Search

The year 2024 marks the 50th anniversary of the discovery of surface-enhanced Raman spectroscopy (SERS). Over recent years, SERS has experienced rapid development and became a critical tool in biomedicine with its unparalleled sensitivity and molecular specificity. This review summarizes the advancements and challenges in SERS substrates, nanotags, instrumentation, and spectral analysis for biomedical applications. We highlight the key developments in colloidal and solid SERS substrates, with an emphasis on surface chemistry, hotspot design, and 3D hydrogel plasmonic architectures. Additionally, we introduce recent innovations in SERS nanotags, including those with interior gaps, orthogonal Raman reporters, and near-infrared-II-responsive properties, along with biomimetic coatings. Emerging technologies such as optical tweezers, plasmonic nanopores, and wearable sensors have expanded SERS capabilities for single-cell and single-molecule analysis. Advances in spectral analysis, including signal digitalization, denoising, and deep learning algorithms, have improved the quantification of complex biological data. Finally, this review discusses SERS biomedical applications in nucleic acid detection, protein characterization, metabolite analysis, single-cell monitoring, and in vivo deep Raman spectroscopy, emphasizing its potential for liquid biopsy, metabolic phenotyping, and extracellular vesicle diagnostics. The review concludes with a perspective on clinical translation of SERS, addressing commercialization potentials and the challenges in deep tissue in vivo sensing and imaging.

A copper-based catalytic system has been described to enable the efficient 1,4-sulfonylindolylation of 1,3-dienes with sulfonyl chloride and indoles. This protocol offers a practical method for the synthesis of allylsulfone-containing indole derivatives with a broad range of compatible functionalities and excellent chemo- and regioselectivities. Mechanistic studies suggest that the copper catalyst plays the dual role of initiating sulfonyl radicals and prompting indole coupling in this conjugated diene-selective 1,4-difunctionalization strategy.

Electrocatalytic nitrate reduction reaction (NO 3 RR) to harmless nitrogen (N 2 ) presents a viable approach for purifying NO 3 - -contaminated wastewater, yet most current electrocatalysts predominantly produce ammonium/ammonia (NH 4 + /NH 3 ) due to challenges in facilitating N-N coupling. This study focuses on identifying metal catalysts that preferentially generate N 2 and elucidating the mechanistic origins of their high selectivity. Our evaluation of 16 commercially available metals reveals that only Pb, Sn, and In demonstrated substantial N 2 -N concentration of 100 mg/L), while others largely favored NH 2 , and an initial NO 3 - -N concentration of 100 mg/L), while others largely favored NH 4 + production. Comprehensive experimental and theoretical analyses indicate that NH 4 + -selective catalysts (e.g., Co) exhibited high water activity that enhances • H coverage, thereby promoting the hydrogenation of NO 3 - to NH 4 + through the hydrogen atom transfer mechanism. In contrast, N 2 -selective catalysts, with their lower water activity, promoted the formation of N-containing intermediates, which likely undergo dimerization to form N 2 via the proton-coupled electron transfer mechanism. Enhancing NO 3 - adsorption was beneficial to improve N 2 selectivity by competitively reducing • H coverage. Our findings highlight the crucial role of water activity in NO 3 RR performance and offer a rational design of electrocatalysts with enhanced N 2 selectivity.

E-cigarette emissions, which contain a variety of hazardous compounds, contribute significantly to indoor air pollution and raise concerns about secondhand exposure to vaping byproducts. Compared to fresh vape emissions, our understanding of chemically aged products in indoor environments remains incomplete. Terpenes are commonly used as flavoring agents in e-liquids, which have the ability to react with the dominant indoor oxidant ozone (O 3 ) to produce reactive oxygenated byproducts and result in new particle formation. In this study, mixtures of propylene glycol (PG), vegetable glycerin (VG), and terpenes as e-liquids were injected into a 2 m 3 FEP chamber to simulate the indoor aging process. 100 ppbv O 3 was introduced into the chamber and allowed to react with the fresh vape emissions for 1 h. Complementary online and offline analytical techniques were used to characterize the changes in the aerosol size distribution and chemical composition during the aging processes. We observed more ultrafine particles and a greater abundance of highly oxygenated species, such as carbonyls, in aged e-cigarette aerosols. Compared with their fresh counterparts, the aged emissions exhibited greater cytotoxic potential, which can be attributed to the formation of these highly oxygenated compounds that are not present in the fresh emissions. This work highlights the dynamic chemistry and toxicity of e-cigarette aerosols in the indoor environment as well as the indirect risks of secondhand exposure.

Herein, a relay strategy incorporating oxidative cross dehydrogenative coupling (CDC) and N 1 - to N 2 -isomerization is disclosed for the formal N 2 -selective alkylation of triazoles with ethers under thermodynamic control conditions. By taking advantage of the different thermodynamical stabilities of N 1 - and N 2 -alkylated triazoles (3.65 kcal/mol), the initially formed N 1 -isomers can be in situ converted into their more stable N 2 -isomers when reaching thermodynamic equilibrium. PhI(OAc) 2 has been discovered to function as both an oxidant for the CDC process and an efficient mediator for the isomerization step.

Multidrug-resistant (MDR) bacteria pose a global health threat, underscoring the need for new antibiotics. Lefamulin, the first novel-mechanism antibiotic approved by the FDA in decades, showcases pleuromutilins' promise due to low mutation frequency. However, their clinical use is limited by poor pharmacokinetics and organ toxicity. To overcome these limitations, we modified lefamulin's C14 side chain via quaternization and incorporated rigid molecular fragments to enhance pharmacological properties. Introducing a quaternary ammonium group improved liver and kidney targeting via organic cation transporters (OCTs). Candidate 8i , a quaternized imidazo[4,5- c ]pyridine pleuromutilin, demonstrated broad-spectrum activity against MDR bacteria, Mycoplasma and Chlamydophila at low doses. 8i targeted transport to infected kidneys, disrupted biofilms, damaged membranes, and inhibited protein synthesis by targeting 50S ribosomal subunit. It cleared rapidly, reducing long-term toxicity. Daily injections were an effective short-course treatment for systemic infections and pyelonephritis. This research presents a novel OCT-mediated, organ-targeted antibiotic design strategy to manage antibiotic-resistant infections.

Electric aircraft such as electric aircraft and electric vehicles play a key role in the future electric aviation industry, but they put forward huge requirements for battery energy density. However, the current high-energy-density lithium battery technology still needs to be broken through. Herein, through the molecular structure design of the polymer electrolyte, a strategy of a fast migration channel and wide electrochemical window is proposed to fabricate high-voltage-resistant solid polymer electrolyte (HVPE) via in situ polymerization. Thus, HVPE exhibits an ultrahigh Li + transfer number ( t Li+ ) of 0.92 and an excellent electrochemical window of 5.1 V to match with a high-voltage lithium cobalt oxide (LCO) cathode. This fast conduction of Li+ allows for stable and uniform lithium plating and stripping deposition for more than 1000 h, which also reveals a well-defined dual interfacial stabilization mechanism. These results endow the assembled LCO|HVPE|Li cell cycles steadily for 500 cycles at 4.5 V and 0.5C with a superior capacity retention of 89.93%. Moreover, the assembled LCO|HVPE|Li pouch cell exhibits a capacity retention rate of up to 94.01% after 50 cycles. More importantly, our proposed HVPE provides new insights into structural design and fabrication strategies for high-energy-density solid-state polymer batteries.

