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Research was conducted to examine the kinetic and thermodynamic aspects of the quenching process by observing the quenching behavior over the series of related Ni(II) complexes. It was observed that the quenching of 3Pt2(pop)(sub 4)(super 4-) by Ni(II) complexes occurred by reductive electron transfer, generating net redox products through a low-efficiency cage escape route that is enhanced in the presence of oxygen.

NMR, IR, UV-vis spectroscopy, elemental analysis, and conductivity measurements were used to synthesize and characterize the complex Co(tacn)(NCS)3 (tacn = 1,4,7-triazacyclononane). The compound was stable in dmso and aqueous/dmso solution at room temperature. On irradiation at 360nm, it displayed parallel photosubstitution. The addition of thiocyanate ion to the solutions enhanced the reaction, apparently by scavenging the radical pair species followed by back electron transfer to the photosubstituted products.

The synthesis and electrical transport properties of 30-nm diameter in-wire metal-self-assembled monolayers (SAMs)-metal junctions that incorporate three different molecules: saturated alkane chains of dodecane (C12), pi-conjugated oligo (phenylene ethynylene) (OPE), and oligo (phenylene vinylene) (OPV) in dithiolacetates and three different metal contacts: Au-SAM-Pd, Au-SAM-Ag, and Pd-SAM-Pd is reported.

As a crucial cathode material with ultrahigh theoretical capacity (865 mAh/g) and energy density (>2100 Wh/kg), fluorinated carbon (CF x ) is promising for lithium primary batteries. However, the operating performance of CF x cathode is hindered by nonuniform volume expansion during discharging. To investigate this, we used operando confocal microscopy to visualize the thickness evolution of two different CF x cathodes and quantified their swelling ratios as a function of the discharge depth. Our findings show that CF x synthesized from hard carbon (FHC), featuring a disordered structure and abundant pores, exhibits a swelling ratio lower than that of conventional layered fluorinated graphite (FG). This is due to different electrochemical mechanisms: lithium enters FG interlayers nonuniformly through "edge propagation" pathways while lithiation occurs homogeneously in FHC, unraveled by single-particle Raman and photoluminescence measurement. This work enhances our understanding on CF x volume expansion, offering important opportunities to address the cathode swelling issue and optimize electrochemical performance in Li/CF x batteries.

Androgen receptor (AR) is a crucial driver of prostate cancer (PCa), but acquired resistance to AR antagonists significantly undermines their clinical efficacy. We previously discovered coumarin derivative 1 , which is capable of disrupting AR ligand-binding domain dimers, offering the potential for overcoming resistance. However, its poor oral bioavailability limited further development. In this study, comprehensive structure optimizations led to compound 4a (IC 50 = 0.051 μM), which exhibited comparable AR antagonistic activity to enzalutamide (IC 50 = 0.060 μM) and demonstrated excellent selectivity over other nuclear receptors in vitro. Especially, 4a showed superior efficacy against AR F876L/T877A and AR W741C mutants compared to darolutamide and enzalutamide. Moreover, 4a exhibited favorable pharmacokinetic profiles ( F = 66.24%) in vivo and significant tumor growth inhibition in an LNCaP xenograft mouse model upon oral administration. These results highlight the potential of 4a as a promising oral AR antagonist for overcoming drug resistance in PCa.

Organic solid-state lasers have received increasing attention due to their great potential for realizing organic continuous-wave or electrically driven lasers. Moreover, they exhibit significant promise for optoelectronic devices due to their chemically tunable optoelectronic properties and cost-effective self-assembly traits. Recently, a great progress has been made in organic solid-state lasers via spatially separated charge injection and lasing. However, making directly electrically driven organic semiconductor lasers is very challenging. It is difficult because of a number of excitonic losses caused by the spin-forbidden nature as well as serious efficiency roll-off at a high current density. Here, a multifunction gain material, functioning both as a thermally activated delayed fluorescence (TADF) emitter with exceptional optical gain and as a source of phosphorescence, was theoretically investigated. The new molecule we designed exhibits a reduction of triplet accumulation through an effective exciton radiative process (5-fold boost in figure of merit) and significantly decreased exciton binding energy (dipole moment from 5.77 to 14.03 D), which benefit amplified spontaneous emission and lasing emission. Our work provides theoretical insights into organic solid-state lasers and may contribute to the development of new and efficient laser-gaining molecules.

The transformation of clinical androgen receptor (AR) antagonists into agonists driven by AR mutations poses a significant challenge in treating prostate cancer (PCa). Novel anti-AR therapeutics combating mutation-induced resistance are required. Herein, by combining structure-based virtual screening and biological evaluation, a high-affinity agonist E10 was first discovered. Then guided by the representative conformation of State 1 at the free energy landscape, the structural optimization of E10 was performed, and pure AR antagonists EL15 (IC 50 = 0.94 μM) and EF2 (IC 50 = 0.30 μM) were successfully identified. Both can antagonize wild-type and variant drug-resistant ARs. Therein, EF2 demonstrated potent inhibition of the AR pathway and effectively suppressed tumor growth in a C4-2B xenograft mouse model following oral administration. Further molecular dynamics simulation and mutagenesis studies revealed atomic insights into the mode of action of EF2 which may serve as a novel lead compound for developing therapeutics against AR-driven PCa.

Salinization is recognized as a global problem, restricting agricultural production and sustainability. Targeting the salinity-induced oxidative stress, antioxidant treatment represents a protective strategy to improve plant salt tolerance. Herein, we report a V 4 C 3 MXene nanozyme (MXenzyme), which exhibits good biocompatibility and excellent reactive oxygen species scavenging activity to ameliorate the salt stress-induced inhibition of seed germination. V 4 C 3 MXenzyme treatment can significantly relieve salinity-induced oxidative stress and restore the antioxidant system in pea seeds, thus improving the phenotypic traits during germination. The molecular mechanism by which antioxidant V 4 C 3 MXenzymes augment salt tolerances is revealed through transcriptomics and metabolomics. V 4 C 3 MXenzymes significantly regulate the gene expression of antioxidant enzymes and molecule biosynthesis that correlate closely with hormone signal transduction genes and energy metabolism genes. With correlation and the combined analysis, redox homeostasis targeted by antioxidant V 4 C 3 MXenzymes plays a critical role in promoting plant growth under salt stress.

