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Immunotherapy holds significant promise for cancer treatment. However, the highly immunosuppressive nature of solid tumors limits its effectiveness. Herein, we developed bioactive zinc-nickel hydroxide (ZnNi(OH) 4 ) nanosheets (NSs) that can effectively initiate the paraptosis-pyroptosis positive feedback cycle through synergistic ionic effect, thereby mitigating the immunosuppression of solid tumors and enhancing the efficacy of immunotherapy. The acid-sensitive ZnNi(OH) 4 NSs releases Ni 2+ and Zn 2+ in the weakly acidic tumor microenvironment. The released Ni 2+ alleviated pyroptosis inhibition by inducing paraptosis and inhibiting autophagic flux. Concurrently, Ni 2+ triggered release of endogenous Zn 2+ within the cell through a coordination competition mechanism, further amplifying zinc overload-mediated pyroptosis. Interestingly, pyroptosis-associated oxidative stress and endoplasmic reticulum stress further promote Ni 2+ -mediated paraptosis, forming a positive feedback loop between pyroptosis and paraptosis. This process not only effectively kills tumor cells but also stimulates a strong inflammatory response, enhancing the antitumor immune response and immunotherapy efficacy. Overall, this study proposes an effective paraptosis-pyroptosis induction strategy based on metal ions and demonstrates the effectiveness of the positive feedback loop of paraptosis-pyroptosis in potentiating immunotherapy.

The enantioselective synthesis of chiral 4-substituted 4,5-dihydro-1 H -[1,5]benzodiazepin-2(3 H )-ones via asymmetric hydrogenation catalyzed by the Pd/f-spiroPhos complex in the presence of hydrochloric acid as an additive has been developed, achieving excellent enantioselectivities and high turnover numbers, up to 99% ee and TON = 4600. More significantly, the asymmetric reductive amination of β-keto esters with 1,2-phenylenediamine has also been successfully realized to afford chiral 4-substituted 4,5-dihydro-1 H -[1,5]benzodiazepin-2(3 H )-ones with comparable enantioselectivities of up to 99% ee.

The thorium bipyridyl metallocene (Cp 3 t Bu ) 2 Th(bipy) ( 1 ; Cp 3 t Bu = η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ) shows a rich reactivity toward a series of small molecules. For example, complex 1 may act as a synthon for the (Cp 3 t Bu ) 2 Th(II) fragment as illustrated by its reactivity toward to CuI, hydrazine derivative (PhNH) 2 , Ph 2 E 2 ( E = S, Se), elemental sulfur (S 8 ) and selenium (Se), organic azides, CS 2 , and isothiocyanates. Moreover, in the presence of polar multiple bonds, such as those in ketones Ph 2 CO and (CH 2 ) 5 CO, aldehydes p -MePhCHO and p -ClPhCHO, seleno-ketone ( p -MeOPh) 2 CSe, nitriles PhCN, Ph 2 CHCN, C 6 H 11 CN, and p -(NC) 2 Ph, and benzoyl cyanide PhCOCN, C-C coupling occurs to furnish (Cp 3 t Bu ) 2 Th[(bipy)(Ph 2 CO)] ( 10 ), (Cp 3 t Bu ) 2 Th[(bipy)((CH 2 ) 5 CO)] ( 11 ), (Cp 3 t Bu ) 2 Th[(bipy)( p -MePhCHO)] ( 12 ), (Cp 3 t Bu ) 2 Th[(bipy)( p -ClPhCHO)] ( 13 ), (Cp 3 t Bu ) 2 Th[(bipy){( p -MeOPh) 2 CSe}] ( 14 ), (Cp 3 t Bu ) 2 Th[(bipy)(PhCN)] ( 16 ), (Cp 3 t Bu ) 2 Th[(bipy)(Ph 2 CHCN)] ( 17 ), (Cp 3 t Bu ) 2 Th[(bipy)(C 6 H 11 CN)] ( 18 ), [(Cp 3 t Bu ) 2 Th] 2 {μ-(bipy)[ p -Ph(CN) 2 ](bipy)} ( 20 ), and (Cp 3 t Bu ) 2 Th{(bipy)[PhC(CN)O]} ( 21 ), respectively. Nevertheless, ketazine (PhCH═N) 2 or benzyl nitrile PhCH 2 CN forms the dimeric complexes [(Cp 3 t Bu )Th] 2 [μ-NC(Ph)(bipy)] 2 ( 15 ) and (Cp 3 t Bu ) 2 Th[(bipy){C(═CHPh)NH}] ( 19 ), respectively. In contrast, C-N bond cleavage and C-C coupling processes occur upon addition of isonitriles Me 3 CNC and C 6 H 11 NC to 1 to yield the thorium isocyanido amido complexes (Cp 3 t Bu ) 2 Th[4-(Me 3 C)bipy](NC) ( 22 ) and (Cp 3 t Bu ) 2 Th[4-(C 6 H 11 )bipy](NC) ( 23 ), respectively. Furthermore, a single-electron transfer (SET) process ensues when 1 equiv of CuI is added to 1 to yield the Th(VI) bipyridyl iodide complex (Cp 3 t Bu ) 2 Th(I)(bipy) ( 3 ).

A highly enantioselective Ir-catalyzed asymmetric hydrogenation of 2,5-disubstituted pyrrolo[1,2- a ][1,2,4]triazolo[5,1- c ]pyrazines containing four nitrogen atoms has been first realized. Under additive-free conditions, a variety of chiral 2,5-disubstituted 5,6-dihydropyrrolo[1,2- a ][1,2,4]triazolo[5,1- c ]pyrazines can be afforded in high yields (86-98%) with excellent enantioselectivities of up to 99% ee. This method provides a straightforward strategy for the efficient synthesis of chiral multinitrogen polyheterocyclic compounds.

Dihydrogen complexes, which retain the H-H bond, have been extensively studied in molecular science and found to be prevalent in homogeneous and enzymatic catalysis. However, their counterparts in heterogeneous catalysis, specifically nondissociative chemisorbed dihydrogen binding on the catalyst surface, are rarely reported experimentally. This scarcity is due to the complexity of typical material surfaces and the lack of effective characterization techniques to prove and distinguish various dihydrogen binding modes. Herein, using high-pressure operando solid-state NMR technology, we report the first unambiguous experimental observation of activated dihydrogen binding on a reduced ceria catalyst through interactions with surface oxygen vacancies. By employing versatile NMR structural and dynamical analysis methods, we establish a proportional relationship between the degree of ceria surface reduction and dihydrogen binding, as evidenced by NMR observations of H-D through-bond coupling ( J HD ), T 1 relaxation, and proton isotropic chemical shifts. In situ NMR analysis further reveals the participation of bound dihydrogen species in a room-temperature ethylene hydrogenation reaction. The remarkable similarities between surface-activated dihydrogen in heterogeneous catalysis and dihydrogen model molecular complexes can provide valuable insights into the hydrogenation mechanism for many other solid catalysts, potentially enhancing hydrogen utilization.

