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One of the most promising approaches to effectively modulate the performance of immunochromatography (ICA) is the rational design of nanomaterials. It is anticipated to facilitate highly sensitive ICA analysis by introducing and controlling the internal defect structures of nanomaterials. Herein, we designed Bi 2 S 3- x @AuNPs with deep-level defect properties, revealing that these deep defects act as electron-hole nonradiative complex centers to promote phonon production, ultimately leading to photothermal analytical performance in ICA. By effectively regulating the defect density, the assay showed extraordinary colorimetric intensity, photothermal performance, and stability, which were conducive to constructing sensitive ICA. With a proof-of-concept for gentamicin (Gen), the limit of detection (LOD) was determined to be 0.0358 ng mL -1 , with overall recoveries ranging from 84.40% to 108.30% in both milk and milk powder samples. It demonstrates the importance of the rational design of internal defect structures to improve analytical performance and broaden the application of ICA.

Photoassisted electrocatalysis is a frontier direction of electrocatalysis for promoting energy conversion. In this work, a metal-free C 3 N 4 /Se-CNTs is reported as a novel catalyst for photoassisted electrocatalytic oxygen evolution reaction (OER). C 3 N 4 has an appropriate bandgap, high specific surface area, and long-term stability. CNTs can modulate the electronic environment of C 3 N 4 by strong π-π interaction and greatly enhance the separation efficiency of photogenerated carriers. The distributed Se nanoparticles in CNTs can further increase the charge transfer ability. As a metal-free catalyst, the C 3 N 4 /Se-CNTs exhibits an overpotential of 231 mV at a current density of 10 mA cm -2 and a small Tafel slope of 52 mV dec -1 under illumination, which ranks among the best catalysts for photoassisted OER performance, surpassing most noble and transition metal-based catalysts. The result demonstrates the great potential of C 3 N 4 -based catalysts in the photoassisted OER process and provides a new perspective to explore the excellent metal-free OER catalysts.

To mitigate the detrimental effects of agricultural pest mites on crop yield, an active substructure splicing strategy was employed to modify etoxazole by introducing an S-S moiety. The target products were obtained efficiently via a bilateral disulfurating reagent (DSMO), which was developed by our group. The leaf dip method was used to evaluate the activities of the designed target compounds against the eggs and larvae of the spider mite ( Tetranychus cinnabarinus ). Most of the target compounds exhibited good efficacy in controlling the larvae and eggs of T. cinnabarinus . Based on these results, a three-dimensional quantitative structure-activity relationship (3D-QSAR) model was established to guide the construction of compound 7l . Notably, compound 7l exhibited a better activity against T. cinnabarinus eggs (LC 50 = 0.0035 mg/L) compared to etoxazole (LC 50 = 0.2990 mg/L). Greenhouse bioassays indicated that compound 7l exhibits excellent acaricidal activity against egg of T. cinnabarinus , which is better than the etoxazole at 1.0 mg/L. Additionally, some of the compounds showed inhibitory effects against Dickeya zeae ( D. zeae ), Xanthomonas campestris pv campestris ( Xcc ), Xanthomonas oryzae pvoryza ( Xoo ), and Xanthomonas oryzae pvoryzicola ( Xoc ). Furthermore, compounds 7l not only exhibited relatively potent against Plutella xylostella activities (LC 50 = 24.0 mg/L) but also had low toxicity (LC 50 > 11.0 μg/bee) to Apis mellifera . In conclusion, the current experimental results suggest that oxazoline derivatives containing an S-S moiety have the potential to serve as lead compounds for the development of novel acaricide agents.

The reasonable design and modulation of the electronic properties of Pd metallene are acknowledged as a promising avenue for enhancing the oxygen reduction reaction (ORR) in anion exchange membrane fuel cells (AEMFCs), yet they remain a formidable challenge. Herein, a thin-sheet structure of Zr-doped Pd metallene (PdZr metallene) with abundant defects is proposed using a facile wet-chemical approach for efficient and highly durable ORR electrocatalysis. Multiple microstructural analyses uncover that orchestrated electronic and oxophilic regulation of PdZr metallene via Lewis-acidic Zr site modulation could concurrently optimize the electronic configuration of Pd, downshift the d-band center of Pd, and, thus, promote the intrinsic activity. Benefiting from the unique two-dimensional morphology and electronic structure optimization facilitated by the Zr coupling effect, the resultant PdZr metallene demonstrates significantly enhanced ORR electrocatalytic performance in basic solutions, with a high half-wave potential ( E 1/2 ) of 0.87 V and commendable stability for 30 000 s, surpassing those of Pd metallene and various advanced Pd-based catalysts reported in the literature. Encouragingly, the PdZr metallene-based AEMFC achieves an increased maximum power density (90.4 mW cm -2 ) and impressive robustness over 12 h in an alkaline environment, manifesting the practical application of PdZr metallene in AEMFCs. This study showcases the applicability of PdZr metallene via Lewis acid site regulation for fabricating highly active electrocatalysts for high-performance AEMFCs.

Nitrites (NO 2 - /HONO), as the primary source of hydroxyl radicals ( • OH) in the atmosphere, play a key role in atmospheric chemistry. However, the current understanding of the source of NO 2 - /HONO is insufficient and therefore hinders the accurate quantification of atmospheric oxidation capacity. Herein, we highlighted an overlooked HONO source by the reaction between nitrophenols (NPs) and • OH in the aqueous phase and provided kinetic data to better evaluate the contribution of this process to atmospheric HONO. Three typical NPs, including 4-nitrophenol (4NP), 2-nitrophenol (2NP), and 4-nitrocatechol (4NC), underwent a denitration process to form aqueous NO 2 - and gaseous HONO through the • OH oxidation, with the yield of NO 2 - /HONO varied from 15.0 to 33.5%. According to chemical composition and structure analysis, the reaction pathway, where the ipso addition of • OH to the NO 2 group on 4NP generated hydroquinone, can contribute to more than 61.9% of the NO 2 - /HONO formation. The aqueous photooxidation of NPs may account for HONO in the atmosphere, depending on the specific conditions. The results clearly suggest that the photooxidation of NPs should be considered in the field observation and calculation to better evaluate the HONO budget in the atmosphere.

