Rapid recombination of photogenerated carriers is significant barrier to the photodegradation of organic contaminants in pharmaceutical wastewater. This study utilized BiOBr nanosheets as modifiers to improve the separation efficiency of photogenerated carriers and enhance the self-cleaning capability of magnetic biochar (Fe3O4/biochar). The photocatalytic performance of the novel system (Fe3O4/biochar/BiOBr) was evaluated by degrading tetracycline (TC) under visible light irradiation, achieving approximately 88.17 % degradation within 20 min. The intermediates and potential degradation pathways were thoroughly analyzed using liquid chromatography-mass spectrometry. The photocatalytic degradation mechanism and the enhancement of degradation activity were investigated using various techniques and DFT calculations. Electron spin resonance (ESR) measurements and trapping experiments identified center dot OH, O-1(2), center dot O-2(-), and h(+) as the primary reactive species involved. The photogenerated charge transfer across the FCB heterojunction interface followed the S-scheme mechanism, as confirmed by optoelectronic experiments and density functional theory (DFT) calculations. This research introduces a novel approach to utilizing biochar-supported photocatalysts for pharmaceutical wastewater treatment.

Traditional Chinese medicine (TCM) pharmaceutical wastewater features high organic concentration, poor biodegradability, and strong biotoxicity, in which chlorogenic acid (CA) is recognized as a typical refractory pollutant. In this work, a BiVO4/BiOBr S-scheme heterojunction photocatalyst was successfully synthesized via a hydrothermal and in-situ precipitation method for efficient visible-light-driven degradation of CA. A series of characterizations confirmed that BiOBr nanosheets were uniformly anchored on the surface of BiVO4, forming intimate interfacial contact. XPS and DFT calculation results verified the spontaneous electron transfer from BiVO4 to BiOBr and the formation of an internal electric field (IEF), which drove the S-scheme charge migration pathway. The optimized 7-BiVO4/BiOBr composite showed significantly enhanced visible-light absorption and charge separation efficiency. The CA degradation efficiency reached 82% within 50min, and the apparent rate constant was 3.1 times higher than pure BiOBr and 425 times higher than pure BiVO4. The composite exhibited excellent stability after four recycling runs. Radical trapping and ESR results confirmed that ·O2⁻ and ·OH were the main active species. The S-scheme charge transfer mechanism driven by an internal electric field effectively preserved strong redox capacity, enabling efficient mineralization of CA. This work provides a promising strategy for the degradation of refractory pollutants in pharmaceutical wastewater treatment.

Bacterial infection represents a critical barrier to the healing of chronic diabetic wounds. Herein, a riboflavin-loaded Bletilla striata polysaccharide (BSP) hydrogel， namely CCBG-50R, was fabricated via dual dynamic crosslinking of hydrogen bonds and imine linkages. Hydrogel integrates the photodynamic bactericidal activity of riboflavin and the inherent anti-inflammatory of BSP to synergistically promote the repair of bacteria-infected diabetic wounds. Specifically, CCBG-50R hydrogel displayed a well-developed porous structure, outstanding water absorption capability with a swelling ratio of 1603 ± 25%, and excellent biocompatibility. Upon visible light irradiation for 7 min, CCBG-50R exhibited superior antibacterial activity, achieving more than 5-log reduction (99.999% inactivation) against both E. coli and S. aureus in vitro by generating reactive oxygen species (ROS: ·OH, ·O2-, 1O2). Mechanistic studies demonstrated that the CCBG-50R hydrogel exerted a synergistic effect between BSP mediated anti-inflammation and riboflavin mediated photodynamic sterilization. The accelerated wound healing can be attributed to the combined functions of efficient antibacterial disinfection, anti-inflammation, macrophage polarization regulation, tissue regeneration, and angiogenesis. This study provides a promising strategy for designing safe and effective polysaccharide-based photodynamic dressings toward infected diabetic wound management.

