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An efficient and sequence-specific translation of DNA templates containing as many as 40 bases of mixed coding sequence into corresponding synthetic peptide nucleic acid polymers is developed. These findings are a key step toward the evolution of sequence-defined synthetic hetropolymers, rather than biological macromolecules, using iterated cycles of DNA-templated translation, in vitro selection, PCR amplification, and sequence diversification.

High-quality (0001)-oriented ZnO epitaxial films have been grown by pulsed laser deposition on Si(111) buffered with a nanometer-thick Gd2O3(Ga2O3), GGO, layer. The structural characteristics of the ZnO epi-layers were studied by X-ray diffraction and transmission electron microscopy (TEM). The in-plane epitaxial relationship between the wurtzite ZnO, cubic GGO, and cubic Si follows {101̅0}ZnO∥{42̅2̅}Gd2O3∥{4̅22}Siand the ZnO/GGO interface can be described by the domain matching epitaxy. TEM contrast analysis reveals that the major defect structures in the ZnO films are edge-type threading dislocations and intrinsic basal plane stacking faults. All the ZnO epi-films studied are under a tensile biaxial strain, but no cracks were found. Temperature-dependent photoluminescence results show the excellent optical properties of the obtained ZnO layers, and the origins of the spectral features are discussed. [ABSTRACT FROM AUTHOR]

High-quality ZnO epitaxial films have been grown by pulsed-laser deposition on Si (111) substrates using a nanothick high-koxide Y2O3buffer layer. Determined by X-ray diffraction and transmission electron microscopy, the epitaxial relationship between ZnO and Y2O3follows (0001)⟨21̅1̅0⟩ZnO||(111)⟨101̅⟩Y2O3. ZnO lattice aligns with the hexagonal O sublattice in Y2O3and the interfacial structure can be well described by domain matching epitaxy with 7 or 8 ZnO {112̅0} planes matching 6 or 7 {44̅0} planes of Y2O3and lead to a significant reduction of residual strain. Superior optical properties were obtained even for ZnO films as thin as 0.21 μm from photoluminescence results. [ABSTRACT FROM AUTHOR]

In this work, temperature-triggered gelation of aqueous laponite dispersions containing a cationic poly(N-isopropylacrylamide) (PNIPAm) graft copolymer was investigated. The copolymer used was PDMAg-(PNIPAm210)14[Liu et al. Langmuir2008, 24, 7099]. DMA quarternarized N,N-dimethylaminoethyl methacrylate. The presence of small concentrations of laponite enabled temperature-triggered gel formation to occur at low copolymer concentrations (e.g., 1 wt %). Dynamic rheological measurements of the gels showed that they had storage modulus values of up to 400 Pa when the total solid volume fraction (polymer and laponite) was only about 0.02. The storage modulus was dependent on both the temperature and the composition of the dispersion used for preparation. The key component that provided the temperature-triggered gels with their elasticity was found to be self-assembled nanocomposite (NC) sheets. These NC sheets spontaneously formed at room temperature upon addition of laponite to the copolymer solution. The NC sheets had lateral dimensions on the order of hundreds of micrometers and a thickness of a few micrometers. The NC sheets were present within the temperature-triggered gels and formed elastically effective chains. The NC sheets exhibited temperature-triggered contraction with a contraction onset temperature of 27 °C. A conceptual model is proposed to qualitatively explain the relationship between gel elasticity and dispersion composition. [ABSTRACT FROM AUTHOR]

In this work temperature-triggered association and gel formation within aqueous solutions of a new family of cationic poly( N-isopropyl acrylamide) (PNIPAm) graft copolymers have been investigated. Five copolymers were synthesized using aqueous atom transfer radical polymerization (ATRP) involving a macroinitiator based on quaternarized N, N-dimethylaminoethyl methacrylate units (DMA +). The PDMA +x- g-(PNIPAm n) ycopolymers have xand yvalues that originate from the macroinitiator; values for ncorrespond to the PNIPAm arm length. The copolymer solutions exhibited temperature-triggered formation of nanometer-sized aggregates at the cloud point temperature, which was 33−34 °C. The aggregates were investigated using variable-temperature turbidity, hydrodynamic diameter, and electrophoretic mobility measurements. The aggregates were clearly evident using SEM and flowerlike or spherical morphologies were observed. Variable-temperature electrophoretic mobility measurements revealed that the zeta potentials of the aggregates increased with DMA +content. A study of the effect of added NaNO 3showed that electrostatic interactions controlled the size of the aggregates. The concentrated graft copolymer solutions showed temperature-triggered gelation when the copolymer concentrations exceeded 5 wt %, Fluid-to-gel phase diagrams were constructed. It was found that electrostatic interactions also controlled the gelation temperature. A correlation was found between aggregate size and the minimum copolymer concentration needed to form a gel. A mechanism for the temperature-triggered structural changes leading to the formation of aggregates (in dilute solution) or gels (in concentrated solutions) is proposed. [ABSTRACT FROM AUTHOR]

The occurrence of organophosphorus compounds has garnered global concern due to their widespread production and potential environmental risks. Limited structural information has hindered a comprehensive understanding of their composition. By characteristic fragmentation-based nontarget analysis, the occurrence and composition of organothiophosphate esters (OTPEs), which are antiwear additives in lubricant oils that have received little attention previously, were investigated in dust from automotive repair shops and surrounding buildings. Fourteen OTPEs were tentatively identified, including four triarylphosphorothionates, six O , O -dialkyl phosphorothioates, and four O -alkyl O -alkyl sulfone phosphorothioates, among which four OTPEs were further confirmed by authentic standards or an industrial product. Triphenyl phosphorothioate (TPhPt) and tris(2,4-di- tert -butylphenyl) phosphorothioate (AO168=S) were prevalently detected in automotive repair shops with median concentrations of 230 and 246 ng/g, respectively, closely comparable to triphenyl phosphate (TPhP, median concentration: 302 ng/g). O,O -Dihexyl phosphorothioate (DHPt), O,O -dioctyl phosphorothioate (DOPt), O -hexyl O -hexyl sulfone phosphorothioate (DHSPt), and O- octyl O -octyl sulfone phosphorothioate (DOSPt) were the abundant analogues in automotive repair shops with semiquantitative median concentrations in the range of 119-1.05 × 10 3 ng/g. Hierarchical cluster analysis showed that OTPEs exhibited similar distribution patterns across automotive repair shops, indicating that these chemicals had similar sources. Moreover, the concentrations of OTPEs were usually higher in automotive repair shops than that in surrounding buildings, suggesting a motor vehicle related emission source. To our knowledge, 12 out of the 14 detected OPTEs were reported in the environment for the first time. The discovery of these OTPEs expanded the scope of known organophosphorus pollutants, highlighting the potential contaminants of OTPEs from lubricant oils for automotive and industrial applications.