The skeleton is highly innervated by numerous nerve fibers. These nerve fibers, in addition to transmitting information within the bone and mediating bone sensations, play a crucial role in regulating bone tissue formation and regeneration. Traditional bone tissue engineering (BTE) often fails to achieve satisfactory outcomes when dealing with large-scale bone defects, which is frequently related to the lack of effective reconstruction of the neurovascular network. In recent years, increasing research has revealed the critical role of nerves in bone metabolism. Nerve fibers regulate bone cells through neurotransmitters, neuropeptides, and peripheral glial cells. Furthermore, nerves also coordinate with the vascular and immune systems to jointly construct a microenvironment favorable for bone regeneration. As a signaling driver of bone formation, neuroregulation spans the entire process of bone physiological activities from the embryonic formation to postmaturity remodeling and repair. However, there is currently a lack of comprehensive summaries of these regulatory mechanisms. Therefore, this review sketches out the function of nerves during bone formation and regeneration. Then, we elaborate on the mechanisms of neurovascular coupling and neuromodulation of bone immunity. Finally, we discuss several novel strategies for neuro-bone tissue engineering (NBTE) based on neuroregulation of bone, focusing on the coordinated regeneration of nerve and bone tissue.

The fusion assembly strategy of supramolecular chemistry combined with dynamic covalent chemistry has provided novel insights into the design of precision nutrition and intelligent drug delivery carriers. This work involved the development of a supramolecular self-assembly originating from entropy- and enthalpy-driven dynamic covalent bonding on Schiff bases between egg white-derived peptide Gln-Ile-Gly-Leu-Phe (QIGLF) and glutaraldehyde (GA), denoted QIGLF-GA. The assembly exhibited outstanding assembly characteristics and multiwavelength autofluorescence properties. Benefiting from the potent facilitation of the dynamic covalent interaction of Schiff base on the noncovalent assembly force network, QIGLF-GA was afforded an encapsulation capacity of curcumin (Cur) of more than 22% (≫ 10%) and rationally inhibited P-glycoprotein-mediated cellular efflux and markedly elevated the efficacy of Cur in overcoming the intestinal epithelial absorption barrier to the circulation with the help of endocytosis. Furthermore, QIGLF-GA-Cur features responsive release under weakly acidic conditions, which dramatically contributes to the intracellular bioavailability of Cur.

Developing small organic molecular phototheranostic agents with second near-infrared (NIR-II) aggregation-induced emission (AIE) is paramount for the phototriggered diagnostic imaging and synchronous in situ therapy of cancer via an excellent balance of the excited states energy dissipations. In this study, a multifunctional iridium(III) complex is exploited by the coordination of an AIE-active N^N ancillary ligand with a trivalent iridium ion. The resultant complex DPTPzIr significantly outperforms its parent ligand in terms of absorption/emission wavelengths, reactive oxygen species (ROS) production, and photothermal conversion, which simultaneously endow DPTPzIr nanoparticles with matched absorption peak to commercial 808 nm laser, the longest NIR-II emission peak (above 1100 nm) among those previously reported AIE iridium(III) complexes, potentiated type-I ROS generation, and as high as 60.5% of photothermal conversion efficiency. Consequently, DPTPzIr nanoparticles perform well in multimodal image-guided photodynamic therapy-photothermal therapy for breast cancer in tumor-bearing mice, enabling precise tumor diagnosis and complete ablation with high biocompatibility. Our present work provides a simple, feasible, and effective paradigm for the development of advanced phototheranostic agents.

The traditional treatment of toxic and refractory copper(II)-ethylenediaminetetraacetic acid chelate (Cu(II)-EDTA) in electroless effluents often generates hazardous waste and secondary nitrogen-containing pollutants without maximizing the resource recovery. This study demonstrates a facile strategy to simultaneously recover Cu and EDTA ligands from Cu(II)-EDTA electroless effluent with commercially available metallic Cu and formaldehyde. In this strategy, metallic Cu is used to activate formaldehyde, a prevalent yet often overlooked cocontaminant in Cu(II)-EDTA effluents, to produce highly reductive hydrogen radical ( • H), which in situ decomplex Cu(II)-EDTA, reduces the central Cu(II) into metallic Cu, and release EDTA ligand. Impressively, this strategy can recover 99.9% of Cu from a real Cu(II)-EDTA effluent (∼2000 mg/L) as a high-purity Cu powder without further treatment, and 99.2% of EDTA from a real Cu(II)-EDTA effluent using a precipitation-acidification post-treatment procedure, earning a net profit of US $72.38 per ton. The proposed approach offers a "pollution-curing-pollution" solution to transform chelated metal waste into valuable resources.

Organic pollutants removal via a polymerization transfer (PT) pathway based on the use of single-atom catalysts (SACs) promises efficient water purification with minimal energy/chemical inputs. However, the precise engineering of such catalytic systems toward PT decontamination is still challenging, and the conventional SACs are plagued by low structural stability of carbon material support. Here, we adopted magnesium oxide (MgO) as a structurally stable alternative for loading single copper (Cu) atoms to drive peroxymonosulfate-based Fenton-like reactions. Through fine-tuning the Cu atom steric location from lattice-embedding to surface-loading, the system exhibited a fundamental transition in the catalytic pathways toward the PT process and drastically improved decontamination efficiency. The catalytic pathway change was mainly ascribed to a downshifted d -band center of the Cu atoms. The optimized catalyst achieved complete, rapid removal of phenolic compounds from water via nearly 100% PT pathway, accompanied by high oxidant utilization efficiency surpassing most state-of-the-art SACs. Moreover, it showed excellent structural stability and environmental robustness and was successfully used for the treatment of lake water and industrial coking wastewater. The adaptability of the spatial engineering strategy to other MgO-supported single atoms, including Fe, Co, and Ni SACs, was also demonstrated. Our work lays a foundation for further advancing SACs-based advanced oxidation technologies toward sustainable water purification applications.

H 2 produced through photocatalytic overall water splitting represents a sustainable energy. However, this approach is geographically constrained by freshwater availability, worsening the crisis in arid regions with abundant solar energy. This study introduces a MOF-801-hydrazine-SrTiO 3 :Al (MS) composite for in situ photocatalytic H 2 production using only atmospheric water and sunlight. The MS benefits from the hygroscopic MOF-801-hydrazine for water capture and the photocatalytic SrTiO 3 :Al for H 2 and O 2 . This system demonstrates effective in situ photocatalytic overall atmospheric water splitting in arid conditions, with a moisture adsorption capacity of 1.02 g H 2 O g MS -1 in 60 min at 30% relative humidity, and H 2 and O 2 production rates of 1033.1 and 494.3 μmol h -1 g S -1 , respectively. This approach offers a novel solution for sustainable H 2 production using natural resources, crucial for water-scarce regions.