Redox-responsive homodimer prodrug nanoassemblies (RHPNs) have emerged as a significant technology for overcoming chemotherapeutical limitations due to their high drug-loading capacity, low excipient-associated toxicity, and straightforward preparation method. Previous studies indicated that α-position disulfide bond bridged RHPNs exhibited rapid drug release rates but unsatisfactory assembly stability. In contrast, γ-disulfide bond bridged RHPNs showed better assembly stability but low drug release rates. Therefore, designing chemical linkages that ensure both stable assembly and rapid drug release remains challenging. To address this paradox of stable assembly and rapid drug release in RHPNs, we developed carbon-spaced double-disulfide bond (CSDD)-bridged RHPNs (CSDD-RHPNs) with two carbon-spaces. Pilot studies showed that CSDD-RHPNs with two carbon-spaces exhibited enhanced assembly stability, reduction-responsive drug release, and improved selective toxicity compared to α-/γ-position single disulfide bond bridged RHPNs. Based on these findings, CSDD-RHPNs with four and six carbon-spaces were designed to further investigate the properties of CSDD-RHPNs. These CSDD-RHPNs exhibited excellent assembly ability, safety, and prolonged circulation. Particularly, CSDD-RHPNs with two carbon-spaces displayed the best antitumor efficacy on 4T1 and B16-F10 tumor-bearing mice. CSDD chemical linkages offer novel perspectives on the rational design of RHPNs, potentially overcoming the design limitations regarding contradictory assembly ability and drug release rate.

Semiconductor magic-size clusters (MSCs), lying in the local minima of the potential landscape, are important intermediates that emerge during the synthesis of colloidal quantum dots. They have definite geometrical and electronic structures, thus serving as atomically precise building blocks for assembling supramolecular structures and devices with unprecedented functionalities. Here we report the intrinsic chiroptical activity in the magic-size cadmium and zinc chalcogenide clusters with magic numbers of 13, 33, and 34 possessing unique core-shell structures. They are responsive to circularly polarized light from the ultraviolet to visible region, with size-tunable energy gap, absorption wavelength, and excitonic characteristics. The origin of the chiroptical activity and the evolution of excitonic states with magic size are disclosed by time-dependent density functional theory calculations within a correlated electron-hole picture. This molecular-level understanding of the photophysical properties of group II-VI MSCs provides essential guidelines for utilizing them for chiral optoelectronics and photonics.

Nanoscale zerovalent iron synthesized using borohydride (B-NZVI) has been widely applied in environmental remediation in recent decades. However, the contribution of boron in enhancing the inherent reactivity of B-NZVI and its effectiveness in removing hexavalent chromium [Cr(VI)] have not been well recognized and quantified. To the best of our knowledge, herein, a core-shell structure of B-NZVI featuring an Fe-B alloy shell beneath the iron oxide shell is demonstrated for the first time. Alloyed boron can reduce H + , contributing to more than 35.6% of H 2 generation during acid digestion of B-NZVIs. In addition, alloyed B provides electrons for Fe 3+ reduction during Cr(VI) removal, preventing in situ passivation of the reactive particle surface. Meanwhile, the amorphous oxide shell of B-NZVI exhibits an increased defect density, promoting the release of Fe 2+ outside the shell to reduce Cr(VI), forming layer-structured precipitates and intense Fe-O bonds. Consequently, the surface-area-normalized capacity and surface reaction rate of B-NZVI are 6.5 and 6.9 times higher than those of crystalline NZVI, respectively. This study reveals the importance of alloyed B in Cr(VI) removal using B-NZVI and presents a comprehensive approach for investigating electron pathways and mechanisms involved in B-NZVIs for contaminant removal.

Introduction of chirality to colloidal semiconductor quantum dots (QDs) triggers a chiroptical effect. However, there remains a knowledge gap in the mechanism of chirality transfer and amplification from molecules to QDs. By time-dependent density functional theory calculations combined with a correlated electron-hole picture, we explored the chiroptical activity of CdSe QDs decorated with different chiral monocarboxylic acids from an excitonic perspective. Our calculations showed strong circular dichroism (CD) signals in the visible region for the chiral CdSe QDs. The excitonic states with large CD originate from QDs, while the chiral molecules break the orthogonality between electric and magnetic transition dipoles, which synergistically facilitates the prominent dissymmetric effect. The considered monocarboxylic acid chiral molecules all favor the bidentate adsorption configuration of the carboxyl group on the CdSe surface, endowing an identical CD signature but distinct excitonic characteristics. These findings are crucial for the regulation of chirality and excitons in semiconductor QDs to develop excitonic devices.

Photopharmacology is an emerging approach for achieving light-controlled drug activity. Herein, we design and synthesize a novel series of photoswitchable PI3K inhibitors by replacing a sulfonamide moiety with an azo group in a 4-methylquinazoline-based scaffold. Through structure-activity relationship studies, compound 6g is identified to be effectively switched between its trans - and cis -configuration under irradiation with proper wavelengths. Molecular docking studies show the cis -isomer of 6g is favorable to bind to the PI3K target, supporting compound 6g in the PSS 365 ( cis -isomer enriched) was more potent than that in the PSS dark ( trans -isomer dominated) in PI3K enzymatic assay, cell antiproliferative assay, Western blotting analysis on PI3K downstream effectors, cell cycle analysis, colony formation assay, and wound-healing assay. Relative to the cis -isomer, the trans -isomer is more metabolically stable and shows good pharmacokinetic properties in mice. Moreover, compound 6g inhibits tumor growth in nude mice and a zebrafish HGC-27 xenograft model.

Being a destructive pest worldwide, the whitefly Bemisia tabaci has evolved resistance to neonicotinoid insecticides. The third-generation neonicotinoid dinotefuran has commonly been applied to the control of the whitefly, but its underlying mechanism is currently unknown. On the base of our transcriptome data, here we aim to investigate whether the cytochrome P450 CYP6EM1 underlies dinotefuran resistance in the whitefly. Compared to the susceptible strain, the CYP6EM1 gene was found to be highly expressed in both laboratory and field dinotefuran-resistant populations. Upon exposure to dinotefuran, the mRNA levels of CYP6EM1 were increased. These results demonstrate the involvement of this gene in dinotefuran resistance. Loss and gain of functional studies in vivo were conducted through RNAi and transgenic Drosophila melanogaster assays, confirming the role of CYP6EM1 in conferring such resistance. In a metabolism assay in vitro, the CYP6EM1 protein could metabolize 28.11% of dinotefuran with a possible dinotefuran-dm-NNO metabolite via UPLC-QTOF/MS. Docking of dinotefuran to the CYP6EM1 protein showed a good binding affinity, with an energy of less than -6.0 kcal/mol. Overall, these results provide compelling evidence that CYP6EM1 plays a crucial role in the metabolic resistance of B. tabaci to dinotefuran. Our work provides new insights into the mechanism underlying neonicotinoid resistance and applied knowledge that can contribute to sustainable control of a global pest such as whitefly.

