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Alcoholic liver disease (ALD) is the predominant type of liver disease worldwide, resulting in significant mortality and a high disease burden. ALD damages multiple organs, including the liver, gut, and brain, causing inflammation, oxidative stress, and fat deposition. In this study, we investigated the effects of rice protein peptides (RPP) on ALD in mice with a primary focus on the gut microbiota and liver metabolites. The results showed that administration of RPP significantly alleviated the symptoms of ALD in mice including adiposity, oxidative stress, and inflammation. The KEGG pathway shows that RPP downregulates the liver metabolite of capric acid and the metabolism of fatty acid biosynthesis compared with the MOD group. Mechanistically, RPP downregulated the PPARγ signaling pathway and suppressed the expression of fatty acid biosynthesis genes (FASN, ACC1, ACSL1, and ACSL3). Furthermore, two active peptides (YLPTKQ and PKLPR) with potential therapeutic functions for ALD were screened by Caco-2 cell modeling and molecular docking techniques. In addition, RPP treatment alleviates gut microbiota dysbiosis by reversing the F/B ratio, increasing the relative abundance of Alloprevotella and Alistipes , and upregulating the level of short-chain fatty acids. In conclusion, RPP alleviates ALD steatosis through the PPARγ signaling pathway by YLPTKQ and PKLPR and regulates gut microbiota.

Microwave Wireless Power Transfer (MWPT) technology is crucial for emergency power supply during natural disasters and powering off-grid equipment. Traditional antenna arrays, however, suffer from low energy capture efficiency, difficult impedance matching, complex synthetic networks, and intricate manufacturing processes. This paper introduces a microwave energy receiver design utilizing Reflective Phase Gradient Metasurfaces (R-PGMs) and surface wave energy convergence technology. The design leverages the effective plane wave-to-surface wave conversion capability of R-PGMs to transform incident microwave energy into a surface wave mode, which is then efficiently harvested using a circular energy convergence array before being output to a coupling port. By optimizing R-PGM parameters, an ideal 60° phase gradient distribution is achieved, facilitating the focus of surface wave energy via dispersion characteristics. These components are integrated into a hybrid antenna array, complemented by a matched energy output port structure. Numerical simulations show that this array can efficiently convert microwave energy from plane waves to surface waves, achieving a conversion efficiency of 85.32% and a collection efficiency of 68.26%. Experimental results corroborate these findings, with peak energy collection efficiency reaching 64.68% at 5.8 GHz and an RF-DC conversion efficiency of 42%, confirming the design's efficacy. Compared to conventional methods, this design simplifies the system by avoiding complex combining networks and significantly enhances the efficiency of microwave MWPT.

The occurrence of adhesive failure under impact poses significant risks, including property damage, structural collapse, and even loss of life. Herein, we have developed a series of impact-resistant adhesives by incorporating dynamic B-O linkages into linear polymeric chains. These adhesives not only possess broad-area adhesion and superior adhesive strength compared to 3 M commercial products but also exhibit a shear-stiffening effect. The shear-stiffening effect provided by the B-O linkages endows the adhesives with remarkable impact resistance, achieving a force attenuation efficiency of 84.3-86.3%. Additionally, when they are bonded to target materials, the resulting sandwich structures retain their excellent impact resistance. Therefore, this class of impact-resistant adhesives with a shear-stiffening effect shows significant potential for applications in protecting precision instruments and buildings.

Owing to the overlapping and cross-interference of absorption lines in multicomponent gases, the simultaneous measurement of such gases via laser absorption spectroscopy frequently necessitates the use of supplementary pressure sensors to distinguish the spectral lines. Alternatively, it requires multiple lasers combined with time-division multiplexing to independently scan the absorption peaks of each gas, thereby preventing interference from other gases. This inevitably escalates both the cost of the system and the complexity of the gas pathway. In response to these challenges, a mid-infrared sensor employing a neural network-based decoupling algorithm for aliasing spectral is developed, enabling the simultaneous detection of methane(CH 4 ), water vapor(H 2 O), and ethane(C 2 H 6 ). The sensor system underwent evaluation in a controlled laboratory environment. Allan deviation analysis revealed that the minimum detection limits for CH 4 ,H 2 O, and C 2 H 6 were 6.04, 118.44, and 1 ppb, respectively, with an averaging time of 3 s. The performance of the proposed sensor demonstrates that the aliasing spectral decoupling algorithm based on neural network combined with wavelength-modulated spectroscopy technology has the advantages of high sensitivity, low cost and low complexity, showing its potential for simultaneous detection of multicomponent trace gases in various fields.

Rice protein peptide (RPP) has been reported to alleviate the symptoms of dextran sulfate sodium (DSS)-induced colitis, but its potential protective effect and fundamental neurobiological mechanisms against DSS-induced inflammatory bowel disease (IBD), coupled with depression and cognitive impairment, remain unclear. In this study, RPP treatment in DSS-induced mice inhibited decreases in body weight and colon length and improved intestinal barrier function and behavioral performance. RPP treatment enhanced phenylalanine and tyrosine metabolism in the brains of mice, and it upregulated metabolites such as l-dopa, phenylethylamine, and 3,4-dihydroxyphenylacetate. Additionally, RPP treatment enhanced the brain-derived neurotrophic factor (BDNF) by upregulating the BDNF/TrkB/CREB signaling pathway. Spearman's correlation analysis revealed that the phenylalanine and tyrosine contents in the brain were significantly negatively correlated with the BDNF/TrkB/CREB signaling pathway and behavioral performance. In conclusion, this study suggested that RPP may serve as a unique nutritional strategy for preventing IBD and its associated cognitive impairment and depression symptoms.

Aldehyde dehydrogenase (ALDH) is an enzyme responsible for converting aldehyde functional groups into carboxylate metabolites. Elevated ALDH activity is a characteristic feature of cancer stem-like cells (CSCs). As a novel approach to target the CSC trait of overexpressing ALDH, we aimed to utilize ALDH activity for the selective accumulation of a photosensitizer in ALDH High CSCs. A novel ALDH substrate photosensitizer, SCHO , with thionylated coumarin and N -ethyl-4-(aminomethyl)benzaldehyde was developed to achieve this goal. Our study demonstrated the efficient metabolism of the aldehyde unit of SCHO into carboxylate, leading to its accumulation in ALDH High MDA-MB-231 cells. Importantly, we established the selectivity of SCHO as an ALDH High cell photosensitizer as it is not a substrate for ABC transporters. SCHO -based photodynamic therapy triggers apoptosis and pyroptosis in MDA-MB-231 cells and further reduces the characteristics of CSCs. Our study presents a novel strategy to target CSCs by exploiting their cellular metabolism to enhance photosensitizer accumulation, highlighting the potential of photodynamic therapy as a powerful tool for eliminating ALDH High CSCs., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Breast cancer is a malignant tumor, with various subtypes showing different behaviors. Endogenous H 2 O 2 is an important marker of tumor progression, which makes it important to study the relationship between breast cancer subtypes and H 2 O 2 for pathogenesis and treatment strategies, but this has rarely been reported so far. In this work, we constructed a three-dimensional (3D) electrochemiluminescence (ECL) sensing platform for the detection of H 2 O 2 released from two typical subtypes of breast cancer cells (MCF-7 cells for luminal A-type and MDA-MB-231 cells for three negative breast cancers, TNBCs). To adequately replicate the tumor microenvironment, the peptide hydrogel was introduced as a scaffold for 3D cell culture. The titanium foam (TF) was used as a 3D electrode to better match the 3D culture substrate. N -(4-Aminobutyl)- N -ethylisoluminol (ABEI) was selected as the ECL emitter and assembled into the peptide hydrogel by hydrogen bonding and π-stacking, which resulted in a stable and homogeneous distribution of ABEI along the hydrogel fibers. Furthermore, basic amino acids were introduced to provide alkaline microenvironment for ABEI. Therefore, ABEI exhibited high ECL efficiency, resulting in a high sensitivity with an ultralow detection limit of 0.023 nM (S/N = 3) for H 2 O 2 of the proposed ECL biosensor. MCF-7 and MDA-MB-231 cells were cultured in a 3D peptide hydrogel/ABEI/TF electrode, respectively, and endogenous H 2 O 2 was successfully monitored. A notably significant difference of H 2 O 2 released between MDA-MB-231 cells and MCF-7 cells without stimulation but similar extra release with stimulation were observed. These findings may help understand the physiological mechanisms behind the various subtypes and reactive oxygen species (ROS)-related treatment for breast cancer.