Iron metabolism has emerged as a promising target for cancer therapy; however, the innate metabolic compensatory capacity of cancer cells significantly limits the effectiveness of iron metabolism therapy. Herein, bioactive gallium sulfide nanodots (GaS x ), with dual functions of "reprogramming" and "interfering" iron metabolic pathways, were successfully developed for tumor iron metabolism therapy. The constructed GaS x nanodots ingeniously harness hydrogen sulfide (H 2 S) gas, which is released in response to the tumor microenvironment, to reprogram the inherent transferrin receptor 1 (TfR1)-ferroportin 1 (FPN1) iron metabolism axis in cancer cells. Concurrently, the gallium ions (Ga 3+ ) derived from GaS x act as a biochemical "Trojan horse", mimicking the role of iron and displacing it from essential biomolecular binding sites, thereby influencing the fate of cancer cells. By leveraging the dual mechanisms of Ga 3+ -mediated iron disruption and H 2 S-facilitated reprogramming of iron metabolic pathways, GaS x prompted the initiation of a paraptosis-apoptosis hybrid pathway in cancer cells, leading to marked suppression of tumor proliferation. Importantly, the dysregulation of iron metabolism induced by GaS x notably increased tumor cell susceptibility to both chemotherapy and immune checkpoint blockade (ICB) therapy. This study underscores the therapeutic promise of gas-based interventions and metal ion interference strategies for the tumor metabolism treatment.

Small extracellular vesicles (sEVs) are proven to hold great promise for diverse therapeutic and diagnostic applications. However, batch preparation of sEVs with high purity and bioactivity is a prerequisite for their clinical translations. Herein, we present an electric field assisted tangential flow filtration system (E-TFF), which integrates size-based filtration with electrophoretic migration-based separation to synergistically achieve the isolation of high-quality sEVs from cell culture medium. Compared with the gold-standard ultracentrifugation (UC) method, E-TFF not only improved the purity of sEVs by 1.4 times but also increased the yield of sEVs by 15.8 times. Additionally, the entire isolation process of E-TFF was completed within 1 h, about one-fourth of the time taken by UC. Furthermore, the biological activity of sEVs isolated by E-TFF was verified by co-incubation of sEVs derived from human umbilical cord mesenchymal stem cells (hUCMSCs) with HT22 mouse hippocampal neuronal cells exposed to amyloid-β (Aβ). The results demonstrated that the sEVs isolated by E-TFF exhibited a significant neuroprotective effect. Overall, the E-TFF platform provides a promising and robust strategy for batch preparation of high-quality sEVs, opening up a broad range of opportunities for cell-free therapy and precision medicine.

Due to the immature intestinal digestion, immunity, and barrier functions, weaned infants are more susceptible to pathogens and develop diarrhea. Microplastics (MPs), pervasive contaminants in food, water, and air, have unknown effects on the intestinal development of weaned infants. This study explored the impact of polystyrene MPs on intestinal development using a weaned piglet model. Piglets in the control group received a basal diet, and those in the experimental groups received a basal diet contaminated with 150 mg/kg polystyrene MPs. The results showed that exposure to polystyrene MPs increased the diarrhea incidence and impaired the intestinal barrier function of weaned piglets. Notably, the exposure led to oxidative stress and inflammation in the intestine. Furthermore, polystyrene MPs-treated weaned piglets showed a reduced level of intestinal angiogenesis. Mechanistically, polystyrene MPs suppressed methyltransferase-like 3 (METTL3) expression by increasing reactive oxygen species (ROS) production, consequently destabilizing angiogenic factors' mRNA and hindering intestinal angiogenesis. In summary, polystyrene MPs contamination in the diet increases diarrhea and compromises intestinal angiogenesis through the ROS/METTL3 pathway, demonstrating their toxic effects on the intestine health of weaned infants.

Rh-catalyzed asymmetric hydrogenation of 2-substituted 4 H -thiochromenes and 4 H -chromenes was successfully developed. This method provided highly efficient access to a series of chiral 2-substituted thiochromanes and chromanes in high yields with excellent enantioselectivities (up to 99% yield, 86-99% ee). The obtained chiral 2-substituted thiochromane products were also successfully transformed to corresponding chiral α- substituted sulfoxides and sulfones with excellent enantioselectivities. Furthermore, this highly enantioselective hydrogenation process could be successfully applied to the concise and practical synthesis of the chiral pharmaceutical BW683C.

The structure of and bonding in two base-free terminal actinide imido metallocenes, [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 An═N( p -tolyl) (An = U ( 1 ), Th ( 1' )) are compared and connected to their individual reactivity. While structurally rather similar, the U(IV) derivative 1 is slightly more sterically crowded. Furthermore, density functional theory (DFT) studies imply that the 5f orbital contribution to the bonding within the individual actinide imido An═N( p -tolyl) moieties is significantly larger for 1 than for 1' , which makes the bonds between the [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 U 2+ and [( p -tolyl)N] 2- fragments more covalent. Therefore, steric and electronic factors impact the reactivity of these imido complexes. For example, complex 1 is inert toward internal alkynes, but it readily forms Lewis base adducts [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 U═N( p -tolyl)(L) (L = OPMe 3 ( 6 ), dmap ( 9 ), PhCN ( 14 ), and 2,6-Me 2 PhNC ( 17 )) with Me 3 PO, 4-dimethylaminopyridine (dmap), nitrile, PhCN, or isonitrile 2,6-Me 2 PhNC. It may also react as a nucleophile or undergo a [2 + 2] cycloaddition with CS 2 , isothiocyanates, thio-ketones, ketones, lactides, and acyl nitriles, forming the four- or five-membered metallaheteroacycles, terminal sulfido, or oxido complexes, and cyanide amidate complexes, respectively. In contrast, after the addition of aldehyde p -tolylCHO, the tetranuclear complex [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 4 [OCH( p -tolyl)CH( p -tolyl)O] 2 U 4 O 4 ( 10 ) is isolated. However, while 1 is unreactive toward dicyclohexylcarbodiimide (DCC), an equilibrium exists in benzene solution between N , N' -diisopropylcarbodiimide (DIC), 1 , and the four-membered metallaheterocycle [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 U[N( p -tolyl)C(═N i Pr)N( i Pr)] ( 12 ). Furthermore, 1 may also engage in single- and two-electron transfer processes. It is singly oxidized by Ph 3 CN 3 , CuI, Ph 2 S 2 , and Ph 2 Se 2 , yielding the uranium(V) imido complexes [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 U═N( p -tolyl)(X) (X = N 3 ( 20 ), I ( 22 ), PhS ( 23 ), and PhSe ( 24 )), or is doubly oxidized by organic azides (RN 3 ) and 9-diazofluorene, forming the uranium(VI) bis-imido metallocenes [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 U═N( p -tolyl)(=NR) (R = p -tolyl ( 18 ), mesityl ( 19 )) and [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 U=N( p -tolyl)[=NN=(9-C 13 H 8 )] ( 21 ), respectively.

The immunosuppressive microenvironment of cervical cancer significantly hampers the effectiveness of immunotherapy. Herein, PEGylated manganese-doped calcium sulfide nanoparticles (MCSP) were developed to effectively enhance the antitumor immune response of the cervical cancer through gas-amplified metalloimmunotherapy with dual activation of pyroptosis and STING pathway. The bioactive MCSP exhibited the ability to rapidly release Ca 2+ , Mn 2+ , and H 2 S in response to the tumor microenvironment. H 2 S disrupted the calcium buffer system of cancer cells by interfering with the oxidative phosphorylation pathway, leading to calcium overload-triggered pyroptosis. On the other hand, H 2 S-mediated mitochondrial dysfunction further promoted the release of mitochondrial DNA (mtDNA), enhancing the activation effect of Mn 2+ on the cGAS-STING signaling axis and thereby activating immunosuppressed dendritic cells. The released H 2 S acted as an important synergist between Mn 2+ and Ca 2+ by modulating dual signaling mechanisms to bridge innate and adaptive immune responses. The combination of MCSP NPs and PD-1 immunotherapy achieved synergistic antitumor effects and effectively inhibited tumor growth. This study reveals the potential collaboration between H 2 S gas therapy and metalloimmunotherapy and provides an idea for the design of nanoimmunomodulators for rational regulation of the immunosuppressive tumor microenvironment.