Calcium phosphate cement (CPC) is an injectable bone cement with excellent biocompatibility, widely used for filling bone defects of various shapes. However, its slow degradation, insufficient mechanical strength, and poor osteoinductivity limit its further clinical applications. In this study, we developed a novel composite magnesium-based calcium phosphate cement by integrating magnesium microspheres into PLGA fibers obtained through wet spinning and incorporating these fibers into CPC. The inclusion of magnesium-based PLGA fibers enhanced the compressive strength and degradation rate of CPC, with the degradation rate of the magnesium microspheres being controllable to allow for the sustained release of magnesium ions. In vitro experiments showed that magnesium-based CPC enhanced the proliferation and migration of MC3T3-E1 and HUVECs. Additionally, the magnesium-based composite CPC not only enhanced osteogenic differentiation of MC3T3-E1 cells but also promoted angiogenesis in HUVECs. In vivo experiments using a vertebral bone defect model in Bama miniature pigs showed that the magnesium-based composite CPC significantly increased new bone formation. Additionally, compared to the CPC group, this composite exhibited significantly higher levels of osteogenic and angiogenic markers, with no inflammation or necrosis observed in the heart, liver, or kidneys, indicating good biocompatibility. These results suggest that magnesium-based composite CPC, with its superior compressive strength, biodegradability, and ability to promote vascularized bone regeneration, holds promise as a minimally invasive injectable material for bone regeneration.

Maintaining normal biomolecular levels in the human body plays a crucial role in controlling various diseases. In this work, we designed a portable microelectrochemical sensor based on laser-induced graphene (LIG) for the simultaneous determination of ascorbic acid (AA), dopamine (DA), and uric acid (UA). A simple electrode surface modification strategy, potentiostatic polarization in an alkali solution, was applied to functionalize the LIG surface with the aim of enhancing the LIG electrocatalytic activity, conductivity, and wettability. After electrochemical pretreatment, the modified electrode displayed significantly enhanced electrocatalytic activity toward AA, DA, and UA, with well-separated characteristic oxidation peaks for each analyte, thus achieving their simultaneous detection without further modification by nanomaterials. Differential pulse voltammetry (DPV) was applied for determining these three analytes. Under optimal conditions, calibration curves were obtained in the ranges 10-5000 μM, 0.1-6000 μM, and 10-8000 nM for AA, DA, and UA, with the detection limits (S/N = 3) of 1.43 μM, 6.83 nM, and 1.07 nM, respectively. The microelectrochemical sensor achieved reliable and satisfactory results in detecting AA, DA, and UA in actual urine samples, demonstrating significant application prospects in human health monitoring and clinical diagnosis.

The sustainable and affordable environmental application of Pd catalysis needs further improvement of Pd mass activity. Besides the well-recognized importance of physical utilization efficiency─the ratio of surface atoms forming reactant-accessible reactive sites─a lesser-known fact is that the congestion of these reactive sites, which we term as the chemical utilization efficiency, also influences the mass activity. Herein, by leveraging the 100% physical utilization efficiency of a fully exposed Pd cluster (Pd n ) and the hydrogenation activity of TiNiN, we developed Pd n /TiNiN as a high physical and chemical utilization efficiency catalyst. During the catalytic hydrodechlorination of 4-chlorophenol and the subsequent hydrogenation of phenol, Pd n focuses on H 2 dissociation and C-Cl cleavage, while TiNiN facilitates the subsequent hydrogenation of phenol into less toxic cyclohexanone via H-spillover. This synergy results in a 20-40-fold increase in the hydrodechlorination rate. The enhanced chemical utilization efficiency of Pd informs the design of Pd n /TiNiN microspheres for the conversion of halogenated organics from pharmaceutical wastewater and the design of a fixed-bed reactor to transfer trace amounts of 4-CP from river water. Ultimately, this approach decentralizes the use of Pd in environmental catalysis and reduction processes.

In the quest to replace fossil fuels and reduce carbon dioxide emissions, developing energy technologies based on clean catalytic processes is fundamental. However, the cost-effectiveness of these technologies strongly relies on the availability of efficient catalysts made of abundant elements. Herein, this study presents a one-step hydrothermal method to obtain a series of Ni 3 Se 4 nanoparticles with a layer of amorphous selenium on their surface. When employed as electrocatalysts for the methanol oxidation reaction (MOR), the optimized proper surface Se-coated Ni 3 Se 4 nanoparticles exhibit a high current density of 160 mA cm -2 at 1.6 V, achieving a high methanol-to-formate Faradaic efficiency above 97.8% and excellent stability with less than 20% current decay after an 18 h chronoamperometry test. This excellent performance is rationalized using density functional theory calculations, which unveil that the electrochemical recombination of SeO x results in a reduction of the energy barrier for the dehydrogenation of methanol during the MOR process.

Pancreatic ductal adenocarcinoma (PDAC) poses a challenge in oncology due to its high lethality and resistance to immunotherapy. Recently, emerging research on the stimulator of interferon gene (STING) pathway offers novel opportunities for immunotherapy. Although STING expression is retained in PDAC cells, the response of PDAC cells to STING agonists remains ineffective. Signal transducer and activator of transcription 3 (STAT3), a downstream pathway of STING, is notably overexpressed in pancreatic cancer and related to tumor survival and immune escape. We observed that inhibiting STAT3 signaling post-STING activation effectively suppressed tumor growth through signal transducer and activator of transcription 1 (STAT1)-mediated apoptosis but led to a potential risk of immune-related adverse events (irAEs). To address this issue, we designed a tumor-penetrating liposome for the codelivery of STING agonist and STAT3 inhibitor. These nanoparticles regulated the STING/STAT3 signaling axis and effectively inhibited the proliferation and survival of tumor. Simultaneously, we found a significant increase in the activation of NK cells and CD8 + T cells after treatment, leading to robust innate immunity and adaptive immune response. We highlight the potential of regulating the STING/STAT3 axis as a promising treatment for improving clinical outcomes in PDAC patients.

Titanium alloys are widely used in marine environments and medical fields due to their excellent corrosion resistance and high specific strength. However, their good biocompatibility can lead to severe biofouling, thereby limiting their effectiveness. To inhibit biofouling on the surface of titanium alloys, this study proposes an antifouling solution, which involves the in situ preparation of Cu-MOF film on titanium alloys by leveraging the antibacterial properties of Cu ions. Here, the dense and stable TiO 2 film on the surface of Ti-6Al-4V titanium alloy was removed by alkali-heat treatment; meanwhile, a porous surface structure was simultaneously obtained where OH - ions were retained. In the subsequent step, the retained OH - ions in the pores attracted Cu 2+ ions in solution to form Cu(OH) 2 in the pores, providing active sites for the formation of Cu-MOFs. Subsequently, Cu(OH) 2 reacted with organic ligand (1,3,5-benzenetricarboxylic acid, BTC) at room temperature to form Cu-MOFs in the pores, which then grew quickly to cover the alkali-heat-treated surface within 1 h. The formation mechanism of Cu-MOF film on Ti-6Al-4V was elucidated, which provides a reference for designing and preparing multifunctional MOF film in situ on titanium alloys. The stability of in situ-grown Cu-MOF samples and their inhibitory effects on bacteria and microalgae have also been verified. The results indicate that although the stability of Cu-MOFs is relatively poor, their bactericidal and algicidal effects are extremely significant, suggesting that this material has significant potential for short-term applications that require high antibacterial performance.