Polymer mechanochemistry has been established as an enabling tool in accessing chemical reactivity and reaction pathways that are distinctive from their thermal counterparts. However, eliciting diversified reaction pathways by activating different constituent chemical bonds from the same mechanophore structure remains challenging. Here, we report the design of a bicyclo[2.2.0]hexene (BCH) mechanophore to leverage its structural simplicity and relatively low molecular symmetry to demonstrate this idea of multimodal activation. Upon changing the attachment points of pendant polymer chains, three different C-C bonds in bicyclo[2.2.0]hexene are specifically activated via externally applied force by sonication. Experimental characterization confirms that in different scenarios of polymer attachment, the regioisomers of BCH undergo different activation reactions, entailing retro-[2+2] cycloreversion, 1,3-allylic migration, and retro-4π ring-opening reactions, respectively. Control experiments with small-molecule analogues reveal that the observed diversified reactivity of BCH regioisomers is possible only with mechanical force. Theoretical studies further elucidate that the differences in the positions of substitution between regioisomers have a minimal impact on the potential energy surface of the parent BCH scaffold. The mechanochemical selectivity between different C-C bonds in each constitutional isomer is a result of selective and effective coupling of force to the aligned C-C bond in each case.

Nanozyme has been proven to be an attractive and promising candidate to alleviate the current pressing medical problems. However, the unknown clinical safety and limited function beyond the catalysis of the most reported nanozymes cannot promise an ideal therapeutic outcome in further clinical application. Herein, we find that ferric maltol (FM), a clinically approved iron supplement synthesized through a facile scalable method, exhibits excellent peroxidase-like activity than natural horseradish peroxidase-like (HRP) and commonly reported Fe-based nanozymes, and also shows high antibacterial performance for methicillin-resistant Staphylococcus aureus (MRSA) elimination (100%) and wound disinfection. In addition, with added effects inherited from contained maltol, FM can accelerate skin barrier recovery. Therefore, the exploration of FM as a safe and desired nanozyme provides a timely alternative to current antibiotic therapy against drug-resistant bacteria.

Expediting the torpid kinetics of the oxygen reduction reaction (ORR) at the cathode with minimal amounts of Pt under acidic conditions plays a significant role in the development of proton exchange membrane fuel cells (PEMFCs). Herein, a novel Pt-N-C system consisting of Pt single atoms and nanoparticles anchored onto the defective carbon nanofibers is proposed as a highly active ORR catalyst (denoted as Pt-N-C). Detailed characterizations together with theoretical simulations illustrate that the strong coupling effect between different Pt sites can enrich the electron density of Pt sites, modify the d-band electronic environments, and optimize the oxygen intermediate adsorption energies, ultimately leading to significantly enhanced ORR performance. Specifically, the as-designed Pt-N-C demonstrates exceptional ORR properties with a high half-wave potential of 0.84 V. Moreover, the mass activity of Pt-N-C reaches 193.8 mA g Pt -1 at 0.9 V versus RHE, which is 8-fold greater than that of Pt/C, highlighting the enormously improved electrochemical properties. More impressively, when integrated into a membrane electrode assembly as cathode in an air-fed PEMFC, Pt-N-C achieved a higher maximum power density (655.1 mW cm -2 ) as compared to Pt/C-based batteries (376.25 mW cm -2 ), hinting at the practical application of Pt-N-C in PEMFCs.

Poly(disulfide)s are an emerging class of sulfur-containing polymers with applications in medicine, energy, and functional materials. However, the constituent dynamic covalent S-S bond is highly reactive in the presence of the sulfide (RS - ) anion, imposing a persistent challenge to control the polymerization. Here, we report an anion-binding approach to arrest the high reactivity of the RS - chain end to control the synthesis of linear poly(disulfide)s, realizing a rapid, living ring-opening polymerization of 1,2-dithiolanes with narrow dispersity and high regioselectivity ( M w / M n ∼ 1.1, P s ∼ 0.85). Mechanistic studies support the formation of a thiourea-base-sulfide ternary complex as the catalytically active species during the chain propagation. Theoretical analyses reveal a synergistic catalytic model where the catalyst preorganizes the protonated base and anionic chain end to establish spatial confinement over the bound monomer, effecting the observed regioselectivity. The catalytic system is amenable to monomers with various functional groups, and semicrystalline polymers are also obtained from lipoic acid derivatives by enhancing the regioselectivity.

This study aimed to explore the effects of preslaughter transport stress on protein S-nitrosylation levels and S-nitrosylated proteome in post-mortem pork longissimus thoracis (LT) muscle. Pigs ( N = 16) were randomly divided into 3 h transport (high-stress group, HS) and 3 h transport followed by 3 h resting treatments (low-stress control group, LS). Results demonstrated that high transport stress levels induced nitric oxide (NO) overproduction by promoting NO synthase (NOS) activity and neuronal NOS (nNOS) expression, which thereby notably increased protein S-nitrosylation levels in post-mortem muscle ( p < 0.05). Proteomic analysis indicated that 133 S-nitrosylation-modified cysteines belonging to 85 proteins were significantly differential, of which 101 cysteines of 63 proteins were higher in the HS group ( p < 0.05). Differential proteins including cytoskeletal and calcium-handling proteins, glycolytic enzymes, and oxidoreductase were mainly involved in the regulation of muscle contraction and energy metabolism that might together mediate meat quality development. Overall, this study provided direct evidence for changes in S-nitrosylation levels and proteome in post-mortem muscle in response to preslaughter transport stress and revealed the potential impact of S-nitrosylated proteins on meat quality.