Deep-water oilfields frequently employ large or superlarge well spacing, leading to significant production dynamics influenced by reservoir factors. Traditional methodologies often disregard these influences, resulting in poor accuracy. Therefore, an enhanced prediction methodology rooted in reservoir characteristics is proposed. This approach introduces the dynamic relative permeability law as a bridge, capturing macroscopic oil/water movement within the reservoir. For the first time, it integrates production dynamics with key controlling reservoir factors, encompassing reservoir architecture, injection-production connectivity, and reservoir heterogeneity. The results indicate that (1) In deep-water turbidite sandstone fields with ultralarge injector-producer well spacings, the distribution of oil-water movement is primarily influenced by reservoir connectivity and heterogeneity. The injection water sweeping ability coefficient can quantitatively describe the water flooding capacity, with a strong negative correlation between the injection water sweeping ability coefficient and interwell nonconnectivity coefficient and reservoir homogeneity coefficient. This suggests that better reservoir connectivity or weaker heterogeneity results in stronger water flooding capacity, leading to a wider range of water flooding under the same injection volume. (2) For regions with strong water flooding capacity (injection water sweeping ability coefficient 0.30-0.80), the water-free production period is the main production stage, with a focus on improving the planar flooding conditions. For regions with poor water flooding capacity (injection water sweeping ability coefficient 0.00-0.10), the middle and late water-cut periods are the main production stages, with a focus on improving interlayer dynamic differences in the later stages. For regions with moderate water flooding capacity (injection water sweeping ability coefficient 0.10-0.30), the initial focus should be on expanding planar flooding, followed by a focus on improving interlayer dynamic differences in the later stages. (3) The dynamic relative permeability law, capable of comprehensively portraying the reservoir's influence on macroscopic oil/water movement, emerges as a rational choice for production performance prediction in such contexts. Our method can improve the accuracy, compared with traditional method without geographical factors, from 45% to 90% during water-cut rising stage and 31% to 81% during production declining stage. The high prediction accuracy (90%) observed in the AKPO oilfields underscores the method's efficacy in directing on-site optimization and adjustments for the development of deep-water turbidite sandstone oilfields., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Inflammatory bowel disease (IBD) is an idiopathic intestinal inflammatory disease, whose etiology is intimately related to the overproduction of hypochlorous acid (HClO). Optical monitoring of HClO in the living body favors real-time diagnosis of inflammatory diseases. However, HClO-activated near-infrared (NIR) fluorescent probes with rapid response and high inflammatory cell uptake are still lacking. Herein, we report an activatable acceptor-π-acceptor (A-π-A)-type NIR fluorescent probe ( Cy-DM ) bearing two d-mannosamine groups for the sensitive detection of HClO in early IBD and stool testing. Once reacted with HClO, nonfluorescent Cy-DM could be turned on within 2 s by generating a donor-π-acceptor (D-π-A) structure due to the enhanced intramolecular charge transfer mechanism, showing intense NIR fluorescence emission at 700 nm and a large Stokes shift of 115 nm. Moreover, it was able to sensitively and selectively image exogenous and endogenous HClO in the lysosomes of living cells with a detection limit of 0.84 μM. More importantly, because of the d-mannosamine modification, Cy-DM was efficiently taken up by inflammatory cells in the intestine after intravenous administration, allowing noninvasive visualization of endogenous HClO in a lipopolysaccharide-induced IBD mouse model with a high fluorescence contrast of 6.8/1. In addition, water-soluble Cy-DM has also been successfully applied in ex vivo optical fecal analysis, exhibiting a 3.4-fold higher fluorescence intensity in the feces excreted by IBD mice. We believe that Cy-DM is promising as an invaluable tool for rapid diagnosis of HClO-related diseases as well as stool testing.

Organic dyes with simultaneously boosted near-infrared-II (NIR-II) fluorescence, type I photodynamic therapy (PDT), and photothermal therapy (PTT) in the aggregate state are still elusive due to the unclear structure-function relationship. Herein, electron-withdrawing substituents are introduced at the 5-indolyl positions of BODIPY dyes to form tight J-aggregates for enhanced NIR-II fluorescence and type I PDT/PTT. The introduction of an electron-rich julolidine group at the meso position and an electron-withdrawing substituent (-F) at the indolyl moiety can enhance intermolecular charge transfer and the hydrogen bonding effect, contributing to the efficient generation of superoxide radicals in the aggregate state. The nanoparticles of BDP-F exhibit NIR-II fluorescence at 1000 nm, good superoxide radical generation ability, and a high photothermal conversion efficiency (50.9%), which enabled NIR-II fluorescence-guided vasculature/tumor imaging and additive PDT/PTT. This work provides a strategy for constructing phototheranostic agents with enhanced NIR-II fluorescence and type I PDT/PTT for broad biomedical applications.

The repair of critical-sized bone defects continues to pose a challenge in clinics. Strontium (Sr), recognized for its function in bone metabolism regulation, has shown potential in bone repair. However, the underlying mechanism through which Sr 2+ guided favorable osteogenesis by modulating macrophages remains unclear, limiting their application in the design of bone biomaterials. Herein, Sr-incorporated bioactive glass (SrBG) was synthesized for further investigation. The release of Sr ions enhanced the immunomodulatory properties and osteogenic potential by modulating the polarization of macrophages toward the M2 phenotype. In vivo , a 3D-printed SrBG scaffold was fabricated and showed consistently improved bone regeneration by creating a prohealing immunological microenvironment. RNA sequencing was performed to explore the underlying mechanisms. It was found that Sr ions might enhance the mitochondrial function of macrophage by activating PI3K/AKT/mTOR signaling, thereby favoring osteogenesis. Our findings demonstrate the relationship between the immunomodulatory role of Sr ions and the mitochondrial function of macrophages. By focusing on the mitochondrial function of macrophages, Sr 2+ -mediated immunomodulation sheds light on the future design of biomaterials for tissue regenerative engineering.