Sodium ion capacitors (SICs) are promising candidates in energy storage for their remarkable power and energy density. However, the inherent disparity in dynamic behavior between the sluggish battery-type anodes and the rapid capacitor-type cathodes constrained their performance. To address this, we fabricated a hollow porous Co 0.85 Se/ZnSe@MXene anode featuring multiheterostructure, utilizing facile etching and electrostatic self-assembly strategies. The hollow porous structure and multiple heterointerfaces stabilize the anode by mitigating the volume changes. Density functional theory (DFT) calculations further revealed that induced multilevel built-in electric fields facilitate the formation of rapid ion diffusion pathways and reduce the Na + adsorption energy, thereby boosting Na + /electron transport kinetics. The fabricated TA-Co 0.85 Se/ZnSe@MXene anode demonstrates outstanding long-term cycling stability of 406 mA h g -1 after 1000 cycles at 1 A g -1 , with an ultrahigh rate performance of 288 mA h g -1 at 10 A g -1 . When paired with the active carbon (AC) cathode, the SICs deliver extraordinary energy/power densities of 144 W h kg -1 and 12000 W kg -1 , maintaining over 80% capacity retention at 1 A g -1 after 10000 cycles. This innovative strategy of engineering multiheterostructured anode with the induced multilevel built-in electric fields holds significant promise for advancing high-energy and high-power energy storage systems.

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.

Knowledge of the biotransformation of tetrabromobisphenol A (TBBPA) and its related contaminants by human gut microbiota (GM) remains unexplored. Here, TBBPA and its four analogs were incubated with mixed GM strains, and nine rhamnosylated or debrominated transformation products (TPs) were discovered. Remarkably, rhamnosylation was identified as a common and unique microbial transformation pathway for these contaminants, and six of the seven rhamnosylated TPs were reported for the first time. Additionally, a kinetic transformation study also showed a rapid and strong bioaccumulation of TBBPA and TPs by Clostridium manihotivorum . Genomic analysis and phylogenetic studies identified C1.1_02053 as the gene encoding the C. manihotivorum working rhamnosyltransferase (CmRT), showing elevated gene expression with higher TBBPA exposure. Molecular docking identified five critical amino acid residues in CmRT that catalyze TBBPA rhamnosylation, and molecular dynamics simulations further confirmed the stability of the CmRT-TBBPA complex. Dynamic metabolomics analysis showed microbial growth-dependent disturbing effects in C. manihotivorum upon TBBPA exposure, and key metabolic pathways related to rhamnosyltransferase showed changes closely related to the transformation process. These findings provide insights into the unique transformation of environmental contaminants by the GM and highlight the disturbing effects of exogenous chemicals on the GM, as well as the potential impacts on overall human health.

All-atom constant pH molecular dynamics simulations offer a powerful tool for understanding pH-mediated and proton-coupled biological processes. As the protonation equilibria of protein side chains are shifted by electrostatic interactions and desolvation energies, p K a values calculated from the constant pH simulations may be sensitive to the underlying protein force field and water model. Here we investigated the force field dependence of the all-atom particle mesh Ewald (PME) continuous constant pH (PME-CpHMD) simulations of a mini-protein BBL. The replica-exchange titration simulations based on the Amber ff19sb and ff14sb force fields with the respective water models showed significantly overestimated p K a downshifts for a buried histidine (His166) and for two glutamic acids (Glu141 and Glu161) that are involved in salt-bridge interactions. These errors (due to undersolvation of neutral histidines and overstabilization of salt bridges) are consistent with the previously reported p K a 's based on the CHARMM c22/CMAP force field, albeit in larger magnitudes. The p K a calculations also demonstrated that ff19sb with OPC water is significantly more accurate than ff14sb with TIP3P water, and the salt-bridge related p K a downshifts can be partially alleviated by the atom-pair specific Lennard-Jones corrections (NBFIX). Together, these data suggest that the accuracies of the protonation equilibria of proteins from constant pH simulations can significantly benefit from improvements of force fields.

Due to their good wearability, smart fabrics have gradually developed into one of the important components of multifunctional flexible electronics. Nevertheless, function integration is typically accomplished through the intricate stacking of diverse modules, which inevitably compromises comfort and elevates processing complexities. The integration of these discrete functional modules into a unified design for smart fabrics represents a superior solution. Here, we put forward a rational approach to functional integration for the typical challenges of thermal management, energy supply, and surface contamination in smart fabrics. This sandwich-structured multilayer fabric (MLF) is obtained by continuous electrospinning of two layer P(VDF-HFP) fabric and one layer P(VDF-HFP) fabric functionalized with core-shell SiO 2 /ZnO/ZIF-8 (SZZ) nanoparticles. Specifically, MLFs achieve effective and stable energy harvesting in triboelectric nanogenerators (TENGs) with hydrophobicity and antibacterial properties. Meanwhile, MLFs also have high mid-infrared emissivity and sunlight reflectivity, successfully realizing radiative cooling under different climates, and have been applied in wearing clothing, roof shading, and car covers. This work may contribute to the design and manufacturing of next-generation thermal comfort smart fabrics and wearable electronics, particularly in terms of the rational design of multifunctional devices.

Efficient electrochemical Li + adsorption holds significant promise for lithium extraction, while the mismatched rate between Li + diffusion and electron transport within the electrode material impedes the electrochemical activity and restricts the adsorption efficiency. To address this challenge, herein, we rationally design and integrate the ion and electron dual-conducting poly(vinyl alcohol)-polyaniline (PVA-PANI) copolymer (CP) within the H 1.6 Mn 1.6 O 4 (HMO) electrode matrix to facilitate Li + diffusion and electron transport. The Li + diffusion coefficient ( D Li+ ) increased from 3.03 × 10 -10 to 5.92 × 10 -10 cm 2 /s, while the charge transfer resistance ( R ct ) decreased from 53.73 to 29.57 ohm. Consequently, the HMO@CP electrode exhibits superior adsorption kinetics and a state-of-the-art high adsorption capacity of up to 49.48 mg/g. Comprehensive mechanistic studies reveal that the negatively charged hydroxyl groups (-OH) in PVA accelerate Li + diffusion and that the conjugated structure and redox-active quinoid sites in PANI offer denser electron distribution and promote electron transport. This synergistic effect in CP significantly enhanced Li + diffusion and electron transport, leading to electrochemical activity and adsorption efficiency. Our work highlights the critical role of simultaneously regulating the ion diffusion and electron transport dual pathways for optimizing Li + adsorption performance and inspires development of the next generation electrochemical adsorption electrodes.