Developing signal tracers (STAs) with large size, multifunctionality, and high retention bioaffinity is believed to be a potential solution for achieving high-performance immunochromatographic assays (ICAs). However, the size limitations of STAs on strips are always a challenge because of the serious steric hindrance. Here, based on metal-quinone coordination and further metal etching, hollow micron-tubular STAs formed by natural alizarin and Fe 3+ ions (named ALIFe) are produced to break through size limitations, provide more active sites, and achieve three-mode ICAs (ALIFe STAs-ICAs). Thanks to the special tubular morphology, ALIFe can successfully pass through the strip and provide an ideal signal intensity within 7 min at low mAb and probe dosages to achieve stable ICA analysis. Importantly, ALIFe shows excellent antibody enrichment and bioaffinity retention capability. With a proof-of-concept for streptomycin, the ALIFe STAs-ICAs showed the limit of detection (LOD) at 0.39 ng mL -1 for colorimetric mode, 0.32 ng mL -1 for catalytic mode, and 0.016 ng mL -1 for photothermal mode with total recoveries ranging from 80.46 to 121.59% in mike and honey samples. We anticipate that our study will help expand the ideas for the design of high-performance STAs with large size and broaden the practical application of ICA.

PARP-1/2 inhibitors have become an important therapeutic strategy for the treatment of HR-deficient tumors. However, discovery of new inhibitors with an improved and distinct pharmacological file still need enormous explorations. Herein, a series of novel highly potent PARP-1/2 inhibitors bearing an N -substituted piperazinone moiety were achieved. In particular, Cpd36 was identified as a distinct PARP inhibitor, showing remarkable enzymatic activity not only toward PARP-1 (IC 50 = 0.94 nM) and PARP-2 (IC 50 = 0.87 nM) but also toward PARP-7 (IC 50 = 0.21 nM), as well as high selectivity over other PARP isoforms. Furthermore, Cpd36 was orally bioavailable and significantly repressed the tumor growth in both breast cancer and prostate cancer xenograft model. The crystal structures of Cpd36 within PARP-1 and PARP-2 together with the predicted binding mode within PARP-7 revealed its binding features and provided insightful information for further developing highly potent and selective PARP-1 and/or PARP-7 inhibitors.

Traditional disposable personal protective equipment (PPE) only blocks pathogenic bacteria by mechanical filtration, with the risk of recontamination and transmission remaining. Herein, inspired by phenolic-enabled nanotechnology (PEN), we proposed engineered polyphenol coatings by plant-derived aromatic aldehydes and metal involvement, denoted as FQM, to obtain the desired photocatalysis-self-Fenton antibacterial performance. Experiments and theoretical analysis proved the dual mechanism of Fe-induced enhancement: (1) tuning of molecular structure realized improved optical properties; (2) Fe(III)/Fe(II) triggered photocatalytic cascade self-Fenton reaction. Mechanism study reveals FQM killing bacteria by direct-contact ROS attack and gene regulation. Further, the FQM was developed as the ideal antibacterial coating on different fabrics (cloth cotton, polyester, and N95 mask), killing more than 93% of bacteria after 5 cycles of use. Such photocatalysis-self-Fenton coatings based on engineered polyphenols endowed with desirable safety, sustainability, and efficient antibacterial features are promising solutions to meet the challenges of the currently available PPE.

The filamin C (FLNC) was hypothesized to be colocalized with its certain binding partners in pork tissues and calpain as well as caspase was assumed responsible for the postmortem degradation of FLNC. Therefore, the specific distribution of pork FLNC and its degradation pattern during postmortem aging were investigated in this study. The longissimus thoracis muscles from 12 pigs were removed from the carcasses and then aged at 4 °C for 1, 6, 12, 24, 72, and 168 h, respectively. The FLNC signals appeared to localize in subsarcolemmal areas by cross-sectional images, while the localization was found surrounding the myofibrils at the level of the Z-discs in longitudinal sections. FLNC displayed a highly overlapped spatial colocalization with actin or integrin. Western blot results showed that the intact 290 kDa FLNC was rapidly degraded to produce an approximately 280 kDa band. An almost overlapped distribution pattern was observed between FLNC and μ-calpain or caspase-3 in porcine skeletal muscle cells. Moreover, both the μ-calpain inhibitor and the caspase-3 inhibitor could inhibit the degradation of FLNC in porcine LT muscles during postmortem aging.

As glutaminase C (GAC) has become an attractive target for cancer treatment by regulating glutaminolysis, thus, interest in GAC inhibitors has risen in recent years. Herein, a potential binding subpocket comprising basic residues was identified, and through extensive structure-activity relationship studies, promising inhibitors 11 and 39 were identified with robust GAC inhibitory activity and A549 cell antiproliferative activity. X-ray crystallography of the 11 -GAC and 27 -GAC complexes revealed a novel binding mode against GAC. The potency of 11 and 27 against GAC K320A further highlighted the importance of the binding. Notably, compounds 11 and 39 regulated the cellular metabolite, thereby increasing reactive oxygen species by blocking glutamine metabolism. Compound 11 also exhibited excellent antiproliferative activity in the A549 cell xenograft model. We further proved that 11 is a safe GAC allosteric inhibitor. A basic subpocket is proposed that might provide new strategies for the development of novel GAC inhibitors in the future., Competing Interests: The authors declare no competing financial interest., (© 2023 American Chemical Society.)

A novel photocaged PI3K inhibitor 2 was designed and synthesized by introducing a cascade photocaging group to block its key interaction with the kinase. Upon UV light irradiation, the photocaged compound released a highly potent PI3K inhibitor to recover its anticancer properties and a fluorescent dye for real-time reporting of drug release, providing a new approach for studying the PI3K signaling transduction pathway as well as developing precisely controlled cancer therapeutics., Competing Interests: The authors declare no competing financial interest., (© 2023 American Chemical Society.)

A convergent (outside-to-center) route was adopted to synthesize the precursors of quinoidal compounds in high yields of 85-93%. With subsequent rearrangement/dehydroxylation and oxidation, a series of thiophene-based quinoids with indandione or oxindole terminal groups were successfully synthesized. This strategy shows good compatibility with versatile central and terminal units, leading to quinoidal compounds with tunable properties.