Exploring the structural basis of membrane proteins is significant for a deeper understanding of protein functions. In situ analysis of membrane proteins and their dynamics, however, still challenges conventional techniques. Here we report the first attempt to immobilize membrane protein complexes on surface-enhanced Raman scattering (SERS)-active supports, titanium dioxide-coated silver (Ag@TiO 2 ) nanoparticles. Biocompatible immobilization of microsomal monooxygenase complexes is achieved through lipid fission and fusion. SERS activity of the Ag@TiO 2 nanoparticles enables in situ monitoring of protein-protein electron transfer and enzyme catalysis in real time. Through SERS fingerprints of the monooxygenase redox centers, the correlations between these protein-ligand interactions and reactive oxygen species generation are revealed, providing novel insights into the molecular mechanisms underlying monooxygenase-mediated apoptotic regulation. This study offers a novel strategy to explore structure-function relationships of membrane protein complexes and has the potential to advance the development of novel reactive oxygen species-inducing drugs for cancer therapy.

A straightforward method for the phosphorylation of electron-deficient alkenes and aryl alkynes has been developed, leading to C(sp 3 )-P and C(sp 2 )-P bond formation. This process involves the generation of phosphorus radical cation intermediates through the photocatalyzed oxidation of ethyl diarylphosphinites. The coupling with electron-deficient alkenes encompasses a variety of heteroaromatics, including pyridine, (benzo)thiazole, and benzoxazole, as well as α,β-unsaturated esters and amides. Impressively, the coupling of radical cations with aryl alkynes demonstrated remarkable regioselectivity, thereby facilitating the synthesis of rare α-aryl vinyl phosphine oxides.

Phase separation of microemulsions occupies a key position in many applications, such as oil recovery, nanomaterial synthesis, and chemical reactions. Achieving an intelligent response is crucial to microemulsion development and application. For this reason, in this study, CO 2 -responsive superamphiphilic molecules were developed as rapidly switchable oil-in-water microemulsions. These superhydrophilic molecules with linear structures were produced by electrostatic interaction of stearic acid and aminotrimethyltriazine COSM-1 in a 1:1 molar ratio. The introduction of n-butanol as a cosurfactant in the CO 2 -responsive microemulsion system resulted in the spontaneous formation of stable microemulsions. The effect of the addition of n-butanol on the carbon dioxide-responsive microemulsion system was investigated, and the optimum amount of n-butanol was determined by optimization. After exposure to CO 2 for 30 s, the superhydrophilic molecules decomposed into inactive components at the interface, leading to a complete phase separation of the microemulsion into oil and water phases. The system was purged with N 2 at 60 °C for 10 min to remove the CO 2 , and the phase separation system was transformed into a clear microemulsion, which was then evaluated for its properties. The rapid response and complete demulsification of these surface CNFS superamphiphiles to CO 2 suggest that they have promising applications in product separation, microemulsion recovery, and enhanced crude oil recovery., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

ConspectusMolecular clusters (MCs) are monodispersed, precisely defined ensembles of atom collections featured with shape-persistent architectures that can deliver certain functions independently. Their molecular compositions and surface functionalities can be tailored feasibly in a predefined manner, and they can be applied as basic structural units to be engineered into materials with desirable hierarchical structures and enriched functions. The chemical systems also offer great opportunities for the design and fabrication of soft structural materials without the chain topologies of polymers. The bulks of MC assemblies demonstrate viscoelasticity that is used to be considered as the unique feature of polymers, while the MC systems are distinct from polymers since their elasticities are resilient even at temperatures 100 K above their glass transition temperatures. The understanding of their anomalous viscoelasticity and the extended studies of general structure-property relationships are desired for the development of new chemical systems for emergent functions and the possibilities to resolve the intrinsic trade-offs of traditional materials.Meanwhile, general macroscopic functions or properties of materials are related to the transportation of mass, momentum, and/or energy, and they are basically realized or directed by the motions of structural units at different length scales. Structural relaxation dynamics research is critical in quantifying motions ranging from fast bond deformation, bond break/formation, and diffusion of ions and particles to the cooperative motions of structure units. Due to the advancement of measurement technology for relaxation dynamics (e.g., quasi-elastic scattering and broadband dielectric spectroscopy), the structural relaxation dynamics of MC materials have been probed for the first time, and their multiple relaxation modes across several temporal scales were systematically studied to bridge the correlation between molecular structures and macroscopic functions. The fingerprint information from dynamics studies, e.g., the temperature dependence of relaxation time and certain property, e.g., ion conductivity, was proposed to quantify the structure-property relationship, and the microscopic mechanism on the mechanical properties, ion conduction, and gas absorption and separation of MC materials can be fully understood.In this Account, to elucidate the uniqueness of MC materials, especially in comparison with polymers, four topics are mainly summarized: structural features, relaxation dynamics characterization techniques, relaxation dynamics characteristics, and quantified understanding of the structure-property relationship. The capability for new function prediction from relaxation dynamics studies is also introduced, and the typical example in impact resistant materials is provided. The Account aims to prove the significance of relaxation dynamics characterization for material innovation, while it also confirms the potential of MCs for functional material fabrications.

Alcohols are the most commercially abundant, synthetically versatile and operationally convenient functional groups in organic chemistry. Therefore, a strategy that utilizes hydroxy-containing compounds to develop novel bond disconnection and formation process would achieve molecular diversity. Herein, a deconstructive strategy for the generation of quinoxalin-2(1H)-one derivatives has been developed from alcohol precursors via oxy-radical-induced β-fragmentation. Additionally, 1,5-HAT and deoxygenation by P(III) along with oxy-radical were demonstrated as alternative pathways for this transformation. Furthermore, with the deep-seated reorganization of a few terpenes carbon framework, a unique activity with inhibition against the growth of pathogenic fungi was observed.