Tryptophan not only serves as a fundamental building block for protein synthesis but also acts as a metabolic precursor for a diverse array of high-value chemicals. Although a few tryptophan-responsive biosensors are currently available, there is a growing interest in developing high-performance biosensors. In this study, we create a miniature toolkit of tryptophan biosensors based upon the leader regulatory region of the tnaCAB operon, which is responsible for tryptophan catabolism in Escherichia coli . Four variants are generated by engineering the tnaC leader sequence, which encodes a leader peptide composed of 24 amino acid residues. Subsequently, the performance of both the natural tnaC sequence and its engineered variants is assessed in a reporter strain based on the MazEF toxin-antitoxin system. The results demonstrate that two engineered variants exhibit increased sensitivity to low levels of tryptophan. Moreover, the engineered biosensors are further optimized by replacing the native promoter of tnaC with a phage-derived constitutive promoter. Intriguingly, the engineered biosensors can be reconstructed for extended application in Pseudomonas putida , a robust microbial chassis for metabolic engineering. In summary, our study expands the toolkit of tryptophan biosensors that can be broadly used for the bioproduction of many other high-value tryptophan-derived products.

Special structures and prominent performance make 2D iodinene more appealing and valuable at the molecular level. Here, new-type electronic devices have been constructed with iodinene-based nanoflakes in different sizes and are theoretically studied for electronic transport properties. Our findings reveal that iodinene-based nanoflakes possess great electron transport suppression, achieving the same function as SiO 2 on single molecule scale. Such transport suppression shows surprisingly nonlinear "V"-shaped trend with the width of the iodinene-based nanoflake. The medium-width iodinene-based nanoflake exhibits the strongest electron transport suppression, while the narrowest and widest ones display the largest electron transmission coefficients due to delocalized transmission eigenstates. Essentially, the weakest electron transport originates from an extremely small DOS and wide HOMO-LUMO gap. Specifically, increasing the width would diminish the extension of electronic states for the dominant transport orbitals, resulting in more butterfly-like electronic states. In non-equilibrium, negative differential resistance effect can be observed in iodinene-based devices, caused by the weakening and staying away from the Fermi level of transmission peaks influenced by the bias. Our findings provide insights into the relationship between the width of iodinene-based nanoflake and electronic transport properties, and lay a foundation in the device design and applications in molecular insulators and controllable-functional devices.

Nanomedicines have been widely used in colorectal cancer treatment, but their suboptimal targeting and deficient penetration capabilities remain obstacles in the delivery of therapeutics. In this study, inspired by the natural tumor tropism and intestinal invasion of Salmonella , we engineered highly biomimetic nanoparticles (SM-AuNRs) utilizing a Salmonella membrane to coat bacilliform Au nanorods. The engineered SM-AuNRs were able to mimic the germ's morphology and biological surface. SM-AuNRs containing the specific proteins inherited from the Salmonella membrane facilitated specific targeting and internalization into tumor cells. Meanwhile, SM-AuNRs with the rod-shaped morphology effectively traversed mucus barriers and tumor stroma. Due to the superior biological barrier penetrating and tumor targeting capabilities, doxorubicin-loaded SM-AuNRs with near-infrared laser irradiation displayed remarkable photothermal-chemotherapeutic antitumor effects in mouse orthotopic colorectal cancer models. Our findings pave the way for the design of bacteria-mimicking nanoparticles, presenting a promising avenue for the targeting and efficient treatment of colorectal cancer.

Target identification, employing chemical proteomics, constitutes a continuous challenging endeavor in the drug development of natural products (NPs). Understanding their targets is crucial for deciphering their mechanisms and developing potential probes or drugs. Identifications fall into two main categories: labeled and label-free techniques. Labeled methods use the molecules tagged with markers such as biotin or fluorescent labels to easily detect interactions with target proteins. Thorough structure-activity relationships are essential before labeling to avoid changes in the biological activity or binding specificity. In contrast, label-free technologies identify target proteins without modifying natural products, relying on changes in the stability, thermal properties, or precipitation in the presence or absence of these products. Each approach has its advantages and disadvantages, offering a comprehensive understanding of the mechanisms and therapeutic potential of the NPs. Here, we summarize target identification techniques for natural molecules, highlight case studies of notable NPs, and explore future applications and directions.

Immunogenic cell death (ICD) has been widely employed to potentiate cancer immunotherapy due to its capability to activate the anticancer immune response. Although various ICD inducers have been described, the development of synthetic materials with intrinsic ICD-inducing competency has rarely been reported. Herein, we identify a derivative of the fourth generation polyamidoamine (PAMAM) modified with multiple seven-membered heterocyclic rings, G4P-C7A, as a robust ICD inducer. G4P-C7A evokes characteristic release of damage-associated molecular patterns in tumor cells and induces efficient dendritic cell maturation. Mechanistic studies suggest that G4P-C7A can selectively accumulate in the endoplasmic reticulum and mitochondria to generate reactive oxygen species. G4P-C7A-treated tumor cells can work as potent vaccines to protect against secondary tumor implantation. Either local or systemic injection of G4P-C7A alone can effectively inhibit tumor growth by eliciting robust antitumor immune response. The combination of G4P-C7A with immunotherapeutic antibodies such as anti-PD1 (aPD-1) and anti-CD47 (aCD47) further potentiates the antitumor effect in either CT26 or 4T1 tumor model. This study offers a simple but effective strategy to induce ICD to boost cancer immunotherapy.

Partial substitution of cations is crucial for suppressing harmful defects in Cu 2 ZnSn(S,Se) 4 thin-film solar cells. In this study, based on the mixed n -butylammonium and butyrate solution system, the alloyed Cu 2 Co x Zn 1- x Sn(S,Se) 4 phase can be prepared by substituting Zn 2+ with Co 2+ , which can suppress harmful defects and optimize the crystallinity of the Cu 2 ZnSn(S,Se) 4 absorption layer, and improve the photoelectric conversion efficiency (PCE) of devices. By systematic investigation of the impact of Co content on the performance of devices, the optimal substitution amount of Zn 2+ with Co 2+ is 0.05. At this time, PCE, the open-circuit voltage ( V OC ), current density ( J SC ), and fill factor (FF) of the devices can reach 9.0%, 416 mV, 33.87 mA/cm 2 , and 64%, respectively. It is the first time that the replacement of Zn 2+ with Co 2+ is applied to optimize PCE of CZTSSe solar cells. The excellent results also demonstrate that the substitution of Zn 2+ with Co 2+ can become a new approach for further performance optimization of Cu 2 ZnSn(S,Se) 4 solar cells.

