A doping strategy to regulate the adsorption energy of Li2S4 and Li2S to promote sulfur reduction on Chevrel phase Mo6Se8 in lithium-sulfur batteries.

Atomic doping in catalysts is an effective strategy for adjusting their catalytic activity, which has recently been applied to promote sulfur reduction reactions (SRRs) on the cathode of lithium-sulfur (Li-S) batteries. Herein, the electrocatalytic SRR mechanism of eight metal atom (Ca, Ti, V, Cr, Mn, Fe, Co or Ni) doped Chevrel phase Mo6Se8 were investigated using density functional theory (DFT) calculations. The results reveal that the interaction between polysulfides and the catalyst mainly originates from the coupling of dz2 and dxz orbitals of doped metals and the 3p orbitals of S. The Ti-doped Mo6Se8 system significantly reduces the overpotential of the SRR to only 0.21 V. After analyzing SRR processes over doped and undoped Mo6Se8, no scalar relationship was found between the adsorption energies (Ead) of various polysulfides. Instead, a linear relationship is established between 4Ead-Li2S* - Ead-Li2S4* and overpotential. Finally, a linear relationship between overpotential and descriptors was established based on a machine learning (ML) method, which can accurately predict the overpotential of the SRR over the Mo6Se8 catalyst. This work provides new theoretical insights into the SRR mechanism over metal-selenides and the rational design of a catalyst for Li-S batteries.

Total Structure, Structural Transformation and Catalytic Hydrogenation of [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- Constructed from Twisted Cu13 Units.

Herein, a remarkable achievement in the synthesis and characterization of an atomically precise copper-hydride nanocluster, [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- via a mild one-pot reaction is presented. Through X-ray crystallography analysis, it is revealed that [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- exhibits a unique shell-core-shell structure. The inner Cu29 kernel is composed of three twisted Cu13 units, connected through Cu4 face sharing. Surrounding the metal core, two Cu6 metal shells, resembling a protective sandwich structure are observed. This arrangement, along with intracluster π···π interactions and intercluster C─H···F─C interactions, contributes to the enhanced stability of [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- . The presence, number, and location of hydrides within the nanocluster are established through a combination of experimental and density functional theory investigations. Notably, the addition of a phosphine ligand triggers a fascinating nanocluster-to-nanocluster transformation in [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- , resulting in the generation of two nanoclusters, [Cu14 (SC6 H3 F2 )3 (PPh3 )8 H10 ]+ and [Cu13 (SC6 H3 F2 )3 (P(PhF)3 )7 H10 ]0 . Furthermore, it is demonstrated that [Cu41 (SC6 H3 F2 )15 Cl3 (P(PhF)3 )6 (H)25 ]2- exhibits catalytic activity in the hydrogenation of nitroarenes. This intriguing nanocluster provides a unique opportunity to explore the assembly of M13 units, similar to other coinage metal nanoclusters, and investigate the nanocluster-to-nanocluster transformation in phosphine and thiol ligand co-protected copper nanoclusters.

Converting commercial Bi2O3 particles into Bi2O2Se@Bi4O8Se nanosheets for "rocking chair" zinc-ion batteries.

The development of a low-cost, high-capacity, and insertion-type anode is key for promoting "rocking chair" zinc-ion batteries. Herein, commercial Bi2O3 (BiO) particles are transformed into Bi2O2Se@Bi4O8Se (BiOSe) nanosheets through a simple selenylation process. The change in morphology from commercial BiO particle to BiOSe nanosheet leads to an increased specific surface area of the material. The enhanced electronic/ionic conductivity results in its excellent electrochemical kinetics. Ex situ XRD and XPS tests prove the intercalation-type mechanism of BiO and BiOSe as well as the superior electrochemical reversibility of BiOSe compared to BiO. Furthermore, the H+/Zn2+ co-insertion mechanism of BiOSe is revealed. This makes BiOSe to have low discharge plateaus of 0.38/0.68 V, a high reversible capacity of 182 mA h g-1 at 0.1 A g-1, and a long cyclic life of 500 cycles at 1 A g-1. Besides, the BiOSe//MnO2 "rocking chair" zinc-ion battery offers a high capacity of ≈90 mA h g-1 at 0.2 A g-1. This work provides a reference for turning commercial material into high-performance anode for "rocking chair" zinc-ion batteries.