Alternaria alternata is a common plant pathogen that can infect crops and reduce their production. In this work, an antagonism experiment between A. alternata and the essential oil of arborvitae ( Platycladus orientalis ) was performed, and it was proven that A. alternata had developed resistance to this plant-derived fungicide. A. alternata facilitated the biotransformation of hinokitiol ( 1 ), the main antifungal compound in the essential oil of arborvitae, into ( R )-2-hydroxy-β-methylbenzeneethanol ( 2 ), which does not have antifungal activity against A. alternata . This biotransformation is an unusual ring-contraction reaction that was verified to be catalyzed by P450 enzyme hydroxylation and Baeyer-Villiger oxidation. In addition, the P450 enzyme inhibitors 1-aminobenzotriazole and piperonyl butoxide effectively prevented the destruction of the hinokitiol structure by A. alternata , and the combined use of these P450 enzyme inhibitors significantly increased the antifungal activity of hinokitiol. This work provides a theoretical reference for the further development of botanical fungicides.

Postmenopausal osteoporosis (PMOP) arises from the disruption in bone remodeling caused by estrogen deficiency, leading to a heightened susceptibility to osteoporotic fractures in aging women. Tetrahydroberberine (THB) is a chemical compound extracted from Corydalis yanhusuo , a member of the traditional Chinese medicine series "Zhejiang eight taste", possessing a variety of pharmacological functions such as lowering lipids and preventing muscle atrophy. However, the impact of THB on PMOP has not been systematically explored. In vitro experiments supported that THB suppresses osteoclast formation and resorption of bone concentration-dependently. Further experiments confirmed that these inhibitory effects of THB were related to inhibition on expressions of osteoclast-specific genes, the mitogen-activated protein kinase (MAPK) pathway, and the nuclear factor kappa-B (NF-κB) pathway and an increased apoptosis level in mature osteoclasts. Additionally, THB treatment mitigated the ovariectomy-induced bone loss and improved the skeletal microarchitecture in vivo. In conclusion, THB has such potential to improve the PMOP status.

Aqueous zinc-ion batteries (AZIBs) exhibit promising prospects in becoming large-scale energy storage systems due to environmental friendliness, high security, and low cost. However, the growth of Zn dendrites and side reactions remain heady obstacles for the practical application of AZIBs. To solve these challenges, a functionalized Janus separator is successfully constructed by coating halloysite nanotubes (HNTs) on glass fiber (GF). Impressively, the different electronegativity on the inner and outer surfaces of HNTs endows the HNT-GF separator with ion-sieving property, leading to a significantly high transference number of Zn 2+ ( t Zn 2+ = 0.71). Meanwhile, the HNT-GF separator works as an interfacial ion comb to regular Zn 2+ flux and realizes multisite progressive nucleation, bringing decreased nucleation overpotential and uniform Zn 2+ deposition. Consequently, the HNT-GF separator enables the Zn anode to display an ultralong plating/stripping life of 3000 h and high rate tolerance with a stable long cycle life even under a density of 50 mA cm -2 . Moreover, the Z n ∥ H N T - G F ∥ M n O 2 full cell represents an ultrastable cycling stability with a high capacity retention of 93.4% even after 1000 cycles at a current density of 2 A g -1 . This work provides a convenient method for the separator modification of AZIBs.

Peptidyl-prolyl cis-trans isomerase NIMA-interacting 1 (PIN1) has emerged as a promising therapeutic target for cancer treatment. However, the current PIN1 inhibitors have shown limited efficacy in animal models, leaving the question of whether PIN1 is a proper oncologic target still unanswered. By screening a 1 trillion DNA-encoded library (DEL), we identified novel nonacidic compounds. Among resynthesized DEL compounds, DEL1067 - 56 - 469 ( A0 ) is the most potent one (KD = 430 nM, IC 50 = 420 nM). Further optimization of A0 resulted in compound C10 with much improved potency (KD = 25 nM, IC 50 = 150 nM). As an alternative approach, C10 was then converted into proteolysis targeting chimeras (PROTACs) in order to achieve deeper downregulation of the PIN1 protein in cancer cell lines. Unfortunately, neither PIN1 inhibitors nor PIN1 PROTACs demonstrated meaningful antiproliferation activity. In addition, siRNA knock-down experiments provided unfavorable evidence of PIN1 as an oncologic target. Our findings highlight the complexity of targeting PIN1 for cancer therapy.

Ligand-based virtual screening (LBVS) has rarely been tested as a method for discovering new structural scaffolds for PET radioligand development. This study used LBVS to discover potential chemotype leads for developing radioligands for PET imaging of tauopathies. ZINC12, a free database of over 12 million commercially available compounds, was searched to discover novel scaffolds based on similarities to four query compounds. Thirteen high-ranking hits were purchased and assayed for their ability to compete against three tritiated radioligands at their distinct binding sites in Alzheimer's disease brain tissue. Three hits were 2-substituted 6-methoxy naphthalenes. Synthetic elaboration of this new chemotype yielded three new ligands ( 25 , 26 , and 28 ) with high affinity for the [ 3 H] 6 (flortaucipur) neurofibrillary tangle binding site. Compound 28 showed remarkably high affinity ( K i , 7 nM) and other desirable properties for a candidate PET radioligand, including low topological polar surface area, moderate computed log  D , and amenability for labeling with carbon-11. LBVS appears to be uniquely valuable for discovering new chemotypes for candidate PET radioligands.

To satisfy the demands of the food industry, innovative flavor enhancers need to be developed urgently to increase the food flavor. In our work, N-lauroyl phenylalanine (LP) was prepared from phenylalanine (l-Phe) and lauric acid (Lau) in water through the use of commercial enzymes (Promatex, Sumizyme FP-G, and Trypsin), and its flavor-presenting properties and mechanism were investigated. The highest LP yields obtained under one-factor optimized conditions were 61.28, 63.43, and 77.58%, respectively. Sensory assessment and an e-tongue test revealed that 1 mg/L LP enhanced the kokumi, saltiness, and umami of the simulated chicken broth solution and attenuated the bitterness of the l-isoleucine solution. The molecular simulation results suggested that the mechanisms of LP enhancement of kokumi and umami were related to hCaSR and hT1R1-hT1R3, and that hydrophobic forces and hydrogen bonds were involved in the binding of LP to taste receptors. The results implied that LP is a potential flavor enhancer for food applications.