The food safety issues caused by environmental pollution have posed great risks to human health that cannot be ignored. Hence, the precise monitoring of hazard factors in food has emerged as a critical concern for the food safety sector. As a novel porous material, covalent organic frameworks (COFs) have garnered significant attention due to their large specific surface area, excellent thermal and chemical stability, modifiability, and abundant recognition sites. This makes it a potential solution for food safety issues. In this research, the synthesis and regulation strategies of COFs were reviewed. The roles of COFs in enriching and detecting food hazards were discussed comprehensively and extensively. Taking representative hazard factors in food as the research object, the expression forms and participation approaches of COFs were explored, along with the effectiveness of corresponding detection methods. Finally, the development directions of COFs in the future as well as the problems existing in practical applications were discussed, which was beneficial to promote the application of COFs in food safety and beyond.

Pressure-induced emission (PIE) is a compelling phenomenon that can activate luminescence within nonemissive materials. However, PIE in nonemissive organic materials has never been achieved. Herein, we present the first observation of PIE in an organic system, specifically within nonemissive azobenzene derivatives. The emission of 1,2-bis(4-(anthracen-9-yl)phenyl)diazene was activated at 0.52 GPa, primarily driven by local excitation promotion induced by molecular conformational changes. Complete photoisomerization suppression of the molecule was observed at 1.5 GPa, concurrently accelerating the emission enhancement to 3.53 GPa. Differing from the key role of isomerization inhibition in conventional perception, our findings demonstrate that the excited-state constituent is the decisive factor for emission activation, providing a potentially universal approach for high-efficiency azobenzene emission. Additionally, PIE was replicated in the analogue 1,2-bis(4-(9 H -carbazol-9-yl)phenyl)diazene, confirming the general applicability of our findings. This work marks a significant breakthrough within the PIE paradigm and paves the novel high-pressure route for crystalline-state photoisomerization investigation.

Producing H 2 O 2 through a selective, two-electron (2e) oxygen reduction reaction (ORR) is challenging, especially when it serves as an advanced oxidation process (AOP) for cost-effective water decontamination. Herein, we attain a 2e-selectivity H 2 O 2 production using a carbon nanotube electrified membrane with ibuprofen (IBU) molecules laden (IBU@CNT-EM) in an ultrafast, single-pass electrofiltration process. The IBU@CNT-EM can generate H 2 O 2 at a rate of 25.62 mol g CNT -1 h -1 L -1 in the permeate with a residence time of 1.81 s. We demonstrated that an interwoven, hydrophilic-hydrophobic membrane nanostructure offers an excellent air-to-water transport platform for ORR acceleration. The electron transfer number of the ORR for IBU@CNT at neutral pH was confirmed as 2.71, elucidating a near-2e selectivity to H 2 O 2 . Density functional theory (DFT) studies validated an exceptional charge distribution of the IBU@CNT for the O 2 adsorption. The adsorption energies of the O 2 and *OOH intermediates are proportional to the H 2 O 2 selectivity (64.39%), higher than that of the CNT (37.81%). With the simple and durable production of H 2 O 2 by IBU@CNT-EM electrofiltration, the permeate can actuate Fenton oxidation to efficiently decompose emerging pollutants and inactivate bacteria. Our study introduces a new paradigm for developing high-performance H 2 O 2 -production membranes for water treatment by reusing environmental functional materials.

The stereoconvergent synthesis of a single stereoisomer from E / Z -olefin mixtures remains one of the foremost challenges in organic synthesis. Herein, we describe a nickel-catalyzed stereoconvergent cross-coupling between E - and Z -mixed monofluoroalkenes and alkenyl electrophiles, which allows the construction of C(sp 2 )-C(sp 2 ) bonds. This defluorinative transformation offers facile access to various 1,3-dienes with E -selectivity and good functional group tolerance. Preliminary mechanistic studies indicate that the reaction most likely proceeds through a migratory insertion/β-F elimination/isomerization process.

In recent years, the rapid expansion of research and application of the Internet of Things and wearable electronics has prompted the development of a variety of sensors to perceive physical or chemical information from both the human body and the environment, among which the proximity sensor is a kind of noncontact sensor used to detect the approach of a target and thus exhibits promising applications in human-machine interactions. Thin-film transistors are one type of key components in modern electronics and have been further developed as electrostatic-induction-type proximity sensors to perceive the approach of electrically charged objects. However, they are immune to the approach of a zero-potential object. Capacitive-induction-type proximity sensors are capable of detecting the approach of conductive targets while being less sensitive to insulated ones. Integration of both electrostatic and capacitive induction mechanisms into one proximity sensor is highly expected to broaden its perception to a variety of targets. Here, an interdigital electrode was introduced as an extended gate into an amorphous metal oxide thin-film transistor to construct proximity sensors that combine both electrostatic and capacitive induction mechanisms and therefore can sensitively perceive the approach of a variety of objects that were electrically charged, grounded, or floated. Besides proximity sensing, remote velocity measurement and positioning of an invasive object were also realized, which further extended its functions as a kind of interdigital-electrode gate transistor.

Understanding the interlayer interaction between 2D layered structures is critical for the construction of various micro- and nanoscale functional devices. However, both the normal and the tangential interlayer interactions between 2D layered materials have rarely been studied simultaneously. In this work, an immersion and lift-up method is proposed to wrap a layer of graphene flakes onto a plasma-pretreated atomic force microscopy (AFM) nanoprobe for the measurements of interaction forces by AFM. The normal interactions (adhesion force and adhesion energy) and tangential interactions (friction force) between two different probes (Pt-coated probe and graphene-wrapped probe) and two different 2D graphene materials [graphene and graphene oxide (GO)] were systematically measured, respectively. The adhesion energies of Pt-GO, Pt-graphene, graphene-GO, and graphene-graphene were measured to be 0.72 ± 0.05, 0.41 ± 0.03, 0.19 ± 0.02, and 0.10 ± 0.02 J m -2 , respectively. The graphene-graphene contact pair showed the lowest adhesion force (5.57 ± 1.03 nN) and adhesion energy (0.10 ± 0.02 J m -2 ), which was attributed to the strong covalent bonds and charge density distribution. The friction coefficients of Pt-GO, graphene-GO, Pt-graphene, and graphene-graphene were determined to be 0.38, 0.14, 0.054, and 0.013. The graphene-graphene tribo-pair exhibited a superlow friction state for a long time, which was attributed to incommensurate contact and weak van der Waals interactions. These findings provide a technical route to reveal the interlayer interactions of various 2D layered materials, which can be widely applied in microelectromechanical systems.

In this work, a smart self-healing coating with long-term anticorrosion ability was developed based on multiresponsive polyaniline (PANI) porous microspheres. The polyaniline porous microspheres loaded with corrosion inhibitor (benzotriazole, BTA) was prepared by the emulsion template method and photopolymerization. The BTA loaded in the polyaniline microspheres acted as a corrosion inhibitor, while the polyaniline in the shell performed the multiple functions of corrosion inhibition, pH-responsive and photoresponsive release, and photothermal conversion. Owing to the inherent corrosion-inhibiting nature of BTA and PANI, the BTA-loaded polyaniline microsphere could endow coating with dual anticorrosive properties. The coating with polyaniline microspheres did not show any corrosion product after 700 h of salt spray testing, while obvious pitting corrosion could be observed for the blank coating after 100 h of the salt spray test. Thanks to the photothermal properties of PANI, the composite coating exhibited self-healing behavior under NIR light irradiation. The coating with 10 wt % polyaniline microspheres could achieve rapid closure and recover its barrier properties within 5 s of NIR irradiation. And the release of BTA could form a passivation film on scratches to further repair coating defects. The on-command responsive release, high healing efficiency, and excellent anticorrosion properties of this dual self-healing anticorrosion coating provide perspectives on extending the service life of metals.