There are many treatments for nasopharyngeal carcinoma (NPC), but none of them are very effective. Radiotherapy is used extensively in NPC treatment, but radioresistance is a major problem. Graphene oxide (GO) has been previously studied in cancer treatment, and this study is aimed to explore its role in radiosensitization of NPC. Therefore, graphene oxide nanosheets were prepared, and the relationship between GO and radioresistance was explored. The GO nanosheets were synthesized by a modified Hummers' method. The morphologies of the GO nanosheets were characterized by field-emission environmental scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The morphological changes and radiosensitivity of C666-1 and HK-1 cells with or without the GO nanosheets were observed by an inverted fluorescence microscopy and laser scanning confocal microscopy (LSCM). Colony formation assay and Western Blot were applied for analysis of NPC radiosensitivity. The as-synthesized GO nanosheets have lateral dimensions (sizes ∼1 μm) and exhibit a thin wrinkled two-dimensional lamellar structure with slight folds and crimped edges (thickness values ∼1 nm). C666-1 cells with the GO was significantly changed the morphology of cells postirradiation. The full field of view visualized by a microscope showed the shadow of dead cells or cell debris. The synthesized graphene oxide nanosheets inhibited cell proliferation, promoted cell apoptosis, and inhibited the expression of Bcl-2 in C666-1 and HK-1 cells but increased the level of Bax. The GO nanosheets could affect the cell apoptosis and reduce the pro-survival protein Bcl-2 related to the intrinsic mitochondrial pathway. The GO nanosheets could enhance radiosensitivity, which might be a radioactive material in NPC cells.

Owing to the unique geometric structure of dendritic amphiphiles with voluminous dendrons, their micelles can harbor a large void space, which provides a new research focus and approach for micellar functionalization. In this work, we used the void space to construct a UV responsive micelle system of the mixed dendritic amphiphile (C 12 -(G3) 2 ) and cationic azobenzene surfactant (C4AzoTAB). The synthesized C 12 -(G3) 2 that possesses double third generation polyglycerol (PG) dendrons and a single alkyl chain is expected to highlight the large void space within the inside of the micelles. Thus, the aims of this work are to achieve the isomerization of C4AzoTAB in situ and to deeply understand the intermolecular interaction in the mixed micelles. The effect of the large void room with a wall decorated with the ether oxygen atoms on the isomerization of C4AzoTAB was studied by isomerization kinetics, conductivity measurements, isothermal titration calorimetry (ITC), and 1 H NMR and 2D NOESY spectroscopies. The isomerization behavior of C4AzoTAB in C 12 -(G3) 2 micelles was presented in terms of its kinetic constant, counterionic association, interaction enthalpy, and position and orientation of C4AzoTAB. The results of NMR and conductivity show that the quaternary ammonium group of C4AzoTAB situates on the surface of the mixed micelles with C 12 -(G3) 2 both before and after UV-irradiation, while the position of azobenzene group in C 12 -(G3) 2 micelles depends on its conformation. The C 12 -(G3) 2 micelles can inhibit the UV response of the trans -isomer and activate the thermal relaxation of the cis -isomer, which has a potential application in the field of light-controlled smart nanocarriers.

Nanoplastics (NPs), as emerging contaminants, have attracted increasing attention for their effects on human exposure and potential health risks. The protein corona formed on the surface of NPs affects the biological activity and fate of the NPs in vivo . However, how environmental aging, an inevitable process once NPs enter the environment, affects the formation of protein corona on NPs is still unclear. This study investigated the changes in the compositions of protein corona formed on photo-aged polystyrene (PS) NPs in human bronchoalveolar lavage fluid (BALF), corresponding to the inhalation exposure pathway. The results demonstrated that both the species and abundance of proteins in the BALF protein corona on the surface of PS NPs were altered by aging. In addition, the aged PS NPs are more hydrophilic and less electronegative than the pristine PS NPs; hence, there is an increased sorption of more negatively charged hydrophilic proteins. Moreover, aging-induced alterations in BALF protein corona enhanced the uptake of aged PS NPs by lung macrophages J774A.1 through phagocytosis and clathrin-mediated endocytosis. These findings highlight the importance of environmental aging processes in the biosafety assessment of nanoplastics.

High levels of steady-state mitochondrial reactive oxygen species (ROS) and glycolysis are hallmarks of cancer. An improved understanding of interactions between tumor energetics and mitochondrial ROS modulation is useful for the development of new anticancer strategies. Here, we show that the natural product chlorogenic acid ( CGA ) specifically scavenged abnormally elevated mitochondrial O 2 •- and exhibited a two-photon fluorescence turn-on response to tumor cells under hypoxia and tumor tissues in vivo . Furthermore, we illustrated that CGA treatment reduced O 2 •- levels in cells, hampered activation of AMP-activated protein kinase (AMPK), and shifted metabolism from glycolysis to oxidative phosphorylation (OXPHOS), resulting in inhibition of tumor growth under hypoxia. This study demonstrates an efficient two-photon fluorescent tool for real-time assessment of mitochondrial O 2 •- and a clear link between reducing intracellular ROS levels by CGA treatments and regulating metabolism, as well as undeniably helpful insights for the development of new anticancer strategies.

Bemisia tabaci has developed high resistance to many insecticides and causes substantial agricultural and economic losses annually. The insecticide resistance of whitefly has been widely reported in previous studies; however, the underlying mechanism remains little known. In this study, we cloned two P450 genes: CYP6DW3 and CYP6DW5v1; these genes were markedly overexpressed in imidacloprid-resistant whitefly populations compared with susceptible populations, and knockdown of these genes decreased the imidacloprid resistance of whitefly. Moreover, heterologous expression of whitefly P450 genes in SF9 cells and metabolic studies showed that the CYP6DW3 protein could metabolize 14.11% imidacloprid and produced imidacloprid-urea in vitro . Collectively, the expression levels of CYP6DW3 and CYP6DW5v1 are positively correlated with imidacloprid resistance in B. tabaci . Our study further reveals that cytochrome P450 enzymes affect the physiological activities related to resistance in insects, which helps scholars more deeply understand the resistance mechanism, and contributes to the development of integrated pest management framework.