Photocatalytic membrane integrates the merits of membrane separation and photocatalytic redox technology, have emerged as a new promising route for wastewater treatment owing to their high catalytic activity and ease of recycling. In this work, a novel FeVO4/BiOBr/PVDF photocatalytic membrane was synthesized for pharmaceutical wastewater treatment. The optimal FeVO4/BiOBr/PVDF photocatalytic membrane achieved 85.84 % tetracycline (TC) degradation efficiency within 90 min under visible light irradiation, and displayed a good selfcleaning ability. The mechanism of TC degradation pathway and enhanced removal property of FeVO4/BiOBr/ PVDF membrane were systematically investigated by several techniques, including UV-Vis diffuse reflectance spectroscopy (DRS), photoelectrochemical measurements, high performance liquid chromatography-mass spectrometry (HPLC-MS), electron spin resonance (ESR) and density functional theory (DFT) calculation. The center dot O2and 1O2 as the primary reactive oxygen species for TC degradation. In addition, the FeVO4/BiOBr/PVDF membrane demonstrated a water absorption rate of 81.63 %, a porosity of 75.61 %, and a 56 % increase in pure water flux (reaching 495.95 L m- 2 h- 1). The study offers new insights into designing a high-efficient and sustainability photocatalytic membrane for pharmaceutical wastewater purification.

Due to the coexistence of nearly free and bound electrons, the first-principles computation of van der Waals (vdW) interactions in metals is extremely challenging. These electrons have different response properties and could not be treated on equal footing. Based on a variant of the many-body dispersion method, here & varepsilon; we introduce a novel vdW-inclusive approach, named MBD-, approach that (i) effectively separates bound and metallic electrons, (ii) screens the Coulomb interaction based on the metallic charge, and (iii) computes the many-body vdW correlation energy between bound states. The remaining long-range correlations due to the nearly homogeneous electron gas are fairly captured by semilocal exchange-correlation functionals. Tests performed on rare-earth elements, transition metals, and main group metals evidence consistent accuracy improvement with respect to broadly adopted vdW approaches. In particular, metallic screening cures systematic overbinding issues, significantly improving equilibrium lattice constants.

Although the theoretical electrocatalytic activity of rhenium (Re) for the hydrogen evolution reaction is comparable to that of platinum, the experimental performance of reported rhenium-based electrocatalysts remains unsatisfactory. Herein, we report a highly efficient and stable electrocatalyst composed of rhenium and cobalt (Co) nanoalloy embedded in nitrogen-doped carbon film (Re3Co2@NCF). The Re3Co2@NCF electrocatalyst exhibited remarkable hydrogen evolution performance, with an overpotential as low as 30 +/- 3 mV to reach a current density of 10 mA cm(-2). In addition, the Re3Co2@NCF demonstrated exceptional stability over several days at a current density of 150 mA cm(-2). Theoretical calculations revealed that alloying cobalt with rhenium altered the electronic structure of the metals, causing partial oxidation of the superficial metal atoms. This modification provided a balance for various intermediates' adsorption and desorption, thereby boosting the intrinsic activity of rhenium for hydrogen evolution reaction. This work improves the electrocatalytic performance of rhenium to its theoretical activity, suggesting a promising future for rhenium-based electrocatalysts.

Precisely designing the atomic coordinate configuration of the reactive center is highly desired to lower the energy barrier and boost photocatalytic ammonia synthesis performance. Here, we describe the isolated asymmetric Fe delta+-O-Bi (2

Fungal infections pose a significant threat to human health, crop production, and food safety. Concurrently, traditional antifungal drugs face challenges such as increasing drug resistance and adverse side effects, creating an urgent need for safer and more efficient therapeutic alternatives. Although significant progress has been made in researching the antifungal activity of plant essential oils (PEOs) in recent years, existing literature primarily focuses on the antifungal effects of individual essential oils (EOs) or their constituents, lacking systematic exploration and summarization of active components, mechanisms of action, and application approaches. Therefore, this review provides a comprehensive overview of the sources of PEOs, their antifungal activities, antifungal active components, mechanisms of action, and application methods (such as drug delivery systems and synergistic effects), aiming to enhance the bioavailability of PEOs. Finally, this review discusses the potential toxicity of PEOs and highlights the need for high-quality studies to systematically evaluate their clinical efficacy and safety in treating fungal infections. By systematically integrating existing research advances, it aims to provide valuable insights for future research directions and promote the widespread application of PEOs in antifungal research.