Reactive oxygen species (ROS) have emerged as a promising treatment option for antibacterial and biofilm eradication. However, their therapeutic efficacy is significantly hampered by the unique microenvironments of diabetic wounds. In this study, we designed and synthesized porphyrin-based Fe covalent organic frameworks (Fe-COF) through a Schiff base condensation reaction. Subsequently, Fe-COF were encapsulated with hyaluronic acid (HA) through electrostatic adsorption, resulting in a novel formulation named HA-Fe-COF for diabetic wound healing. HA-Fe-COF were engineered to respond to hyaluronidase in the infected wound, leading to the controlled release of Fe-COF. Those released Fe-COF served a dual role as photosensitizers, generating singlet oxygen and localized heating when exposed to dual light sources. Additionally, they acted as peroxidase-like nanozymes, facilitating the production of ROS through enzymatic reactions. This innovative approach enabled a synergistic therapeutic effect combining photodynamic, photothermal, and chemodynamic modalities. Furthermore, the sustained release of HA from HA-Fe-COF promoted angiogenesis, collagen deposition, and re-epithelialization during the diabetic wound healing process. This "all-in-one" strategy offers a novel approach for the development of antimicrobial and biofilm eradication strategies that minimize damage to healthy tissues in vivo.

P2-type Na 2/3 Ni 1/3 Mn 2/3 O 2 (PNNMO) has been extensively studied because of its desirable electrochemical properties as a positive electrode for sodium-ion batteries. PNNMO exhibits intralayer transition-metal ordering of Ni and Mn and intralayer Na + /vacancy ordering. The Na + /vacancy ordering is often considered a major impediment to fast Na + transport and can be affected by transition-metal ordering. We show by neutron/X-ray diffraction and density functional theory (DFT) calculations that Li doping (Na 2/3 Li 0.05 Ni 1/3 Mn 2/3 O 2 , LFN5) promotes ABC-type interplanar Ni/Mn ordering without disrupting the Na + /vacancy ordering and creates low-energy Li-Mn-coordinated diffusion pathways. A structure model is developed to quantitatively identify both the intralayer cation mixing and interlayer cationic stacking fault densities. Quasielastic neutron scattering reveals that the Na + diffusivity in LFN5 is enhanced by an order of magnitude over PNNMO, increasing its capacity at a high current. Na 2/3 Ni 1/4 Mn 3/4 O 2 (NM13) lacks Na + /vacancy ordering but has diffusivity comparable to that of LFN5. However, NM13 has the smallest capacity at a high current. The high site energy of Mn-Mn-coordinated Na compared to that of Ni-Mn and higher density of Mn-Mn-coordinated Na + sites in NM13 disrupts the connectivity of low-energy Ni-Mn-coordinated diffusion pathways. These results suggest that the interlayer ordering can be tuned through the control of composition, which has an equal or greater impact on Na + diffusion than the Na + /vacancy ordering.

The early detection of nonalcoholic fatty liver disease (NAFLD) through bioluminescent probes is of great significance. However, there remains a challenge to apply them in nontransgenic natural animals due to the lack of exogenous luciferase. To address this issue, we herein report a new strategy for in situ monitoring of endogenous hydrogen sulfide (H 2 S) in the liver of NAFLD mice by leveraging a H 2 S-responsive bioluminescent probe ( H-Luc ) combined with firefly luciferase (fLuc) mRNA delivery. The probe H-Luc was created by installing a H 2 S recognition moiety, 2,4-dinitrophenol, onto the luciferase substrate (d-luciferin), which is allowed to release cage-free d-luciferin in the presence of H 2 S via a nucleophilic aromatic substitution reaction. In the meantime, the intracellular luciferase was introduced by lipid nanoparticle (LNP)-mediated fLuc mRNA delivery, rendering it suitable for bioluminescence (BL) imaging in vitro and in vivo. Based on this luciferase-luciferin system, the endogenous H 2 S could be sensitively and selectively detected in living cells, showing a low limit of detection (LOD) value of 0.72 μM. More importantly, after systematic administration of fLuc mRNA-loaded LNPs in vivo, H-Luc was able to successfully monitor the endogenous H 2 S levels in the NAFLD mouse model for the first time, displaying a 28-fold higher bioluminescence intensity than that in the liver of normal mice. We believe that this strategy may shed new light on the diagnosis of inflammatory liver disease, further elucidating the roles of H 2 S.

Transition metal oxides are promising catalysts for catalytic oxidation reactions but are hampered by low room-temperature activities. Such low activities are normally caused by sparse reactive sites and insufficient capacity for molecular oxygen (O 2 ) activation. Here, we present a dual-stimulation strategy to tackle these two issues. Specifically, we import highly dispersed nickel (Ni) atoms onto MnO 2 to enrich its oxygen vacancies (reactive sites). Then, we use molecular ozone (O 3 ) with a lower activation energy as an oxidant instead of molecular O 2 . With such dual stimulations, the constructed O 3 -Ni/MnO 2 catalytic system shows boosted room-temperature activity for toluene oxidation with a toluene conversion of up to 98%, compared with the O 3 -MnO 2 (Ni-free) system with only 50% conversion and the inactive O 2 -Ni/MnO 2 (O 3 -free) system. This leap realizes efficient room-temperature catalytic oxidation of transition metal oxides, which is constantly pursued but has always been difficult to truly achieve.

Herein, a new intramolecular palladium(II)-catalyzed regioselective 6- endo-trig or 6- exo-trig annulation through direct C-H activation is presented as a method for the diversity-oriented synthesis of highly substituted quinolinones from pyridones. The reaction occurs under mild conditions and exhibits excellent regioselectivity, good functional group tolerance, and broad applications. This innovative approach has been successfully utilized in the synthesis of Glycopentanolone A and an intermediate of ( R )-(+)-Tipifarnib.

Engineering symmetry breaking in thermoelectric materials holds promise for achieving an optimal thermoelectric efficiency. van der Waals (vdW) layered transition metal dichalcogenides (TMDCs) provide critical opportunities for manipulating the intrinsic symmetry through in-plane symmetry breaking interlayer twists and out-of-plane symmetry breaking heterostructures. Herein, the symmetry-dependent thermoelectric properties of MoS 2 and MoSe 2 obtained via first-principles calculations are reported, yielding an advanced ZT of 2.96 at 700 K. The underlying mechanisms reveal that the in-plane symmetry breaking results in a lowest thermal conductivity of 1.96 W·m -1 ·K -1 . Additionally, the electric properties can be significantly modulated through band flattening and bandgap alteration, stemming directly from the modified interlayer electronic coupling strength owing to spatial repulsion effects. In addition, out-of-plane symmetry breaking induces band splitting, leading to a decrease in the degeneracy and complex band structures. Consequently, the power factor experiences a notable enhancement from ∼1.32 to 1.71 × 10 -2 W·m -1 ·K -2 , which is attributed to the intricate spatial configuration of charge densities and the resulting intensified intralayer electronic coupling. Upon simultaneous implementation of in-plane and out-of-plane symmetry breaking, the TMDCs exhibit an indirect bandgap to direct bandgap transition compared to the pristine structure. This work demonstrates an avenue for optimizing thermoelectric performance of TMDCs through the implementation of symmetry breaking.