Targeting the colchicine binding site on tubulin is a promising strategy to develop cancer therapeutics. Herein, we describe our systematic structure-activity relationship studies of benzamide derivatives that lead to an identification of a potent and orally active tubulin inhibitor 48 , which occupied all three zones of the colchicine binding site in the X-ray co-crystal structure, inhibited tubulin polymerization, promoted mitotic blockade and apoptosis, and exhibited significant antiproliferative activities against various cancer cell lines. Compound 48 demonstrated favorable pharmacokinetic profiles, robust in vivo antitumor efficacies, and acceptable safety profiles. Furthermore, 48 overcame drug resistance in the paclitaxel-resistant A549 xenograft model. Collectively, 48 has been advanced into further preclinical evaluation for the development of next-generation microtubule-targeting drugs.

The high systemic blood glucose concentration of hyperglycemic wound microenvironment (WME) severely impedes the disinfection and healing of infected skin wounds. Herein, a WME-activated smart natural product, integrated GOx-GA-Fe nanozyme (GGFzyme), is engineered, which combines a nanozyme and natural enzyme to promote reactive oxygen species (ROS) generation in situ for hyperglycemic wound disinfection. GGFzyme can consume a high concentration of glucose in hyperglycemia wounds and generate H 2 O 2 . The conversion of glucose into gluconic acid not avails starvation treatment but reduces the pH of WME to elevate the catalytic activities of both the nanozyme (GA-Fe) and natural enzyme (GOx). And H 2 O 2 is then high efficiently catalyzed into • OH and O 2 •- in situ to combat pathogenic bacteria and promote wound disinfection. The high catalytic antibacterial capacity and superior biosafety, combined with beneficial WME modulation, demonstrate that GGFzyme is a promising therapeutic agent for hyperglycemic wounds.

Daytime radiative cooling technology can release heat into outer space without consuming any electricity during the day while reflecting as much solar radiation as possible. This characteristic gives radiative cooling materials considerable application potential in the fields of energy-saving buildings, fabrics, and photovoltaic cells. The radiative cooling coating (RC coating) applied to a building should cover a large area of the building surface, so a RC coating was prepared by spraying. The RC coating consisted of highly near-infrared reflective yttrium oxide (Y 2 O 3 ), titanium dioxide (TiO 2 ), and polydimethylsiloxane (PDMS). The RC coating could reach a high solar reflectance of 92.2% and a high atmospheric window emissivity of 94.9%. The complementary reflectivity of TiO 2 and Y 2 O 3 was the key to obtaining high reflectivity for RC coatings. The results of field tests showed that the cavity where the RC coating is cooled was 7.7 °C lower than the ambient temperature under direct sunlight. Moreover, the average radiative cooling power of the RC coating was 72.5 W/m 2 on a hot summer day. In addition, the RC coating has good stability and thus can be used in various conditions, such as on outdoor buildings.

Selectively anchoring active centers on the external surface for forming highly exposed acid sites is a highly desirable but challenging task in zeolite catalyst synthesis. Herein, a defect-guided etching-regrowth strategy is rationally designed for facilely positioning Sn Lewis acid sites on the outer surface of the Sn-B-Beta while fabricating a bifunctional hierarchical structure. The synthesis was conducted by hydrothermal treatment of the as-made B-Beta (uncalcined), which has intrinsic defects of the BEA structure, with Sn source and basic organic structure directing agent (SDA). Under a moderate SDA concentration, with blocked micropore channels, such SDA-triggered etching-regrowth will proceed along the defect defined pathway, which ensures Sn selectively anchored on the external surface. Moreover, this methodology has exclusively introduced tetrahedrally coordinated framework Sn with open Sn sites as the predominated species. Mono- and disaccharide isomerizations in ethanol over different Sn-Beta catalysts proved the prominent advantages of the hierarchical structure with highly exposed and synergetic acid sites.

Simultaneously improving the strength and toughness of materials is a major challenge. Inorganic-polymer hybrids offer the potential to combine mechanical properties of a stiff inorganic glass with a flexible organic polymer. However, the toughening mechanism at the atomic scale remains largely unknown. Based on combined experimental and molecular dynamics simulation results, we find that the deformation and fracture behavior of hybrids are governed by noncovalent intermolecular interactions between polymer and silica networks rather than the breakage of covalent bonds. We then attempt three methods to improve the balance between strength and toughness of hybrids, namely the total inorganic/organic (I/O) weight ratio, the size of silica nanoparticles, and the ratio of -C-O vs -C-C bonds in the polymer chains. Specifically, for a hybrid with matched silica size and I/O ratio, we demonstrate optimized mechanical properties in terms of strength (1.75 MPa at breakage), degree of elongation at the fracture point (31%), toughness (219 kPa), hardness (1.08 MPa), as well as Young's modulus (3.0 MPa). We also demonstrate that this hybrid material shows excellent biocompatibility and ability to support cell attachment as well as proliferation. This supports the possible application of this material as a strong yet tough bone scaffold material.

Globally, bladder cancer (BLC) is one of the most common cancers and has a high recurrence and mortality rate. Current clinical diagnostic approaches are either invasive or inaccurate. Here, we report on a cost-efficient, artificially intelligent chemiresistive sensor array made of polyaniline (PANI) derivatives that can noninvasively diagnose BLC at an early stage and maintain postoperative surveillance through ″smelling″ clinical urine samples at room temperature. In clinical trials, 18 healthy controls and 76 BLC patients (60 and 16 at early and advanced stages, respectively) are assessed by the artificial olfactory system. With the assistance of a support vector machine (SVM), very high sensitivity and accuracy from healthy controls are achieved, exceeding those obtained by the current techniques in practice. In addition, the recurrences of both early and advanced stages are diagnosed well, with the effect of confounding factors on the performance of the artificial olfactory system found to have a negligible influence on the diagnostic performance. Overall, this study contributes a novel, noninvasive, easy-to-use, inexpensive, real-time, accurate method for urine disease diagnosis, which can be useful for personalized care/diagnosis and postoperative surveillance, resulting in saving more lives.