Aqueous ammonium ion hybrid supercapacitor (A-HSC) is an efficient energy storage device based on nonmetallic ion carriers (NH 4 + ), which combines advantages such as low cost, safety, and sustainability. However, unstable electrode structures are prone to structural collapse in aqueous electrolytes, leading to fast capacitance decay, especially in host materials represented by vanadium-based oxidation. Here, the Co 2+ preintercalation strategy is used to stabilize the VO 2 tunnel structure and improve the electrochemical stability of the fast NH 4 + storage process. In addition, the understanding of the NH 4 + storage mechanism has been deepened through ex situ structural characterization and electrochemical analysis. The results indicate that Co 2+ preintercalation effectively enhances the conductivity and structural stability of VO 2 , and inhibits the dissolution of V in aqueous electrolytes. In addition, the charge storage mechanisms of NH 4 + intercalation/deintercalation and the reversible formation/fracture of hydrogen bonds were revealed.

Linear polyisoprene (PI) and SiO 2 - g -PI particle brushes were synthesized by both conventional and activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP). The morphology and solution state study on the particle brushes by transmission electron microscopy (TEM) and dynamic light scattering (DLS) confirmed the successful grafting of PI ligands on the silica surface. The presence of nanoparticle clusters suggests low grafting density (associated with the limited initiation efficiency of ARGET for PI). Nevertheless, particle brushes with very high molecular weights, M n > 300,000, were prepared, which significantly improved the dispersion of silica nanoparticles and also contributed to excellent mechanical performance. The reinforcing effects of SiO 2 nanofillers and very high molecular weight PI ligands were investigated by dynamic mechanical analysis (DMA) as well as computational simulation for the cured linear PI homopolymer/SiO 2 - g -PI particle brush bulk films.

Immunotherapy has emerged as a potential approach for breast cancer treatment. However, the rigid stromal microenvironment and low immunogenicity of breast tumors strongly reduce sensitivity to immunotherapy. To sensitize patients to breast cancer immunotherapy, hyaluronic acid-modified zinc peroxide-iron nanocomposites (Fe-ZnO 2 @HA, abbreviated FZOH) were synthesized to remodel the stromal microenvironment and increase tumor immunogenicity. The constructed FZOH spontaneously generated highly oxidative hydroxyl radicals (·OH) that degrade hyaluronic acid (HA) in the tumor extracellular matrix (ECM), thereby reshaping the tumor stromal microenvironment and enhancing blood perfusion, drug penetration, and immune cell infiltration. Furthermore, FZOH not only triggers pyroptosis through the activation of the caspase-1/GSDMD-dependent pathway but also induces ferroptosis through various mechanisms, including increasing the levels of Fe 2+ in the intracellular iron pool, downregulating the expression of FPN1 to inhibit iron efflux, and activating the p53 signaling pathway to cause the failure of the SLC7A11-GSH-GPX4 signaling axis. Upon treatment with FZOH, 4T1 cancer cells undergo both ferroptosis and pyroptosis, exhibiting a strong immunogenic response. The remodeling of the tumor stromal microenvironment and the immunogenic response of the cells induced by FZOH collectively compensate for the limitations of cancer immunotherapy and significantly enhance the antitumor immune response to the immune checkpoint inhibitor αPD-1. This study proposes a perspective for enhancing immune therapy for breast cancer.

Despite the extensive industrial and research interests in zeolites, their intrinsic catalytic nature is not fully understood due to the complexity of the hydroxyl-aluminum moieties. 17 O NMR would provide irreplaceable opportunities for much-needed fine structural determination given the ubiquitous presence of oxygen atoms in nearly all species; however, the low sensitivity and quadrupolar nature of oxygen-17 make its NMR spectroscopic elucidation challenging. Here, we show that state-of-the-art double resonance solid-state NMR techniques have been combined with spectral editing methods based on scalar (through-bond) and dipolar (through-space) couplings, which allowed us to address the subtle protonic structures in zeolites. Notably, the often-neglected and undesired second-order quadrupolar-dipolar cross-term interaction ("2nd-QD interaction") can actually be exploited and can help gain invaluable information. Eventually, a comprehensive set of 1 H- 17 O/ 1 H- 27 Al double resonance NMR with J -/ D -coupling spectral editing techniques have been designed in this work and enabled us to reveal atomic-scale precise structural and dynamical details in zeolites including: 1) The jump rate of the bridging acid site (BAS) proton is relatively low, i.e., far less than 100 s -1 at room temperature. 2) The Al-OH groups with 1 H chemical shift at 2.6-2.8 ppm, at least for nonseverely dealuminated H-ZSM-5 catalysts, exhibit a rigid bridging environment similar to that of BAS. 3) The Si-OH groups at 2.0 ppm are not hydrogen bonded and undergo fast cone-rotational motion. The results in this study predict the 2nd-QD interaction to be universal for any rigid - 17 O-H environment, such as those in metal oxide surfaces or biomaterials.

In recent years, the utilization of medical devices has gradually increased and implantation procedures have become common treatments. However, patients are susceptible to the risk of implant infections. This study utilized chemical grafting to immobilize polyethylenimine (QPEI) and hyaluronic acid (HA) on the surface of the mesh to improve biocompatibility while being able to achieve antifouling antimicrobial effects. From the in vitro testing, PP-PDA-Q-HA exhibited a high antibacterial ratio of 93% against S. aureus , 93% against E. coli , and 85% against C. albicans . In addition, after five rounds of antimicrobial testing, the coating continued to exhibit excellent antimicrobial properties; PP-PDA-Q-HA also inhibits the formation of bacterial biofilms. In addition, PP-PDA-Q-HA has good hemocompatibility and cytocompatibility. In vivo studies in animal implantation infection models also demonstrated the excellent antimicrobial properties of PP-PDA-Q-HA. Our study provides a promising strategy for the development of antimicrobial surface medical materials with excellent biocompatibility.

Human respiratory adenovirus (ADV) is a highly infectious respiratory virus with potential for pandemics. There are currently no specific drugs to treat ADV worldwide, so early rapid detection of ADV infection is essential. In this study, we developed an innovative magnetic-optical triple-mode lateral flow immunoassay (LFIA) using magnetic quantum dots as immunomarkers. This novel approach addresses the need for rapid and accurate ADV detection, allowing for multimodal quantitative/semiquantitative analysis of magnetic, fluorescent, and visible signals within a mere 15 min. The lower limit of detection (LOD) for magnetic, fluorescent, and visual signals was determined to be 5.6 × 10 3 , 1.2 × 10 3 , and 1.95 × 10 4 copies/mL, respectively. The detection range for ADV using this approach was 1.2 × 10 3 -5 × 10 7 copies/mL. Additionally, semiquantitative analysis, which is user-friendly and does not necessitate specialized equipment, was successfully implemented. Notably, seven respiratory viruses showed no cross-reactivity with the generated LFIA test strips. The intrabatch repeatability exhibited a coefficient of variation (CV) of less than 5%, while the interbatch repeatability had a CV of less than 15%. Furthermore, recovery values ranged from 95% to 106.8% for samples analyzed concurrently with dual signals at the same spiking concentration. The assay developed in this study boasts a wide detection range and exceptional sensitivity and specificity. This technique is exceptionally well-suited for on-site rapid detection, with the potential for personal self-testing and early ADV infection diagnosis. Its versatility extends to a broad array of application scenarios.