Drug-induced liver injury (DILI) is a common liver disease with a high rate of morbidity, and its pathogenesis is closely associated with the overproduction of highly reactive hypochlorite (ClO - ) in the liver. However, bioluminescence imaging of endogenous hypochlorite in nontransgenic natural mice remains challenging. Herein, to address this issue, we report a strategy for imaging ClO - in living cells and DILI mice by harnessing a bioluminescent probe formylhydrazine luciferin ( ClO-Luc ) combined with firefly luciferase (fLuc) mRNA-loaded lipid nanoparticles (LNPs). LNPs could efficiently deliver fLuc mRNA into living cells and in vivo, expressing abundant luciferase in the cytoplasm in situ. In the presence of ClO - , probe ClO-Luc locked by formylhydrazine could release cage-free d-luciferin through oxidation and follow-up hydrolysis reactions, further allowing for bioluminescence imaging. Moreover, based on the luciferase-luciferin system, it was able to sensitively and selectively detect ClO - in vitro with a limit of detection of 0.59 μM and successfully monitor the endogenous hypochlorite generation in the DILI mouse model for the first time. We postulate that this work provides a new method to elucidate the roles of ClO - in related diseases via bioluminescence imaging.

Rice protein peptides (RPP) are a potentially valuable source of high-quality calcium chelating properties. However, there is a lack of information regarding the calcium-absorption-promoting effect of RPP and its underlying mechanism. The present study adopted molecular docking methodologies to analyze the 10 most potent peptide segments from RPP. Results revealed that the peptide AHVGMSGEEPE (AHV) displayed optimal calcium binding properties (calcium-chelating capacity 55.69 ± 0.66 mg/g). Quantum chemistry analysis revealed that the AHV peptide effectively binds and forms stable complexes with calcium via the carbonyl oxygen atoms in valine at position 3 and the carbonyl of the C-terminal carboxyl group of glutamate at position 11. The spectral analysis results indicated that AHV may bind to calcium through carboxyl oxygen atoms, resulting in a transition from a smooth surface block-like structure to a dense granular structure. Furthermore, this study demonstrated that the 4 mmol/L AHV-Ca chelate (61.75 ± 13.23 μg/well) significantly increases calcium absorption compared to 1 mM CaCl 2 (28.57 ± 8.59 μg/well) in the Caco-2 cell monolayer. In terms of mechanisms, the novel peptide-calcium chelate AHV-Ca derived from RPP exerts a cell-level effect by upregulating the expression of TRPV6 calcium-ion-channel-related genes and proteins (TRPV6 and Calbindin-D9k). This study provides a theoretical basis for developing functional foods with the AHV peptide as ingredients to improve calcium absorption.

Dry reforming of methane (DRM) is a promising technique for converting greenhouse gases (namely, CH 4 and CO 2 ) into syngas. However, traditional thermocatalytic processes require high temperatures and suffer from low selectivity and coke-induced instability. Here, we report high-entropy alloys loaded on SrTiO 3 as highly efficient and coke-resistant catalysts for light-driven DRM without a secondary source of heating. This process involves carbon exchange between reactants (i.e., CO 2 and CH 4 ) and oxygen exchange between CO 2 and the lattice oxygen of supports, during which CO and H 2 are gradually produced and released. Such a mechanism deeply suppresses the undesired side reactions such as reverse water-gas shift reaction and methane deep dissociation. Impressively, the optimized CoNiRuRhPd/SrTiO 3 catalyst achieves ultrahigh activity (15.6/16.0 mol g metal h -1 for H -1 /CO production), long-term stability (∼150 h), and remarkable selectivity (∼0.96). This work opens a new avenue for future energy-efficient industrial applications.2 /CO production), long-term stability (∼150 h), and remarkable selectivity (∼0.96). This work opens a new avenue for future energy-efficient industrial applications.

Suspended particulate matter (SPM) carries a major fraction of metals in turbid coastal waters, markedly influencing metal bioaccumulation and posing risks to marine life. However, its effects are often overlooked in current water quality criteria for metals, primarily due to challenges in quantifying SPM's contribution. This contribution depends on the SPM concentration, metal distribution coefficients ( K d ), and the bioavailability of SPM-bound metals (assimilation efficiency, AE), which can collectively be integrated as a modifying factor (MF). Accordingly, we developed a new stable isotope method to measure metal AE by individual organisms from SPM, employing the widely distributed filter-feeding clam Ruditapes philippinarum as a representative species. Assessing SPM from 23 coastal sites in China, we found average AEs of 42% for Zn, 26% for Cd, 20% for Cu, 8% for Ni, and 6% for Pb. Moreover, using stable isotope methods, we determined metal K d of SPM from these sites, which can be well predicted by the total organic carbon and iron content ( R 2 = 0.977). We calculated MFs using a Monte Carlo method. The calculated MFs are in the range 9.9-43 for Pb, 8.5-37 for Zn, 2.9-9.7 for Cu, 1.4-2.7 for Ni, and 1.1-1.6 for Cd, suggesting that dissolved-metal-based criteria values should be divided by MFs to provide adequate protection to aquatic life. This study provides foundational guidelines to refine water quality criteria in turbid waters and protect coastal ecosystems.

After spinal cord injury (SCI), successive systemic administration of microtubule-stabilizing agents has been shown to promote axon regeneration. However, this approach is limited by poor drug bioavailability, especially given the rapid restoration of the blood-spinal cord barrier. There is a pressing need for long-acting formulations of microtubule-stabilizing agents in treating SCI. Here, we conjugated the antioxidant idebenone with microtubule-stabilizing paclitaxel to create a heterodimeric paclitaxel-idebenone prodrug via an acid-activatable, self-immolative ketal linker and then fabricated it into chondroitin sulfate proteoglycan-binding nanomedicine, enabling drug retention within the spinal cord for at least 2 weeks and notable enhancement in hindlimb motor function and axon regeneration after a single intraspinal administration. Additional investigations uncovered that idebenone can suppress the activation of microglia and neuronal ferroptosis, thereby amplifying the therapeutic effect of paclitaxel. This prodrug-based nanomedicine simultaneously accomplishes neuroprotection and axon regeneration, offering a promising therapeutic strategy for SCI.

The combination of anti-rheumatoid arthritis (RA) drugs methotrexate (MTX) and baricitinib (BTN) has been reported to improve RA treatment efficacy. However, study on the strategy of combination is elusive when considering the benefit of the synergy between MTX and BTN. In this study, we found that the N-heterocyclic rings in the MTX and BTN offer hydrogen bonds and π-π stacking interactions, driving the formation of exquisite vesicular morphology of nanovesicles, denoted as MB NVs. The MB NVs with the MTX/BTN weight ratio of 2:1, MB NVs (2:1), showed an improved anti-RA effect through the synergy between the anti-inflammatory and antiproliferative responses. This work presents that the intermolecular interactions between drug molecules could mediate the coassembly behavior into nanomedicine as well as the therapy synergy both in vitro and in vivo , which may provide further understanding on the rational design of combination nanomedicine for therapeutic purposes.

We present a direct δ-amination reaction of sp 3 C-H bonds, employing molecular iodine (I 2 ) as the sole oxidant under transition-metal-free conditions. This remote C-H functionalization approach is operationally simple and provides facile, efficient access to pyrrolidines and related heterocyclic derivatives from readily accessible substrates.

