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Pulsed dipolar electron paramagnetic resonance (PD-EPR) measurement is a powerful technique for characterizing the interactions and conformational changes of biomolecules. The extraction of these distance restraints from PD-EPR experiments relies on manipulation of spin-spin pairs. The orthogonal spin labeling approach offers unique advantages by providing multiple distances between different spin-spin pairs. Here, we report an efficient orthogonal labeling approach based on exploiting the cyclization between the 1,2-aminothiol moiety in a protein (e.g., the N-terminal cysteine) with the aldehyde group in a spin label and a thiol substitution (or addition) reaction with a different spin label. We demonstrated that this orthogonal spin labeling method enables high accuracy and precision of multiple protein distance constraints through the PD-EPR measurement from a single sample. This spin labeling approach was applied to characterize the oligomeric state of the trigger factor (TF) protein of Escherichia coli , an important protein chaperone, in solution and cell lysates by distance measurements between different spin-spin pairs. Contrary to popular belief, TF exists mainly in the monomeric state and not as a dimer in the cell lysate.

The electrocatalytic reaction pathway is highly dependent on the intrinsic structure of the catalyst. CO 2 /CO electroreduction has recently emerged as a potential approach for obtaining C 2+ products, but it is challenging to achieve high selectivity for a single C 2+ product. Herein, we develop a Cu atomic ensemble that satisfies the appropriate site distance and coordination environment required for electrocatalytic CO-to-acetate conversion, which shows outstanding overall performance with an acetate Faradaic efficiency of 70.2% with a partial current density of 225 mA cm -2 and a formation rate of 2.1 mmol h -1 cm -2 . Moreover, a single-pass CO conversion rate of 91% and remarkable stability can be also obtained. Detailed experimental and theoretical investigations confirm the significant advantages of the Cu atomic ensembles in optimizing C-C coupling, stabilizing key ketene intermediate (*CCO), and inhibiting the *HOCCOH intermediate, which can switch the CO reduction pathway from the ethanol/ethylene on the conventional metallic Cu site to the acetate on the Cu atomic ensembles.

Glutaminyl cyclases, including glutaminyl-peptide cyclotransferase (QPCT) and glutaminyl-peptide cyclotransferase-like protein (QPCTL), primarily catalyze the cyclization of N-terminal glutamine or glutamate to pyroglutamate (pGlu). QPCTL, in particular, modifies the N-terminus of CD47, thereby regulating its interaction with signal-regulatory protein alpha (SIRPα) and modulating phagocytosis of tumor cells by immune cells. Additionally, QPCTL cyclizes the N-termini of CCL2, CCL7, and CX3CL1, influencing the tumor microenvironment and inflammatory responses in cancer and other disorders. Consequently, QPCTL is considered a valuable therapeutic target for several human diseases. However, the development of QPCTL inhibitors remains in its early stages. This perspective summarizes the structural features, catalytic mechanisms, and biological functions of QPCTL, along with its recent advances in small-molecule inhibitors. It provides valuable insights into the development of novel QPCTL inhibitors.

Cardiac troponin I (cTnI) is a highly sensitive and important serological marker for clinical diagnosis of myocardial injury. Its rapid detection is crucial for the early diagnosis of cardiovascular diseases such as acute myocardial infarction. In this study, based on nucleic acid molecular hybridization and aptamer-specific binding to target molecules, a label-free liquid crystal aptamer sensor based on single-stranded nucleic acid π-structures was developed and applied for the quantitative detection of cTnI. The CP1 and CP2 oligonucleotide chains, complementary to the bases at both ends of the aptamer, are covalently bonded to the sensor substrate via APTES and GA-mediated molecules. The aptamer forms a π-structure with CP1 and CP2 through nucleic acid hybridization, serving as a target molecule capture probe. When cTnI is present in the system, cTnI and the complementary oligonucleotide chains competitively bind with the aptamer, causing the breakdown of the π-structure within the sensor. This reinstates the long-range ordered alignment of the 5CB liquid crystal molecules within the sensor, enabling quantitative measurement of cTnI through variations in optical images. Experimental results show that within the range of 0.01 to 25 ng/mL for cTnI concentration, there is a linear correlation between the brightness area coverage (Br) in the polarized light microscopy images of the sensor and the logarithm of the cTnI concentration, with a correlation coefficient ( r ). The detection limit is 5.16 pg/mL. This method is label-free, simple to operate, and low-cost, with good specificity and a low detection limit, achieving cTnI detection in serum samples.

For Cu-exchanged zeolite catalysts, Cu 2+ ions existing as Cu 2+ -2Z and [Cu(OH)] + -Z (where Z represents a framework negative charge) are considered the active sites for the selective catalytic reduction of NO x with NH 3 (NH 3 -SCR). Cu 2+ -2Z is more hydrothermally stable and sulfur poisoning-resistant than [Cu(OH)] + -Z. In this work, Cu-CHA and Cu-LTA catalysts containing only Cu 2+ -2Z species were successfully synthesized by a novel impregnation (NIM) method, exhibiting remarkably enhanced hydrothermal stability and sulfur resistance compared with any reported Cu-exchanged zeolite catalysts. It was also found that the [Cu(OH)] + -Z sites can convert to Cu 2+ -2Z by treating at high temperature (850 °C) due to the self-reduction of Cu 2+ to highly mobile Cu + . The use of the NIM method not only significantly simplifies the preparation of the catalysts but also can precisely control the Cu loading, which is very important for the control of Cu species. Many other zeolite catalysts can be prepared by this method.

One of the important factors leading to lithium dendrites is a slow lithium-ion mass transport and imbalanced distribution of the Li + concentration and nuclei sites on the anode surface. To achieve uniform lithium deposition during the charge and discharge process, we introduce a homemade new copolymer (with the quaternary ammonium group N 3 R + I - on its side chain as the main functional group), named P35, as a functional electrolyte additive to regulate the lithium deposition. Theoretical calculations show that under the strong coordinating interaction between I - and N 3 R + , P35 preferentially adsorbs onto the lithium foil surface, effectively countering the adsorption of lithium salt anions such as PF 6 - . Moreover, the positive charge carried by the quaternary ammonium salt group of P35 could interact with PF 6 - to limit their mobility. Consequently, the dipole interaction on lithium ions is diminished, leading to an enhancement in the transport rate and a decrease in the concentration gradient of lithium ions. Furthermore, a more efficient SEI was formed due to the dual charges electrostatic shield formed by N 3 R + I - . Li-Li symmetric cells and Li-LiFePO 4 full cells assembled with electrolytes with P35 exhibit better rate performance, smaller polarization, and smoother deposition morphology in comparison to the cells without the P35 additive.