Multimodal measurement of single cells provides deep insights into the intricate relationships between individual molecular layers and the regulatory mechanisms underlying intercellular variations. Here, we reported DMF-DM-seq, a highly integrated, sensitive, and automated platform for single-cell mRNA and microRNA (miRNA) co-sequencing based on digital microfluidics. This platform first integrates the processes of single-cell isolation, lysis, component separation, and simultaneous sequencing library preparation of mRNA and miRNA within a single DMF device. Compared with the current half-cell measuring strategy, DMF-DM-seq enables complete separation of single-cell mRNA and miRNA via a magnetic field application, resulting in a higher miRNA detection ability. DMF-DM-seq revealed differential expression patterns of single cells of noncancerous breast cells and noninvasive and aggressive breast cancer cells at both mRNA and miRNA levels. The results demonstrated the anticorrelated relationship between miRNA and their mRNA targets. Further, we unravel the tumor growth and metastasis-associated biological processes enriched by miRNA-targeted genes, along with important miRNA-interaction networks involved in significant signaling pathways. We also deconstruct the miRNA regulatory mechanisms underlying different signaling pathways across different breast cell types. In summary, DMF-DM-seq offers a powerful tool for a comprehensive study of the expression heterogeneity of single-cell mRNA and miRNA, which will be widely applied in basic and clinical research.

Photoluminescence (PL) metal nanoclusters (NCs) have attracted extensive attention due to their excellent physicochemical properties, good biocompatibility, and broad application prospects. However, developing water-soluble PL metal NCs with a high quantum yield (QY) and high stability for visual drug delivery remains a great challenge. Herein, we have synthesized ultrabright l-Arg-ATT-Au/Ag NCs (Au/Ag NCs) with a PL QY as high as 73% and excellent photostability by heteroatom doping and surface rigidization in aqueous solution. The as-prepared Au/Ag NCs can maintain a high QY of over 61% in a wide pH range and various ionic environments as well as a respectable resistance to photobleaching. The results from structure characterization and steady-state and time-resolved spectroscopic analysis reveal that Ag doping into Au NCs not only effectively modifies the electronic structure and photostability but also significantly regulates the interfacial dynamics of the excited states and enhances the PL QY of Au/Ag NCs. Studies in vitro indicate Au/Ag NCs have a high loading capacity and pH-triggered release ability of doxorubicin (DOX) that can be visualized from the quenching and recovery of PL intensity and lifetime. Imaging-guided experiments in cancer cells show that DOX of Au/Ag NCs-DOX agents can be efficiently delivered and released in the nucleus with preferential accumulation in the nucleolus, facilitating deep insight into the drug action sites and pharmacological mechanisms. Moreover, the evaluation of anticancer activity in vivo reveals an outstanding suppression rate of 90.2% for mice tumors. These findings demonstrate Au/Ag NCs to be a superior platform for bioimaging and visual drug delivery in biomedical applications.

Visible-light-promoted thiolation of benzyl chlorides with thiosulfonates is disclosed via an electron donor-acceptor complex strategy. In addition to efficiently delivering a series of arylbenzylsulfide compounds, versatile thioglycosides were also successfully constructed by applying the metal- and photocatalyst-free protocol. Preliminary mechanistic studies suggest that a radical-radical coupling process was involved in this transformation.

Li-ion-based electric field control has been attracting significant attention, since it is able to penetrate deep into materials to exhibit diverse and controllable electrochemical processes, which offer more degrees of freedom to design multifunctional devices with low power consumption. As opposed to previous studies that mainly focused on single lithiation/delithiation mechanisms, we reveal three Li-ion modulation mechanisms in the same NiFe 2 O 4 spinel ferrite by in situ magnetometry, i.e ., intercalation, conversion, and space charge, which are respectively demonstrated in high, medium, and low voltage range. During the intercalation stage, the spinel structure is preserved, and a reversible modulation of magnetization arises from the charge transfer-induced variation of Fe valence states (Fe 2+ /Fe 3+ ). Conversion-driven change in magnetization is the largest up to 89 emu g -1 , due to the structural and magnetic phase transitions. Although both intercalation and conversion exhibit sluggish kinetics and long response times, the space charge manifests a faster switching speed and superior durability due to its interface electrostatic effect. These results not only provide a clear and comprehensive understanding on Li-based modulation mechanisms but also facilitate multifunctional and multiscenario applications, such as multistate memory, micromagnetic actuation, artificial synapse, and energy storage.

Pregnant women are physiologically prone to glucose intolerance, while the puerperium represents a critical phase for recovery. However, how air pollution disrupts glucose homeostasis during the gestational and early postpartum periods remains unclear. This prospective cohort study conducted an oral glucose tolerance test and measured the insulin levels of 834 pregnant women in Guangzhou, with a follow-up for 443 puerperae at 6-8 weeks postpartum. Residential PM 2.5 and five chemical components were estimated by an established spatiotemporal model. The adjusted linear model showed that an IQR increase in gestational PM 2.5 exposure was associated with an increase of 0.17 mmol/L (95% CI: 0.06, 0.28) in fasting plasma glucose (FPG) and 0.24 (95% CI: 0.05, 0.42) in the insulin resistance index. Postpartum PM 2.5 exposure was linked to a 0.17 mmol/L (95% CI: 0.05, 0.28) elevation in FPG per IQR, with a strengthened association found in women with gestational diabetes ( P interaction = 0.003). In the quantile-based g-computation model, NO 3 - consistently contributed to the combined effect of PM 2.5 components on gestational and postpartum FPG. This study was the first to suggest that PM 2.5 components were associated with exacerbated gestational insulin resistance and elevated postpartum FPG. Targeted interventions reducing the emissions of toxic PM 2.5 components are essential to improving maternal glucose metabolism.