The structural exploration of three-dimensional covalent organic frameworks (3D COFs) is of great significance to the development of COF materials. Different from structurally diverse MOFs, which have a variety of connectivity (3-24), now the valency of 3D COFs is limited to only 4, 6, and 8. Therefore, the exploration of organic building blocks with higher connectivity is a necessary path to broaden the scope of 3D COF structures. Herein, for the first time, we have designed and synthesized a 12-connected triptycene-based precursor (triptycene-12-CHO) with 12 symmetrical distributions of aldehyde groups, which is also the highest valency reported until now. Based on this unique 12-connected structure, we have successfully prepared a novel 3D COF with lnj topology (termed 3D-lnj-COF). The as-synthesized 3D COF exhibits honeycomb main pores and permanent porosity with a Brunauer-Emmett-Teller surface area of 1159.6 m 2 g -1 . This work not only provides a strategy for synthesizing precursors with a high connectivity but also provides inspiration for enriching the variety of 3D COFs.

Glioblastoma (GBM) is the most complex and lethal primary brain cancer. Adequate drug diffusion and penetration are essential for treating GBM, but how the spatial heterogeneity in GBM impacts drug diffusion and transport is poorly understood. Herein, we report a new method, photoactivation of plasmonic nanovesicles (PANO), to measure molecular diffusion in the extracellular space of GBM. By examining three genetically engineered GBM mouse models that recapitulate key clinical features including the angiogenic core and diffuse infiltration, we found that the tumor margin has the lowest diffusion coefficient (highest tortuosity) compared with the tumor core and surrounding brain tissue. Analysis of the cellular composition shows that tortuosity in the GBM is strongly correlated with neuronal loss and astrocyte activation. Our all-optical measurement reveals the heterogeneous GBM microenvironment and highlights the tumor margin as a diffusion barrier for drug transport in the brain, with implications for therapeutic delivery.

Structurally, FL118 is a camptothecin analogue and possesses exceptional antitumor efficacy against human cancer through a novel mechanism of action (MOA). In this report, we have synthesized and characterized 24 FL118 Position 7-substituted and 24 FL118 Position 9-substituted derivatives. The top compounds were further characterized for their MOA in colorectal cancer (CRC) models using CRC patient-derived xenograft (PDX) models and pancreatic cancer PDX models to evaluate their antitumor activities. Four FL118 Position 7-substituted derivatives showed significantly better antitumor efficacy than the FL118 Position 9-substituted derivatives. The four identified compounds also appeared to have better antitumor activity than their parental platform FL118. Interestingly, RNA-Seq analyses indicated that three of the four compounds exerted antitumor effects via an MOA similar to FL118, which provided an intriguing opportunity for follow-up studies. Extended in vivo studies revealed that FL77-6 (7-(4-ethylphenyl)-FL118), FL77-9 (7-(4-methoxylphenyl)-FL118), and FL77-24 (7-(3, 5-dimethoxyphenyl)-FL118) exhibit potential for further development toward clinical trials.

Biocompatible fluorescent probes have emerged as essential tools in life sciences for visualizing subcellular structures and detecting specific analytes. Herein, we report the synthesis and characterization of a novel fluorescent probe (TPE-FdU), incorporated with hydrophilic 2'-fluoro-substituted deoxyuridine and hydrophobic ethynyl tetraphenylethene moieties, which possessed typical aggregation-induced emission (AIE) behavior. In comparison to the TPE-FdU (p K a 7.68) treated in neutral conditions, it performed well at pH 4, exhibiting an enhanced 450 nm emission signal of approximately four times stronger. As the pH value was increased to 10, the fluorescence intensity was completely quenched. The TEM images of TPE-FdU in an acidic environment (nanospherical morphology, AIE enhance, pH = 4) and in a basic environment (microrods, fluorescence quenching, pH = 9) revealed that it was a pH-dependent self-assembled probe, which was also illustrated by the interpretation of the NMR spectrum. Furthermore, the TPE-FdU probe exhibited a specific response to trace Hg 2+ ions. Interestingly, the quenched fluorescence of the TPE-FdU probe caused by Hg 2+ can be recovered by the addition of GSH due to the formation of the Hg-S bond being released away. MTT assay and CLSM images demonstrated that TPE-FdU was nontoxic and selectively visualized in the intracellular mitochondria. These results contributed to the development of advanced fluorescent probes with diverse applications in cell imaging, environment protection, and biomedical research.

Niobium pentoxide (Nb 2 O 5 ) is a promising negative electrode for sodium ion batteries (SIBs). By engineering the morphology and crystallinity of nanochanneled niobium oxides (NCNOs), the kinetic behavior and charge storage mechanism of Nb 2 O 5 electrodes were investigated. Amorphous and crystalline NCNO samples were made by modulating anodization conditions (20-40 V and 140-180 °C) to synthesize nanostructures of varying pore sizes and wall thicknesses with identical chemical composition. The electrochemical energy storage properties of the NCNOs were studied, with the amorphous samples showing better overall rate performance than the crystalline samples. The enhanced rate performance of the amorphous samples is attributed to the higher capacitive contributions and Na-ion diffusivity analyzed from cyclic voltammetry (CV) and the galvanostatic intermittent titration technique (GITT). It was found that the amorphous samples with smaller wall thicknesses facilitated improved kinetics. Among samples with similar pore size and wall thickness, the difference in their power performance stems from the crystallinity effect, which plays a more significant role in the resulting kinetics of the materials for Na-ion batteries., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Mouthguards are used to prevent craniomaxillofacial injuries when collisions happen during contact and high-speed sports. However, poor compliance with mouthguard wear in athletes is attributed to discomfort because of its thickness and hardness. These drawbacks significantly restrict their protective performance for oral tissues and applications during contact sports; as a result, the incidence of craniomaxillofacial injuries increases. In this study, non-Newton material is introduced into mouthguard material and then a mouthguard with shear-stiffening behavior is fabricated, which is named the shear-stiffening mouthguard (SSM). Compared with commercial mouthguard materials (Erkoflex and Erkoloc-pro), SSMs show remarkable enhancement of shock absorption ability with an approximately 60% reduction in peak force relative to commercial materials and approximately 3-fold extensive buffer time. Moreover, Young's modulus of SSMs (average 0.48 MPa) is extremely lower compared to commercial materials (22.88 MPa for Erkoflex and 26.71 MPa for Erkoloc-pro). This manifests that SSMs have not only excellent shock absorption ability but also softness perception. Moreover, SSMs show biocompatibility in vitro. In conclusion, this work provides a platform to develop a new type of thin and soft mouthguard with a shear-stiffening effect and broadens the horizon in protecting oral tissues with shear-stiffening materials.