Detections of internal substances and morphologies for label-free living cells are crucial for revealing malignant diseases. With the phase serving as a coupling of refractive index (RI) (marker for substances) and thickness (morphology), existing decoupling methods mainly rely on complex integrated systems or extensive optical field information. Developing simple and rapid decoupling methods remains a challenge. This study introduces a refractive index morphology imaging microscope (RIMIM) system utilizing polarization multiplexing for label-free single living cells. By simultaneous degree of circular polarization (DOCP) imaging and noninterferometric quantitative phase imaging (QPI), the intracellular refractive index distribution (IRID) and morphology can be decoupled. The optical thickness calculated from the phase is input into the circular depolarization decay model (CDDM) of degree of circular polarization to retrieve IRID. Subsequently, the thickness can be decoupled from phase result using retrieved IRID. Experiments conducted on mouse forestomach carcinoma (MFC) cells and human kidney-2 cells (HK-2) demonstrated the RIMIM system's ability to retrieve IRID and decouple fine morphology. Additionally, the RIMIM system effectively detected membrane damage and changes in erastin-induced ferroptotic HK-2 cells, with average and root-mean-square of surface folds 65.5% and 70.0% higher than those of normal HK-2 cells. Overall, the RIMIM system provides a simple and rapid method for decoupling RI and fine morphology, showing great potential for label-free live cells' cytopathology detection.

Intrinsic stereochemical activity of the 5s 2 electron configuration in Sb 3+ leads to structural distortion within [SbCl n ] 3- n units, which, while stabilizing the material, paradoxically diminishes luminescence intensity due to induced asymmetry. To address this issue, a strategy, which encompasses increasing the structural dimensions and introducing In 3+ doping, was developed to mitigate the geometrical distortion in the [SbCl n ] 3- n units within the metal-organic perovskite (DABCO) 2 Sb 2 Cl 10 ·H 2 O and (DABCO) 2 SbCdCl 9 ·2H 2 O (DABCO = triethylenediamine). This dimensional augmentation confines lattice distortion effectively, and the In 3+ doping modifies the 5s 2 electron configuration of Sb 3+ , thereby reducing the distortion at its origin. The unique suitability of indium-based halides as a matrix for Sb 3+ doping is underscored by our approach, which capitalizes on their ability to regulate the electron configuration of Sb 3+ . This strategy has been validated through crystallographic data from single-crystal X-ray diffraction. By effectively reducing the adverse effects of geometric distortion, several hundred-fold enhancements in the luminescent intensity of the material have been achieved by our methodology, leading to potential applications in white-light LEDs. This advancement not only highlights the pivotal role of structural symmetry in the optical properties of materials but also exemplifies the power of material engineering to optimize the optical performance.

We herein report a photochemical Truce-Smiles rearrangement reaction of N -sulfinyl acrylamides with bromodifluoroacetamides resulting in the synthesis of a series of aryl difluoroglutaramides in moderate to good yields. The asymmetric synthesis using chiral sulfinamides produced quaternary carbon - centered glutaramide products with a modest enantioselectivity. This protocol effectively complements previous Truce-Smiles rearrangement methods involving N -sulfonyl acrylamides.

Nonlinearities are fundamental to modern optical technologies. Exciton polaritons in semiconductor microcavities provide a promising route to strong nonlinearities. Monolayer TMDs, with tightly bound excitons and strong oscillator strength, enable polaritonic phenomena under ambient conditions but face challenges from weak polariton interactions due to small exciton Bohr radius. Although spatial confinement can boost polariton nonlinearity, the dynamics of trapped polaritons remain underexplored. Here we study the transient nonlinearities of confined polaritons in monolayer WS 2 mesa cavities. We observe increasingly pronounced blueshifts within the first few picoseconds as trapping sizes decrease or excitonic fractions increase. Furthermore, our findings reveal that exciton-photon detuning, not trapping size, predominantly influences the time to reach the peak of transient nonlinearity. This insight aligns with the experimentally observed and theoretically simulated relaxation dynamics of trapped polaritons. Our findings pave the way for developing ultrafast all-optical polaritonic devices in TMD systems.

Hydrogels have been identified as a promising material platform for solar-driven interfacial evaporation. However, designing durable hydrogel solar evaporators that can combine effective photothermal conversion, superior water transport, salt resistance, and robust mechanical properties to ensure stable and efficient evaporation remains a significant challenge. Herein, a robust and antifouling hydrogel-based solar evaporator composed of poly(vinyl alcohol), sodium alginate, and MXene is successfully constructed through directional freeze-casting and salting-out processes. The directional freeze-casting aids in forming vertically aligned, well-interconnected channels within the hydrogel that facilitate rapid upward water transfer and effective salt ion discharging, while the optimized salting-out process promotes the cross-linking of polymer chains, creating a sponge-like porous structure that enhances key mechanical properties such as high elasticity and exceptional flexibility. The developed hydrogel evaporator achieves an impressive evaporation rate of 2.53 kg m -2 h -1 with an energy efficiency of 93%, as well as excellent salt resistance and long-term evaporation stability even when desalinating high-concentration brines. These exceptional characteristics make this composite hydrogel evaporator highly suitable for practical applications in seawater desalination and wastewater purification.

With the growing demand for clean energy, efficient uranium extraction technologies are needed, especially from seawater, where uranium reserves are huge. Here, we developed a composite membrane by inserting Escherichia coli engineered with super uranyl-binding protein (SUP) within a two-dimensional (2D) MXene (Ti 3 C 2 T x ) layer. SUP endowed the bioinorganic hybrid membrane with ultrahigh selectivity for uranyl ions, while the engineered E. coli improved the mechanical strength and economy of the membranes. Experimental results showed that the membranes achieved precise recognition of uranyl ions and excellent ion screening performance (SF U/V ≈ 43, SF Na/U ≈ 158). Excellent separation performance and cyclic stability tests demonstrated the industrial application potential of the membrane. This method offers a green and sustainable solution, combining biological engineering and nanomaterial innovation, providing an environmentally friendly and efficient approach for uranium extraction from seawater, marking a significant advancement in the field of clean energy resource development.

Sulfur-containing volatile organic compounds emitted during wildfire events, such as dimethyl sulfide, are known to form secondary aerosols containing inorganic sulfate (SO 4 2- ) and surfactant-like organic compounds; however, little is known about the fate of sulfur in other emitted reduced organosulfur species. This study aimed to determine the sulfurous product distribution resulting from the nighttime oxidation of thiophene as a model system. Ion chromatography (IC) and aerosol mass spectrometry (a mini aerosol mass spectrometer, mAMS) were used to constrain the proportions of sulfurous compounds produced under wildfire-relevant conditions ([NO 2 ]/[O 3 ] = 0.1). With constraints from IC, results indicated that the sulfurous particle mass consisted of 30.3 ± 6.6% SO 4 2- , while mAMS fractionation attributed 24.5 ± 1.6% of total sulfate signal to SO 4 2- , 15.4 ± 1.9% to organosulfates, and 60.1 ± 0.9% to sulfonates. Empirical formulas of organosulfur products were identified as C1-C8 organosulfates and sulfonates using complementary mass spectrometry techniques. This study highlights the nighttime oxidation of thiophene and its derivatives as a source of SO 4 2- and particulate organosulfur compounds, which have important implications for the atmospheric sulfur budget and aerosol/droplet physical and chemical properties., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The utilization of lanthanide (Ln) complexes in the realm of organic light-emitting diodes (OLEDs) has garnered extensive interest, particularly in their role as luminescent materials or electron trappers. A series of gadolinium (Gd) complexes with energy levels of high HOMO/LUMO and different triplet state energies were designed and synthesized by introducing substituents with different electronic effects onto the pyrazolone derivative ligands. Subsequently, these complexes were precisely purified by vacuum sublimation and codoped into the light-emitting layer (EML) of the OLEDs. This process was facilitated through the well-matched HOMO/LUMO levels and triplet energies among various functional materials. Consequently, the maximum external quantum efficiencies of blue, red, and green OLEDs were simultaneously enhanced with the ratios of 119%, 28%, and 71%, respectively. This improvement can be credited to the introduction of Gd(III) complex molecules within EMLs, which helps to capture excess holes and improve carriers' balance.