Herein, a novel zinc-organic gel with self-catalysis-enhanced electrochemiluminescence (ECL) performance was prepared as an emitter for the first time to assemble a biosensor for ultrasensitive detection of microRNA-221 (miR-221) related to liver cancer. Interestingly, Zn 2+ served as a central ion to coordinate with multidentate ligands 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (TATB) at room temperature to form Zn-TATB-MOGs with excellent ECL intensity. More importantly, compared to metal ions (e.g., Al 3+ , Fe 3+ , and Eu 3+ ) in the reported MOGs with the role of central ions, Zn 2+ in Zn-TATB-MOGs not only served as the central ion but also as a coreaction promoter to facilitate the transformation of S 2 O 8 2- into free radicals SO 4 •- to react with Zn-TATB-MOGs •- for further enhancing the ECL signal of Zn-TATB-MOGs. This was the first time to explore the promotion function of metal ions for coreaction reagents and realize the self-catalysis-enhanced ECL of MOGs. Additionally, the double domino-like cascade strand displacement amplification (DC-SDA) methods could overcome the shortcomings of time-consuming procedures and low DNA utilization in traditional cascade-free amplification methods, which significantly shortened the response time of the biosensor and improved the utilization rate of DNA. Consequently, the constructed biosensor achieved ultrasensitive detection of miR-221 with a detection limit of 2.19 aM, which was lower than reported works. This work provided new insight into broadening the development and improving the performance of MOGs as emitters, holding promise for applications in trace detection of biomarkers and early disease diagnosis.

Developing precious metal-free catalysts for organic reactions under mild conditions is urgent. Herein, we report a three-dimensional covalent organic framework (3D-COF) with high crystallinity and permanent pores, termed 3D-TABPA-COF, for the oxidation of tetrahydroquinoline to quinoline. The 3D-TABPA-COF assembled based on N 4 , N 4 -bis(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine (TABPA) is the catalytic active center for the conversion of tetrahydroquinoline. The triphenylamine in the structure is an effective photosensitizer, which not only enhances the light absorption capacity but also facilitates the rapid transfer of photogenerated electrons and ensures effective carrier separation. The obtained 3D-TABPA-COF has a high specific surface area (2745.06 m 2 g -1 ) and mesopores of 3.57 nm. This is attributed to the fact that the bor topology is not easy to interpenetrate. It can oxidize tetrahydroquinoline to obtain quinoline efficiently under visible light irradiation. In addition, we also performed various photochemical characterizations combined with density functional theory calculations to elucidate the reaction mechanism from tetrahydroquinoline to quinoline. This work provides a feasible strategy for constructing 3D-COF to achieve efficient photocatalytic organic reactions.

Single-crystalline Ni-rich layered oxides are one of the most promising cathode materials for lithium-ion batteries due to their superior structural stability. However, sluggish lithium-ion diffusion kinetics and interfacial issues hinder their practical applications. These issues intensify with increasing Ni content in the ultrahigh-Ni regime (≥90%), significantly threatening the practical viability of the single-crystalline strategy for ultrahigh-Ni layered oxide cathodes. Herein, by developing a high-entropy coating strategy, we successfully constructed an epitaxial lattice-coherent high-entropy rock-salt layer (∼3 nm) via Zr and Al doping on the surface of the single-crystalline cathode LiNi 0.92 Co 0.05 Mn 0.03 O 2 through an in situ modification process. The surface high-entropy rock-salt layer with tailored Ni valence and lattice coherence not only greatly improves lithium-ion diffusion kinetics but also suppresses interface parasitic reactions and surface structural degradations. The high-entropy surface layer-stabilized ultrahigh-Ni single-crystalline cathode (SC-Ni92-ZA) demonstrates significantly improved rate and cycling performances (127.5 mAh g -1 at 20C, capacity retention of 74.9% after 500 cycles at 1C) in a half-cell. The SC-Ni92-ZA exhibits a capacity retention of 87.1% after 600 cycles at 1C in a full-cell. This epitaxial lattice-coherent high-entropy coating strategy develops a promising avenue for developing high-capacity, long-life cathode materials.

The efficacy of immunotherapy in treating triple-negative breast cancer (TNBC) has been restricted due to its low immunogenicity and suppressive immune microenvironment. Bacterial outer membrane vesicles (OMVs) have emerged as innovative immunotherapeutic agents in antitumor therapy by stimulating the innate immune system, but intricate modifications and undesirable multiple dose administration severely hinder their utility. Herein, a two-step bacterial metabolic labeling technique was utilized for the bioorthogonal engineering of OMVs. At first, d-propargylglycine (DPG, an alkyne-containing d-amino acid) was introduced into the incubation process of probiotic Escherichia coli 1917 (Ecn) to produce DPG-functionalized OMVs, which were subsequently conjugated with azide-functionalized new indocyanine green (IR820) to yield OMV-DPG-IR820. The combination of phototherapy and immunostimulation of OMV-DPG-IR820 effectively arouses adaptive immune responses, causing maturation of dendritic cells, infiltration of T cells, repolarization of the M2 macrophage to the M1 macrophage, and upregulation of inflammatory factors. Remarkably, OMV-DPG-IR820 demonstrated tumor-targeting capabilities with guidance provided by near-infrared II (NIR-II) fluorescence imaging, leading to remarkable inhibition on both primary and distant tumors and preventing metastasis without causing noticeable adverse reactions. This study elucidates a sophisticated bioorthogonal engineering strategy for the design and production of functionalized OMVs and provides novel perspectives on the microbiome-mediated reversal of TNBC through a precise and efficient immunotherapy.

Enhancing the hydrophobic and photothermal characteristics of the coating can significantly boost its anti-icing/ice-melting capabilities. In this study, an epoxy resin thermal insulation layer is interposed between the aluminum sheet substrate and the C/TiN/WC/PDMS photothermal composite coating. This method not only equips the coating with exceptional superhydrophobic properties but also markedly elevates its photothermal and anti-icing/ice-melting performance. The incorporation of the thermal insulation layer has been observed to elevate the water contact angle from approximately 125° to 155° ± 0.5° while simultaneously reducing the water sliding angle from over 90° to about 4° ± 0.5°. In an environmental setting of -15 °C and 65% ± 5% humidity, under irradiation of 1.0, 0.7, 0.5, and 0.3 kW/m 2 , the coating with the thermal insulation layer exhibited saturation temperature increments of roughly 4.7, 3.4, 5.4, and 4.6 °C, respectively, compared to the photothermal coating without the insulation layer. In the absence of irradiation, the coating with the insulation layer delayed the freezing time of 80 μL water droplets by up to three and six times compared to the coating without an insulation layer and the bare aluminum sheet substrate, respectively. Furthermore, under 0.3 kW/m 2 irradiation, the coating with the insulation layer reduced the initial melting time and complete melting time of ice beads by nearly half and one-third, respectively, whereas the ice beads on the aluminum sheet substrate remained unmelted throughout the observation period.