Ideal bone implant materials need to provide multiple functions such as biocompatibility, non-cytotoxicity, and bone tissue regeneration guidance. To tackle this challenge, according to our previous work, carbon fiber (40 mm)-reinforced polyetheretherketone (CFPEEK) composites were developed by using 3D needle-punched CFPEEK preform molding technology. Because of the excellent mechanical properties, the CFPEEK needled felt matrix composites have a broad application prospect in orthopedic internal fixation and implant materials. In order to expand the application range of composite materials, it is very necessary to improve the surface bioactivity of composite materials. The surface modification of CFPEEK with 2D titanium carbide (MXene) nanosheets (sulfonated CFPEEK (SCFPEEK)-polydopamine (PDA)-Ti 3 C 2 T x ) for enhanced photothermal antibacterial activity and osteogenicity was explored in this study. Here, the new composites we constructed are composed of Ti 3 C 2 T x nanosheets, PDA, and biologically inert SCFPEEK, which gave the bio-inert composites bimodal therapeutic features: photothermal antibacterial activity and in vivo osseointegration. To our knowledge, this is the first time that a CFPEEK implant with a bioactive surface modified by Ti 3 C 2 T x nanosheets was demonstrated. Due to the synergistic photothermal therapy (PTT) treatment of Ti 3 C 2 T x /PDA, SCFPEEK-PDA-Ti 3 C 2 T x (SCP-PDA-Ti) absorbed heat and the temperature increased to 40.8-59.6 °C─the high temperature led to bacterial apoptosis. The SCP-PDA-Ti materials could effectively kill bacteria after 10 min of near-infrared (NIR) irradiation at 808 nm. SCP-PDA-Ti (2.5) and SCP-PDA-Ti (3.0) achieved a 100% bacteriostasis rate. More importantly, the multifunctional implant SCP-PDA-Ti shows good cytocompatibility and an excellent ability to promote bone formation in terms of cytotoxicity, diffusion, alkaline phosphatase activity, alizarin red activity, real-time polymerase chain reaction analysis, and in vivo bone defect osteogenesis experiments. This provides a more extendable development idea for the application of carbon fiber-reinforced composites as orthopedic implants.

The effects of antibiotics on bacterial infections are gradually weakened, leading to the wide development of nanoparticle-based antibacterial agents with unique physical and chemical properties and antibacterial mechanisms different from antibiotics. In this study, we fabricated the uniform and stable graphene oxide (GO)/Ni colloidal nanocrystal cluster (NCNC) nanocomposite by electrostatic self-assembly and investigated its synergistic antibacterial activity against Staphylococcus aureus ( S. aureus ) and Escherichia coli ( E. coli ) in vitro. The GO/NCNC nanocomposite was shown to possess higher inhibition efficiency than a pure NCNC or GO suspension, with 99.5 and 100% inhibition against S. aureus and E. coli at a 125 μg/mL concentration, respectively. Antibacterial mechanism analysis revealed that (i) NCNCs decorated on GO can further enhance the antibacterial properties of GO by binding and capturing bacteria, (ii) the leaching of Ni 2+ was detected during the interaction of GO/NCNCs and bacteria, resulting in a decrease in the number of bacteria, and (iii) the GO/NCNC nanocomposite can synergistically destroy the bacterial membrane through physical action and induce the reactive oxygen species generation, so as to further damage the cell membrane and affect ATPase, leakage of intercellular contents, and ultimately bacterial growth inhibition. Meanwhile, cell culture experiments demonstrated no adverse effect of GO/NCNCs on cell growth. These preliminary results indicate the high antibacterial efficiency of the GO/NCNC nanocomposite, suggesting the possibility to develop it into an effective antibacterial agent in the future against bacterial infections., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Wound healing greatly affects patients' health and produces medical burden. Therefore, we developed a multifunctional electrospun nanofiber dressing, which can inhibit methicillin-resistant Staphylococcus aureus (MRSA), drain excessive biofluid to promote wound healing, and simultaneously monitor wound pH level. The polyoxometalate (α-K 6 P 2 W 18 O 62 ·14H 2 O, P 2 W 18 ) and oxacillin (OXA) are encapsulated in hydrophobic polylactide (PLA) nanofiber to synergistically inhibit MRSA. The phenol red (PSP) is encapsulated in hydrophilic polyacrylonitrile (PAN) nanofiber to sensitively indicate wound pH in situ . The PSP/PAN nanofiber is directly electrospun on the patterning OXA/P 2 W 18 /PLA nanofiber layer to form a Janus dressing. By taking advantage of the wettability difference between the two layers, the excess biofluid can be drained away from the wound. In addition, the Janus dressing exhibits good biocompatibility and accelerates wound healing via its antimicrobial activity and skin repairing function. This multifunctional Janus electrospun nanofiber dressing would be beneficial for wound management and treatment.

Phosphate-based cathode materials attract much more attention and are widely used as energy storage materials based on their high economic efficiency and eco-friendly property, their stable potential plateau, and their high thermodynamic stability. A new phosphate family member, Zn 2 Fe(PO 4 ) 2 (ZFP), was successfully explored and synthesized by the scalable high-temperature annealing method, followed by coating a thin carbon layer to optimize the electrotonic conductivity. This obtained ZFP featuring with a tunnel structure can be utilized as a cathode material for Zn 2+ ion extraction and insertion, in which Zn 2+ ion diffusion behaviors primarily contribute the specific capacity. Based on the actual reversible capacity of ZFP@C of 73 mA h g -1 , the application for zinc ion batteries (ZIBs) has potential due to its long life span. The electrochemical performance is primarily contributed from the high Zn 2+ ion diffusion rate and low apparent activation energy. This new explored ZFP can accelerate the development of realizing ZIBs with long life span.

Oxidative stress is related to many diseases, but available clinical treatment methods are currently limited. Exploitation of enzyme-mimicking nanomaterials (nanozymes) is a promising way for scavenging reactive oxygen species (ROS) and treatment of ROS-related diseases. Herein, the catalase (CAT), superoxide dismutase (SOD), and glutathione peroxidase (GP x ) mimicking activities are expressed by MnO 2 nanoparticles (MnO 2 - BSA NPs) coated with BSA. Effective • OH removal activity is also expressed by MnO 2 - BSA NPs at neutral pH. Apoptosis inhibition and ROS scavenging capabilities of MnO 2 - BSA NPs are evident on the H 2 O 2 -exposed BEAS-2B cells line. Western blot analysis indicates that MnO 2 - BSA NPs inhibit H 2 O 2 -induced apoptosis by mediating the expression of apoptosis-related proteins.