A comprehensive understanding of intermolecular π-π stacking effects is vital for advancing novel materials in fields such as organic semiconductors and optoelectronic devices. In this study, we engineered a series of molecular wires composed of pyridine, thiazole, and thiophene units arranged in various configurations. Using the single-molecule scanning tunnelling microscopy-break junction (STM-BJ) technique, we investigated their charge transport properties and stacking effects. Through detailed single-molecule conductance measurements, flicker noise analysis, and current-voltage (I-V) studies, we demonstrated that the degree of intramolecular charge polarization was directly correlated with stacking capability. Additionally, by integrating theoretical analyses, we elucidated the mechanism for manipulating the intermolecular π-π stacking effect at the microscale. These insights establish a structure-property relationship between intramolecular charge polarization and intermolecular stacking-driven charge transport, providing a foundation for designing advanced materials based on tunable intermolecular interactions.

Smart hydrogels with multi-fluorescent properties hold great promise for information encryption. However, conventional fluorescent hydrogels often lack adequate mechanical properties and multiple responsiveness, limiting their range of applications. In this study, a multifunctional hydrogel featuring an interpenetrating polymer network (IPN) composed of poly(vinyl alcohol) (PVA) and poly(acrylic amide-co-2-acrylamido-2-methylpropane sulfonic acid) P(AM/AMPS) chemical cross-linking networks is designed. Through the coordination of lanthanide ions (Eu3+, Tb3+) and glycine, the hydrogel achieves exceptional stretchability (over 900%) and adjustable photoluminescence properties. Due to the sulfonic acid groups on 2-acrylamide-2-methylpropanesulfonic acid (AMPS), which support various noncovalent interactions, the PVA-P(AM/AMPS)-Gly-Ln3+ hydrogel displays strong and reversible adhesive properties on diverse substrates. Ultimately, the hydrogel is assembled into a multifunctional, flexible sensor, boasting satisfactory sensitivity (GF = 5.3), rapid response rate (100 ms), and outstanding photoluminescence characteristics, highlighting its potential for applications in human motion detection and information encryption.

Single-atom engineering offers a promising method to transform CO2 into high-value chemicals. The local coordination structure design of the metal-support is crucial for overcoming slow reaction kinetics. In this study, Cu single atoms are immobilized on curved Bi12O17Br2 surface to create a tip-like metal site structure named CutipBi12O17Br2. Due to the high curvature Bi12O17Br2 surface with tensile strain, the tip Cu creates significant electronegativity differences between adjacent Bi atomic sites, creating the vigorous polarization centers. The strong charge redistribution character of tip asymmetric Cu-Bi site favor the polarization of C--O bond in nonpolar CO2 and adjust the noncovalent to covalent interaction of reaction intermediates. Benefiting from these features, the optimized Cutip-Bi12O17Br2 enhance the CO production rate by a factor of 34 relative to bulkBi12O17Br2, reaching a rate of 96.99 mu mol g-1 h-1. This work provides a comprehensive understanding of the structural regulation of single-atom on high curvature surface for CO2 photoreduction.

Layered double hydroxides (LDHs) are potential catalysts for water oxidation, and it is recognized that they undergo dynamic evolution during the operation. However, little is known about the interfacial behaviors at the nanoscale under working conditions nor the underlying effects on electrocatalytic performance. Herein, using electrochemical atomic force microscopy, we in situ visualize the heterogeneous evolution of LDH nanosheets during oxygen evolution reaction (OER). By further combining density functional theory calculations, we elucidate the origin of the heterogeneous dynamics and their impact on the OER efficiency. Our findings demonstrate that NiCo LDHs transform to the catalytically active NiCoOx(OH)2-x phase during OER, and the redox transition between is accompanied by compressive and tensile strain, leading to in-plane contraction and reversible expansion of the nanosheets. Nonisotropic strain and out-of-plane strain relaxation due to defects and interparticle interactions result in cracking and wrinkling in the nanostructure, which is responsible for the partial activation and long-term deterioration of LDH electrocatalysts toward the OER. With this knowledge, we suggest and validate that engineering defects can precisely tune these dynamic behaviors, improving the OER activity and stability among LDH-based electrocatalysts.