The vast compositional space available in high-entropy oxide semiconductors offers unique opportunities for electronic band structure engineering in an unprecedented large room. In this work, with wide band gap semiconductor lithium niobate (LiNbO 3 ) as a model system, we show that the substitutional addition of high-entropy metal cation mixtures within the Nb sublattice can lead to the formation of a single-phase solid solution featuring a substantially narrowed band gap and intense broadband visible light absorption. The resulting high-entropy LiNbO 3 [denoted as Li(HE)O 3 ] crystallizes as well-faceted nanocubes; atomic-resolution imaging and elemental mapping via transmission electron microscopy unveil a distinct local chemical complexity and lattice distortion, characteristics of high-entropy stabilized solid solution phases. Because of the presence of high-entropy stabilized Co 2+ dopants that serve as active catalytic sites, Li(HE)O 3 nanocubes can accomplish the visible light-driven photocatalytic water splitting in an aqueous solution containing methanol as a sacrificial electron donor without the need of any additional co-catalysts.

Nuclear power plays a pivotal role in the global energy supply. The adsorption-based extraction of uranium from seawater is crucial for the rapid advancement of nuclear power. The phosphorus nitride imide (PN) nanotubes were synthesized in this study using a solvothermal method, resulting in chemically stable cross-linked tubular hollow structures that draw inspiration from the intricate snowflake fractal pattern. Detailed characterization showed that these nanotubes possess a uniformly distributed five-coordinated nanopocket, which exhibited great selectivity and efficiency in binding uranium. PN nanotubes captured 97.34% uranium from the low U-spiked natural seawater (∼355 μg L -1 ) and showed a high adsorption capacity (435.58 mg g -1 ), along with a distribution coefficient, K d U > 8.71 × 10 7 mL g -1 . In addition, PN nanotubes showed a high adsorption capacity of 7.01 mg g -1 in natural seawater. The facile and scalable production of PN nanotubes presented in this study holds implications for advancing their large-scale implementation in the selective extraction of uranium from seawater.

Organic emitters with a simultaneous combination of aggregation-induced emission (AIE) and thermally activated delayed fluorescence (TADF) characteristics are in great demand due to their excellent comprehensive performances toward efficient organic light-emitting diodes (OLEDs), biomedical imaging, and the telecommunications field. However, the development of efficient AIE-TADF materials remains a substantial challenge. In this work, light-emitting properties of two AIE-TADF molecules with different bridging groups ICz-BP and ICz-DPS are theoretically investigated in the solid state with the combined quantum mechanics/molecular mechanics (QM/MM) method and the thermal vibration correlation function (TVCF) theory. The research indicates that the C═O bridging bond in ICz-BP is more favorable than the S═O bridging bond in ICz-DPS for enhancing the planarity of the acceptor, increasing conjugation, and thereby elevating the transition dipole moment density. Simultaneously, the stacking pattern of ICz-BP in the solid facilitates a reduction in energy gap between S 1 and T 1 (Δ E ST ), achieving rapid reverse intersystem crossing rate ( k RISC ). Furthermore, compared to toluene, the stacking patterns of ICz-BP and ICz-DPS in the solid effectively suppress the out-of-plane wagging vibration of the acceptor, thereby inhibiting the loss of nonradiative energy in the excited state and realizing aggregation-induced emission. Moreover, the charge transport properties of both electrons and holes in ICz-BP are found to be higher than the corresponding rates in ICz-DPS, attributed to the smaller internal reorganization energy of ICz-BP in the solid state. Additionally, the calculations reveal a more balanced charge transport characteristic in ICz-BP, contributing to efficient exciton recombination and emission and ultimately mitigating efficiency roll-off. Based on these computational results, we aim to unveil the relationship between molecular structure and light-emitting properties, aiding in the design and development of efficient AIE-TADF devices.

Thermal radiation control has garnered growing interest for its ability to provide localized cooling and heating without energy consumption. However, its direct application for energy harvesting remains largely underexplored. In this work, we demonstrate a novel system that leverages daytime radiative cooling and solar heating technologies to continuously power charging-free thermally regenerative electrochemical cycle (TREC) devices, turning ubiquitous low-grade ambient heat into electricity. Notably, by harnessing a substantial 35 °C temperature differential solely through passive cooling and heating effects, the integrated system exhibits a cell voltage of 50 mV and a specific capacity exceeding 20 mAh g -1 of PB. This work unlocks the potential of readily available low-grade ambient heat for sustainable electricity generation.

Methylene blue (MB) is an FDA (Food and Drug Administration)-approved contrast agent with donor-acceptor (D-A) structure integrated with carbonyl-containing nitrogen-heterocycles. MB can be converted into MBH (protonated MB) by protonation, which not only induces the fluorescence emission red-shifted from the first near-infrared window (NIR-I, 650-950 nm) to the second near-infrared window (NIR-II, 1000-1700 nm) but also achieves ACQ-to-AIE conversion. MB has been successfully demonstrated in hyperacidemia imaging with an extremely low pH value (<1)., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Co-published by Nanjing University and American Chemical Society.)

Personalized in situ tumor vaccination is a promising immunotherapeutic modality. Currently, seeking immunogenic cell death (ICD) to generate in situ tumor vaccines is still mired by insufficient immunogenicity and an entrenched immunosuppressive tumor microenvironment (TME). Herein, a series of tetrazine-functionalized ruthenium(II) sonosensitizers have been designed and screened for establishing a bioorthogonal-activated in situ tumor vaccine via oncolytic pyroptosis induction. Based on nanodelivery-augmented bioorthogonal metabolic glycoengineering, the original tumor is selectively remolded to introduce artificial target bicycle [6.1.0] nonyne (BCN) into cell membrane. Through specific bioorthogonal ligation with intratumoral BCN receptors, sonosensitizers can realize precise membrane-anchoring and synchronous click-activation in desired tumor sites. Upon ultrasound (US) irradiation, the activated sonosensitizers can intensively disrupt the cell membrane with dual type I/II reactive oxygen species (ROS) generation for a high-efficiency sonodynamic therapy (SDT). More importantly, the severe membrane damage can eminently evoke oncolytic pyroptosis to maximize tumor immunogenicity and reverse immunosuppressive TME, ultimately eliciting powerful and durable systemic antitumor immunity. The US-triggered pyroptosis is certified to effectively inhibit the growths of primary and distant tumors, and suppress tumor metastasis and recurrence in "cold" tumor models. This bioorthogonal-driven tumor-specific pyroptosis induction strategy has great potential for the development of robust in situ tumor vaccines.