Anatase TiO 2 is commonly used as a catalyst/support in reactions involving H 2 O 2 , yet the understanding of interactions between common TiO 2 surfaces and H 2 O 2 remains limited. Herein, we synthesized well-defined TiO 2 crystallites with (101), (001), and fluorine-modified (001) [F-(001)] surfaces to examine how surface features, including the arrangement of five-coordinated Ti (Ti 5c ) sites and the presence of fluorine, influence H 2 O 2 activation. Our findings reveal that these surface features significantly affect the physiochemical properties of adsorbed H 2 O 2 . Specifically, fluorine on the F-(001) surface introduces an additional hydrogen bond to the Ti 5c -peroxo species, altering the electronic structure of H 2 O 2 compared to those with the (101) and (001) surfaces. Using cyclohexene as a probe substrate, we successfully distinguished the reactivities of the Ti 5c -peroxo species. The activity of those on the F-(001) surface was significantly higher than the activity of those on the (001) surface, while the (101) surface showed negligible oxidation activity. These insights can guide the design of TiO 2 -based catalysts for H 2 O 2 -related reactions.

The creation of complex multilayer periosteal graft structures is challenging. This study introduced a novel bottom-up approach to assemble cell-laden nanofiber mats into a three-dimensional (3D) multilayer periosteum mimic, successfully replicating the hierarchical complexity of the natural periosteum. These nanofiber mats, which were fabricated by electrospinning, surface modification, and stimulated body fluid (SBF) immersion, are composed of nanoscale polycaprolactone (PCL) fibers coated with a mineralized collagen layer along the fiber orientation. They closely resembled the natural periosteal matrix, thereby promoting osteogenic differentiation of rat bone marrow mesenchymal stem cells (rBMSCs) in vitro. The biomimetic periosteum, constructed via layer-by-layer assembly, offered advantages such as a multilayer nanofibrous structure, controlled cell distribution, a reservoir for osteoprogenitors, and enhanced pro-osteogenic potential. The rat calvarial bone defect model confirmed its potent bone repair capacity. This study presents an efficient approach to construct tissue-engineered periosteum mimics, holding promise for serving as periosteal grafts in orthopedic applications.

Bees produce honey through the collection and transformation of nectar, whose botanical origin impacts the taste, nutritional value, and, therefore, the market price of the resulting honey. This phenomenon has led some to mislabel their honey so that it can be sold at a higher price. Metabolomics has been gaining popularity in food authentication, but rapid data mining algorithms are needed to facilitate the discovery of new authenticity markers. A nontargeted high-resolution liquid chromatography-mass spectrometry (HR/LC-MS) analysis of 262 monofloral honey samples, of which 50 were blueberry honey, was performed. Data mining methods were demonstrated for the discovery of binary single-markers (compound was only detected in blueberry honey), threshold single-markers (compound had the highest concentration in blueberry honey), and interval ratio-markers (the ratio of two compounds was within a unique interval in blueberry honey). A novel convolutional algorithm was developed for the discovery of interval ratio-markers, which trained 14× faster and achieved a 0.2 Matthews correlation coefficient (MCC) units higher classification score than existing open-source implementations. The convolutional algorithm also had classification performance similar to that of a brute-force search but trained 1521× faster. A pipeline for shortlisting candidate authenticity markers from the LC-MS spectra that may be suitable for chemical structure identification was also demonstrated and led to the identification of niacin as a blueberry honey threshold single-marker. This work demonstrates an end-to-end approach to mine the honey metabolome for novel authenticity markers and can readily be applied to other types of food and analytical chemistry instruments.

Immunofluorescence assays are extensively used for the detection of disease-associated biomarkers within patient samples for direct diagnosis. Unfortunately, these 2D microarrays suffer from low repeatability and fail to attain the low limits of detection (LODs) required to accurately discern disease progression for clinical monitoring. While three-dimensional microarrays with increased biorecognition molecule density stand to circumvent these limitations, their viscous component materials are not compatible with current microarray fabrication protocols. Herein, we introduce a platform for 3D microarray bioprinting, wherein a two-step printing approach enables the high-throughput fabrication of immunosorbent hydrogels. The hydrogels are composed entirely of cross-linked proteins decorated with clinically relevant capture antibodies. Compared to two-dimensional microarrays, these proteinaceous microarrays offer 3-fold increases in signal intensity. When tested with clinically relevant biomarkers, ultrasensitive single-plex and multiplex detection of interleukin-6 (LOD 0.3 pg/mL) and tumor necrosis factor receptor 1 (LOD 1 pg/mL) is observed. When challenged with clinical samples, these hydrogel microarrays consistently discern elevated levels of interleukin-6 in blood plasma derived from patients with systemic blood infections. Given their easy-to-implement, high-throughput fabrication, and ultrasensitive detection, these three-dimensional microarrays will enable better clinical monitoring of disease progression, yielding improved patient outcomes.