Herein, 16 traditional and 13 novel organophosphate esters (OPEs) in skin wipes, personal PM 2.5 , sputum, and nails (fingernails and toenails) and 7 OPE metabolites in urine synchronously obtained from 64 college students were analyzed. Similar compositional profiles of the OPEs were found in skin wipes and nails and in personal PM 2.5 and induced sputum. Significant correlations were observed between the concentrations of high-lipophilicity low-volatility OPEs in skin wipes and nails and between the concentrations of high-volatility low-lipophilicity OPEs in personal PM 2.5 and sputum. These results imply that OPEs in fingernails and toenails may mainly come from external sources rather than internal exposure, and human nails and sputum can be used as indicators of human exposure to OPEs. A comparison between the daily exposure doses of the OPEs in personal PM 2.5 and sputum shows that more volatile compounds may have higher inhalation bioavailability, which should be considered to improve the accuracy of inhalation exposure assessments. According to comprehensive external and internal exposure assessment, dermal absorption may be a more dominant pathway than inhalation, and skin wipes may be the best representative environmental matrix of human exposure to OPEs.

Glioma remains one of the most challenging primary brain malignancies to treat. Long noncoding RNAs (lncRNAs) and mRNAs (mRNAs) are implicated in regulating the malignant phenotypes of cancers including glioma. This study aimed to elucidate the functions and mechanisms of lncRNA LINC00265 and mRNA IFI30 in the pathogenesis of glioma. Quantitative real-time polymerase chain reaction (RT-qPCR) analysis revealed the upregulated expression of LINC00265 and IFI30 in glioma cells compared to normal human astrocytes. Western blot (WB) quantified the associated proteins. Glioma stemness and epithelial-to-mesenchymal transition (EMT) were assessed by aldehyde dehydrogenase 1 (ALDH1) activity, sphere formation, and WB. Mechanistic and rescue assays evaluated the LINC00265/miR-let-7d-5p/IFI30/ZNF384/IGF2BP2 axis. The results demonstrated that LINC00265 and IFI30 were highly expressed in glioma cells, promoting stemness and EMT. ZNF384 was identified as a transcription factor that upregulates IFI30. Moreover, LINC00265 elevated ZNF384 by sponging miR-let-7d-5p and recruiting IGF2BP2. In conclusion, LINC00265 and IFI30 act as oncogenes in glioma by driving stemness and EMT, underscoring their potential as therapeutic targets.

A Rh-catalyzed highly chemo- and enantioselective hydrogenation of 2-CF 3 -chromen/thiochromen-4-ones was successfully established achieving excellent selectivity and high turnover numbers. Under mild conditions, a series of 2-CF 3 -chromen-4-ones were hydrogenated to provide the corresponding chiral 2-CF 3 -chroman-4-ones with excellent enantioselectivities (up to 99.9% ee) and achieve high turnover numbers (TON of up to 11,800). Moreover, the obtained hydrogenation products were also successfully transformed into other derivatives including the important intermediate of plasmepsin inhibitors with maintained enantiopurity.

Rh-( R , R )-f-spiroPhos complex-catalyzed asymmetric hydrogenation of α-substituted alkenyl sulfones has been achieved, affording the chiral γ-keto sulfones and simple α-alkyl-substituted sulfones in high yields (96-99%) with excellent chemo-/enantioselectivities (86-96% ee) and high turnover numbers (TONs) of up to 4000. The method provides an efficient and high-enantioselectivity strategy for chiral γ-keto sulfones and simple α-substituted sulfones under mild conditions. Moreover, the obtained hydrogenation product was transformed into other important chiral α-substituted sulfones.

Ferroptosis holds great potential in cancer treatment, but its efficacy is severely limited by a low Fenton reaction efficacy. Meanwhile, the interactive relationship between Ferroptosis and the PD-1 blockade is still vague. Herein, a hydrazide/Cu/Fe/indocyanine green coordinated nanoplatform (TCFI) is constructed by a hydrazide-metal-sulfonate coordination process. The TCFI nanoplatform exhibits Fenton-/catalase-/glutathione oxidase-like triple activities and accordingly can trigger lipid peroxidation, relieve hypoxia, and downregulate the glutathione/glutathione peroxidase 4 axis, thus achieving positively and negatively dually enhanced Ferroptosis in B16F10 cancer cells. Under near-infrared laser irradiation, the TCFI nanoplatform induces robust immunogenic cancer cell death by elevating the intracellular reactive oxygen species level through synergistic photodynamic therapy/Ferroptosis, which significantly potentiates CD8 + T cell infiltration into tumors and interferon-γ secretion. Moreover, upregulated interferon-γ efficiently inhibits system x c - activity and sensitizes cancer cells to Ferroptosis. Interestingly, the PD-1 blockade may strengthen the reciprocal process. The combination of the TCFI nanoplatform and αPD-1 can eliminate primary tumors and inhibit distant tumor growth, lung metastasis, and tumor recurrence. This study presents a simple and novel coordination strategy to fabricate tumor microenvironment-responsive nanodrugs and highlights the enhancement effect of photodynamic therapy on reciprocal Ferroptosis and antitumor immunity.

Aluminum-doped zinc oxide (AZO) is considered as a promising candidate as transparent conductive oxide (TCO) for silicon heterojunction solar cells due to its high carrier density, nontoxic nature, and low cost. Herein, it is presented that the transparency of the AZO film can be optimized through co-sputtering of AZO and molybdenum oxide (MoO x ). Furthermore, aluminum and molybdenum co-doped zinc oxide (MAZO) can be used as both the TCO layer and electron-selective contact (ESC) for silicon heterojunction solar cells. The surface morphology, cation oxidation state, and optical and electrical properties of all MAZO films are characterized. It is found that the transmittance of all MAZO films is significantly increased at a wavelength of 450-800 nm due to MAZO with a stronger Zn-O bond and a wider band gap. The conductivity of MAZO films is approximate to AZO films at a low MoO x target deposit power (50 W), and the sheet resistance of MAZO films increases significantly by increasing the deposition power up to 100 W. Finally, the optimized MAZO films are used as TCO and ESC for silicon heterojunction solar cells, showing a power conversion efficiency of 19.58%. The results show an effective stage to improve the optical properties of AZO through co-doping and the possibility of applying MAZO as a dual-functional layer for silicon solar cells.

Terminal uranium oxido, sulfido, and selenido metallocenes were synthesized, and their reactivity was comprehensively studied. Heating of an equimolar mixture of [η 5 -1,2,4-(Me 3 Si) 3 C 5 H 2 ] 2 UMe 2 ( 2 ) and [η 5 -1,2,4-(Me 3 Si) 3 C 5 H 2 ] 2 U(NH- p -tolyl) 2 ( 3 ) in the presence of 4-dimethylaminopyridine (dmap) in refluxing toluene forms [η 5 -1,2,4-(Me 3 Si) 3 C 5 H 2 ] 2 U═N( p -tolyl)(dmap) ( 4 ), which is a useful precursor for the preparation of the terminal uranium oxido, sulfido, and selenido metallocenes [η 5 -1,2,4-(Me 3 Si) 3 C 5 H 2 ] 2 U═E(dmap) (E = O ( 5 ), S ( 6 ), Se ( 7 )) employing a cycloaddition-elimination methodology with Ph 2 C═E (E = O, S) or ( p -MeOPh) 2 CSe, respectively. Metallocenes 5 - 7 are inert toward alkynes, but they act as nucleophiles in the presence of alkylsilyl halides. The oxido and sulfido metallocenes 5 and 6 undergo [2 + 2] cycloadditions with isothiocyanate PhNCS or CS 2 , while the selenido derivative 7 does not. The experimental studies are complemented by density functional theory (DFT) computations.