Delta machine learning (DML) models have paved a new way to obtaining high fidelity ab initio simulation results of materials by using quantities with lower computational cost as learning materials. However, the low out-of-sample extrapolative ability and the requirement of large training sets have limited broader applications of conventional DML models. In this work, we proposed the concept of non-trivial electron energy, an intermediary energy quantity decoded from the electron total energy but exhibiting high Pearson's correlation with various thermodynamic energies, to build up mediated machine learning (MML) models. By hybridizing the intermediary non-trivial electron energy (N) with a bond descriptor (B) and a spatial matrix (S) of organic molecules, our integrated NBS descriptor shows excellent predictive power of thermodynamic energies with errors close to 1 kcal/mol for MML models when trained by a database with 100 entries and tested by a database with 500 entries. Moreover, adding supplemental sets with 10 similar to 20 entries into the original training set could greatly improve the out-of-sample extendibility of NBS MML models, such as the molecules with obviously larger size, with disparate bond-type, and even with different elemental compositions. The method of mediated learning provides alternative ways to breakthrough limitations of traditional DML models and can be applied conveniently to study formation enthalpy, thermodynamic energy barriers, multi-dimensional Gibbs free energy surface, and other quantum chemical quantities related to materials' internal energy, enthalpy, and free energy under various conditions at tunable training cost, prediction efficiency, and accuracy.

The role of vacancy associates in photocatalytic CO2 reduction is an open question. Herein, the Nb─O vacancy associates (VNb─O) are engineered into niobic acid (NA) atomic layers to tailor the CO2 photoreduction performance. The intrinsic charge compensation from O to Nb around Nb─O vacancy associates can manipulate the active electronic states, leading to the asymmetric electron redistribution. These local symmetry breaking sites show a charge density gradient, forming a localized polarization field to polarize nonpolar CO2 molecules and tune the noncovalent interaction of reaction intermediates. This unique configuration contributes to the 9.3 times increased activity for photocatalytic CO2 reduction. Meantime, this VNb─O NA also shows excellent photocatalytic activity for NO3 --NH4 + synthesis, with NH4 + formation rate up to 3442 µmol g-1 h-1. This work supplies fresh insights into the vacancy associate design for electron redistribution and noncovalent interaction tuning in photocatalysis.

Over the past decades, water pollution caused by organic dyes has attracted extensive attention. The development of efficient, environmental friendly photocatalysts is a promising route for wastewater purification. Herein, a novel wild jujube shell derived biochar/g-C3N4 (BC/CN) composite has been prepared via a one-step calcination route. Although the specific surface area (9.37 m(2)/g) and pore size (14.57) of the BC/CN composite are smaller than those of g-C3N4, it exhibits enhanced photocatalytic activity. Especially, the 0.25-BC/CN composite (sour jujube shell powder/melamine ratio = 0.25) displays excellent photocatalytic activity, and can degrade similar to 97.1 % of RhB under 40 min light irradiation, which is similar to 46.51 times to that of pure g-C3N4. The actives species of h(+), OH, O-2(-) and O-1(2) active species play the important roles in the photocatalytic system of the BC/CN composite. The results mechanistic study demonstrates that the enhanced photocatalytic activity of the BC/CN composite can be mainly attributed to the improved light absorption and charge separation efficiency of the catalyst. This work provides a simple method for preparing of novel highly efficient g-C3N4-based photocatalyts for wastewater purification, and provides a new idea for the recycling, and high-value utilization of the organic solid waste from traditional Chinese medicine.

Conventional methodology for accurate identification of breast tumor subtypes is complex and time-consuming. Label-free SERS (surface-enhanced Raman scattering) enables rapid detection of biomolecules and provides intrinsic fingerprint information of analytes. Exploring reliable SERS bioprobes with high sensitivity and repeatability is essential for efficient typing of cancer cells. In this study, a novel core-shell noble metal-semiconductor Cu2O@Ag heterostructure with uniform morphology and outstanding SERS activity for label-free detection has been proposed. The Cu2O@Ag SERS substrates exhibit exceptional sensitivity to detect 4 nitrophenthiol (4NTP) at extreme low concentration (10−15 M), and the SERS spectra demonstrate excellent selectivity and repeatability (RSD ≈ 8.84%). The enhancement mechanism is attributed to the synergistic enhancement of photoinduced charge transfer and boosted surface plasmon resonance effect, confirmed by reduced fluorescence lifetime of methylene blue on SERS substrates and enhanced electromagnetic field intensity via finite-difference time-domain computational simulation. The ultrahigh sensitivity and good signal stability endow Cu2O@Ag SERS bioprobe potential for accurate detection of four breast cancer cells subtypes. The rich fingerprint information from SERS spectra is processed using linear differentiation analysis, revealing a high accuracy of 93.3% for subtypes classification. These results demonstrate an excellent SERS bioprobe with high sensitivity and repeatability for precision diagnosis has been developed.