The effects of sulfur dioxide (SO 2 ) in the catalytic purification of short-chain hydrocarbons are still controversial, and the exact role of SO 2 on adsorption and reaction pathways during the catalytic oxidation of different volatile organic compounds (VOCs) remains unclear. Herein, a three-dimensional ordered macroporous Ce 0.8 Zr 0.2 O 2 supported Pt nanoparticle monolithic catalyst (Pt/OM CZO) was synthesized to investigate these effects. Our findings uncover the diverse effects of SO 2 : Upon SO 2 treatment, the coupling between the S 3p and Pt 5d orbitals promotes the Pt-O-SO 3 structure in situ formed on the catalyst surface. The propene (C 3 H 6 ) molecule readily binds with the oxygen atom in Pt-O-SO 3 , resulting in the accumulation of acetone and carbon deposition, thereby hindering C 3 H 6 oxidation. Conversely, a cleaved oxygen atom within the Pt-O-SO 3 structure enhances propane (C 3 H 8 ) adsorption and activates the C-H bond, facilitating C 3 H 8 oxidation. These insights are pivotal for advancing the frontier of sulfur-tolerant catalysts, addressing both economic and environmental challenges.

High-temperature shock (HTS) is an emerging material synthesis technology with advantages, such as rapid processing, low energy consumption, and high controllability. This technology can prepare ultrafine nanoparticles with uniform particle size distribution and introduce additional oxygen vacancies, offering significant potential for the preparation of key materials for solid oxide electrochemical cells (SOCs). In this study, the La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) air electrode was successfully prepared using HTS technology. Compared to the conventional muffle furnace calcination, the HTS-prepared LSCF exhibits a larger specific surface area and a higher oxygen vacancy concentration, and it demonstrates significant improvements in performance. The oxygen ion conducting SOC (O-SOC) with the HTS-LSCF air electrode achieved a peak power density (PPD) of 960 mW cm -2 and a current density of 0.38 A cm -2 (at 1.3 V) at 700 °C. Meanwhile, the proton conducting SOC (P-SOC) with HTS-LSCF air electrode reached a PPD value of 1.34 W cm -2 and a current density of 3.43 A cm -2 (at 1.3 V) at 700 °C. Additionally, the P-SOC with HTS-LSCF air electrode showed no significant degradation during over 200 h of long-term testing, reflecting the excellent stability of HTS-LSCF. This work provides a fast, efficient, and economical approach for synthesizing high-performance, high-stability SOC air electrode materials.

This study aimed to explore the effects of S-nitrosylation on caspase-3 modification and its subsequent effects on beef myofibril degradation in vitro. Recombinant caspase-3 was reacted with different concentrations of S-nitrosoglutathione (GSNO, nitric oxide donor) at 37 °C for 30 min and subsequently incubated with purified myofibrillar protein from bovine semimembranosus muscle. Results indicated that the activity of caspase-3 was significantly reduced after GSNO treatments ( P < 0.05) and showed a dose-dependent inhibitory effect, which was attributed to the increased S-nitrosylation extent of caspase-3. LC-MS/MS analysis revealed that caspase-3 was S-nitrosylated at cysteine sites 116, 170, 184, 220, and 264. Moreover, the degradation of desmin and troponin-T was notably suppressed by S-nitrosylated caspase-3 ( P < 0.05). To conclude, protein S-nitrosylation could modify the cysteine residues of caspase-3, which accounts for the reduced caspase-3 activity and further represses its proteolytic ability on beef myofibrillar protein.

Prussian white (PW) is considered a promising cathode material for sodium-ion batteries. However, challenges, such as lattice defects and poor conductivity limit its application. Herein, the composite materials of manganese-iron based Prussian white and reduced graphene oxide (PW/rGO) were synthesized via a one-step in situ synthesis method with sodium citrate, which was employed both as a chelating agent to control the reaction rate during the coprecipitation process of PW synthesis and as a reducing agent for GO. The low precipitation speed helps minimize lattice defects, while rGO enhances electrical conductivity. Furthermore, the one-step in situ synthesis method is simpler and more efficient than the traditional synthesis method. Compared with pure PW, the PW/rGO composites exhibit significantly improved electrochemical properties. Cycling performance tests indicated that the PW/rGO-10 sample exhibited the highest initial discharge capacity and the best cyclic stability. The PW/rGO-10 has an initial discharge capacity of 128 mAh g -1 at 0.1 C (1 C = 170 mA g -1 ), and retains 49.53% capacity retention after 100 cycles, while the PW only delivers 112 mAh g -1 with a capacity retention of 17.79% after 100 cycles. Moreover, PW/rGO-10 also shows better rate performance and higher sodium ion diffusion coefficient ( D Na + ) than the PW sample. Therefore, the incorporation of rGO not only enhances the electrical conductivity but also promotes the rapid diffusion of sodium ions, effectively improving the electrochemical performance of the composite as a cathode material for sodium-ion batteries.

Organic amines (OAs) have gained substantial interest in atmospheric chemistry due to their distinctive acid-base neutralization characteristics for secondary organic aerosols and new particle formation. To address the need for sensitive and online analysis of OAs, including dimethylamine (DMA), diethylamine (DEA), trimethylamine (TMA), and triethylamine (TEA), in seawater, a home-built photoelectron-induced chemical ionization TOFMS, coupled with online derivatization and dynamic purge-release apparatus, has been developed. Sodium hypochlorite is used to derivatize high-solubility DMA and DEA, substituting hydrogen atoms with chlorine atoms to obtain more volatile derivatives, [DMA-H + Cl] and [DEA-H + Cl]. Sodium carbonate is used to reduce the solubility of the OAs in solution to enhance detection sensitivity. Microbubbles generated from 250 to 300 mL/min of zero air at the gas-liquid interface efficiently transfer dissolved OAs into the gas phase. Water vapor in the purged gas is ionized by photoelectrons to form (H 2 O) n ·H + , which ionizes OAs and their derivatives to produce characteristic ions [OAs + H] + or [OAs-H + Cl]·H + characteristic ion. After optimizing the experimental conditions, the limits of quantification (S/N = 10) of the four OAs including DMA, DEA, TMA, and TEA can be as low as 1.1 0.68, 0.85, and 0.49 nmol/L, respectively within a 5 min analysis time, using only 5 mL of seawater sample. This method enhances sensitivity by over 5-fold and reduces analysis time to 21.7%, respectively, compared with conventional methods. Subsequently, this method was successfully applied to quantify 15 seawater samples from 5 typical marine environments, which demonstrates its practicability and reliability for analysis of trace amines in seawater.