Theoretical Insights into Single-Atom Catalysts Supported on N-Doped Defective Graphene for Fast Reaction Redox Kinetics in Lithium-Sulfur Batteries.

Single-atom catalysts are proven to be an effective strategy for suppressing shuttle effect at the source by accelerating the redox kinetics of intermediate polysulfides in lithium-sulfur (Li-S) batteries. However, only a few 3d transition metal single-atom catalysts (Ti, Fe, Co, Ni) are currently applied for sulfur reduction/oxidation reactions (SRR/SOR), which remains challenging for screening new efficient catalysts and understanding the relationship between structure-activity of catalysts. Herein, N-doped defective graphene (NG) supported 3d, 4d, and 5d transition metals are used as single-atom catalyst models to explore electrocatalytic SRR/SOR in Li-S batteries by using density functional theory calculations. The results show that M1 /NG (M1 = Ru, Rh, Ir, Os) exhibits lower free energy change of rate-determining step ( Δ G Li 2 S ∗ ) $( {\Delta {G}_{{\mathrm{Li}}_{\mathrm{2}}{{\mathrm{S}}}^{\mathrm{*}}\ }} )$ and Li2 S decomposition energy barrier, which significantly enhance the SRR and SOR activity compared to other single-atom catalysts. Furthermore, the study accurately predicts the Δ G Li 2 S ∗ $\Delta {G}_{{\mathrm{Li}}_{\mathrm{2}}{{\mathrm{S}}}^{\mathrm{*}}\ }$ by machine learning based on various descriptors and reveals the origin of the catalyst activity by analyzing the importance of the descriptors. This work provides great significance for understanding the relationships between the structure-activity of catalysts, and manifests that the employed machine learning approach is instructive for theoretical studies of single-atom catalytic reactions.

Synchronous Metal Rearrangement on Two-Dimensional Equatorial Surfaces of Au-Cu Alloy Nanoclusters.

Understanding the growth of nanoclusters and the relationship between structure-activity depends on the precise arrangement of metals on their surface. In this work, we realized the synchronous rearrangement of metal atoms on the equatorial plane of Au-Cu alloy nanoclusters. Upon adsorption of the phosphine ligand, the Cu atoms on the equatorial plane of the Au52Cu72(SPh)55 nanocluster are irreversibly rearranged. The whole metal rearrangement process can be understood from a synchronous metal rearrangement mechanism initiated by the adsorption of the phosphine ligand. Furthermore, this metal rearrangement can effectively improve the efficiency of A3 coupling reactions without increasing the amount of catalyst.

Acid sphingomyelinase promotes diabetic cardiomyopathy via NADPH oxidase 4 mediated apoptosis.