Lipid nanoparticles (LNPs) represent the most clinically advanced nonviral mRNA delivery vehicles; however, the full potential of the LNP platform is greatly hampered by inadequate endosomal escape capability. Herein, we rationally introduce a disulfide bond-bridged ester linker to modularly synthesize a library of 96 linker-degradable ionizable lipids (LDILs) for improved mRNA delivery in vivo. The top-performing LDILs are composed of one 4A3 amino headgroup, four disulfide bond-bridged linkers, and four 10-carbon tail chains, whose unique GSH-responsive cone-shaped architectures endow optimized 4A3-SCC-10 and 4A3-SCC-PH lipids with superior endosomal escape and rapid mRNA release abilities, outperforming their parent lipids 4A3-SC-10/PH without a disulfide bond and control lipids 4A3-SSC-10/PH with a disulfide bond in the tail. Notably, compared to DLin-MC3-DMA via systematic administration, 4A3-SCC-10- and 4A3-SCC-PH-formulated LNPs significantly improved mRNA delivery in livers by 87-fold and 176-fold, respectively. Moreover, 4A3-SCC-PH LNPs enabled the highly efficient gene editing of 99% hepatocytes at a low Cre mRNA dose in tdTomato mice following intravenous administration. Meanwhile, 4A3-SCC-PH LNPs were able to selectively deliver firefly luciferase mRNA and facilitate luciferase expression in tumor cells after intraperitoneal injection, further improving cancer metastasis delineation and surgery via bioluminescence imaging. We envision that the chemistry adopted here can be further extended to develop new biodegradable ionizable lipids for broad applications such as gene editing and cancer immunotherapy.

Green pea hull is a processing byproduct of green pea and rich in polyphenols. Nonalcoholic fatty liver disease (NAFLD) is a chronic metabolic disease characterized by accumulation of lipids in the liver for which there are no effective treatment strategies. Here, a mouse model of NAFLD induced by a DSS+high-fat diet (HFD) was established to investigate the effect of green pea hull polyphenol extract (EGPH). The results show that EGPH relief of NAFLD was a combined effect, including reducing hepatic fat accumulation, improving antioxidant activity and blood lipid metabolism, and maintaining glucose homeostasis. Increased intestinal permeability aggravated NAFLD. Combined metabolomics and transcriptomic analysis showed that vitamin B6 is the key target substance for EGPH to alleviate NAFLD, and it may be the intestinal flora metabolite. After EGPH intervention, the level of vitamin B6 in mice was significantly increased, and more than 60% in the blood enters the liver, which activated or inhibited PPAR and TLR4/NF-κB signaling pathways to relieve NAFLD. Our research could be a win-win for expanding the use of green pea hull and the search for NAFLD prophylactic drugs.

Electrochemical CO or CO 2 reduction reactions (CO (2) RR), powered by renewable energy, represent one of the promising strategies for upgrading CO 2 to valuable products. To design efficient and selective catalysts for the CO (2) RR, a comprehensive mechanistic understanding is necessary, including a comprehensive understanding of the reaction network and the identity of kinetically relevant steps. Surface-adsorbed CO (CO ad ) is the most commonly reported reaction intermediate in the CO (2) RR, and its surface coverage (θ CO ) and binding energy are proposed to be key to the catalytic performance. Recent experimental evidence sugguests that θ CO on Cu electrode at electrochemical conditions is quite low (∼0.05 monolayer), while relatively high θ CO is often assumed in literature mechanistic discussion. This Perspective briefly summarizes existing efforts in determining θ CO on Cu surfaces, analyzes mechanistic impacts of low θ CO on the reaction pathway and catalytic performance, and discusses potential fruitful future directions in advancing our understanding of the Cu-catalyzed CO (2) RR., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

In this study, we developed an innovative highly specific nucleic acid isothermal detection assay based on prokaryotic DNA polymerase I with exquisitely designed fluorescent probes, achieving high sensitivity and 100% specificity within 30 min. The fluorescent nucleic acid probe was designed and constructed based on the specific flap cleavage endonuclease activity of prokaryotic DNA polymerase I (including the Bst, Bsu, Bsm , and Klenow DNA polymerases). The flap endonuclease activity depends on the length of the flap DNA and polymerization activity, which greatly reduces the false-positive rate caused by primer dimerization. This robust assay was also validated by the detection of rotavirus with great specificity and sensitivity. It could be a great alternative to qPCR in the field of point-of-care detection of pathogens.

Intracellular dynamic assembly of DNA structures may be beneficial for the development of multifunctional nanoplatforms for the regulation of cell behaviors, providing new strategies for disease diagnosis and intervention. Herein, we propose the dynamic assembly of DNA coacervates in living cells triggered by miRNA-21 and K + , which can be used for both miRNA imaging and mitochondrial intervention. The rationale is that miRNA-21 can trigger the hybridization chain reaction to generate G-quadruplex precursors, and K + can mediate the assembly of G-quadruplex-based coacervates, allowing the colorimetric detection of miRNA-21 ranging from 10 pM to 10 μM. Moreover, the as-formed DNA coacervates can specifically target mitochondria in MCF-7 breast cancer cells using the MCF-7 cell membrane as delivery carriers, which further act as an anionic shielding to inhibit communication between mitochondria and environments, with a significant inhibitory effect on ATP production and cellular migration behaviors. This work provides an ideal multifunctional nanoplatform for rationally interfering with cellular metabolism and migration behaviors through the dynamic assembly of DNA coacervates mediated by endogenous molecules, which has a large number of potential applications in the biomedical field, especially theranostics for cancer metastasis.

Low-dimensional perovskites (LDPs) have enormous potential for the development of advanced optoelectronic devices and tackling the stability issue for the commercial application of perovskites. However, quantified structural dimensionality prediction for LDPs is still an intractable issue. Herein, we develop a self-established machine learning (ML)-assisted approach to predict the dimensionality of LDPs based on 195 reported amines that are classified as two-dimensional, one-dimensional, and zero-dimensional. The optimal K-nearest neighbor model allows us to realize an accuracy rate of 92.3% for the test data set containing 39 reported amines. Two features, i.e., ATSC1pe and SlogP_VSA2, associated with polarity and electrostatic potential on the van der Waals surface of an organic spacer, are identified from >1800 descriptors as key controlling factors determining the structure dimensionality. This work develops a typical paradigm for the application of a multiple-classification strategy of ML with an extremely high accuracy rate, which would thereby motivate the development of new types of LDPs.

Developing stable cathode materials that are resistant to storage degradation is essential for practical development and industrial processing of Na-ion batteries as many sodium layered oxide materials are susceptible to hygroscopicity and instability upon exposure to ambient air. Among the various layered compounds, Fe-substituted O3-type Na(Ni 1/2 Mn 1/2 ) 1- x Fe x O 2 materials have emerged as a promising option for high-performance and low-cost cathodes. While previous reports have noted the decent air-storage stability of these materials, the role and origin of Fe substitution in improving storage stability remain unclear. In this study, we investigate the air-resistant effect of Fe substitution in O3-Na(Ni 1/2 Mn 1/2 ) 1- x Fe x O 2 cathode materials by performing systematic surface and structural characterizations. We find that the improved storage stability can be attributed to the multifunctional effect of Fe substitution, which forms a surface protective layer containing an Fe-incorporated spinel phase and decreases the thermodynamical driving force for bulk chemical sodium extraction. With these mechanisms, Fe-containing cathodes can suppress the cascades of cathode degradation processes and better retain the electrochemical performance after air storage.

