(1·-)2]2-, where the two molecular halves are connected by four σ bonds. The cyclodimerization is driven by the pronounced reactivity and strain of the central six-membered ring within the [3]phenylene subunit. The structure and diradical nature of [(Na+)2(1·-)2] were confirmed through X-ray crystallography, DFT computations, and 1H NMR and ESR spectra. These investigations revealed that the two spins, one on each molecular half, exhibit minimal mutual interaction.