Antisolvent-assisted spin coating has been widely used for fabricating metal halide perovskite films with smooth and compact morphology. However, localized nanoscale inhomogeneities exist in these films owing to rapid crystallization, undermining their overall optoelectronic performance. Here, we show that by relaxing the requirement for film smoothness, outstanding film quality can be obtained simply through a post-annealing grain growth process without passivation agents. The morphological changes, driven by a vaporized methylammonium chloride (MACl)-dimethylformamide (DMF) solution, lead to comprehensive defect elimination. Our nanoscale characterization visualizes the local defective clusters in the as-deposited film and their elimination following treatment, which couples with the observation of emissive grain boundaries and excellent inter- and intragrain optoelectronic uniformity in the polycrystalline film. Overcoming these performance-limiting inhomogeneities results in the enhancement of the photoresponse to low-light (<0.1 mW cm -2 ) illumination by up to 40-fold, yielding high-performance photodiodes with superior low-light detection.

Multiplex lateral flow immunoassay (mLFIA) has attracted great attention due to the increasing need for rapid detection of multiple analytes. However, it has a number of disadvantages with regard to accuracy and interference because of difficulties in simplifying the process of preparing nanomaterial-based probes. In this work, inspired by protein self-assembly, for the first time, a facile natural antibody network (NAN)-based mLFIA for multiple chloramphenicol (CAP) and streptomycin (STR) determination was designed. The NAN structure was constructed by introducing a second antibody (Ab 2 ) as a scaffold to noncovalently combine with various monoclonal antibodies (mAbs), thus permitting each mAb to act as an independent functional unit to maintain bioactivity. Furthermore, the NAN was colored by simple one-step staining using coomassie brilliant blue R-250 (CBBR) to form a chromogenic probe, eliminating the need for complex nanomaterials to improve reproducibility and precision. Under optimal conditions, a satisfactory detection performance (the visual limit of detection (v-LOD) of 3 ng mL -1 for CAP and 20 ng mL -1 for STR) was obtained for whole milk analysis, which met the basic requirement of detection and had good specificity, reproducibility (relative standard deviation (RSD) < 15%), and robustness. In addition, the precision of the detection results was improved usefully since the test procedure was simplified. Overall, the developed system enables fast, simple, and reliable point-of-care assays of multiple analytes.

Phosphorene nanoribbons (PNRs) have been widely predicted to exhibit a range of superlative functional properties; however, because they have only recently been isolated, these properties are yet to be shown to translate to improved performance in any application. PNRs show particular promise for optoelectronics, given their predicted high exciton binding energies, tunable bandgaps, and ultrahigh hole mobilities. Here, we verify the theorized enhanced hole mobility in both solar cells and space-charge-limited-current devices, demonstrating the potential for PNRs improving hole extraction in universal optoelectronic applications. Specifically, PNRs are demonstrated to act as an effective charge-selective interlayer by enhancing hole extraction from polycrystalline methylammonium lead iodide (MAPbI 3 ) perovskite to the poly(triarylamine) semiconductor. Introducing PNRs at the hole-transport/MAPbI 3 interface achieves fill factors above 0.83 and efficiencies exceeding 21% for planar p-i-n (inverted) perovskite solar cells (PSCs). Such efficiencies are typically only reported for single-crystalline MAPbI 3 -based inverted PSCs. Methylammonium-free PSCs also benefit from a PNR interlayer, verifying applicability to architectures incorporating mixed perovskite absorber layers. Device photoluminescence and transient absorption spectroscopy are used to demonstrate that the presence of the PNRs drives more effective carrier extraction. Isolation of the PNRs in space-charge-limited-current hole-only devices improves both hole mobility and conductivity, demonstrating applicability beyond PSCs. This work provides primary experimental evidence that the predicted superlative functional properties of PNRs indeed translate to improved optoelectronic performance.

Thin films of amorphous alumina (a-Al 2 O 3 ) have recently been found to deform permanently up to 100% elongation without fracture at room temperature. If the underlying ductile deformation mechanism can be understood at the nanoscale and exploited in bulk samples, it could help to facilitate the design of damage-tolerant glassy materials, the holy grail within glass science. Here, based on atomistic simulations and classification-based machine learning, we reveal that the propensity of a-Al 2 O 3 to exhibit nanoscale ductility is encoded in its static (nonstrained) structure. By considering the fracture response of a series of a-Al 2 O 3 systems quenched under varying pressure, we demonstrate that the degree of nanoductility is correlated with the number of bond switching events, specifically the fraction of 5- and 6-fold coordinated Al atoms, which are able to decrease their coordination numbers under stress. In turn, we find that the tendency for bond switching can be predicted based on a nonintuitive structural descriptor calculated based on the static structure, namely, the recently developed "softness" metric as determined from machine learning. Importantly, the softness metric is here trained from the spontaneous dynamics of the system ( i . e ., under zero strain) but, interestingly, is able to readily predict the fracture behavior of the glass ( i . e ., under strain). That is, lower softness facilitates Al bond switching and the local accumulation of high-softness regions leads to rapid crack propagation. These results are helpful for designing glass formulations with improved resistance to fracture.

Additive engineering is emerging as a powerful strategy to further enhance the performance of perovskite solar cells (PSCs), with the incorporation of bulky cations and amino acid (AA) derivatives being shown as a promising strategy for enhanced device stability. However, the incorporation of such additives typically results in photocurrent losses owing to their saturated carbon backbones, hindering charge transport and collection. Here, we investigate the use of AAs with varying carbon chain lengths as zwitterionic additives to enhance the PSC device stability, in air and nitrogen, under illumination. We, however, discovered that the device stability is insensitive to the chain length as the anticipated photocurrent drops as the chain length increases. Using glycine as an additive results in an improvement in the open circuit voltage from 1.10 to 1.14 V and a resulting power conversion efficiency of 20.2% (20.1% stabilized). Using time-of-flight secondary ion mass spectrometry, we confirm that the AAs reside at the surfaces and interfaces of our perovskite films and propose the mechanisms by which stability is enhanced. We highlight this with glycine as an additive, whereby an 8-fold increase in the device lifetime in ambient air at 1 sun illumination is recorded. Short-circuit photoluminescence quenching of complete devices is reported, which reveals that the loss in photocurrent density observed with longer carbon chain AAs results from the inefficient charge extraction from the perovskite absorber layer. These combined results demonstrate new fundamental understandings about the photophysical processes of additive engineering using AAs and provide a significant step forward in improving the stability of high-performance PSCs.