BACKGROUND: Increased acid sphingomyelinase (ASMase) activity is associated with insulin resistance and cardiac dysfunction. However, the effects of ASMase on diabetic cardiomyopathy (DCM) and the molecular mechanism(s) underlying remain to be elucidated. We here investigated whether ASMase caused DCM through NADPH oxidase 4-mediated apoptosis. METHODS AND RESULTS: We used pharmacological and genetic approaches coupled with study of murine and cell line samples to reveal the mechanisms initiated by ASMase in diabetic hearts. The protein expression and activity of ASMase were upregulated, meanwhile ceramide accumulation was increased in the myocardium of HFD mice. Inhibition of ASMase with imipramine (20 mg Kg-1 d-1) or siRNA reduced cardiomyocyte apoptosis, fibrosis, and mitigated cardiac hypertrophy and cardiac dysfunction in HFD mice. The similar effects were observed in cardiomyocytes treated with high glucose (HG, 30 mmol L-1) + palmitic acid (PA, 100 µmol L-1) or C16 ceramide (CER, 20 µmol L-1). Interestingly, the cardioprotective effect of ASMase inhibition was not accompanied by reduced ceramide accumulation, indicating a ceramide-independent manner. The mechanism may involve activated NADPH oxidase 4 (NOX4), increased ROS generation and triggered apoptosis. Suppression of NOX4 with apocynin prevented HG + PA and CER incubation induced Nppb and Myh7 pro-hypertrophic gene expression, ROS production and apoptosis in H9c2 cells. Furthermore, cardiomyocyte-specific ASMase knockout (ASMaseMyh6KO) restored HFD-induced cardiac dysfunction, remodeling, and apoptosis, whereas NOX4 protein expression was downregulated. CONCLUSIONS: These results demonstrated that HFD-mediated activation of cardiomyocyte ASMase could increase NOX4 expression, which may stimulate oxidative stress, apoptosis, and then cause metabolic cardiomyopathy.

Analysis of clinical characteristics of mesalazine-induced cardiotoxicity.

Background: Mesalazine is the first-line inflammatory bowel disease (IBD) treatment. However, it can cause fatal cardiotoxicity. We aimed to analyze the clinical characteristics of mesalazine-induced cardiotoxicity and provide evidence for clinical diagnosis, treatment, and prevention. Methods: We collected Chinese and English literature on mesalazine-induced cardiotoxicity from 1970 to 2021 for retrospective analysis. Results: A total of 52 patients (40 males and 12 females) were included, with a median age of 24.5 years (range 9-62) and a median onset time of 14 days (range 2-2880). Cardiotoxicity manifested as myocarditis, pericarditis, and cardiac pericarditis. The main clinical manifestations are chest pain (82.7%), fever (46.2%), and respiratory symptoms such as dyspnea and cough (40.4%). The levels of troponin T, creatine kinase, C-reactive protein, leukocyte count, erythrocyte sedimentation rate, and other biochemical markers were significantly increased. Cardiac imaging often suggests myocardial infarction, pericardial effusion, myocardial necrosis, and other symptoms of cardiac injury. It is essential to discontinue mesalamine immediately in patients with cardiotoxicity. Although corticosteroids are a standard treatment option, the benefits remain to be determined. Re-challenge of mesalamine should be carefully considered as cardiotoxic symptoms may reoccur. Conclusion: Mesalazine may cause cardiotoxicity in patients with inflammatory bowel disease, which should be comprehensively diagnosed based on clinical manifestations, biochemical indicators, and cardiac function imaging examinations. Mesalazine should be immediately discontinued, and corticosteroids may be an effective treatment for cardiotoxicity.

Few-Atomic-Layered Co-Doped BiOBr Nanosheet: Free-Standing Anode with Ultrahigh Mass Loading for "Rocking Chair" Zinc-Ion Battery.

Insertion host materials are considered as a candidate to replace metallic Zn anode. However, the high mass loading anode with good electrochemical performances is reported rarely. Herein, a few-atomic-layered Co-doped BiOBr nanosheet (Co-UTBiOBr) is prepared via one-step hydrothermal method and a free-standing flexible electrode consisting of Co-UTBiOBr and CNTs is designed. Ultrathin nanosheet (3 atomic layers) and CNTs accelerate Zn2+ and electron transfer respectively. The Co-doping is conducive to the reduced Zn2+ diffusion barrier, the improved volume expansion after Zn2+ intercalation, and the enhanced electronic conductivity of BiOBr, verified by experimental and theoretical studies. An insertion-conversion mechanism is proposed according to ex situ characterizations. Benefiting from many advantages, Co-UTBiOBr displays a high capacity of 150 mAh g-1 at 0.1 A g-1 and a long-term cyclic life with ≈100% capacity attention over 3000 cycles at 1 A g-1 . Remarkably, excellent electrochemical performances are maintained even at an ultrahigh mass loading of 15 mg cm-2 . Co-UTBiOBr//MnO2 "rocking chair" zinc-ion battery exhibits a stable capacity of ≈130 mAh g-1 at 0.2 A g-1 during cyclic test and its flexible quasi-solid-state battery shows outstanding stability under various bending states. This work provides a new idea for designing high mass loading anode.