Melamine-derived mesoporous carbon, which was obtained from pyrolysis of modified melamine, was employed for the purpose of eliminating trace amounts of Hg(II) from honeysuckle decoction. The specific surface area of the mesoporous carbons with N-functional (MCN 1 ) was 648.372 m 2 ·g -1 . The chemical composition and morphology of MCN 1 were thoroughly examined, and a comprehensive analysis led to the identification of its formation mechanism. A noteworthy association has been identified between the adsorption efficacy and the chemical composition of MCN 1 . In the elimination of trace mercury in aqueous solutions over a broad pH range (pH 2-9), MCN 1 demonstrates high effectiveness, approaching 100%. Adsorption kinetics and isotherm results indicate that a more accurate representation of Hg(II) adsorption on MCN 1 is provided by pseudo-second-order kinetics and Freundlich models, with chemical adsorption being the dominant mechanism. This study further examined the removal of chlorogenic acid, a bioactive component, by MCN 1 . The findings imply that MCN 1 has a noteworthy 80% efficacy in removing mercury from honeysuckle decoction while maintaining the purity of its medicinal ingredients, particularly chlorogenic acid. As a result, utilizing MCN 1 for the adsorption of Hg(II) in honeysuckle decoction appears to be a reasonable approach., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Phytoremediation efficiency can be enhanced by regulating rhizosphere processes, and the Cd isotope is a useful approach for deciphering Cd transport processes in soil-plant systems. However, the effects of adsorption and complexation on Cd isotope fractionation during the rhizosphere processes remain unclear. Here, we cultivated the Cd hyperaccumulator Sedum alfredii and Cd-tolerance Sedum spectabile in three different soils with citric acid applied as a degradable rhizosphere biostimulant. Cellular elemental distributions in the tissues and Cd isotope compositions were determined through NanoSIMS and MC-ICP-MS, respectively. Cd precipitation/adsorption on cell walls and intracellular regional distribution were the main mechanisms of Cd tolerance in S. spectabile . Plant roots became enriched with heavier Cd isotopes relative to the surrounding soils upon increasing secretion of rhizosphere organic acids. This indicates that organic matter with O and N functional groups preferentially chelates heavy Cd isotopes. In addition, Cd isotope fractionation between roots and shoots varies within the three soils, which could be due to the influence of protein and metallothionein contents in roots and leaves. The finding indicates that sulfur-containing ligands preferentially chelate light Cd isotopes. This study suggests that organic ligands play a vital role in Cd isotope fractionation and consequent hyperaccumulation of soil-plant systems.

Biomass energy recovery from sewage sludge through anaerobic treatment is vital for environmental sustainability and a circular economy. However, large amounts of pharmaceutical and personal care products (PPCPs) remain in sludge, and their interactions with microbes and enzymes would affect resource recovery. This article reviews the effects and mechanisms of PPCPs on anaerobic sludge treatment. Most PPCPs posed adverse impacts on methane production, while certain low-toxicity PPCPs could stimulate volatile fatty acids and biohydrogen accumulation. Changes in the microbial community structure and functional enzyme bioactivities were also summarized with PPCPs exposure. Notably, PPCPs such as carbamazepine could bind with the active sites of the enzyme and induce microbial stress responses. The fate of various PPCPs during anaerobic sludge treatment indicated that PPCPs featuring electron-donating groups (e.g., ·-NH 2 and ·-OH), hydrophilicity, and low molecular weight were more susceptible to microbial utilization. Key biodegrading enzymes (e.g., cytochrome P450 and amidase) were crucial for PPCP degradation, although several PPCPs remain refractory to biotransformation. Therefore, remediation technologies including physical pretreatment, chemicals, bioaugmentation, and their combinations for enhancing PPCPs degradation were outlined. Among these strategies, advanced oxidation processes and combined strategies effectively removed complex and refractory PPCPs mainly by generating free radicals, providing recommendations for improving sludge detoxification.

Microwave-assisted photocatalysis offers a novel approach for degrading antibiotics, while the mechanism of enhancement of microwave-induced photocatalysis remains poorly understood. In this study, tetracycline (TC) was degraded using the method of microwave-assisted photocatalysis with a ZnO catalyst, which was synthesized by the combination of hydrothermal and calcination methods. The self-assembled mesoporous ZnO catalyst exhibited superior catalytic activity in degrading TC. It is found that the degradation efficiency of TC by the ZnO catalysts with microwave-assisted photocatalysis is 4.27 times higher than that of photocatalysis alone. Of particular significance, we found that the optical absorption range of ZnO increased and the band gap decreased when microwave was introduced into the photocatalytic system. Semi-in situ photochemical tests demonstrated that more photogenerated electron-hole pairs were detected under microwave, thus further improving the photocatalytic activity of ZnO. The separation efficiency and charge transfer efficiency of photogenerated electron-hole pairs also improved due to the increase of oxygen vacancies in the synergistic effect. Meanwhile, h + and ·OH were the main active species in the degradation system. The mechanism of microwave-induced photocatalysis is illustrated, and an efficient way for degrading antibiotic is provided in this work.

This study examines the kinetic origins of the temperature dependence of photoelectrochemical water oxidation on nanostructured titania photoanodes. We observe that the photocurrent is enhanced at 50 °C relative to 20 °C, with this enhancement being most pronounced (by up to 70%) at low anodic potentials (<+0.6 V vs RHE). Over this low potential range, the photocurrent magnitude is largely determined by kinetic competition between water oxidation catalysis (WOC) and recombination between surface holes and bulk electrons (back electron-hole recombination, BER). We quantify the BER process by transient photocurrent analyses under pulsed irradiation. Remarkably, we find that the kinetics of BER (∼90 ms half-time) are independent of temperature. In contrast, the kinetics of WOC, determined from the analysis of the photoinduced absorption of accumulated surface holes, are found to accelerate up to 2-fold at 50 °C relative to 20 °C. We conclude that the enhanced photocurrent densities observed in the low-applied potential region result primarily from the accelerated WOC, reducing losses due to the competing BER pathway. At higher applied potentials (>+0.6 V vs RHE), a smaller (∼10%) enhancement in photocurrent density is observed at 50 °C relative to 20 °C. Photoinduced absorption studies, correlated with studies using triethanolamine as a hole scavenger, indicate that this more modest enhancement at anodic potentials primarily results from an enhanced charge separation efficiency. We conclude by discussing the implications of these results for the practical application of photoanodic WOC under solar irradiation, influenced by these temperature-independent and -dependent underlying kinetic processes., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

To overcome the light power fluctuation and frequency mismatch in photoacoustic spectroscopy (PAS), we proposed a self-corrected 1 f -only resonant cell-based PAS (1 f -RCPAS) gas analyzer. Based on the theoretical analysis of the 1 f signal, a signal processing algorithm considering laser power-current nonlinearity is proposed. The 1 f -only algorithm is well-tailored for the resonant systems, requiring no time-division multiplexing. The algorithm is further improved to extend the dynamic range. The T-type resonant cell incorporating a graphene sticker is utilized for effectively amplifying the acoustic signals from both the gas and solid to achieve normalization. No optical path alignment is needed. For the low resonance frequency, a digital orthogonal-vector lock-in amplifier is used, further simplifying the system setup. The gas analyzer is used to measure methane (CH 4 ) with the near-infrared absorption peak at 1651 nm. The experiments demonstrated immunity to fiber coupling loss, laser power drift over time, and frequency mismatch caused by property differences between air and standard gases. The R 2 value in the concentration calibration reaches 0.99995, and the minimum detection limit given by the Allan variance reaches 3.5 ppb at an average time of 105 s.