An innovative and potent nanozyme with reductase-like activity was developed by integrating the in situ synthesis of gold nanoparticles (Au NPs) onto the surface of a covalent organic framework (COF). Based on the reductase-like activity of the COF-hybridized Au NPs, this nanozyme could efficiently catalyze the reduction of 4-nitrophenol (4-NPH). Moreover, the prepared nanohybrid was utilized as an excellent surface-enhanced Raman scattering (SERS) substrate for highly sensitive SERS detection by combining the excellent adsorption properties of COFs and the large number of Raman hotspots between the high-density Au NPs. For the first time, 4-NPH was used as an SERS marker to detect the electron receptor acetylcholine (Ach), with high sensitivity; Ach acted as an inhibitor in this catalytic reaction. The linear range of Ach was 1.0 pM to 10 nM, the correlation coefficient was 0.993, the detection limit was approximately 0.3 pM with a signal-to-noise ratio (s/n) of 3, and the acceptable recovery in the serum was 97.2% to 104.5%. The results from this study show that the nanozyme-SERS system has great potential for chemical and bioassay applications.

In this study, we developed a flexible, biocompatible, and high-output electrical performance triboelectric nanogenerator (TENG) employing a silk fibroin (SF)-MXene composite film (SF-MXene-F) and a PDMS film as the friction layer. The inclusion of MXene in the SF film increased its surface charge density, presenting a practical approach to designing high-performance SF composite film-based TENGs. At a MXene content of 40%, our SF-MXene composite film-based TENG (SF-MXene-FTENG) achieved optimal output electrical performance, featuring a maximum open-circuit voltage (Voc) of 418 V, a maximum short-circuit current (Isc) of 11.6 μA, and a maximum output power density of 9.92 W/m 2 . The Voc and power densities of the SF-MXene-FTENG surpassed previously reported optimal values for SF-based TENGs by 1.6 and 3.8 times, respectively. Furthermore, leveraging the exceptional biocompatibility and light shading performance of TENGs, we designed a wearable smart TENG eye mask capable of diagnosing insomnia symptoms and monitoring sleep quality in real time. The SF-MXene-FTENG holds promising application potential as a wearable electronic device for diagnosing sleep-related diseases.

Using chemical fungicides is the main strategy for controlling potato late blight (PLB), a devastating pre- and postharvest disease caused by Phytophthora infestans , resulting in environmental pollution and health risks. It is of great importance to develop a biofungicide from microorganisms. Through isolating potato rhizosphere microorganisms, CQUSh011 was found to have antioomycete activity with strong inhibition on vegetative growth and virulence of P. infestans . Morphological and molecular identification indicated that CQUSh011 belongs to Streptomyces rapamycinicus . Based on genome, metabolome, and HPLC quantification, rapamycin and salicylic acid were found to be the two active metabolites against P. infestans . Continuous field trials showed that CQUSh011 has sustainable control efficiency against PLB, and the efficiency was better when combined with Infinito, along with an increased endophytic microbial community and biodiversity in potato roots. The results demonstrated the potential of CQUSh011 as a biofungicide against PLB and provided an alternative strategy for reducing the application of chemical fungicides.

Triple-negative breast cancer (TNBC) is highly heterogeneous, lacks accessible therapeutic targets, and features an immunosuppressive tumor microenvironment (TME). Anthracycline-based chemotherapy remains the primary treatment method for TNBC, while the current popular immune checkpoint inhibitors persistently encounter therapeutic resistance. Therefore, there is an urgent need to explore combined therapeutic strategies to remodel the TME and improve the treatment response. Considering the highly specific homing ability of tumor cell-derived vesicles and the key role of the signal transduction and activation of the transcription factor 3 (STAT3) pathway in TNBC, we propose a synergistic therapeutic strategy that integrates gene therapy, chemotherapy, and immunotherapy based on STAT3 short interfering RNA (siSTAT3) and doxorubicin (DOX)-functionalized tumor-derived extracellular vesicles (TEVs) (siSTAT3-DOX@TEV). The in vitro and in vivo results demonstrate that siSTAT3-DOX@TEV target tumor tissues precisely, downregulate STAT3 expression, and synergistically and efficiently induce immunogenic death, thereby reversing the immunosuppressive TME. Moreover, mass cytometry and immunohistochemistry reveal the local immune activation effect of siSTAT3-DOX@TEV, with a significant increase in M1 macrophages, CD4 + T cells, and CD8 + T cells in tumor tissues. These results provide strong hints for the development of TEV-based chemo-gene therapeutic agents for TNBC treatment at the clinical level.

Reactive sulfur species (RSS) including persulfides (RSSHs), biothiols, and hydrogen sulfide (H 2 S) are key regulators in various physiological processes. To better understand the symbiotic relationship and interconversion of these RSS, it is highly desirable but challenging to develop analytical techniques that are capable of detecting and quantifying them. Herein, we report the rational design and synthesis of novel trityl-radical-based electron paramagnetic resonance (EPR) probes dubbed CT02-TNB and OX-TNB. CT02-TNB underwent fast sulfur exchange reactions with two reactive RSSHs (PS1 and PS2) which were released from their corresponding donors PSD1 and PSD2 to afford the specific conjugates. The resulting conjugates exhibit characteristic EPR spectra, thus enabling discriminative detection and quantitation of the two RSSHs. Moreover, CT02-TNB showed good response toward other RSS including glutathione (GSH), cysteine (Cys), H 2 S, and sulfite as well. Importantly, based on the updated EPR spectral simulation program, simultaneous quantitation of multiple RSS (e.g., PS1/GSH/Cys or PS1/GSH/H 2 S) by CT02-TNB was also achieved. Finally, the levels of released PS1 from PSD1 and endogenous GSH in isolated mouse livers were measured by the hydrophilic OX-TNB. This work represents the first study achieving discriminative and quantitative detection of different persulfides and other RSS by a spectroscopic method.

We disclose herein an efficient and facile method for the synthesis of SF 5 -containing isoquinolinediones with an all-carbon quaternary stereocenter via intramolecular pentafluorosulfanylation of acrylamides using SF 5 Cl as a pentafluorosulfanylation reagent. The protocol proceeds under mild reaction conditions and enjoys a broad substrate scope, wide functional group compatibility, and high atom- and step-economy. A radical mechanism involving the SF 5 radical cascade addition/cyclization of acrylamides is proposed.