Graphene, serving as electrodes, is widely applied in electronic and optoelectronic devices. Work function as one of the fundamental intrinsic characteristics of graphene directly affects the interfacial properties of the electrodes, thereby affecting the performance of the devices. Much work has been done to regulate the work function of graphene to expand its application fields, and doping has been demonstrated as an effective method. However, the numerous types of doped graphene make the investigation of its work function time-consuming and labor-intensive. In order to quickly obtain the relationship between the structure and property, a deep learning method is employed to predict the work function in this study. Specifically, a data set of over 30,000 compositions with the work function on boron-doped graphene at different concentrations and doping positions via density functional theory simulations was established through ab initio calculations. Then, a novel fusion model (GT-Net) combining transformers and graph neural networks (GNNs) was proposed. After that, improved effective GNN-based descriptors were developed. Finally, three different GNN methods were compared, and the results show that the proposed method could accurately predicate the work function with the R 2 = 0.975 and RMSE = 0.027. This study not only provides the possibility of designing materials with specific properties at the atomic level but also demonstrates the performance of GNNs on graph-level tasks with the same graph structure and atomic number.

The investigation of pharmaceuticals as emerging contaminants in marine biota has been insufficient. In this study, we examined the presence of 51 pharmaceuticals in edible oysters along the coasts of the East and South China Seas. Only nine pharmaceuticals were detected. The mean concentrations of all measured pharmaceuticals in oysters per site ranged from 0.804 to 15.1 ng g -1 of dry weight, with antihistamines being the most common. Brompheniramine and promethazine were identified in biota samples for the first time. Although no significant health risks to humans were identified through consumption of oysters, 100-1000 times higher health risks were observed for wildlife like water birds, seasnails, and starfishes. Specifically, sea snails that primarily feed on oysters were found to be at risk of exposure to ciprofloxacin, brompheniramine, and promethazine. These high risks could be attributed to the monotonous diet habits and relatively limited food sources of these organisms. Furthermore, taking chirality into consideration, chlorpheniramine in the oysters was enriched by the S -enantiomer, with a relative potency 1.1-1.3 times higher when chlorpheniramine was considered as a racemate. Overall, this study highlights the prevalence of antihistamines in seafood and underscores the importance of studying enantioselectivities of pharmaceuticals in health risk assessments.

Resulting from the dense packing of subnanometer molecular clusters, molecular granular materials (MGMs) are shown to maintain high elasticity far above their apparent glass transition temperature ( T g *). However, our microscopic understanding of their structure-property relationship is still poor. Herein, 1 nm polyhedral oligomeric silsesquioxanes (POSSs) are appended to a backbone chain in a brush configuration with different flexible linker chains. Assemblies of these brush polymers exhibit hierarchical relaxation dynamics with the glass transition arising from the cooperative dynamics of packed POSSs. The interaction among the assemblies can be strengthened by increasing the rigidity of linkers with the MGM relaxation modes changing from colloid- to polymer chain-like behavior, rendering their tunable viscoelasticity. This finally contributes to the decoupling of mechanical and thermal properties by showing elasticity dominant mechanical properties at a temperature 150 K above the T g *.

An organo-photoredox catalyzed gem -difluoroallylation of glycine with α-trifluoromethyl alkenes via direct C(sp 3 )-H functionalization of glycine and C-F bond activation of α-trifluoromethyl alkenes has been described. As a consequence, a broad range of gem -difluoroalkene-containing unnatural amino acids are afforded in moderate to excellent yields. This reaction exhibits multiple merits such as readily available starting materials, broad substrate scope, and mild reaction conditions. The feasibility of this reaction has been highlighted by the late-stage modification of several peptides as well as the improved in vitro antifungal activity of compound 3v toward Valsa mali compared to that with commercial azoxystrobin.

Thermally activated delayed fluorescence (TADF) molecules with aggregation-induced emission (AIE) properties hold tremendous potential in biomedical sensing/imaging and telecommunications. In this study, a multiscale method combined with thermal vibration correlation function (TVCF) theory is used to investigate the photophysical properties of the novel TADF molecule CNPy-SPAC in toluene and crystal and amorphous states. In the crystal state, an increase in radiative rates and a decrease in nonradiative rates lead to AIE. Additionally, conformational isomerization effects result in significantly different luminescent efficiencies between the two crystal structures. Furthermore, the isomerization effect allows for the coexistence of three configurations in the amorphous state. Among them, the non-TADF quasi-axial (Qa) configuration may facilitate energy transfer to the TADF-characteristic quasi-equal/quasi-equal-H (Qe/Qe-H) configurations, enhancing AIE. Moreover, the Qa configuration enables rapid electron transport, offering the potential for self-doped devices. Our work elucidates a new mechanism for the isomerization effect in AIE-TADF molecules.

Hepatocellular carcinoma (HCC) is susceptible to early recurrence, but it lacks effective predictive biomarkers. In this study, we retrospectively selected 179 individuals as a discovery cohort (126 HCC patients and 53 liver cirrhosis (LC) patients) for screening candidate serum biomarkers of early recurrence based on data independent acquisition-mass spectrometry strategy. And then, the candidate biomarkers were validated in an additional independent cohort with 192 individuals (142 HCC patients and 50 LC patients) using parallel reaction monitoring targeted quantitative techniques (PXD047852). Eventually, we validated that gelsolin (GSN) concentrations were significantly lower in HCC than in LC ( p < 0.0001), patients with low GSN concentrations had a poor prognosis ( p < 0.0001), and GSN concentrations were significantly lower in early recurrence HCC than in late recurrence HCC ( p < 0.0001). These trends were also observed in alpha-fetoprotein (AFP)-negative HCC patients. The area under the curve of machine-learning-based predictive model (GSN and microvascular invasion) for predicting early recurrence risk reached 0.803 (95% confidence interval (CI): 0.786-0.820) and maintained the same efficacy in AFP-negative patients. In conclusion, GSN is a novel serum biomarker for early recurrence of HCC. The model could provide timely warning to HCC patients at high risk of recurrence.