A limiting factor to the efficiency of water Oxygen Evolution Reaction (OER) in metal oxide nanoparticle photocatalysts is the rapid recombination of holes and electrons. Facet-engineering can effectively improve charge separation and, consequently, OER efficiency. However, the kinetics behind this improvement remain poorly understood. This study utilizes photoinduced absorption spectroscopy to investigate the charge yield and kinetics in facet-engineered BiVO 4 (F-BiVO 4 ) compared to a non-faceted sample (NF-BiVO 4 ) under operando conditions. A significant influence of preillumination on hole accumulation is observed, linked to the saturation and, thus, passivation of deep and inactive hole traps on the BiVO 4 surface. In DI-water, F-BiVO 4 shows a 10-fold increase in charge accumulation (∼5 mΔOD) compared to NF-BiVO 4 (∼0.5 mΔOD), indicating improved charge separation and stabilization. With the addition of Fe(NO 3 ) 3 , an efficient electron acceptor, F-BiVO 4 demonstrates a 30-fold increase in the accumulation of long-lived holes (∼45 mΔOD), compared to NF-BiVO 4 (∼1.5 mΔOD) and an increased half-time, from 2 to 10 s. Based on a simple kinetic model, this increase in hole accumulation suggests that facet-engineering causes at least a 50-100 meV increase in band bending in BiVO 4 particles, thereby stabilizing surface holes. This energetic stabilization/loss results in a retardation of OER relative to NF-BiVO 4 . This slower catalysis is, however, offset by the observed increase in density and lifetime of photoaccumulated holes. Overall, this work quantifies how surface faceting can impact the kinetics of long-lived charge accumulation on metal oxide photocatalysts, highlighting the trade-off between lifetime gain and energetic loss critical to optimizing photocatalytic efficiency.

Tire wear particles (TWPs) containing tire wear chemicals (TWCs) are of global concern due to their large emissions and potential toxicity. However, TWP contributions to urban fine particles are poorly understood. Here, 72 paired gas-phase and PM 2.5 samples were collected in the urban air of the Pearl River Delta, China. The concentrations of 54 compounds were determined, and 28 TWCs were detected with total concentrations of 3130-317,000 pg/m 3 . Most p-phenylenediamines (PPDs) were unstable in solvent, likely leading to their low detection rates. The TWCs were mainly (73 ± 26%) in the gas phase. 2-OH-benzothiazole contributed 82 ± 21% of the gas-phase TWCs and benzothiazole-2-sulfonic acid contributed 74 ± 18% of the TWCs in PM 2.5 . Guangzhou and Foshan were "hotspots" for atmospheric TWCs. Most TWC concentrations significantly correlated with the road length nearby. More particulate TWCs were observed than model predictions, probably due to the impacts of nonexchangeable portion and sampling artifacts. Source apportionment combined with characteristic molecular markers indicated that TWPs contributed 13 ± 7% of urban PM 2.5 . Our study demonstrates that TWPs are important contributors to urban air pollution that could pose risks to humans. There is an urgent need to develop strategies to decrease TWP emissions, along with broader urban air quality improvement strategies.

The effect of liquid nitrogen freeze-thaw fracturing on coal seams can be potentially evaluated by the complex resistivity method. The real part (Reρ) and the imaginary part (Imρ) of the complex resistivity and permeability of coal were determined under different cycle times and in different bedding directions. The reason for permeability enhancement was discussed, and the dispersion mechanism of complex resistivity during cyclic freeze-thaw fracturing was analyzed. The results indicated that (1) the complex resistivity parameters have a good response to the cycle times; Reρ, |Imρ|, and the dispersion degree (α) are positively correlated with cycle time; the fully polarized frequency ( f p ) of Reρ, the characteristic frequency ( f c ) of Imρ, and variation are negatively correlated with cycle time. (2) The difference in complex resistivity parameters between the vertical bedding direction and the parallel bedding direction is significant, and the difference in electrical properties of the bedding structure continuously decreases with the increase in cycle time. (3) Under the effect of liquid nitrogen cyclic freeze-thaw, a complex network of fractures in coal is formed, the anisotropic characteristics of coal are weakened, and effective conductive channels are damaged. The peak frost heave force decreases exponentially with the increase in cycle time, and the difference in bedding electrical properties gradually disappears. (4) Comparing the inversion degree of measured data with three conductive models, ρ 0 and τ are selected as the optimum parameters for evaluating the effect of liquid nitrogen cyclic freeze-thaw. A logarithmic permeability evaluation model is constructed based on ρ 0 and τ. This work provides a new perspective based on electrical detection for evaluating the permeability enhancement of coal during liquid nitrogen cyclic freeze-thaw., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The urgent need for real-time and noninvasive monitoring of health-associated biochemical parameters has motivated the development of wearable sweat sensors. Existing electrochemical sensors show promise in real-time analysis of various chemical biomarkers. These sensors often rely on labels and redox probes to generate and amplify the signals for the detection and quantification of analytes with limited sensitivity. In this study, we introduce a molecularly imprinted polymer (MIP)-based biochemical sensor to quantify a molecular biomarker in sweat using electrochemical impedance spectroscopy, which eliminates the need for labels or redox probes. The molecularly imprinted biosensor can achieve sensitive and specific detection of cortisol at concentrations as low as 1 pM, 1000-fold lower than previously reported MIP cortisol sensors. We integrated multimodal electrochemical sensors with an iontophoresis sweat extraction module and paper microfluidics for real-time sweat analysis. Several parameters can be simultaneously quantified, including sweat volume, secretion rate, sodium ion, and cortisol concentration. Paper microfluidic modules not only quantify sweat volume and secretion rate but also facilitate continuous sweat analysis without user intervention. While we focus on cortisol sensing as a proof-of-concept, the molecularly imprinted wearable sensors can be extended to real-time detection of other biochemicals, such as protein biomarkers and therapeutic drugs.

Despite the extensive development of non-noble metals for the N -alkylation of amines with alcohols, the exploitation of catalysts with high selectivity, activity, and stability still faces challenges. The controllable modification of single-atom sites through asymmetric coordination with a second heteroatom offers new opportunities for enhancing the intrinsic activity of transition metal single-atom catalysts. Here, we prepared the asymmetric N/P hybrid coordination of single-atom Co 1 -N 3 P 1 by absorbing the Co-P complex on ZIF-8 using a concise impregnation-pyrolysis process. The catalyst exhibits ultrahigh activity and selectivity in the N -alkylation of aniline and benzyl alcohol, achieving a turnover number (TON) value of 3480 and a turnover frequency (TOF) value of 174 -h . The TON value is 1 order of magnitude higher than the reported catalysts and even 37-fold higher than that of the homogeneous catalyst CoCl 2 (PPh 3 ) 2 . Furthermore, the catalyst maintains its high activity and selectivity even after 6 cycles of usage. Controlling experiments and isotope labeling experiments confirm that in the asymmetric Co 1 -N 3 P 1 system, the N -alkylation of aniline with benzyl alcohol proceeds via a transfer hydrogenation mechanism involving the monohydride route. Theoretical calculations prove that the superior activity of asymmetric Co 1 -N 3 P 1 is attributed to the higher d-band energy level of Co sites, which leads to a more stable four-membered ring transition state and a lower reaction energy barrier compared to symmetrical Co 1 -N 4 .