The inevitable dealumination process of zeolite Y is closely related to ultrastabilization, enhanced Bro̷nsted acidity, and deactivation throughout its life cycle, producing complex aluminum and acidic hydroxyl species. Most investigations on dehydrated zeolites have focused on the Bro̷nsted acidity of tetra-coordinated Al (Al(IV)) and Lewis acidity associated with tricoordinated Al (Al(III)) sites, which has left the penta-coordinated Al (Al(V)) in dealuminated zeolites scarcely discussed. This is largely due to the oversimplified view of detectable Al(V) as an exclusively extra-framework species with Lewis acidity. Here we report the formation of Bro̷nsted acidic penta-coordinated Al species (Al(V)-BAS) in the dealumination process. Two-dimensional (2D) through-bond and multiquantum 1 H-{ 27 Al} correlation solid-state NMR experiments demonstrate the presence of a bridging Si-OH-Al(V) structure in dealuminated Y zeolites. Different from the conventional belief that water attack leads to the breaking of zeolite framework Al-O bonds in the initial stage of zeolite dealumination, the observed Al(V) as a dealumination intermediate is directly correlated with a BAS pair because of the direct dissociation of water on the framework tetrahedral aluminum (Al(IV)), thus bypassing the cleavage of Al-O bonds. 1 H double-quantum solid-state NMR experiments and theoretical calculations provide further evidence for this mechanism, whereas pyridine adsorption experiments confirm stronger acidity of Al(V)-BASs than the traditional bridging hydroxyl groups associated with Al(IV). We were also able to detect the Al(V)-BAS site from dealuminated SSZ-13 zeolite with CHA topology, suggesting that its creation is not specific to the framework structure of zeolites.

Transition metal-catalyzed spiroannulations are practical strategies for constructing spirocyclic skeletons of pharmaceutical and biological significance, yet the microscopic mechanism still lacks in-depth explorations. Here, the palladium-catalyzed [2 + 2 + 1] spiroannulation between aryl halides and alkynes was studied by employing the density functional theory (DFT) method. Based on comprehensive explorations on a couple of possible reaction pathways, it is found that the reaction probably experiences C-I oxidative addition, alkyne migration insertion, Cs 2 CO 3 -assisted aryl C-H activation, C-Br bond oxidative addition, C-C coupling, arene dearomatization and reductive elimination in sequence and leads to the formation of the spiro[4,5]decane pentacyclic product ( P ) ultimately. Among these, the C-Br bond oxidative addition step acts as the rate-determining step (RDS) of the whole reaction, featuring a practical free energy barrier of 32.4 kcal·mol -1 at 130 °C. Computationally predicted kinetics such as half-life transferred from the RDS step's barrier on the optimal reaction pathway (1.2 × 10 1 h) coincides well with corresponding experimental results (91% yield of the spiro[4,5]decane pentacyclic product P after reacting 10 h at 130 °C). In addition, theoretical predictions regarding the solvent/ligand effects and base additive role in the reaction, rationalized by distortion-interaction/natural population/noncovalent interaction analyses, are also in good agreement with experimental data and trend. This good agreement between experiment and theory makes sense for new designations and further experimental improvements of such Pd-catalyzed transformations.

A novel and efficient palladium-catalyzed highly regioselective reaction of 1-[2-(2,2-dibromoethenyl)phenyl]-1 H -pyrrole with allenes was realized to synthesize pyrrolo[1,2- a ]quinolones. The tandem process involves intermolecular cyclization and intramolecular direct arylation, leading to the formation three new C-C bonds and two new rings. Notably, this transformation exhibits broad substrate scope and high functional group tolerance.

Without intervention, the natural wound healing process can often result in scarring, which can have detrimental effects on both the physical and mental well-being of patients. Therefore, it is crucial to develop biomaterials that can promote healing without scarring. Regulating the Yes-associated protein-1/PDZ-binding motif (YAP/TAZ) signaling pathway is possible to reduce excessive fibrosis of fibroblasts and proliferation of vascular endothelial cells, ultimately impacting scar formation. Arsenic trioxide (ATO), an ancient drug with medicinal and toxic properties, has shown promise in regulating this pathway. An ATO-loaded hydrogel dressing (ATO@CS/SA) was created to facilitate scarless wound healing, utilizing chitosan (CS) and sodium alginate (SA) to prevent direct contact of ATO with the wound tissue and minimize potential side effects. In vitro studies demonstrated that low concentrations of ATO did not impact cell viability and even promoted proliferation and migration. Co-culturing the hydrogel with fibroblasts and vascular endothelial cells led to decreased expression levels of YAP and TAZ. Animal studies over a 90-day period revealed significant inhibition of scar formation with this system. Histological experiments further confirmed that the decreased expression of YAP and TAZ was responsible for this outcome. In conclusion, when administered at the appropriate dose, ATO can be repurposed from a traditional poison to a therapeutic agent, effectively suppressing excessive cell fibrosis and blood vessel proliferation and offering a novel approach to scar-free treatment.

Larock isoquinoline synthesis is one of the most efficient and straightforward approaches to the construction of 3,4-disubstituted isoquinolines. However, there have been no asymmetric versions for the synthesis of axially chiral isoquinolines since their initial report in 2001. Herein, we documented the first example of an asymmetric Larock isoquinoline synthesis by employing Pd(OAc) 2 /Walphos SL-W002-1 as the catalyst, affording the axially chiral 3,4-disubstituted isoquinolines with up to 97.5:2.5 er and 98% yield. Density Functional Theory (DFT) calculations clearly clarified the catalytic mechanism and the origin of the experimentally observed enantioselectivity.

Emission trading schemes (ETS) are increasingly becoming a popular policy instrument to balance carbon abatement and economic growth. As a globally unified carbon pricing system has not yet been established, whether regionally operated ETSs cause carbon leakage remains a major concern. Taking China's regional pilot ETSs as a quasi-natural experiment, the study uses the spatial difference-in-differences method to examine how regional ETSs affect carbon emissions in and outside cities of policy implementation. Our analysis finds that China's regional ETS policy contributes to a 6.1% reduction in urban CO 2 emissions and a 6.6% decline in emissions intensity in regulated cities, causing carbon leakages that increase CO 2 emissions in neighboring cities by 1.7% on average. Our finding further suggests that regional ETSs mitigate local CO 2 emissions through outsourcing production, improving energy efficiency and decarbonizing energy structure, whereas the outsourcing of industrial production drives up CO 2 emissions in adjacent cities. Moreover, the performances of regional ETSs vary largely by socioeconomic context and mechanism design. China's regional ETSs reduce CO 2 emissions more effectively in central and industrial cities but with more severe carbon leakage, while rigorous compliance mechanisms and active market trading help deepen carbon abatement and alleviate carbon leakage.