Identification of α-thalassemia silent carriers is challenging with conventional phenotype-based screening methods. A liquid chromatography tandem mass spectrometry (LC-MS/MS)-based approach may offer novel biomarkers to address this conundrum. In this study, we collected dried blood spot samples from individuals with three α-thalassemia subtypes for biomarker discovery and validation. We observed differential expression patterns of hemoglobin subunits among various α-thalassemia subtypes and normal controls through proteomic profiling of 51 samples in the discovery phase. Then, we developed and optimized a multiple reaction monitoring (MRM) assay to measure all detectable hemoglobin subunits. The validation phase was conducted in a cohort of 462 samples. Among the measured hemoglobin subunits, subunit μ was significantly upregulated in all the α-thalassemia groups with distinct fold changes. The hemoglobin subunit μ exhibits great potential as a novel biomarker for α-thalassemia, especially for silent α-thalassemia. We constructed predictive models based on the concentrations of hemoglobin subunits and their ratios to classify the various subtypes of α-thalassemia. In the binary classification problems of silent α-thalassemia vs normal, non-deletional α-thalassemia vs normal, and deletional α-thalassemia vs normal, the best performance of the models achieved average ROCAUCs of 0.9505, 0.9430, and 0.9976 in the cross-validation, respectively. In the multiclass model, the best performance achieved an average ROCAUC of 0.9290 in cross-validation. The performance of our MRM assay and models demonstrated that the hemoglobin subunit μ would play a vital role in screening silent α-thalassemia in clinical practice.

An efficient Ni-( S , S )-Ph-BPE complex that catalyzed asymmetric hydrogenation of cyclic N -acyl hydrazones has been developed to produce various chiral cyclic hydrazines in high yields with excellent enantioselectivities of up to >99% enantiomeric excess. Moreover, the hydrogenation can not only proceed smoothly on a gram scale under lower catalyst loading (S/C = 3000) without any decrease of enantioselectivity but can also be applied to the asymmetric synthesis of a RIP-1 kinase inhibitor.

Oleylamine/oleic acid (OAm/OA) as the commonly used ligand is indispensable in the synthesis of perovskite nanocrystals (PNCs). Unfortunately, poor colloidal stability and unsatisfactory photoluminescence quantum yield (PLQY) are observed, resulting from a highly dynamic binding nature between ligands. Herein, we adopt a facile hybrid ligand (DDAB/ZnBr 2 ) passivation strategy to reconstruct the surface chemistry of CsPbBr 3 NCs. The hybrid ligand can detach the native surface ligand, in which the acid-base reactions between ligands are suppressed effectively. Also, they can substitute the loose capping ligand, anchor to the surface firmly, and supply sufficient halogens to passivate the surface trap, realizing an exceptional PLQY of 95% and an enhanced tolerance toward ambient storage, UV irradiation, anti-solvents, and thermal treatment. Besides, the as-fabricated white light-emitting diode (WLED) utilizing the PNCs as the green-emitting phosphor has a luminous efficiency around 73 lm/W; the color gamut covers 125% of the NTSC standard.

Bistable materials with multiphysical channels, such as optical, electrical, and magnetic properties, have been paid dramatic attention due to their alternativity of the signal status in electronic devices. Herein, three stable supramolecular radicals ([(NH 3 -TEMPO)(18-crown-6)][XF 6 ] ( 1 , X = P; 2 , X = As; 3 , X = Sb)) were synthesized and characterized. The former two molecules present ferroelectric phase transitions around 381.7 and 382.7 K, respectively, with bistability in dielectric property and second-harmonic generation (SHG) effect, which are first found in supramolecular radicals. Their ferroelectric transition and bistable properties are generated from a net polar crystal structure owing to the static ordered packing of NH 3 -TEMPO radical cations in the low-temperature phase (LTP) to a nonpolar structure owing to a distinctive symmetric scissoring motion of NH 3 -TEMPO radical cations between two 18-crown-6 molecules in the high-temperature phase (HTP). Both of them exhibit paramagnetic properties in HTP and LTP states since no intermolecular spin-spin interaction occurs due to the long distances among the radicals in their crystals. These results make us possible to design bistable optoelectronic radical materials with bistability in magnetic property in the future.

In addition to biocompatibility and bioactivity, scaffolds with superior bone tissue regenerative capacity should possess excellent functionality (e.g., electroactivity and conductivity) and biodegradability matching with the rate of bone reconstruction. However, current conductive scaffolds display a reduced biodegradability rate and weakened biocompatibility. In this study, injectable conductive porous scaffolds were fabricated, incorporating camphor sulfonic acid-doped polyaniline (PANI) into hydroxyapatite/poly(lactide- co -glycolide) (HA/PLGA) scaffolds, using solvent-casting/particulate-leaching methodology. These scaffolds demonstrated excellent electroactivity, conductivity, hydrophilicity, thermodynamic properties, antibacterial properties, and biocompatibility. Their degradation behavior was explored by regulating the PANI content. The results demonstrated that adding an appropriate content of PANI would increase the pore size, porosity, and water absorption of the conductive scaffold and promote the formation of filamentous fiber byproducts with acidic hydrolysates, which accelerated the degradation rate of the scaffold. Owing to π-π stacking and hydrogen bonding, the conductive scaffold with 10 wt % PANI efficiently retarded the decrease in the thermal and mechanical properties of the scaffolds during a 16 week degradation. Thus, better regulation of degradation behavior and correlation would allow conductive porous scaffolds, such as bone implants, to achieve better bone ingrowth and restoration.

Because of the growing interest in the applications of zeolitic materials and the various challenges associated with traditional synthesis methods, the development of novel synthesis approaches remains of fundamental importance. Herein, we report a general route for the synthesis of aluminophosphate (AlPO) zeotypes by simple calcination of amorphous precursors at moderate temperatures (250-450 °C) for short reaction times (3-60 min). Accordingly, highly crystalline AlPO zeotypes with various topologies of AST , SOD , LTA , AEL , AFI , and -CLO , ranging from ultra-small to extra-large pores, have been successfully synthesized. Multinuclear multidimensional solid-state NMR techniques combined with complementary operando mass spectrometry (MS), powder X-ray diffraction, high-resolution transmission electron microscopy, and Raman characterizations reveal that covalently bonded fluoride in the intermediates catalyze the bond breaking and remaking processes. The confined organic structure-directing agents with high thermal stability direct the ordered rearrangement. This novel synthesis strategy not only shows excellent synthesis efficiency in terms of a simple synthesis procedure, a fast crystallization rate, and a high product yield, but also sheds new light on the crystallization mechanism of zeolitic materials.

Black phosphorus (BP), a promising 2D material for electronics, energy storage, catalysis, and sensing, has sparked a research boom. However, exfoliated thin-layered BP is unstable and can easily be degraded under environmental conditions, severely limiting its practical applications. In this context, a simple and cost-effective method has been proposed that involves electrochemically exfoliating BP and simultaneously electrochemically depositing aluminum oxide (AlO x ) for passivation of the exfoliated BP. The ambient stability of the exfoliated BP is studied using a time-dependent atomic force microscope (AFM). The AlO x capping layer significantly improves the environmental stability of BP compared to uncapped BP. The thermal stability of the resulting BP is evaluated using power-dependent Raman spectroscopy. The results show that the AlO x -passivated BP has increased thermal stability, with only a slight shift in peak position toward higher Raman power intensity. These properties can make the material suitable for stable energy storage devices. Interestingly, the electrochemical exfoliation and passivation processes resulted in the BP with a twist angle (9.86°), which is expected to exhibit unique electronic properties similar to those of graphene with a twist angle., Competing Interests: The authors declare no competing financial interest., (© 2023 American Chemical Society.)