Photocatalytic selective oxidation of organic substances coupled with hydrogen production is believed to be one of the most favorable pathways to make full use of photogenerated charge carriers. However, this catalytic reaction is often discouraged due to the rapid recombination of photogenerated carriers in practical applications. In this work, a core-shell CdS@Cu-TCPP-Pt nanorod heterojunction was dexterously designed for boosting the photocatalytic dehydrogenation performance of benzylamine. The transient absorption results revealed that the photogenerated electron-holes could be effectively separated by properly matching the energy levels in CdS@Cu-TCPP. Surprisingly, Pt embedded in Cu-TCPP not only provided abundant hydrogen production active sites but also facilitated ultrafast charge transfer, which endowed CdS@Cu-TCPP-Pt with remarkable photocatalytic performances for the coproductions of N -benzylidenebenzylamine (1 mL) with a conversion of 23.48% and H 2 (20.75 mmol g -1 h -1 ) under visible irradiation, far surpassing those of CdS and Cu-TCPP. Obviously, the present work verifies that designing and fabricating a hybrid photocatalyst with high separation efficiency of electron-hole pairs is also a significant avenue for other high-performance cooperative dual-functional photocatalytic reactions.

The crystallization and growth of perovskite crystals are two crucial factors influencing the performance of perovskite solar cells (PSCs). Moreover, iodoplumbate complexes such as PbI 2 , PbI 3 - , and PbI 4 2- in perovskite precursor solution dictate both the quality of perovskite crystals and the optoelectrical performance of PSCs. Here, we propose an iodoplumbate-coordination strategy that employs pentafluorophenylsulfonyl chloride (PTFC) as an additive to tailor the crystal quality. This strategy directly affects the thermodynamics and kinetics of perovskite crystal formation by regulating hydrogen bonds or coordination bonds with Pb 2+ or I - ions. Subsequently, the synergistic effect of the PTFC and FA + complex was beneficial for intermediate-to-perovskite phase transition, improving the crystalline quality and reducing the defect density in the perovskite film to suppress nonradiative recombination loss. Consequently, the treated PSCs achieved a power conversion efficiency (PCE) of 24.61%, demonstrating enhanced long-term stability under both light and thermal stress. The developed device retained 92.53% of its initial PCE after 1200 h of continuous illumination and 88.6% of its initial PCE after 600 h of 85 °C thermal stability tests, respectively, both conducted in N 2 atmospheres.

Herein, we report an unprecedented P(NMe 2 ) 3 -mediated reductive insertion of 1,2-dicarbonyl compounds including α-keto esters and isatins into phthalic anhydride-derived alkenes and phthalic anhydrides, which furnishes the corresponding isochroman-1-ones and isochroman-1,4-diones, respectively, in moderate to excellent yields with high chemo- and regioselectivity. Furthermore, the asymmetric version of the ring expansion reaction could be realized by using a chiral auxiliary strategy. Mechanistically, the nucleophilic attack of the Kukhtin-Ramirez adduct, generated from P(NMe 2 ) 3 and 1,2-dicarbonyl compound, to the anhydride derivative, followed by a cascade ring-opening and ring-closure process, affords the ring expansion product. The reaction represents a novel metal-free carbon insertion ring expansion of aliphatic rings and also the first [1 + 5] annulation involving the Kukhtin-Ramirez adducts.

As a nonenzymatic DNA signal amplification technique, localized hybridization chain reaction (LHCR) was designed to improve the limitations in response speed and low sensitivity of conventional free diffusional HCR (hybridization chain reaction). However, it is still confronted with the challenges of complicated DNA scaffolds with low loading capacity and a time-consuming process of diffusion. Herein, we introduced modular assembly of a DNA minimal scaffold for coassembly of DNA hairpins for amplified fluorescence imaging of mRNA in situ. DNA hairpins were spatially bound to two Y-shaped modules to form H-shaped DNA modules, and then multiple H-shaped DNA modules can further assemble into an H-module-based hairpin scaffold (HHS). Benefiting from highly spatial localization and high loading capacity, the HHS system showed higher sensitivity and faster speed. It has also been proven to work perfectly in vitro and in vivo, which could provide a promising bioanalysis system for low abundance biomolecule detection.

Antibiotic residues have been found in several aquatic ecosystems as a result of the widespread use of antibiotics in recent years, which poses a major risk to both human health and the environment. At present, photocatalytic degradation is the most effective and environmentally friendly method. Titanium silicon molecular sieve (TS-1) has been widely used as an industrial catalyst, but its photocatalytic application in wastewater treatment is limited due to its small pores and few active sites. In this paper, we report a method for preparing multistage porous TS-1 with a high specific surface area by alkali treatment. In the photocatalytic removal of CIP (ciprofloxacin) antibiotic wastewater experiments, the alkali-treated catalyst showed better performance in terms of interfacial charge transfer efficiency, which was 2.3 times higher than that of TS-1 synthesized by the conventional method, and it was found to maintain better catalytic performance in the actual water source. In addition, this research studied the effects of solution pH, contaminant concentration, and catalyst dosage on CIP degradation, while liquid chromatography-mass spectrometry (LC-MS) was used to identify intermediates in the degradation process and infer possible degradation pathways and the toxicity of CIP, and its degradation product was also analyzed using ECOSAR 2.2 software, and most of the intermediates were found to be nontoxic and nonharmful. Finally, a 3:5:1 artificial neural network model was established based on the experiments, and the relative importance of the influence of experimental conditions on the degradation rate was determined. The above results confirmed the feasibility and applicability of photocatalytic treatment of wastewater containing antibiotics using visible light excitation alkali post-treatment TS-1, which provided technical support and a theoretical basis for the photocatalytic treatment of wastewater containing antibiotics.

Developing low-cost and multifunctional adsorbents for adsorption separation to obtain high-purity (>99.9%) gases is intriguing yet challenging. Notably, the ongoing trade-off between adsorption capacity and selectivity in separating multicomponent mixed gases still persists as a pressing scientific challenge requiring urgent attention. Herein, the ultrastable TJT-100 exhibits unique structural characteristics including uncoordinated carboxylate oxygen atoms, coordinated water molecules directed toward the pore surface, and sufficient Me 2 NH 2 + cations in channels. TJT-100 exhibits a high adsorption capacity and exceptional separation performance, particularly notable for its high C 2 H 2 capacity of 127.7 cm 3 /g and remarkable C 2 H 2 selectivity over CO 2 (5.4) and CH 4 (19.8), which makes it a standout material for various separation applications. In a breakthrough experiment with a C 2 H 2 /CO 2 mixture (v/v = 50/50), TJT-100 achieved a record-high C 2 H 2 productivity of 69.33 L/kg with a purity of 99.9%. Additionally, TJT-100 demonstrates its effectiveness in separating CO 2 from natural gas and flue gas. Its exceptional selectivity for CO 2 /CH 4 (10.7) and CO 2 /N 2 (11.9) results in a high CO 2 productivity of 21.23 and 22.93 L/kg with 99.9% purity from CO 2 /CH 4 (v/v = 50/50) and CO 2 /N 2 (v/v = 15/85) mixtures, respectively.