4-Quinolone derivatives undergo an unexpected ring expansion reaction with α-halo esters/phosphonates/sulfones in the presence of a base, such as NaH, to produce novel benzazepinones. Under these mild and transition-metal-free conditions, most substrates gave moderate to excellent yields. The reaction could be applied in gram-scale synthesis of drug-like molecules that greatly accelerated our structure-activity relationship studies. A plausible mechanism was proposed.

Formation of new chemical species has been achieved under an electric field by the use of the scanning tunneling microscope break junction technique, yet simultaneous implementation of catalytic reactions both at the organic/metal interface and in the bulk solution remains a challenging task. Herein, we show that n -butyl-substituted organotin-terminated benzene undergoes both an efficient cleavage of the terminal tributyltin group to form a covalent Au-C bond and a homocoupling reaction to yield biphenyl product when subjected to an electric field in the vicinity to Au electrodes. By using ex situ characterization of high-performance liquid chromatography with an UV-vis detector, we demonstrate that the homocoupling reaction can occur with high efficiency under an extremely low tip bias voltage of ∼5 mV. Additionally, we show that the efficiency of the homocoupling reaction varies significantly in different solvents; the choice of the solvent proves to be one of the methods for modulating this reaction. By synthesizing and testing varied molecular backbone structures, we show that an extended biphenyl backbone undergoes homocoupling to form a quarterphenylene backbone, and the C-C coupling reactions are prohibited when additional aurophilic or bulky chemical groups that exhibit a steric blockage are introduced.

Iron-nitrogen-carbon (Fe-N-C) materials have been identified as a promising class of platinum (Pt)-free catalysts for the oxygen reduction reaction (ORR). However, the dissolution and oxidation of Fe atoms severely restrict their long-term stability and performance. Modulating the active microstructure of Fe-N-C is a feasible strategy to enhance the ORR activity and stability. Compared with common 3d transition metals (Co, Ni, etc.), the 4d transition metal atom Nb has fewer d electrons and more unoccupied orbitals, which could potentially forge a more robust interaction with the Fe site to optimize the binding energy of the oxygen-containing intermediates while maintaining stability. Herein, an asymmetric Fe-Nb diatomic site catalyst (FeNb/c-SNC) was synthesized, which exhibited superior ORR performance and stability compared with those of Fe single-atom catalysts (SACs). The strong interaction within the Fe-Nb diatomic sites optimized the desorption energy of key intermediates (*OH), so that the adsorption energy of Fe-*OH approaches the apex of the volcano plot, thus exhibiting optimal ORR activity. More importantly, introducing Nb atoms could effectively strengthen the Fe-N bonding and suppress Fe demetalation, causing an outstanding stability. The zinc-air battery (ZAB) and hydroxide exchange membrane fuel cell (HEMFC) equipped with our FeNb/c-SNC could deliver high peak power densities of 314 mW cm -2 and 1.18 W cm -2 , respectively. Notably, the stable operation time for ZAB and HEMFC increased by 9.1 and 5.8 times compared to Fe SACs, respectively. This research offers further insights into developing stable Fe-based atomic-level catalytic materials for the energy conversion process.

Holographic data storage technology is a cost-effective solution for long-term archival data storage. However, the development of suitable holographic recording materials remains a challenge. Among these materials, phenanthraquinone-doped poly(methyl methacrylate) (PQ/PMMA) stands out due to its low cost and controllable thickness. Nevertheless, its limited photosensitivity and diffraction efficiency hinder its widespread application. In order to solve these problems, we put forward a kind of convenient and simple, low cost strategy, by adding plasticizer N , N -dimethylformamide (DMF) for preparation of DMF-PQ/PMMA photopolymer, avoid the use of complex compounds. The addition of DMF not only influences the thermal polymerization stage but also forms weak interactions with PQ during the photoreaction process, thereby enhancing the holographic performance of DMF-PQ/PMMA. Consequently, we achieved a remarkable 9.1-fold increase in photosensitivity (from ∼0.35 to 3.18 cm J -1 ), improved diffraction efficiency by 20% (from 65% to 80%), and reduced volume shrinkage by a factor of 8 (from 0.4% to 0.05%). Furthermore, utilizing a collinear holographic storage system with multiplexing shift at a scale of 5 μm resulted in an impressively low minimum bit error rate (BER) of only 0.36% (with an average BER of 1.4%), highlighting the fast processing capability and potential for low BER applications in holographic information storage using DMF-PQ/PMMA.

Stable magnetic core-shell nanostructures are developed by lattice locking lanthanide-iron (La-Fe) oxide shells with magnetite cores to prevent the release of La from the surfaces of the magnetite nanostructures. The resulting core-shell nanostructures demonstrate excellent outstanding regeneration performance and high adsorption capacity for phosphate (115 mg P·g -1 ). These nanostructures release minimal La from the magnetite core surfaces after adsorbent regeneration, with a La loss of only 20% compared to the control sample, Mag@La(OH) 3 . La 3+ ions were released at concentrations ranging from 1 to 2.3 μg·L -1 at pH levels of 4 to 8, which is within the metal content range found in natural aquatic environments. These results demonstrate the high stability of the nanostructures after regeneration. Furthermore, the adsorbent exhibits high extraction capacity across a wide pH range of 4 to 10 and performs well even in the presence of interfering anions at phosphate-to-anion molar ratios of 1:5, 1:25, and 1:100. Microscopic and spectroscopic analyses reveal that the primary extraction mechanism of phosphate in the La-containing shells is surface precipitation. This approach not only improves the use of magnetic core-shell nanostructures as adsorbents but also demonstrates the creation of a broad range of stable magnetic functional materials for diverse applications.

Ion preintercalation is an effective method for fine-tuning the electrochemical characteristics of electrode materials, thereby enhancing the performance of aqueous ammonium-ion hybrid supercapacitors (A-HSCs). However, much of the current research on ion preintercalation lacks controllability, and the underlying mechanisms remain unclear. In this study, we employ a two-step electrochemical activation approach, involving galvanostatic charge-discharge and cyclic voltammetry, to modulate the preintercalation of NH 4 + in MnO 2 . An in-depth analysis of the electrochemical activation mechanism is presented. This two-step electrochemical activation approach endows the final MnO 2 /AC electrode with a high capacitance of 917.4 F g -1 , approximately 2.4 times higher than that of original MnO 2 . Furthermore, the MnO 2 /AC electrode retains approximately 93.4% of its capacitance after 10 000 cycles at a current density of 25 mA cm -2 . Additionally, aqueous A-HSC, comprising MnO 2 /AC and P-MoO 3 , achieves a maximum energy density of 87.6 Wh kg -1 . This study offers novel insights into the controllable ion preintercalation approach via electrochemical activation.