Solid-state NMR spectroscopy is one of the most commonly used techniques to study the atomic-resolution structure and dynamics of various chemical, biological, material, and pharmaceutical systems spanning multiple forms, including crystalline, liquid crystalline, fibrous, and amorphous states. Despite the unique advantages of solid-state NMR spectroscopy, its poor spectral resolution and sensitivity have severely limited the scope of this technique. Fortunately, the recent developments in probe technology that mechanically rotate the sample fast (100 kHz and above) to obtain "solution-like" NMR spectra of solids with higher resolution and sensitivity have opened numerous avenues for the development of novel NMR techniques and their applications to study a plethora of solids including globular and membrane-associated proteins, self-assembled protein aggregates such as amyloid fibers, RNA, viral assemblies, polymorphic pharmaceuticals, metal-organic framework, bone materials, and inorganic materials. While the ultrafast-MAS continues to be developed, the minute sample quantity and radio frequency requirements, shorter recycle delays enabling fast data acquisition, the feasibility of employing proton detection, enhancement in proton spectral resolution and polarization transfer efficiency, and high sensitivity per unit sample are some of the remarkable benefits of the ultrafast-MAS technology as demonstrated by the reported studies in the literature. Although the very low sample volume and very high RF power could be limitations for some of the systems, the advantages have spurred solid-state NMR investigation into increasingly complex biological and material systems. As ultrafast-MAS NMR techniques are increasingly used in multidisciplinary research areas, further development of instrumentation, probes, and advanced methods are pursued in parallel to overcome the limitations and challenges for widespread applications. This review article is focused on providing timely comprehensive coverage of the major developments on instrumentation, theory, techniques, applications, limitations, and future scope of ultrafast-MAS technology.

The dispute over the effect of cavitation heat on material surface intensifies the fuzziness of cavitation erosion (CE) mechanism and limits the development of protective materials. Here, an anti-CE Al 10 Cr 28 Co 28 Ni 34 high-entropy alloy (HEA) coating with single face-centered cubic (FCC), prepared by high-velocity oxy-fuel (HVOF) spraying technologies, was designed by inducing mechanical and thermal energy-induced behaviors to transform or counteract each other. The results showed that, on the one hand, this coating underwent the refinement of the average grain size from 1.22 to 1.02 μm, the increase in dislocation density from 1.28 × 10 -10 to 1.83 × 10 -10 m -2 , and the martensitic transformation from FCC to body-centered cubic (BCC) under the cavitation load; on the other hand, cavitation heat could indeed induce grain growth and realize structural relaxation, which confirmed that cavitation heat acting on the material surface at temperatures theoretically above 1206.28 K also played a significant role in the CE mechanism. That is, the surface microstructure of this coating was always in a dynamic cycle during the CE process. Therefore, the coating achieved the simultaneous absorption of mechanical impact energy and thermal energy released by the bubble collapse while effectively avoiding the overenrichment of crystal defects and finally exhibited a CE resistance 2 times better than that of the classical AlCrCoFeNi HEA coating. This design concept of inducing different energy restraints or neutralization through the special response behaviors of surface microstructure provides a completely new way for the development of CE-resistant materials.

Direct neuronal reprogramming of somatic cells into induced neurons (iNs) has been recently established as a promising approach to generating neuron cells. Previous studies have reported that the biophysical cues of the in vitro microenvironment are potent modulators in the cell fate decision; thus, the present study explores the effects of a customized pattern (named colloidal self-assembled patterns, cSAPs) on iN generation from human fibroblasts using small molecules. The result revealed that the cSAP, composed of binary particles in a hexagonal-close-packed (hcp) geometry, is capable of improving neuronal reprogramming efficiency and steering the ratio of the iN subtypes. Cells exhibited distinct cell morphology, upregulated cell adhesion markers (i.e., SDC1 and ITGAV), enriched signaling pathways (i.e., Hippo and Wnt), and chromatin remodeling on the cSAP compared to those on the control substrates. The result also showed that the iN subtype specification on cSAP was surface-dependent; therefore, the defined physicochemical cue from each cSAP is exclusive. Our findings show that direct cell reprogramming can be manipulated through specific biophysical cues on the artificial matrix, which is significant in cell transdifferentiation and lineage conversion.

Lithium-oxygen batteries have received extensive attention due to their high theoretical specific capacity, but problems such as high charging overpotential and poor cycling performance hinder their practical application. Herein, a pulsed current, which merits its relaxation phenomenon, is applied during the charging cycle to address the abovementioned problems. Pulsed charging can not only reduce the charging overpotential, but also control the mass transfer and distribution of lithium ions. As a result, the uniform deposition of lithium ions on the anode surface is realized, the repeated rupture and formation of the solid electrolyte interphase is reduced, and the growth of the lithium dendrites is successfully suppressed, thereby achieving the purpose of protecting lithium metal from excessive consumption. When the pulsed charging duty ratio ( T on / T off ) is 1:1, after 25 cycles, the lithium-oxygen battery anode still presents a relatively flat and dense deposition surface, which is obviously better than the loose and rough surface after normal cycling. In addition, the protective effect of pulsed charging on the lithium metal anodes of lithium-oxygen batteries is also verified by the construction of other lithium-based batteries.

Highly efficient and durable flexible solid-state supercapacitors (FSSSCs) are emerging as low-cost devices for portable and wearable electronics due to the elimination of leakage of toxic/corrosive liquid electrolytes and their capability to withstand elevated mechanical stresses. Nevertheless, the spread of FSSSCs requires the development of durable and highly conductive solid-state electrolytes, whose electrochemical characteristics must be competitive with those of traditional liquid electrolytes. Here, we propose an innovative composite solid-state electrolyte prepared by incorporating metallic two-dimensional group-5 transition metal dichalcogenides, namely, liquid-phase exfoliated functionalized niobium disulfide (f-NbS 2 ) nanoflakes, into a sulfonated poly(ether ether ketone) (SPEEK) polymeric matrix. The terminal sulfonate groups in f-NbS 2 nanoflakes interact with the sulfonic acid groups of SPEEK by forming a robust hydrogen bonding network. Consequently, the composite solid-state electrolyte is mechanically/dimensionally stable even at a degree of sulfonation of SPEEK as high as 70.2%. At this degree of sulfonation, the mechanical strength is 38.3 MPa, and thanks to an efficient proton transport through the Grotthuss mechanism, the proton conductivity is as high as 94.4 mS cm -1 at room temperature. To elucidate the importance of the interaction between the electrode materials (including active materials and binders) and the solid-state electrolyte, solid-state supercapacitors were produced using SPEEK and poly(vinylidene fluoride) as proton conducting and nonconducting binders, respectively. The use of our solid-state electrolyte in combination with proton-conducting SPEEK binder and carbonaceous electrode materials (mixture of activated carbon, single/few-layer graphene, and carbon black) results in a solid-state supercapacitor with a specific capacitance of 116 F g -1 at 0.02 A g -1 , optimal rate capability (76 F g -1 at 10 A g -1 ), and electrochemical stability during galvanostatic charge/discharge cycling and folding/bending stresses.