The metal indium sulfides have attracted extensive research interest in photocatalysis due to regulable atomic configuration and excellent optoelectronic properties. However, the synthesis of metal indium sulfide atomic layers is still challenging since intrinsic non-van-der-Waals layered structures of some components. Here, a surfactant self-assembly growth mechanism is proposed to controllably synthesize metal indium sulfide atomic layers. Eleven types of atomic layers with tunable compositions, thickness, and defect concentrations are successfully achieved namely In2S3, MgIn2S4, CaIn2S4, MnIn2S4, FeIn2S4, ZnIn2S4, Zn2In2S5, Zn4In16S33, CuInS2, CuIn5S8, and CdIn2S4. The typical CaIn2S4 shows a defect-dependence activity for CO2 photoreduction. The designed S vacancies in CaIn2S4 can serve as catalytic centers to activate CO2 molecules via localized electrons for pi-back-donation. The engineered S vacancies tune the non-covalent interaction with CO2 and intermediates, manages to tune the free energy, and lower the reaction energy barrier. As a result, the defect-rich CaIn2S4 displays 2.82x improved reduction rate than defect-poor CaIn2S4. Meantime, other components also display promising photocatalytic performance, such as Zn2In2S5 with a H2O2 photosynthesis rate of 292 mu mol g-1 h-1 and CuInS2 with N2-NH4+ conversion rate of 54 mu mol g-1 h-1. This work paves the way for the multidisciplinary exploration of metal indium sulfide atomic layers with unique photocatalysis properties. A surfactant self-assembly growth mechanism is proposed to controllably synthesize the metal indium sulfide atomic layers. Eleven types of metal indium sulfide atomic layers with tunable compositions, thickness, and defect concentrations are successfully achieved. 2D metal indium sulfides provide a unique platform to explore the correlation between surface atomic structure, electronic state, and photocatalytic performance. image

In recent years, biodegradable medical polymer materials (BMPMs) have stood out among many biomedical materials due to their unique advantages, such as high mechanical strength, good biocompatibility, strong corrosion resistance and excellent processability. In this review, we first provide a brief introduction of biodegradable medical materials from both natural and synthetic perspectives, and then systematically categorize BMPMs based on their applications in clinical medicine and highlight the great progress they have made in recent years. Additionally, we also point out several overlooked areas in the research of BMPMs, offering guidance for comprehensive future exploration of these materials. Finally, in view of the complex challenges faced by BMPMs today, their future directions are scientifically proposed. This work contributes to the ongoing efforts of BMPMs in the biomedical field and provides a steppingstone for developing more effective BMPM-based products for clinical applications.

In this work, a novel biochar decorated Bi4O5Br2/g-C3N4 S-scheme heterojunction was successfully prepared for Norfloxacin (NOR) degradation, and it was found that the 5%-Bi4O5Br2/g-C3N4/C heterojunction exhibited the excellent photocatalytic degradation activity toward NOR, degrading 92.5% of NOR within 72 min under visible light irradiation. The effects of pH, dosage, and concentration of the NOR on the photocatalytic activity were also systematically investigated. The mechanism studies revealed that the active species like hole (h+), hydroxyl radical (·OH), and superoxide radical(·O2–) play a predominant role in the NOR degradation, and the enhanced removal rate of Bi4O5Br2/g-C3N4/C heterojunction can be attributed to the synergistic effect of adsorption and photocatalytic process. In addition, an S-scheme transfer channel in the interface of the Bi4O5Br2/g-C3N4/C heterojunction is proposed, which can effectively improve the separation of the photogenerated carriers and enhance the photocatalytic performance. This research provides inspiration for designing S-scheme heterojunction for wastewater treatment.