Electrocatalytic coupling of CO 2 and NO 3 - to urea is a promising way to mitigate greenhouse gas emissions, reduce waste from industrial processes, and store renewable energy. However, the poor selectivity and activity limit its application due to the multistep process involving diverse reactants and reactions. Herein, we report the first work to design heterostructured Cu-Bi bimetallic catalysts for urea electrosynthesis. A high urea Faradaic efficiency (FE) of 23.5% with a production rate of 2180.3 μg h -1 mg cat -1 was achieved in H-cells, which surpassed most reported electrocatalysts in the literature. Moreover, the catalyst had a remarkable recycling stability. Experiments and density functional theory calculations demonstrated that introduction of moderate Bi induced the formation of the Bi-Cu/O-Bi/Cu 2 O heterostructure with abundant phase boundaries, which are beneficial for NO 3 - , CO 2 , and H 2 O activation and enhance C-N coupling and promote *HONCON intermediate formation. Moreover, favorable *HNCONH 2 protonation and urea desorption processes were also validated, further explaining the reason for high activity and selectivity toward urea.

Acute alcoholic liver injury (AALI) has become an important cause of liver disease worldwide, and there is an urgent need to develop noninvasive and sensitive methods to detect and evaluate AALI. We report herein three novel but readily available mitochondrial targeting fluorescence probes ( ICR , ICJ , and ICQ ) for AALI detection. These probes contain different electron-donating groups, among which ICQ exhibits NIR fluorescence (740 nm), a large Stokes shift (110 nm), and a sensitive response to viscosity (73-fold enhancement in fluorescence from water to glycerol), making it suitable for in vivo imaging. ICQ also exhibits an excellent ability to image mitochondrial viscosity changes in cells. More importantly, ICQ can target the liver selectively and image the viscosity changes in the liver noninvasively. Through establishing an AALI mouse model, ICQ was successfully applied to the in situ imaging changes in liver viscosity during the AALI process. The results showed a significant increase in liver viscosity in AALI mice, indicating that viscosity can serve as a marker for AALI, and ICQ is a promising noninvasive and sensitive tool for detecting and evaluating AALI.

Convenient and accurate quantification of disease-relevant multitargets is essential for community disease screening. However, in the field of photoelectrochemical (PEC) sensors for multisubstance detection, research on the continuous detection of multiple targets using a polarity-switching mode is scarce. In this study, a multiplexed PEC bioassay was developed based on a target-triggered "anodic-cathodic-anodic" multiple-polarity-switchable mode. Employing miRNA-21 and miRNA-141 as model analytes, the photosensitive material combinations of Cu 2 O/gold nanoparticles (AuNPs)/TiO 2 and CdS/AuNPs/TiO 2 were successively formed through the specific binding of different whisker branches of Whisker-DNA to Cu 2 O-H1 and the CdS-tripod DNA ring, respectively. This process reverses the photocurrent polarity from anodic to cathodic and then back to anodic upon detecting different targets, resulting in the high-sensitivity quantification of various biological targets with reduced interference. To enhance the device's utility and affordability in community disease screening, integrating a capacitor and a multimeter-smartphone connection simplifies the assembly and reduces costs. In developing the PEC sensor, the device demonstrated linear detection ranges for miRNA-21 and miRNA-141 from 0.01 fM to 10 nM. Detection limits for miRNA-21 and miRNA-141 were established at 3.2 and 4.3 aM, respectively. The innovative target-triggered multiple-polarity-switchable mode offers adaptability for other multitarget detections by simply modifying the structure of the whisker branches and the combination of photosensitive materials.

Atmospheric water harvesting has attracted much attention because of its potential to escalate the global freshwater shortage. However, the water collection efficiency is hindered by the trade-off between fast droplet nucleating and rapid droplet dripping due to the opposite requirements in the chemistry and the morphology of surfaces. Herein, the hierarchical porous composite film (ZIF-8@PVDF/PMMA, HPCF) with superhydrophobicity is designed for highly efficient and stable water harvesting. It indicates that the HPCF film has a large water contact angle (WCA) of 155.50° and ultralow sliding angle (SA) of 2°, exhibiting the self-cleaning function. Significantly, it is demonstrated that the water collection efficiency of HPCF can achieve 1.13 g·cm -2 ·h -1 , which is much higher than the value of the blank sample, as well as most of the reported values. It is attributed to the hierarchical porous structure with the ZIF-8 crystals enhancing the surface roughness and endowing the film with the hydrophilic/superhydrophobic regions. This design promotes an optimal balance between droplet nucleation and shedding, significantly enhancing the water harvesting efficiency. Consequently, this work introduces an effective approach for water collection materials suitable for fog/mist conditions and provides an effective solution for the foggy area with water scarcity, demonstrating significance for advancing research aimed at mitigating the worldwide water shortage.

Preventing microbial infections and accelerating wound closure are essential in the process of wound healing. In this study, various concentrations of carvacrol (CA) were loaded into polyacrylonitrile/poly(ethylene oxide) (PAN/PEO) nanofiber membranes to develop potential wound dressing materials via an electrospinning technique. The morphology and structure of the PAN/PEO/CA nanofiber membrane were analyzed by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), respectively. Subsequently, antimicrobial performance testing showed that the PAN/PEO/CA nanofiber membrane exhibited antimicrobial activity in a concentration-dependent manner. Moreover, SEM and transmission electron microscopy revealed that the number of Staphylococcus aureus decreased significantly and the microstructure of the biofilm was seriously damaged. Next, compared with the control and PAN/PEO groups, the PAN/PEO/5% CA group in a full-thickness skin infection model not only exhibited reduced wound exudate on day 2 after infection but also displayed a greater ability to achieve complete skin regeneration, with faster wound healing. Finally, the Kyoto Encyclopedia of Genes and Genomes pathway analysis revealed that the downregulated differentially expressed genes between PAN/PEO- and PAN/PEO/5% CA-treated S. aureus were enriched in the two-component system and S. aureus infection. In conclusion, the antimicrobial materials of PAN/PEO/CA inhibited microbial growth and promoted wound healing with potential applications in the clinical management of wounds., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

As histone modification enzymes, EZH2 mediates H3K27 trimethylation (H3K27me3), whereas LSD1 removes methyl groups from H3K4me1/2 and H3K9me1/2. Synergistic anticancer effects of combining inhibitors of these two enzymes are observed in leukemia and prostate cancer. Thus, a series of EZH2/LSD1 dual inhibitors are designed and synthesized to evaluate their anticancer activity. After the structure-activity study, one of the best compounds, ML234 , displayed excellent antiproliferative capacity against prostate cancer cell lines LNCAP, PC3, and 22RV1. Enzymatic assays ascertained that the anticancer potency of ML234 was mediated through coinhibition of EZH2 and LSD1. Moreover, the accumulation of H3K4me2 and H3K9me2 and the decrease of H3K27me3 induced by ML234 were verified by Western blot analysis. More importantly, the compound remarkably suppressed the tumor growth and enhanced the therapeutic efficacy of clinical drug enzalutamide in the 22RV1 xenograft mouse model, indicating that it may have potential as an anticancer agent in prostate cancer.