Although ketene has been proposed to be an active intermediate in a number of reactions including OXZEO (metal oxide-zeolite)-catalyzed syngas conversion, dimethyl ether carbonylation, methanol to hydrocarbons, and CO 2 hydrogenation, its chemistry and reaction pathway over zeolites are not well understood. Herein, we study the pathway of ketene transformation to gasoline range hydrocarbons over the molecular sieve H-SAPO-11 by kinetic analysis, in situ infrared spectroscopy, and solid-state nuclear magnetic resonance spectroscopy. It is demonstrated that butene is the reaction intermediate on the paths toward gasoline products. Ketene transforms to butene on the acid sites via either acetyl species following an acetic acid ketonization pathway or acetoacetyl species with keto-enol tautomerism following an acetoacetic acid decarboxylation pathway when in the presence of water. This study reveals experimentally for the first time insights into ketene chemistry in zeolite catalysis.

Surface metal hydrides (M-H) are ubiquitous in heterogeneous catalytic reactions, while the detailed characterizations are frequently hindered by their high reactivity/low concentration, and the complicated surface structures of the host solids, especially in terms of practical solid catalysts. Herein, combining instant quenching capture and advanced solid-state NMR methodology, we report the first direct and unambiguous NMR evidence on the highly reactive surface gallium hydrides (Ga-H) over a practical Ga 2 O 3 catalyst during direct H 2 activation. The spectroscopic effects of 69 Ga and 71 Ga isotopes on the 1 H NMR signal are clearly differentiated and clarified, allowing a concrete discrimination of the Ga-H signal from the hydroxyl crowd. Accompanied with quantitative and two-dimensional NMR spectroscopical methods, as well as density functional theory calculations, information on the site specification, structural configuration, and formation mechanism of the Ga-H species has been revealed, along with the H 2 dissociation mechanism. More importantly, the successful spectroscopic identification and isolation of the surface Ga-H allow us to clearly reveal the critical but ubiquitous intermediate role of this species in catalytic reactions, such as propane dehydrogenation and CO 2 hydrogenation reactions. The analytic approach presented in this work can be extended to other M-H analysis, and the insights will benefit the design of more efficient Ga-based catalysts.

A facile strategy for the synthesis of isoxazoles has been efficaciously developed, which involves oxidation of propargylamines to the corresponding oximes followed by CuCl-mediated intramolecular cyclization of the latter. This protocol shows a straightforward way to construct a series of isoxazole cores with a wide range of functional group compatibility. Meanwhile, a gram-scale experiment and synthetic applications can be successfully operated.

Considerable advances have been made in developing materials that promote wound healing and inhibit scar formation in clinical settings. However, some challenges, such as cumbersome treatment processes and determination of optimal treatment time, remain unresolved. Thus, developing a multifunctional wound dressing with both wound healing and scar inhibition properties is crucial. Here, we present an integrated electrospun fibrous composite membrane (MPC12) for wound healing and scar inhibition, consisting of a quaternized chitosan-loaded inner membrane (PCQC5) and quaternized silicone-loaded outer membrane (MQP12). The inner membrane effectively coagulates blood and promotes wound healing, and the outer membrane moisturizes, resists bacteria, and inhibits scar formation. In vivo evaluation in a rabbit ear model revealed that MPC12 treatment results in faster wound healing and better alleviation of scar hypertrophy than treatment with commercial products (KELO-COTE and MSSG). Our strategy offers an excellent solution for the potential integration of wound healing and scar inhibition., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

It is of great significance to accurately quantify the Brønsted acid sites (BASs) at different positions of mordenite (MOR) zeolite. However, H-MOR obtained from Na-MOR can hardly avoid dealumination under hydrothermal conditions, which causes difficulty in the acid characterization. Herein, 23 Na- 27 Al D -HMQC was performed combined with high-field 23 Na MQ MAS NMR and DFT calculation, which provided an unambiguous attribution of the 23 Na chemical shifts and further helped to improve the resolution of 27 Al MAS NMR. By fitting the 23 Na and 1 H MAS NMR spectra of Na/H-MOR, the intrinsic BAS contents in different T-sites were measured by characterizing the location and content of sodium ions. These Na/H-MOR zeolites with various acid distributions were used for DME carbonylation and showed that the amount of BASs in the T3 site was proportional to the activity of carbonylation. This study provides a new method for investigating the intrinsic acid properties of zeolites.

With the development of NMR methodology and technology during the past decades, solid-state NMR (ssNMR) has become a particularly important tool for investigating structure and dynamics at atomic scale in biological systems, where the recoupling techniques play pivotal roles in modern high-resolution MAS NMR. In this review, following a brief introduction on the basic theory of recoupling in ssNMR, we highlight the recent advances in dipolar and chemical shift anisotropy recoupling methods, as well as their applications in structural determination and dynamical characterization at multiple time scales (i.e., fast-, intermediate-, and slow-motion). The performances of these prevalent recoupling techniques are compared and discussed in multiple aspects, together with the representative applications in biomolecules. Given the recent emerging advances in NMR technology, new challenges for recoupling methodology development and potential opportunities for biological systems are also discussed.

The uranium bipyridyl metallocene, [η 5 -1,3-(Me 3 Si) 2 C 5 H 3 ] 2 U(bipy) ( 2 ), is readily accessible in good yield by adding potassium graphite (KC 8 ) to a mixture of [η 5 -1,3-(Me 3 Si) 2 C 5 H 3 ] 2 UCl 2 ( 1 ) and 2,2'-bipyridine. Compound 2 was fully characterized and employed for small-molecule activation. It has been demonstrated that 2 may serve as a synthon for [η 5 -1,3-(Me 3 Si) 2 C 5 H 3 ] 2 U(II) fragment in the presence of Ph 2 E 2 (E = S, Se), alkynes, and a variety of hetero-unsaturated molecules such as diazabutadienes, azine (Ph 2 C═N) 2 , o -benzoquinone, pyridine N -oxide, CS 2 , isothiocyanates, and organic azides. However, upon exposure of 2 to thio-ketone Ph 2 CS, aldehyde p -MePhCHO, ketone Ph 2 CO, imine PhCH═NPh, azine (PhCH═N) 2 , and nitrile PhCN, it may also promote C-C coupling reactions forming [η 5 -1,3-(Me 3 Si) 2 C 5 H 3 ] 2 U[(bipy)(Ph 2 CS)] ( 16 ), [η 5 -1,3-(Me 3 Si) 2 C 5 H 3 ] 2 U[(bipy)( p -MePhCHO)] ( 17 ), [η 5 -1,3-(Me 3 Si) 2 C 5 H 3 ] 2 U[(bipy)(Ph 2 CO)] ( 18 ), [η 5 -1,3-(Me 3 Si) 2 C 5 H 3 ] 2 U[(bipy)(PhCHNPh)] ( 19 ), [η 5 -1,3-(Me 3 Si) 2 C 5 H 3 ] 2 U[(bipy)(PhCHNN═CHPh)] ( 20 ), and [η 5 -1,3-(Me 3 Si) 2 C 5 H 3 ] 2 U[(N 2 C 10 H 7 C(Ph)NH)] ( 22 ), respectively, in quantitative conversion. Furthermore, in the presence of CuI, a single-electron transfer (SET) process is observed to yield the uranium(III) iodide complex [η 5 -1,3-(Me 3 Si) 2 C 5 H 3 ] 2 U(I)(bipy) ( 15 ).

A highly efficient asymmetric hydrogenation of a series of γ-keto acid derivatives, including γ-keto acids, esters, and amides, using a Ni-( R , R )-QuinoxP* complex as the catalyst has been developed to afford chiral γ-hydroxy acid derivatives with excellent enantioselectivities, up to 99.9% ee. This method provides not only an economical one-pot approach for the synthesis of chiral γ-lactones but also access to ( S )-norfluoxetine, an inhibitor of neural serotonin reuptake and an essential intermediate for pharmaceutical synthesis.