Electrode scaling poses a critical barrier to the adoption of electrochemical processes in wastewater treatment, primarily due to electrode inactivation and increased internal reactor resistance. We introduce an antiscaling strategy using tip-enhanced electric fields to redirect scale-forming compounds (e.g., Mg(OH) 2 and CaCO 3 ) from the electrode-electrolyte interface to the bulk solution. Our study utilized Cu nanowires (Cu NW) with high-curvature nanostructures as the cathode, in contrast to Cu nanoparticles (Cu NP), Cu foil (CF), and Cu mesh (CM), to evaluate the electrochemical nitrate reduction reaction (NO 3 RR) performance in hard water conditions. The Cu NW/CF cathode demonstrated superior NO 3 RR efficiency, with an apparent rate constant ( K app ) of 1.04 h -1 , significantly outperforming control electrodes under identical conditions ( K app < 0.051 h -1 ). Through experimental and theoretical analysis, including COMSOL simulations, we show that the high-curvature design of Cu NW induced localized electric field enhancements, propelling OH - ions away from the electrode surface into the bulk solution, thus mitigating scale formation on the cathode. Testing with real nitrate-contaminated wastewater confirms that the Cu NW/CF cathode maintained excellent denitrification efficiency over a 60-day period. This study offers a promising perspective on preventing electrode scaling in electrochemical wastewater treatment, paving the way for more efficient and sustainable practices.

Here, we explored a new manufacturing strategy that uses the mask laser interference additive manufacturing (MLIAM) technique, which combines the respective strengths of laser interference lithography and mask lithography to efficiently fabricate across-scales three-dimensional bionic shark skin structures with superhydrophobicity and adhesive reduction. The phenomena and mechanisms of the MLIAM curing process were revealed and analyzed, showing the feasibility and flexibility. In terms of structural performance, the adhesive force on the surface can be tuned based on the growth direction of the bionic shark skin structures, where the maximum rate of the adhesive reduction reaches about 65%. Furthermore, the evolution of the directional diffusion for the water droplet, which is based on the change of the contact angle, was clearly observed, and the mechanism was also discussed by the models. Moreover, no-loss transportations were achieved successfully using the gradient adhesive force and superhydrophobicity on the surface by tuning the growth direction and modifying by fluorinated silane. Finally, this work gives a strategy for fabricating across-scale structures on micro- and nanometers, which have potential application in bioengineering, diversional targeting, and condenser surface.

Beta-1,3-glucuronosyltransferase (B3GAT3), overexpressed in hepatocellular carcinoma (HCC) and negatively correlated to prognosis, is a promising target for cancer therapy. Currently, no studies have reported small molecule inhibitors of B3GAT3. In this study, we designed and synthesized a series of small-molecule inhibitors of B3GAT3 through virtual screening and structure optimization. The lead compound TMLB-C16 exhibited potent B3GAT3 inhibitory activity (KD = 3.962 μM) by effectively suppressing proliferation and migration, and inducing cell cycle arrest and apoptosis in MHCC-97H (IC 50 = 6.53 ± 0.18 μM) and HCCLM3 (IC 50 = 6.22 ± 0.23 μM) cells. Furthermore, compound TMLB-C16 demonstrated favorable pharmacokinetic properties with a relatively high bioavailability of 68.37%. It significantly inhibited tumor growth in both MHCC-97H and HCCLM3 xenograft tumor models without causing obvious toxicity. These results indicate that compound TMLB-C16 is an effective small molecule inhibitor of B3GAT3, providing a basis for the future development of B3GAT3-targeted drugs.

Multiscale design of catalyst layers (CLs) is important to advancing hydrogen electrochemical conversion devices toward commercialized deployment, which has nevertheless been greatly hampered by the complex interplay among multiscale CL components, high synthesis cost and vast design space. We lack rational design and optimization techniques that can accurately reflect the nanostructure-performance relationship and cost-effectively search the design space. Here, we fill this gap with a deep generative artificial intelligence (AI) framework, GLIDER, that integrates recent generative AI, data-driven surrogate techniques and collective intelligence to efficiently search the optimal CL nanostructures driven by their electrochemical performance. GLIDER achieves realistic multiscale CL digital generation by leveraging the dimensionality-reduction ability of quantized vector-variational autoencoder. The powerful generative capability of GLIDER allows the efficient search of the optimal design parameters for the Pt-carbon-ionomer nanostructures of CLs. We also demonstrate that GLIDER is transferable to other fuel cell electrode microstructure generation, e.g ., fibrous gas diffusion layers and solid oxide fuel cell anode. GLIDER is of potential as a digital tool for the design and optimization of broad electrochemical energy devices.

Significant progress has been made previously in the research and development of graphene oxide (GO) membranes for water purification, but their biofouling behavior remains poorly understood. In this study, we investigated the biofilm formation and biofouling of GO membranes with different surface microstructures in the context of filtering natural surface water and for an extended operation period (110 days). The results showed that the relatively hydrophilic and smooth Fe(OH) 3 /GO membrane shaped a thin and spatially heterogeneous biofilm with high stable flux. However, the ability to simultaneously mitigate biofilm formation and reduce biofouling was not observed in the weakly hydrophilic and wrinkled Fe/GO and H-Fe(OH) 3 /GO membranes. Microbial analyses revealed that the hydrophilicity and roughness distinguished the bacterial communities and metabolic functions. The organic matter-degrading and predatory bacteria were more adapted to hydrophilic and smooth GO surfaces. These functional taxa were involved in the degradation of extracellular polymeric substances (EPS), and improved biofilm heterogeneity. In contrast, the weakly hydrophilic and wrinkled GO surfaces had reduced biodiversity, while unexpectedly boosting the proliferation of EPS-secreting bacteria, resulting in increased biofilm formation and aggravated biofouling. Moreover, all GO membranes achieved sustainable water purification during the entire operating period.

The production of e-cigarette aerosols through vaping processes is known to cause the formation of various free radicals and reactive oxygen species (ROS). Despite the well-known oxidative potential and cytotoxicity of fresh vaping emissions, the effects of chemical aging on exhaled vaping aerosols by indoor atmospheric oxidants are yet to be elucidated. Terpenes are commonly found in e-liquids as flavor additives. In the presence of indoor ozone (O 3 ), e-cigarette aerosols that contain terpene flavorings can undergo chemical transformations, further producing ROS and reactive carbonyl species. Here, we simulated the aging process of the e-cigarette emissions in a 2 m 3 FEP film chamber with 100 ppbv of O 3 exposure for an hour. The aged vaping aerosols, along with fresh aerosols, were collected to detect the presence of ROS. The aged particles exhibited 2- to 11-fold greater oxidative potential, and further analysis showed that these particles formed a greater number of radicals in aqueous conditions. The aging process induced the formation of various alkyl hydroperoxides (ROOH), and through iodometric quantification, we saw that our aged vaping particles contained significantly greater amounts of these hydroperoxides than their fresh counterparts. Bronchial epithelial cells exposed to aged vaping aerosols exhibited an upregulation of the oxidative stress genes, HMOX-1 and GSTP1 , indicating the potential for inhalation toxicity. This work highlights the indirect danger of vaping in environments with high ground-level O 3 , which can chemically transform e-cigarette aerosols into new particles that can induce greater oxidative damage than fresh e-cigarette aerosols. Given that the toxicological characteristics of e-cigarettes are mainly associated with the inhalation of fresh aerosols in current studies, our work may provide a perspective that characterizes vaping exposure under secondhand or thirdhand conditions as a significant health risk.