In this study, we utilized the Olink Cardiovascular III panel to compare the expression levels of 92 cardiovascular-related proteins between patients with dilated cardiomyopathy combined with heart failure (DCM-HF) (n = 20) and healthy normal people (Normal) (n = 18). The top five most significant proteins, including SPP1, IGFBP7, F11R, CHI3L1, and Plaur, were selected by Olink proteomics. These proteins were further validated using ELISA in plasma samples collected from an additional cohort. ELISA validation confirmed significant increases in SPP1, IGFBP7, F11R, CHI3L1, and Plaur in DCM-HF patients compared to healthy controls. GO and KEGG analysis indicated that NT-pro BNP, SPP1, IGFBP7, F11R, CHI3L1, Plaur, BLM hydrolase, CSTB, Gal-4, CCL15, CDH5, SR-PSOX, and CCL2 were associated with DCM-HF. Correlation analysis revealed that these 13 differentially expressed proteins have strong correlations with clinical indicators such as LVEF and NT-pro BNP, etc. Additionally, in the GEO-DCM data sets, the combined diagnostic value of these five core proteins AUC values of 0.959, 0.773, and 0.803, respectively indicating the predictive value of the five core proteins for DCM-HF. Our findings suggest that these proteins may be useful biomarkers for the diagnosis and prediction of DCM-HF, and further research is prompted to explore their potential as therapeutic targets.

Regional analgesia based on the local anesthetic ropivacaine plays a crucial role in postoperative pain management and recovery; however, the short duration of analgesia limits its clinical potential. Various drug delivery systems such as microparticles and lipid carriers have been used to prolong the analgesic effect, yet most of them are prone to abrupt release from the site of administration or have poor analgesic effects of less than 48 h, which fail to meet the needs of postoperative analgesia. In this study, a low-molecular-weight gelator sodium deoxycholate-based hydrogel loaded with ropivacaine (DC-ROP gel) was designed for long-acting analgesia. The noncovalent interaction between ropivacaine and sodium deoxycholate helps to improve the stability and sustained release performance of the gel. This internal drug-binding hydrogel also avoids experiencing the burst release effect commonly seen in polymer hydrogels previously reported for the slow release of local anesthetics. DC-ROP gel exhibited the dual advantages of self-healing after compression and long-term controlled release. In mice with inflammatory pain, DC-ROP gel achieved peripheral nerve block for more than 1 week after a single injection. Histological and blood biochemical analyses confirmed that the DC-ROP gel did not produce systemic toxicity, and cytotoxicity experiments demonstrated that the DC-ROP gel resulted in low irritation. These results suggest that DC-ROP gel provides a promising strategy for local anesthetics in long-term postoperative pain management, broadening the potential of bile salt-based low-molecular-weight hydrogels for drug delivery.

Wound rehabilitation is invariably time-consuming, scar formation further weakens therapeutic efficacy, and detailed mechanisms at the molecular level remain unclear. In this work, a Mo 4/3 B 2- x nanoscaffold was fabricated and utilized for wound healing and scar removing in a mice model, while metabolomics was used to study the metabolic reprogramming of metabolome during therapy at the molecular level. The results showed that transition metal borides, called Mo 4/3 B 2- x nanoscaffolds, could mimic superoxide dismutase and glutathione peroxidase to eliminate excess reactive oxygen species (ROS) in the wound microenvironment. During the therapeutic process, the Mo 4/3 B 2- x nanoscaffold could facilitate the regeneration of wounds and removal of scars by regulating the biosynthesis of collagen, fibers, and blood vessels at the pathological, imaging, and molecular levels. Subsequent metabolomics study revealed that the Mo 4/3 B 2- x nanoscaffold effectively ameliorated metabolic disorders in both wound and scar microenvironments through regulating ROS-related pathways including the amino acid metabolic process (including glycine and serine metabolism and glutamate metabolism) and the purine metabolic process. This study is anticipated to illuminate the potential clinical application of the Mo 4/3 B 2- x nanoscaffold as an effective therapeutic agent in traumatic diseases and provide insights into the development of analytical methodology for interrogating wound healing and scar removal-related metabolic mechanisms.

Surface-enhanced Raman spectroscopy (SERS) is a powerful technique for discrimination of bimolecules in complex systems. However, its practical applications face challenges such as complicated manufacturing procedures and limited scalability of SERS substrates, as well as poor reproducibility during detection which compromises the reliability of SERS-based analysis. In this study, we developed a convenient method for simultaneous fabrication of massive SERS substrates with an internal standard to eliminate the substrate-to-substrate differences. We first synthesized Au@CN@Au nanoparticles (NPs) which contain embedded internal standard molecules with a single characteristic peak in the Raman-silent region, and then deposited the NPs on 6 mm glass wafers in a 96-well plate simply by centrifugation for 3 min. The one-time obtained 96 SERS substrates have excellent intrasubstrate uniformity and intersubstrate repeatability for SERS detection by using the internal standard (relative standard deviation = 10.47%), and were able to detect both charged and neutral molecules (crystal violet and triphenylphosphine) at a concentration of 10 -9 M. Importantly, cells can be directly cultured on glass wafers in the 96-well plate, enabling real time monitoring of the secretes and metabolism change in response to external stimulation. We found that the release of nucleic acids, amino acids and lipids by MDA-MB-231 cells significantly increased under hypoxic conditions. Overall, our approach enables fast and large-scale production of Au@CN@Au NPs-coated glass wafers as SERS substrates, which are homogeneous and highly sensitive for monitoring trace changes of biomolecules.

This study presents the fabrication of an ultralight, porous, and high-performance triboelectric nanogenerator (TENG) utilizing silk fibroin (SF) aerogels and PDMS sponges as the friction layer. The transition from two-dimensional film friction layers to three-dimensional porous aerogels significantly increased the specific surface area, offering an effective strategy for designing high-performance SF aerogel-based TENGs. The TENG incorporating the porous SF aerogel exhibited optimal output performance at a 3% SF concentration, achieving a maximum open circuit voltage of 365 V, a maximum short-circuit current of 11.8 μA, and a maximum power density of 7.52 W/m 2 . In comparison to SF-film-based TENGs, the SF-aerogel based TENG demonstrated a remarkable 6.5-fold increase in voltage and a 4.5-fold increase in current. Furthermore, the power density of our SF-based TENG surpassed the previously reported optimal values for SF-based TENGs by 2.4 times. Leveraging the excellent mechanical stability and biocompatibility of TENGs, we developed an SF-based TENG self-powered sensor for the real-time monitoring of subtle biological movements. The SF-based TENG exhibits promising potential as a wearable bioelectronic device for health monitoring.