Lithium-sulfur batteries (LSBs) have the advantages of high energy density and low cost and are considered promising next-generation energy storage systems, but the shuttle effect and slow sulfur redox kinetics severely limit their practical applications. Herein, MoP quantum dot-modified N,P-doped hollow PPy substrates are adopted as separator modification coatings for LSBs. The MoP quantum dots exhibit excellent chemisorption and catalytic conversion capabilities for polysulfides, while the N,P-doped PPy substrates can provide flexible channels for Li + /electron transport and act as a physical barrier to suppress the shuttle effect. As a result, LSBs assembled with modified separators exhibit excellent rate capability (739 mAh/g at 3 C) and cycle performance (600 mAh/g at 1 C after 600 cycles, 0.052% decay per cycle). Moreover, even under a high sulfur loading of 3.68 mg/cm 2 , areal capacities of 3.58 and 2.92 mAh/cm 2 for the 1st cycle and 110th cycle are achieved. In addition, according to density functional theory calculations, MoP quantum dots have large adsorption energy for S 8 and Li 2 S n , which further confirms the possibility of lowering the initial nucleation energy barrier of Li 2 S and helps to improve the kinetics of the subsequent Li 2 S reaction. This study proposes a novel method for using transition-metal phosphides as catalysts in high-performance LSBs.

Bacterial infection and delayed healing are two major obstacles in cutaneous wound management, and developing multifunctional hydrogels with antibacterial and prohealing capabilities presents a promising strategy to dress wounds. However, the simple and facile fabrication of such hydrogel dressings remains challenging. Herein, we report the first observation on hydrazide-metal coordination crosslinking that is utilized to successfully construct a series of hyaluronan (HA)-metal hydrogels by mixing hydrazided HA and metal ion solutions. Considering the antibacterial, prohealing, and proangiogenic properties of HA and Cu(II), as a proof of principle, a HA-Cu hydrogel was systematically investigated as a wound dressing. Surprisingly, the hydrazide-Cu(II) coordination was dynamic in nature and imparted the HA-Cu hydrogel with physicochemical multifunctions, including spontaneous self-healing, shear-thinning injectability, reversible pH/redox/ion pair triple responsiveness, etc. Moreover, the HA-Cu hydrogel exhibited a robust broad-spectrum antibacterial activity and could significantly accelerate infectious wound healing. Impressively, glutathione-triggered hydroxyl radical generation further potentiated wound healing, providing a paradigm for on-demand antibacterial activity enhancement. Hence, the HA-Cu hydrogel is a clinically applicable "smart" dressing for multi-scenario wound healing. We envision that the simple and versatile coordination approach opens up a new avenue to develop multifunctional hydrogels and shows great potential in frontier fields, such as biomedicine, wearable devices, and soft robots.

High-entropy materials, with complex compositions and unique cocktail characteristics, have recently drawn significant attention. Additionally, a family of sodium super ion conductors (NASICONs)-structured phosphates in energy storage areas shows a comprehensive application for traditional alkaline ion batteries and, in particular, solid-state electrolytes. However, there is no precedent in fabricating this kind of NASICON-type high-entropy phase. Here, we report the successful fabrication of two well-crystallized high-entropy phosphates, namely, Na 3 (Ti 0.2 V 0.2 Mn 0.2 Cr 0.2 Zr 0.2 ) 2 (PO 4 ) 3 (HE-N 3 M 2 P 3 ) and Na(Ti 0.2 V 0.2 Mn 0.2 Cr 0.2 Zr 0.2 ) 2 PO 4 O x (HE-NMP). The prepared materials in which the transition metals (TMs) of Ti, V, Mn, Cr, and Zr occupy the same 12c Wykoff position can form a structure analogous to R 3̅ c Na 3 V 2 (PO 4 ) 3 that is carefully determined by X-ray diffraction, neutron diffraction, and transmission electron microscopy. Further, their performance for sodium ion batteries and sodium-based solid-state electrolytes was evaluated. The HE-N 3 M 2 P 3 might exhibit a promising electrochemical performance for sodium storage in terms of its structure resembling that of Na 3 V 2 (PO 4 ) 3 . Meanwhile, the HE-NMP shows considerable electrochemical activity with numerous broad redox ranges during extraction and insertion of Na + , related to the coexistence of several TM elements. The evaluated temperature-dependent ionic conductivity for HE-NMP solid electrolyte varies from 10 -6 to 10 -5 S cm -1 from room temperature to 398.15 K, offering high potential for energy storage applications as a new high-entropy system.

Chemotherapy is a primary cancer treatment strategy, the monitoring of which is critical to enhancing the survival rate and quality of life of cancer patients. However, current chemotherapy monitoring mainly relies on imaging tools with inefficient sensitivity and radiation invasiveness. Herein, we develop the bowl-shaped submicroreactor chip of Au-loaded 3-aminophenol formaldehyde resin (denoted as APF-bowl&Au) with a specifically designed structure and Au loading content. The obtained APF-bowl&Au, used as the matrix of laser desorption/ionization mass spectrometry (LDI MS), possesses an enhanced localized electromagnetic field for strengthened small metabolite detection. The APF-bowl&Au enables the extraction of serum metabolic fingerprints (SMFs), and machine learning of the SMFs achieves chemotherapy monitoring of ovarian cancer with area-under-the-curve (AUC) of 0.81-0.98. Furthermore, a serum metabolic biomarker panel is preliminarily identified, exhibiting gradual changes as the chemotherapy cycles proceed. This work provides insights into the development of nanochips and contributes to a universal detection platform for chemotherapy monitoring.

Fluorescent gold nanoclusters (Au NCs) with excellent one-photon and multiphoton properties have been demonstrated as promising candidates in many application fields. However, small multiphoton absorption (MPA) cross sections and weak multiphoton excitation (MPE) fluorescence impede their practical applications under near-infrared (NIR) excitation for biological imaging. Here, we report the regulated one-photon and multiphoton properties and mechanisms of arginine-stabilized 6-aza-2-thiothymine Au NCs (Arg/ATT-Au NCs) and the applications for MPE fluorescence imaging. The introduction of arginine into the capping layer of ATT-Au NCs significantly modifies the electronic structure, the absorption cross sections, and the relaxation dynamics of the lowest excited state, drastically reducing the nonradiative relaxation, suppressing the blinking, and greatly enhancing the fluorescence. Besides the improved one-photon properties, Arg/ATT-Au NCs demonstrate remarkable MPE fluorescence with a large MPA cross section. The two-photon (λ ex = 850 nm), three-photon (λ ex = 1400 nm), and four-photon (λ ex = 1700 nm) absorption cross sections have been determined to be 6.1 × 10 -47 cm 4 s 1 photon -1 , 1.5 × 10 -78 cm 6 s 2 photon -2 , and 5.5 × 10 -108 cm 8 s 3 photon -3 , respectively, much higher than those of conventional organic compounds and previously reported Au NCs. Moreover, Arg/ATT-Au NCs have been successfully applied in two-photon and three-photon excitation fluorescence imaging of living cells with NIR excitation. The manifold advantages of small size, high quantum yield, suppressed blinking, good photostability and cytocompatibility, large MPA cross sections, and excellent MPE fluorescence imaging performances make fluorescent Arg/ATT-Au NCs a great candidate of imaging probes with vis-NIR excitation.