Noninvasive visualization of liver polarity by using fluorescence imaging technology is helpful to better understand drug-induced liver injury (DILI). However, cell membrane-targeted polarity-sensitive near-infrared (NIR) fluorescent probes are still scarce. Herein, we report a non-solvatochromic cell membrane-targeted NIR small molecular probe ( N-BPM-C 10 ) for monitoring the polarity changes on cell membranes in living cells and in vivo. N-BPM-C 10 exhibits polarity-dependent fluorescence around 655 nm without an obvious solvatochromic effect, which endows it with good capability for the in vivo imaging study. Moreover, it can rapidly and selectively light up the cell membranes as well as distinguish tumor cells from normal cells due to its excellent polarity-sensitive ability. More importantly, N-BPM-C 10 has been successfully applied to visualize liver polarity changes in vivo, revealing the reduction of liver polarity in DILI mice. We believe that N-BPM-C 10 provides a new way for the diagnosis of DILI.

Oral administration of probiotics is a promising method to alleviate inflammatory bowel diseases (IBDs). However, gastrointestinal environmental sensitivity and inferior intestinal colonization of probiotics hinder the alleviation effect. Here, we developed a simple yet effective modified prebiotic-based "shield" (Fe-TA@mGN) composed of an Fe 3+ -tannic acid cross-linking network and carboxymethylated β-glucan for arming Escherichia coli Nissle 1917 (EcN@Fe-TA@mGN). The Fe-TA@mGN "shield" not only acted as a dynamic barrier to enhance the gastrointestinal stress resistance ability of EcN but also aided the intestinal colonization of EcN as well as synergized with EcN for the alleviation of dextran sulfate sodium (DSS) induced colitis. More specifically, with the protection of the Fe-TA@mGN "shield", the survival rate of armed EcN could be up to ∼1720 times higher than that of bare EcN after exposure to simulated gastric fluid. Excitingly, the intestinal retention rate of EcN@Fe-TA@mGN was as high as 47.54 ± 6.06% at 16 h post-administration, while almost all bare EcNs were excreted out at 8 h post-administration. With all of the aforementioned attributes, EcN@Fe-TA@mGN efficiently alleviated colitis, verified by the repair of the intestinal barrier and the attenuation of inflammation. Moreover, for EcN@Fe-TA@mGN, mGN synergized with EcN to positively modulate gut microbiota and promote the production of short-chain fatty acids (SCFAs, especially for butyric acid, a primary source for maintaining intestinal health), both of which would further advance the alleviation of colitis. We envision that the strategy developed here will inspire the exploitation of various prebiotics to arm probiotics for the effective alleviation of IBD.

Solid-electrolyte interphases (SEIs) in advanced rechargeable batteries ensure reversible electrode reactions at extreme potentials beyond the thermodynamic stability limits of electrolytes by insulating electrons while allowing the transport of working ions. Such selective ion transport occurs naturally in biological cell membranes as a ubiquitous prerequisite of many life processes and a foundation of biodiversity. In addition, cell membranes can selectively open and close the ion channels in response to external stimuli (e.g., electrical, chemical, mechanical, and thermal), giving rise to "gating" mechanisms that help manage intracellular reactions. We wondered whether the chemistry and structure of SEIs can mimic those of cell membranes, such that ion gating can be replicated. That is, can SEIs realize a reversible switching between two electrochemical behaviors, i.e., the ion intercalation chemistry of batteries and the ion adsorption of capacitors? Herein, we report such SEIs that result in thermally activated selective ion transport. The function of open/close gate switches is governed by the chemical and structural dynamics of SEIs under different thermal conditions, with precise behaviors as conducting and insulating interphases that enable battery and capacitive processes within a finite temperature window. Such an ion gating function is synergistically contributed by Arrhenius-activated ion transport and SEI dissolution/regrowth. Following the understanding of this new mechanism, we then develop an electrochemical method to heal the SEI layer in situ. The knowledge acquired in this work reveals the possibility of hitherto unknown biomimetic properties of SEIs, which will guide us to leverage such complexities to design better SEIs for future battery chemistries.

Inflammation-related diseases affect large populations of people in the world and cause substantial healthcare burdens, which results in significant costs in time, material, and labor. Preventing or relieving uncontrolled inflammation is critical for the treatment of these diseases. Herein, we report a new strategy for alleviating inflammation by macrophage reprogramming via targeted reactive oxygen species (ROS) scavenging and cyclooxygenase-2 (COX-2) downregulation. As a proof of concept, we synthesize a multifunctional compound named MCI containing a mannose-based macrophage targeting moiety, an indomethacin (IMC)-based segment for inhibiting COX-2, and a caffeic acid (CAF)-based section for ROS clearance. As revealed by a series of in vitro experiments, MCI could significantly attenuate the expression of COX-2 and the level of ROS, leading to M1 to M2 macrophage reprogramming, as evidenced by the reduction and the elevation in the levels of pro-inflammatory M1 markers and anti-inflammatory M2 markers, respectively. Furthermore, in vivo experiments show MCI's promising therapeutic effects on rheumatoid arthritis (RA). Our work illustrates the success of targeted macrophage reprogramming for inflammation alleviation, which sheds light on the development of new anti-inflammatory drugs.

Resistance to traditional antiepileptic drugs is a major challenge in chronic epilepsy treatment. MicroRNA-based gene therapy is a promising alternative but has demonstrated limited efficacy due to poor blood-brain barrier permeability, cellular uptake, and targeting efficiency. Adenosine is an endogenous antiseizure agent deficient in the epileptic brain due to elevated adenosine kinase (ADK) activity in reactive A1 astrocytes. We designed a nucleic acid nanoantiepileptic drug (tFNA-ADK ASO @AS1) based on a tetrahedral framework nucleic acid (tFNA), carrying an antisense oligonucleotide targeting ADK (ADK ASO ) and A1 astrocyte-targeted peptide (AS1). This tFNA-ADK ASO @AS1 construct effectively reduced brain ADK, increased brain adenosine, mitigated aberrant mossy fiber sprouting, and reduced the recurrent spontaneous epileptic spike frequency in a mouse model of chronic temporal lobe epilepsy. Further, the treatment did not induce any neurotoxicity or major organ damage. This work provides proof-of-concept for a novel antiepileptic drug delivery strategy and for endogenous adenosine as a promising target for gene-based modulation.

Although cytotoxic treatments hold tremendous potential in boosting antitumor immunity, efferocytosis of tumor-associated macrophages (TAMs) could negatively remove apoptotic tumor cells through LC3-associated phagocytosis (LAP), resulting in inefficient tumor antigen presentation and immunosuppressive tumor microenvironment. To address this issue, we developed TAM-targeting nanospores (PC-CW) inspired by the predominant tropism of Rhizopus oryzae toward macrophages. To construct PC-CW, we disguised poly(sodium- p -styrenesulfonate) (PSS)-coated polyethylenimine (PEI)-shRNA nanocomplexes with the cell wall of R. oryzae conidia. LAP blockade by PC-CW delayed the degradation of engulfed tumor debris within TAMs, which not only enhanced antigen presentation but also initiated the domino effect of the antitumor immune response through STING signaling and TAM repolarization. Benefiting from this, PC-CW successfully sensitized the immune microenvironment and amplified CD8 + T cell responses following chemo-photothermal therapy, leading to substantial tumor growth control and metastasis prevention in tumor-bearing mouse models. The bioengineered nanospores represent a simple and versatile immunomodulatory strategy targeting TAMs for robust antitumor immunotherapy.