Graphene quantum dots (GQDs) are used in diverse fields from chemistry-related materials to biomedicines, thus causing their substantial release into the environment. Appropriate visual function is crucial for facilitating the decision-making process within the nervous system. Given the direct interaction of eyes with the environment and even nanoparticles, herein, GQDs, sulfonic acid-doped GQDs (S-GQDs), and amino-functionalized GQDs (A-GQDs) were employed to understand the potential optic neurotoxicity disruption mechanism by GQDs. The negatively charged GQDs and S-GQDs disturbed the response to light stimulation and impaired the structure of the retinal nuclear layer of zebrafish larvae, causing vision disorder and retinal degeneration. Albeit with sublethal concentrations, a considerably reduced expression of the retinal vascular sprouting factor sirt1 through increased DNA methylation damaged the blood-retina barrier. Importantly, the regulatory effect on vision function was influenced by negatively charged GQDs and S-GQDs but not positively charged A-GQDs. Moreover, cluster analysis and computational simulation studies indicated that binding affinities between GQDs and the DNMT1-ligand binding might be the dominant determinant of the vision function response. The previously unknown pathway of blood-retinal barrier interference offers opportunities to investigate the biological consequences of GQD-based nanomaterials, guiding innovation in the industry toward environmental sustainability.

Peptide-based therapeutics hold immense promise for the treatment of various diseases. However, their effectiveness is often hampered by poor cell membrane permeability, hindering targeted intracellular delivery and oral drug development. This study addressed this challenge by introducing a novel graph neural network (GNN) framework and advanced machine learning algorithms to build predictive models for peptide permeability. Our models offer systematic evaluation across diverse peptides (natural, modified, linear and cyclic) and cell lines [Caco-2, Ralph Russ canine kidney (RRCK) and parallel artificial membrane permeability assay (PAMPA)]. The predictive models for linear and cyclic peptides in Caco-2 and RRCK cell lines were constructed for the first time, with an impressive coefficient of determination ( R 2 ) of 0.708, 0.484, 0.553, and 0.528 in the test set, respectively. Notably, the GNN framework behaved better in permeability prediction with larger data sets and improved the accuracy of cyclic peptide prediction in the PAMPA cell line. The R 2 increased by about 0.32 compared with the reported models. Furthermore, the important molecular structural features that contribute to good permeability were interpreted; the influence of cell lines, peptide modification, and cyclization on permeability were successfully revealed. To facilitate broader use, we deployed these models on the user-friendly KNIME platform (https://github.com/ifyoungnet/PharmPapp). This work provides a rapid and reliable strategy for systematically assessing peptide permeability, aiding researchers in drug delivery optimization, peptide preselection during drug discovery, and potentially the design of targeted peptide-based materials.

The effective repair of bone defects has long been a major challenge in clinical practice. Currently, research efforts mostly focus on achieving sufficiently good bone repair, with little attention paid to achieving both good and fast repair. However, achieving highly efficient (H-efficient) bone repair, which is both good and fast, can shorten the treatment cycle and facilitate rapid patient recovery. Therefore, the development of a H-efficient bone repair material is of significant importance. This study incorporated the previously developed osteoinductive photothermal agent (PTA) BP ICT into printing paste to prepare a near-infrared (NIR)-responsive BP ICT scaffold. Subsequently, the effects of photothermal therapy (PTT) on bone repair and drug release were assessed in vitro. To further validate the H-efficient bone repair properties of the BP ICT scaffold, the scaffold was implanted into bone defects and its ability to promote bone repair in vivo was evaluated through radiology and histopathological analysis. The results indicated that compared to scaffolds containing only Icaritin (ICT), the BP ICT scaffold can achieve PTT to promote bone repair through NIR irradiation, while also enabling the controlled release of ICT from the scaffold to enhance bone repair. Within the same observation period, the BP ICT scaffold achieves more efficient bone repair than the ICT scaffold, significantly shortening the bone repair cycle while ensuring the effectiveness of bone repair. Therefore, the NIR-responsive scaffold based on PTT-mediated controlled release of bone growth factors represents a feasible solution for promoting H-efficient bone repair in the area of bone defects.

Currently, clinical therapeutic strategies for nasopharyngeal carcinoma (NPC) confront insurmountable dilemmas in which surgical resection is incomplete and chemotherapy/radiotherapy has significant side effects. Phototherapy offers a maneuverable, effective, and noninvasive pattern for NPC therapy. Herein, we developed a lysosome-targeted and pH-responsive nanophototheranostic for near-infrared II (NIR-II) fluorescence imaging-guided photodynamic therapy (PDT) and photothermal therapy (PTT) of NPC. A lysosome-targeted S-D-A-D-S-type NIR-II phototheranostic molecule (IRFEM) is encapsulated within the acid-sensitive amphiphilic DSPE-Hyd-PEG2k to form IRFEM@DHP nanoparticles (NPs). The prepared IRFEM@DHP exhibits a good accumulation in the acidic lysosomes for facilitating the release of IRFEM, which could disrupt lysosomal function by generating an amount of heat and ROS under laser irradiation. Moreover, the guidelines of NIR-II fluorescence enhance the accuracy of PTT/PDT for NPC and avoid damage to normal tissues. Remarkably, IRFEM@DHP enable efficient antitumor effects both in vitro and in vivo , opening up a new avenue for precise NPC theranostics.

Celangulin V is a novel botanical insecticide with significant bioactivity and a unique molecular target, but its complex polyol ester structure hinders its broader application in agriculture. To discover new analogues of celangulin V with a simpler structure and enhanced biological activities, we initiated a research project aimed at simplifying its structure and assessing insecticidal efficacy. In this study, a series of novel 1-tetralone derivatives were designed via a structure-based rational design approach and synthesized by a facile method. The biological activities of the target compounds were determined against Mythimna separata ( M. separata ), Plutella xylostella , and Rhopalosiphum padi . The results revealed that most of the synthesized compounds exhibited superior activities compared to celangulin V. Remarkably, the insecticidal activity of compound 6.16 demonstrated 102-fold greater stomach toxicity than celangulin V against M. separata . In addition, certain compounds showed significant contact toxicity against M. separata , a finding not reported previously in the structural optimization studies of celangulin V. Molecular docking analysis illustrated that the binding pocket of compound 6.16 with the H subunit of V-ATPase was the same as celangulin V. This study presents novel insights into the structural optimization of botanical pesticides.