Ferroptosis and apoptosis are two types of regulated cell death that are closely associated with the pathophysiological processes of many diseases. The significance of ferroptosis-apoptosis crosstalk in cell fate determination has been reported, but the underlying molecular mechanisms are poorly understood. Herein mitochondria-mediated molecular crosstalk is explored. Based on a comprehensive spectroscopic investigation and mass spectrometry, cytochrome c-involved Fenton-like reactions and lipid peroxidation are revealed. More importantly, cytochrome c is found to induce ROS-independent and cardiolipin-specific lipid peroxidation depending on its redox state. In situ Raman spectroscopy unveiled that erastin can interrupt membrane permeability, specifically through cardiolipin, facilitating cytochrome c release from the mitochondria. Details of the erastin-cardiolipin interaction are determined using molecular dynamics simulations. This study provides novel insights into how molecular crosstalk occurs around mitochondrial membranes to trigger ferroptosis and apoptosis, with significant implications for the rational design of mitochondria-targeted cell death reducers in cancer therapy.

The cooling power of a radiative cooler is more than halved in the tropics, e.g., Singapore, because of its harsh weather conditions including high humidity (84% on average), strong downward atmospheric radiation (∼40% higher than elsewhere), abundant rainfall, and intense solar radiation (up to 1200 W/m 2 with ∼58% higher UV irradiation). So far, there has been no report of daytime radiative cooling that well achieves effective subambient cooling. Herein, through integrated passive cooling strategies in a hydrogel with desirable optofluidic properties, we demonstrate stable subambient (4-8 °C) cooling even under the strongest solar radiation in Singapore. The integrated passive cooler achieves an ultrahigh cooling power of ∼350 W/m 2 , 6-10 times higher than a radiative cooler in a tropical climate. An in situ study of radiative cooling with various hydration levels and ambient humidity is conducted to understand the interaction between radiation and evaporative cooling. This work provides insights for the design of an integrated cooler for various climates.

A rational combination of photoredox catalyst anthraquinone and hydrogen atom transfer (HAT) catalyst methyl thioglycolate allows for the rapid and straightforward conversion of a range of 2-amidated acetylenic alcohols to multifunctional N , O -spirocycles under visible light irradiation. With oxygen as the sole terminal oxidant, these reactions can be carried out efficiently at room temperature without the involvement of transition metals or strong oxidants. The successful application of this mild catalytic strategy in the late-stage functionalization of bioactive skeletons further highlights its practical value.

The selective interaction of cytochrome c (Cyt c ) with cardiolipin (CL) is involved in mitochondrial membrane permeabilization, an essential step for the release of apoptosis activators. The structural basis and modulatory mechanism are, however, poorly understood. Here, we report that Cyt c can induce CL peroxidation independent of reactive oxygen species, which is controlled by its redox states. The structural basis of the Cyt c -CL binding was unveiled by comprehensive spectroscopic investigation and mass spectrometry. The Cyt c -induced permeabilization and its effect on membrane collapse, pore formation, and budding are observed by confocal microscopy. Moreover, cytochrome c oxidase dysfunction is found to be associated with the initiation of Cyt c redox-controlled membrane permeabilization. These results verify the significance of a redox-dependent modulation mechanism at the early stage of apoptosis, which can be exploited for the design of cytochrome c oxidase-targeted apoptotic inducers in cancer therapy.

Photoelectrochemical (PEC) conversion is a promising way to use methane (CH 4 ) as a chemical building block without harsh conditions. However, the PEC conversion of CH 4 to value-added chemicals remains challenging due to the thermodynamically favorable overoxidation of CH 4 . Here, we report WO 3 nanotube (NT) photoelectrocatalysts for PEC CH 4 conversion with high liquid product selectivity through defect engineering. By tuning the flame reduction treatment, we carefully controlled the oxygen vacancies of WO 3 NTs. The optimally reduced WO 3 NTs suppressed overoxidation of CH 4 showing a high total C1 liquid selectivity of 69.4% and a production rate of 0.174 μmol cm -2 h -1 . Scanning electrochemical microscopy revealed that oxygen vacancies can restrain the production of hydroxyl radicals, which, in excess, could further oxidize C1 intermediates to CO 2 . Additionally, band diagram analysis and computational studies elucidated that oxygen vacancies thermodynamically suppress overoxidation. This work introduces a strategy for understanding and controlling the selectivity of photoelectrocatalysts for direct conversion of CH 4 to liquids.

An efficient fluorinated alcohol-driven cascade [1,5]-hydride transfer/cyclization between o -amino pyridyl aldehydes and primary amines has been developed. This unique transformation enabled an array of tetrahydropyridino[2,3- d ]pyrimidine construction. Furthermore, the encouraging antifungal activity of Thanatephorus cucumeris was demonstrated by this tetrahydropyridino[2,3- d ]pyrimidine core structure.

As a core chromatin-regulatory scaffolding protein, WDR5 mediates numerous protein-protein interactions (PPIs) with other partner oncoproteins. However, small-molecule inhibitors that block these PPIs exert limited cell-killing effects. Here, we report structure-activity relationship studies in pancreatic ductal adenocarcinoma (PDAC) cells that led to the discovery of several WDR5 proteolysis-targeting chimer (PROTAC) degraders, including 11 (MS132), a highly potent and selective von Hippel-Lindau (VHL)-recruiting WDR5 degrader, which displayed positive binding cooperativity between WDR5 and VHL, effectively inhibited proliferation in PDAC cells, and was bioavailable in mice and 25 , a cereblon (CRBN)-recruiting WDR5 degrader, which selectively degraded WDR5 over the CRBN neo-substrate IKZF1. Furthermore, by conducting site-directed mutagenesis studies, we determined that WDR5 K296, but not K32, was involved in the PROTAC-induced WDR5 degradation. Collectively, these studies resulted in a highly effective WDR5 degrader, which could be a potential therapeutic for pancreatic cancer and several potentially useful tool compounds.

The orbital angular momentum (OAM) generation as well as its associated orbital torque is currently a matter of great interest in spin-orbitronics and is receiving increasing attention. In particular, recent theoretical work predicts that the oxidized light metal Cu can serve as an efficient OAM generator through its surface orbital Rashba effect. Here, for the first time, the crucial current-induced magnetic-field-free in-plane magnetization reversal is experimentally demonstrated in CoFeB/CuO x bilayers without any heavy elements. We show that the critical current density can be comparable to that of strong spin-orbit coupling systems with heavy metals (Pt and Ta) and that the magnetization reversal mechanism is governed by coherent rotation in the grains through the second-harmonic and magneto-optical Kerr effect measurements. Our results indicate that light metal oxides can play an equally important role as heavy metals in magnetization reversal, broadening the choice of materials for engineering spintronic devices.