Biocompatible nanoparticles as drug carriers can improve the therapeutic efficiency of hydrophobic drugs. However, the synthesis of biocompatible and biodegradable polymeric nanoparticles can be time-consuming and often involves toxic solvents. Here, a simple method for protein-based stable drug-loaded particles with a narrow polydispersity is introduced. In this process, lysozyme is mixed with hydrophobic drugs (curcumin, ellipticine, and dasatinib) and fructose to prepare lysozyme-based drug particles of around 150 nm in size. Fructose is mixed with the drug to generate nanoparticles that serve as templates for the lysozyme coating. The effect of lysozyme on the physicochemical properties of these nanoparticles is studied by transmission electron microscopy (TEM) and scattering techniques (e.g., dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS)). We observed that lysozyme significantly stabilized the curcumin fructose particles for 7 days. Moreover, additional drugs, such as ellipticine and dasatinib, can be loaded to form dual-drug particles with narrow polydispersity and spherical morphology. The results also reveal that lysozyme dual ellipticine/dasatinib curcumin particles enhance the cytotoxicity and uptake on MCF-7 cells, RAW 264.7 cells, and U-87 MG cells due to the larger and rigid hydrophobic core. In summary, lysozyme in combination with fructose and curcumin can serve as a powerful combination to form protein-based stable particles for the delivery of hydrophobic drugs.

Methylesterases (MESs) hydrolyze carboxylic ester and are important for plant metabolism and defense. However, the understanding of MES' role in strawberries against pathogens remains limited. This study identified 15 FvMESs with a conserved catalytic triad from the Fragaria vesca genome. Spatiotemporal expression data demonstrated the upregulated expression of FvMESs in roots and developing fruits, suggesting growth involvement. The FvMES promoter regions harbored numerous stress-related cis -acting elements and transcription factors associated with plant defense mechanisms. Moreover, FvMES 2 exhibited a significant response to Botrytis cinerea stress and showed a remarkable correlation with the salicylic acid (SA) signaling pathway. Molecular docking showed an efficient binding potential between FvMES2 and methyl salicylate (MeSA). The role of FvMES2 in MeSA demethylation to produce SA was further confirmed through in vitro and in vivo assays. After MeSA was applied, the transient overexpression of FvMES 2 in strawberries enhanced their resistance to B. cinerea compared to wild-type plants.

The biotransformation of ginsenosides using microorganisms represents a promising and ecofriendly approach for the production of rare ginsenosides. The present study reports on the biotransformation of ginsenoside Rb1 using the fungus Irpex lacteus , resulting in the production of ginsenoside Rd and seven rare ginsenosides with novel structures. Employing high-performance liquid chromatography coupled with high-resolution tandem mass spectrometry, the identities of the transformation products were rapidly determined. Two sets of isomers with molecular weights of 980.56 and 962.55 were discovered among the seven rare ginsenosides, which were generated through the isomerization of the olefin chain in the protopanaxadiol (PPD)-type ginsenoside skeleton. Each isomer exhibited characteristic fragment ions and neutral loss patterns in their tandem mass spectra, providing evidence of their unique structures. Time-course experiments demonstrated that the transformation reaction reached equilibrium after 14 days, with Rb1 initially generating Rd and compound 5 , followed by the formation of other rare ginsenosides. The biotransformation process catalyzed by I. lacteus was found to involve not only the typical deglycosylation reaction at the C-20 position but also hydroxylation at the C-22 and C-23 positions, as well as hydrogenation, transfer, and cyclization of the double bond at the C-24(25) position. These enzymatic capabilities extend to the structural modification of other PPD-type ginsenosides such as Rc and Rd, revealing the potential of I. lacteus for the production of a wider range of rare ginsenosides. The transformation activities observed in I. lacteus are unprecedented among fungal biotransformations of ginsenosides. This study highlights the application of a medicinal fungi-based biotransformation strategy for the generation of rare ginsenosides with enhanced structural diversity, thereby expanding the variety of bioactive compounds derived from ginseng., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Coacervate microdroplets, a protocell model in exploring the origin of life, have gained significant attention. Clay minerals, catalysts during the origin of life, are crucial in the chemical evolution of small molecules into biopolymers. However, our understanding of the relationship between clay minerals and the formation and evolution of protocells on early Earth remains limited. In this work, the nanoclay montmorillonite nanosheet (MMT-Na) was employed to investigate its interaction with coacervate microdroplets formed by oligolysine (K10) and adenine nucleoside triphosphate (ATP). As an anionic component, MMT-Na was noted to promote the formation of coacervate microdroplets. Furthermore, the efficiency of ssDNA enrichment and the degree of ssDNA hybridization within these microdroplets were significantly improved. By combining inorganic nanoclay with organic biopolymers, our work provides an efficient way to enrich genetic biomolecules in the primitive Earth environment and builds a nanoclay-based coacervate microdroplets, shedding new light on life's origin and protocell evolution.

This study reports a comparison of the kinetics of electrochemical (EC) versus photoelectrochemical (PEC) water oxidation on bismuth vanadate (BiVO 4 ) photoanodes. Plots of current density versus surface hole density, determined from operando optical absorption analyses under EC and PEC conditions, are found to be indistinguishable. We thus conclude that EC water oxidation is driven by the Zener effect tunneling electrons from the valence to conduction band under strong bias, with the kinetics of both EC and PEC water oxidation being determined by the density of accumulated surface valence band holes. We further demonstrate that our combined optical absorption/current density analyses enable an operando quantification of the BiVO 4 photovoltage as a function of light intensity.

Microcystin-LR (MC-LR), the most prevalent and diverse cyanotoxin produced by harmful cyanobacterial blooms, has been linked to gastrointestinal toxicity. Therefore, we conducted a case-control study across four regions in China to investigate this relationship. Inflammatory bowel disease (IBD) cases (219) were matched with healthy controls (438) based on age and gender and conditional logistic regression models and Restricted cubic splines were used to evaluate the association between MC-LR exposure and IBD risk. We used quantitative real-time polymerase chain reaction to measure the expression levels of inflammatory factors. The levels of protein expression in the colorectum were determined using Western blotting (WB). Compared to the lowest quartile of serum MC-LR levels, the adjusted odds ratios and 95% confidence intervals (CI) for the highest quartiles of serum MC-LR levels were 5.51 (2.70, 11.21). The RCS was shown the association between serum MC-LR levels and IBD risk was nonlinear ( P nonlinear < 0.001). In the animal experiments, MC-LR resulted in colorectal injury via the PI3K/AKT signaling pathway. Our study provides the evidence that serum MC-LR exposure is significantly associated with the risk of IBD in China. Animal study results indicate that MC-LR probably causes IBD via the PI3K/AKT signaling pathway., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Co-published by Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, and American Chemical Society.)

In this study, concise, efficient, and modular hydrophosphinylation and hydroamidation of gem -difluorocyclopropenes were disclosed in a mild and transition-metal-free pattern. Through this approach, phosphorus, and nitrogen-containing gem -difluorocyclopropanes were produced in moderate to good yields with excellent regio- and diastereoselectivity. Readily available gem -difluorocyclopropenes and nucleophilic reagents, along with inexpensive inorganic bases, were employed. Multiple synthetic applications, including gram-scale and derivatization reactions and modification of bioactive molecules, were subsequently elaborated.