The inherent metal elements and structures of Prussian blue analogue (PBA) nanozymes have restricted their enzyme-mimicking activity. Therefore, the rational regulation of PBA nanozymes to improve their catalytic activity is highly desirable for biosensing applications. Herein, we propose a structure remodeling strategy to construct an open-cage Fe PBA-anchored NiFePBA (NiFe@Fe bis-PBA) nanozyme with significantly enhanced enzyme-mimicking activity. The formation process and mechanism for this bis-PBA nanozyme were studied in detail. Specifically, a cubic NiFePBA precursor was first synthesized and modified with polyvinylpyrrolidone (PVP). With the aid of hydrochloric acid, the added potassium ferricyanide was reduced by PVP and re-coordinated on the surface of NiFePBA to form the NiFe@Fe bis-PBA nanozyme with a special open-cage core-shell structure. The resultant NiFe@Fe bis-PBA nanozyme was further exploited to immobilize secondary antibodies, serving as a novel signal probe for developing highly sensitive electrochemical immunosensors for monitoring tumor markers. The constructed electrochemical immunosensor possesses a very wide linear range of 0.005-100 ng/mL and a low detection limit of 0.89 pg/mL for alpha-fetoprotein with high specificity and acceptable reproducibility and stability. This work offers a general and promising strategy for remodeling PBA nanozymes with a very favorable structure and metal element distribution, which enhances their enzyme-mimicking properties for applications in different fields.

Graphene chemical vapor deposition (CVD) growth directly on target using substrates presents a significant route toward graphene applications. However, the substrates are usually catalytic-inert and special-shaped; thus, large-scale, high-uniformity, and high-quality graphene growth is challenging. Herein, graphene-skinned glass fiber fabric (GGFF) was developed through graphene CVD growth on glass fiber fabric, a Widely used engineering material. A fluid dynamics rectification strategy was first proposed to synergistically regulate the distribution of carbon species in 3D space and their collisions with hierarchical-structured substrates, through which highly uniform deposition of high-quality graphene on fibers in large-scale 3D-woven fabric was realized. This strategy is universal and applicable to CVD systems using various carbon precursors. GGFF exhibits high electrical conductivity and photothermal conversion capability, based on which a natural energy harvester was first developed. It can harvest both solar and raindrop energy through solar heating and droplet-based electricity generating, presenting promising potentials to alleviate energy burdens.

The absence of intrinsic p-type 2D layered semiconductors has hampered the development of 2D devices, particularly in complementary metal-oxide-semiconductor (CMOS) devices and integrated circuits. Developing practical p-type semiconductors and advanced modulation techniques for precise carrier control is paramount to advancing electronic devices and systems. Here, by applying pressure to continuously tune the Peierls distortion in NbOI 2 , we effectively control the polarity and concentration of carriers and significantly enhance its photoelectric properties. The results demonstrate that by suppressing the off-center displacement of Nb atoms along the in-plane b direction under pressure, NbOI 2 undergoes a semiconductor-to-semiconductor phase transition from C2 to C2/m, leading to a significant transition from n-type to p-type carrier behavior. Additionally, the gradual inhibition of internal interactions within Nb-Nb dimers along the in-plane c direction under high pressure facilitates electron delocalization, substantially enhancing the photoelectric properties. The photocurrent is increased by more than 3 orders of magnitude under xenon irradiation, and the spectral response range is continuously red-shifted and extended to 1450 nm. These findings highlight the potential of pressure engineering to adjust photoelectric properties effectively and flexibly, offering valuable insights for designing high-performance p-type two-dimensional semiconductors.

Biomass-derived hard carbon materials are attractive for sodium-ion batteries due to their abundance, sustainability, and cost-effectiveness. However, their widespread use is hindered by their limited specific capacity. Herein, a type of bamboo-derived hard carbon with adjustable pore structures is developed by employing a ball milling technique to modify the carbon chain length in the precursor. It is observed that the length of the carbon chain in the precursor can effectively control the rearrangement behavior of the carbon layers during the high-temperature carbonization process, resulting in diverse pore structures ranging from closed pores to open pores, which significantly impact the electrochemical properties. The optimized hard carbon with abundant closed pores exhibits a high specific capacity of 356 mAh g -1 at 20 mA g -1 , surpassing that of bare hard carbon (243 mAh g -1 ) and hard carbon with abundant open pores (129 mAh g -1 at 20 mA g -1 ). However, the kinetic analysis reveals that hard carbon with open pores shows better sodium-ion diffusion kinetics, indicating that a balance between the closed and open pores should be considered. This research offers valuable insights into pore design and presents a promising approach for enhancing the performance of hard carbon anode materials derived from biomass precursors.

The free energy perturbation (FEP) method is a powerful technique for accurate binding free energy calculations, which is crucial for identifying potent ligands with a high affinity in drug discovery. However, the widespread application of FEP is limited by the high computational cost required to achieve equilibrium sampling and the challenges in obtaining converged predictions. In this study, we present the convergence-adaptive roundtrip (CAR) method, which is an enhanced adaptive sampling approach, to address the key challenges in FEP calculations, including the precision-efficiency tradeoff, sampling efficiency, and convergence assessment. By employing on-the-fly convergence analysis to automatically adjust simulation times, enabling efficient traversal of the important phase space through rapid propagation of conformations between different states and eliminating the need for multiple parallel simulations, the CAR method increases convergence and minimizes computational overhead while maintaining calculation accuracy. The performance of the CAR method was evaluated through relative binding free energy (RBFE) calculations on benchmarks comprising four diverse protein-ligand systems. The results demonstrated a significant speedup of over 8-fold compared to conventional FEP methods while maintaining high accuracy. The overall R 2 values of 0.65 and 0.56 were obtained using the combined-structure FEP approach and the single-step FEP approach, respectively, in conjunction with the CAR method. In-depth case studies further highlighted the superior performance of the CAR method in terms of convergence acceleration, improved predicted correlations, and reduced computational costs. The advancement of the CAR method makes it a highly effective approach, enhancing the applicability of FEP in drug discovery.

Polypeptides have the same or similar backbone structures as proteins and peptides, rendering them as suitable and important biomaterials. Amino acid N -carboxyanhydrides (NCA) ring-opening polymerization has been the most efficient strategy for polypeptide preparation, with continuous advance in the design of initiators, catalysts and reaction conditions. This Perspective first summarizes the recent progress of NCA synthesis and purification. Subsequently, we focus on various initiators for NCA polymerization, catalysts for accelerating polymerization or enhancing the controllability of polymerization, and recent advances in the reaction approach of NCA polymerization. Finally, we discuss future research directions and open challenges.