CaO 2 nanoparticles (CNPs) can produce toxic Ca 2+ and H 2 O 2 under acidic pH, which accounts for their intrinsic anticancer activity but at the same time raises safety concerns upon systemic exposure. Simultaneously realizing minimized Ca 2+ /H 2 O 2 production and enhanced anticancer activity poses a dilemma. Herein, we introduce a "crystallinity gradient-based selective etching" (CGSE) strategy, which is realized by creating a crystallinity gradient in a CNP formed by self-assembled nanocrystals. The nanocrystals distributed in the outer layer have a higher crystallinity and thus are chemically more robust than those distributed in the inner layer, which can be selectively etched. CGSE not only leads to CNPs with tailored single- and double-shell hollow structures and metal-doped compositions but more surprisingly enables significantly enhanced anticancer activity as well as tumor growth inhibition under limited Ca 2+ /H 2 O 2 production, which is attributed to an alkalinity-reinforced lysosome-dependent cell death pathway.

Non-noble metal oxides have emerged as potential candidate electrocatalysts for acidic oxygen evolution reactions (OERs) due to their earth abundance; however, improving their catalytic activity and stability simultaneously in strong acidic electrolytes is still a major challenge. In this work, we report Co 3 O 4 @carbon core-shell nanoparticles on 2D graphite sheets (Co 3 O 4 @C-GS) as mixed-dimensional hybrid electrocatalysts for acidic OER. The obtained Co 3 O 4 @C-GS catalyst exhibits a low overpotential of 350 mV and maintains stability for 20 h at a current density of 10 mA cm -2 in H 2 SO 4 (pH = 1) electrolyte. X-ray photoelectron and X-ray absorption spectroscopies illustrate that the higher content of Co 3+ sites boosts acidic OER. Operando Raman spectroscopy reveals that the catalytic stability of Co 3 O 4 @C nanoparticles during the acidic OER is enhanced by the introduction of graphite sheets. This interface engineering of non-noble metal sites with high valence states provides an efficient approach to boost the catalytic activity and enhance the stability of noble-metal-free electrocatalysts for acidic OER.

With the increasing prevalence of microbial infections, which results in prolonged inflammation and delayed wound healing, the development of effective and safe antimicrobial wound dressings of multiple properties remains challenging for public health. Despite their various formats, the available developed dressings with limited functions may not fulfill the diverse demands involved in the complex wound healing process. In this study, multifunctional sandwich-structured electrospinning nanofiber membranes (ENMs) were fabricated. According to the structural composition, the obtained ENMs included a hydrophilic inner layer loaded with curcumin and gentamicin sulfate, an antibacterial middle layer consisting of bovine serum albumin stabilized silver oxide nanoparticles, and a hydrophobic outer layer. The prepared sandwich-structured ENMs (SNM) exhibited good biocompatibility and killing efficacy on Escherichia coli , Staphylococcus aureus, and Methicillin-resistant S. aureus ( MRSA ). In particular, transcriptomic analysis revealed that SNM inactivated MRSA by inhibiting its carbohydrate and energy metabolism and reduced the bacterial resistance by downregulating mecA . In the animal experiment, SNM showed improved wound healing efficiency by reducing the bacterial load and inflammation. Moreover, 16S rDNA sequencing results indicated that SNM treatment may accelerate wound healing without observed influence on the normal skin flora. Therefore, the constructed sandwich-structured ENMs exhibited promising potential as dressings to deal with the infected wound management.

Restoring damaged myocardial tissue with therapeutic exogenous cells still has some limitations, such as immunological rejection, immature cardiac properties, risk of tumorigenicity, and a low cell survival rate in the ischemic myocardium microenvironment. Activating the endogenous stem cells with functional biomaterials might overcome these limitations. Research has highlighted the multiple differentiation potential of epicardial cells via epithelial-mesenchymal transition (EMT) in both heart development and cardiac regeneration. In our previous research, a carboxylic gelatin-methacrylate (carbox-GelMA) nanoparticle (NP) was fabricated to carry ammonium persulfate (APS), and APS-loaded carbox-GelMA NPs (NPs/APS) could drive the EMT of MCF-7 cells in vitro and promote cancer cell migration and invasion in vivo . The present study explored the roles of functional NPs/APS in the EMT of Wilms' tumor 1-positive (WT1 + ) epicardial cells and in the repair of myocardial infarction (MI). The WT1 + epicardial cells transformed into endothelial-like cells after being treated with NPs/APS in vitro , and the cardiac functions were improved significantly after injecting NPs/APS into the infarcted hearts in vivo . Furthermore, simultaneous activation of both autophagy and the mTOR pathway was confirmed during the NPs/APS-induced EMT process in WT1 + epicardial cells. Together, this study highlights the function of NPs/APS in the repair of MI.

Inflammatory bowel disease (IBD) is a common inflammatory bowel disease with a high incidence rate and serious consequences. Attempts in this area are focusing on developing efficient delivery systems for relieving IBD. Herein, we present a kind of near-infrared-II (NIR-II)-activated pollen-derived micromotor (PDMM) as an efficient delivery system for treating IBD. These PDMMs are pollen grains with half of them covered by a gold (Au) layer, which can result in an asymmetric thermal gradient around the PDMMs under NIR-II irradiation, thereby forming a thermophoretic force to drive PDMMs to move spontaneously. Besides, the inherent spiny and hollow architectures of pollen grains endowed the PDMMs with outstanding capacity of adherence and drug delivery, respectively. Based on these features, we have demonstrated that the PDMMs could move actively in vivo with the irradiation of NIR-II light and adhere to the surrounding tissues for drug delivery. Thus, the PDMMs loaded with dexamethasone show desirable curative effects on treating IBD. These results indicated that the proposed PDMM-based delivery system has great potential in clinic gastrointestinal administration.