Boron-based nonmetallic materials (such as B 2 O 3 and BN) emerge as promising catalysts for selective oxidation of light alkanes by O 2 to form value-added products, resulting from their unique advantage in suppressing CO 2 formation. However, the site requirements and reaction mechanism of these boron-based catalysts are still in vigorous debate, especially for methane (the most stable and abundant alkane). Here, we show that hexagonal BN ( h -BN) exhibits high selectivities to formaldehyde and CO in catalyzing aerobic oxidation of methane, similar to Al 2 O 3 -supported B 2 O 3 catalysts, while h -BN requires an extra induction period to reach a steady state. According to various structural characterizations, we find that active boron oxide species are gradually formed in situ on the surface of h -BN, which accounts for the observed induction period. Unexpectedly, kinetic studies on the effects of void space, catalyst loading, and methane conversion all indicate that h -BN merely acts as a radical generator to induce gas-phase radical reactions of methane oxidation, in contrast to the predominant surface reactions on B 2 O 3 /Al 2 O 3 catalysts. Consequently, a revised kinetic model is developed to accurately describe the gas-phase radical feature of methane oxidation over h -BN. With the aid of in situ synchrotron vacuum ultraviolet photoionization mass spectroscopy, the methyl radical (CH 3 ) is further verified as the primary reactive species that triggers the gas-phase methane oxidation network. Theoretical calculations elucidate that the moderate H-abstraction ability of predominant CH • ) is further verified as the primary reactive species that triggers the gas-phase methane oxidation network. Theoretical calculations elucidate that the moderate H-abstraction ability of predominant CH 3 • and CH 3 OO • radicals renders an easier control of the methane oxidation selectivity compared to other oxygen-containing radicals generally proposed for such processes, bringing deeper understanding of the excellent anti-overoxidation ability of boron-based catalysts.

The pursuit of better sensitivity has always been one of the central themes in Raman spectroscopy. Recently, all-far-field single-molecule Raman spectroscopy has been demonstrated by a novel hybrid spectroscopy that couples Raman scattering with fluorescence emission. However, such frequency-domain spectroscopy lacks efficient hyperspectral excitation methods and encounters intrinsic strong fluorescence backgrounds from electronic transitions, hindering its applications in advanced Raman spectroscopy and microscopy. Here we report the ultrafast time-domain spectroscopy counterpart named transient stimulated Raman excited fluorescence (T-SREF): excited by two successive broadband femtosecond pulse pairs (i.e., the pump and Stokes pulses) with time-delay scanning, strong vibrational wave packet interference is revealed on the time-domain fluorescence trace, resulting in background-free spectra of the corresponding Raman modes after the Fourier transform. T-SREF achieves background-free Raman spectra of electronic-coupled vibrational modes with sensitivity up to the level of a few molecules, which paves the way for supermultiplexed fluorescence detection and molecular dynamics sensing.

A Fe(NO 3 ) 3 -mediated ring-opening arylation of cyclopropanol with the electron-rich pyrrole has been developed, which might proceed through oxidative radical ring opening of cyclopropanol followed by cyclization to the pyrrole motif and then aromatization. This method enables direct arylation of cyclopropanol without prefunctionalization and thus allows rapid access to a diverse array of chiral 5,6,7,8-tetrahydroindolizines from easily available chiral amino acid esters. The synthetic utility has been demonstrated by the asymmetric synthesis of alklaoids (-)-indolizidine 167B, (+)-indolizidine 209D, (+)-monomorine I, and a natural product analogue.

Electron-induced structural changes influence the characterizations of the local structure of various materials by electron microscope. However, for beam-sensitive materials, it is still challenging to detect such changes by electron microscopy, which may help us quantitatively reveal how electrons interact with materials under electron irradiation. Here, we use an emergent phase contrast technique in electron microscopy to clearly image a metal-organic framework, UiO-66 (Zr), at an ultralow electron dose and dose rate. The effects of both the dose and dose rate on the UiO-66 (Zr) structure are visualized, which induce obvious missing organic linkers. The kinetics of the missing linker based on the radiolysis mechanism are semiquantitatively expressed by the different intensities of the imaged organic linkers. Deformation of the UiO-66 (Zr) lattice after the missing linker is also observed. These observations make it possible to visually investigate the electron-induced chemistry in various beam-sensitive materials and avoid electron damage to them.

Neuropeptides are abundant and essential signaling molecules in the nervous system involved in modulating neural circuits and behavior. Neuropeptides are generally released extrasynaptically and signal via volume transmission through G-protein-coupled receptors (GPCR). Although substantive functional roles of neuropeptides have been discovered, many questions on neuropeptide transmission remain poorly understood, including the local diffusion and transmission properties in the brain extracellular space. To address this challenge, intensive efforts are required to develop advanced tools for releasing and detecting neuropeptides with high spatiotemporal resolution. Because of the rapid development of biosensors and materials science, emerging tools are beginning to provide a better understanding of neuropeptide transmission. In this perspective, we summarize the fundamental advances in understanding neuropeptide transmission over the past decade, highlight the tools for releasing neuropeptides with high spatiotemporal solution in the brain, and discuss open questions and future directions in the field.

n s 2 -Metal halide perovskites have attracted wide attention due to their fascinating photophysical properties. However, achieving high photoluminescence (PL) properties is still an enormous challenge, and the relationship between the lattice environment and n s 2 -electron expression is still elusive. Herein, an organic-inorganic Bi 3+ -based halide (C 5 H 14 N 2 ) 2 BiCl 6 ·Cl·2H 2 O (C 5 H 14 N 2 2+ = doubly protonated 1-methylpiperazine) with a six-coordinated structure has been successfully prepared, which, however, exhibits inferior PL properties due to the chemically inert expression of Bi 3+ -6s 2 lone-pair electrons. After reasonably embedding Sb 3+ with 5s 2 H 5 H 14 N 2 ) 2 BiCl 6 ·Cl·2H 2 H 5 H 14 N 2 ) 2 BiCl 6 ·Cl·2H 2 O, the expression of Sb 3+ -5s 2 lone-pair electrons is improved and thus promotes the radiative recombination from the Sb 3+ - 3 P 1 state, resulting in the enhanced PL efficiency. This work will provide an in-depth insight into the effect of the local structure on the expression of Sb 3+ -5s 2 lone-pair electrons.

Surface and interface, with unique local characteristics different from bulk structure, are of great significance in various applications of metal-organic frameworks (MOFs), which should be studied by real-space imaging methods, such as electron microscopy. However, it is still challenging to atomically resolve these local structures in MOFs, because they are even more sensitive to electron irradiation. Here, we use integrated differential phase contrast scanning transmission electron microscopy (iDPC-STEM) to achieve the atomic imaging of both the metal nodes and organic linkers in UiO-66 (Zr) nanocrystals and their assembly. After adding acetic acid, we modulate the whole process of MOF assembly and observe the organic linkers at both the surfaces and twin interfaces in the chemically assembled UiO-66 (Zr) crystals by the iDPC-STEM. These results bring us a deeper understanding on the role of acid modulators that promote the MOF assembly by generating the missing-linker defects on the crystal surface.