BiOI Nanopaper As a High-Capacity, Long-Life and Insertion-Type Anode for a Flexible Quasi-Solid-State Zn-Ion Battery.

The development of intercalation anodes with high capacity is key to promote the progress of "rocking-chair" Zn-ion batteries (ZIBs). Here, layered BiOI is considered as a promising electrode in ZIBs due to its large interlayer distance (0.976 nm) and low Zn2+ diffusion barrier (0.57 eV) obtained by density functional theory, and a free-standing BiOI nanopaper is designed. The process and mechanism of Zn(H2O)n2+ insertion in BiOI are proved by ex situ X-ray diffraction, Raman, and X-ray photoelectron spectroscopy. The suitable potential (0.6 V vs Zn/Zn2+), high reversible capacity (253 mAh g-1), good rate performance (171 mAh g-1 at 10 A g-1), long cyclic life (113 mAh g-1 after 5000 cycles at 5 A g-1), and dendrite-free operation of BiOI nanopaper prove its potential as a superior anode. When it is coupled with Mn3O4 cathode, the quasi-solid-state battery exhibits a high initial capacity of 149 mAh g-1 (for anode) and a good capacity retention of 70 mAh g-1 after 400 cycles. The self-assembled flexible battery also shows stable charge-discharge during the cyclic test. This work shows the feasibility of BiOX anode for dendrite-free ZIBs.

Fluorescence turn-on immunosensing of HE4 biomarker and ovarian cancer cells based on target-triggered metal-enhanced fluorescence of carbon dots.

Rapid and sensitive detection of tumor biomarkers and cancer cells is of crucial importance for the early diagnosis and prognosis prediction of cancer. The present report describes a target-induced fluorescence enhancement immunosensor that utilizes the optical property of carbon dots (CDs) and the metal-enhanced fluorescence effect (MEF) property of silver nanoparticles (AgNPs) for the sensitive detection of the cancer biomarker human epididymis protein 4 (HE4) and ovarian cancer cells. Nitrogen and sulfur co-doped CDs with a quantum yield of 85.6% were prepared and served as the fluorophore in MEF. The HE4 antibody (Ab) specific to the HE4 antigen was linked covalently to the surface of the synthesized CDs as the capture. The HE4 Ab-conjugated AgNPs (AgNPs-Ab) were prepared and utilized as signal amplification elements. In the presence of the target HE4, composite sandwich structures were formed between the labeled CDs-Ab and AgNPs-Ab, which brought the CDs and AgNPs into proximity, resulting in the fluorescence of CDs enhancement owing to MEF. The intensity of fluorescence enhancement was positively correlated with the HE4 concentration in the clinically important range of 0.01-200 nM with a limit detection of 2.3 pM. Moreover, the immunosensor was also successfully applied to specific fluorescence labeling and quantitative determination of HE4-positive ovarian cancer cells. The proposed target-triggered MEF sensor platform demonstrated high sensitivity, excellent anti-interference ability, along with successful validation in complex biological matrices, providing a new approach for HE4 detection in early diagnosis and therapeutic monitoring.

[Au16Ag43H12(SPhCl2)34]5-: An Au-Ag Alloy Nanocluster with 12 Hydrides and Its Enlightenment on Nanocluster Structural Evolution.

The structural determination of alloy hydride nanoclusters with high nuclearity remains challenging. We herein report the synthetic procedure and the structural elucidation of an Au-Ag alloy nanocluster with 12 hydride ligands-[Au16Ag43H12(SPhCl2)34]5-. The structure of [Au16Ag43H12(SPhCl2)34]5- comprises an Au16Ag3 kernel that is stabilized by 12 hydride ligands, 8 thiol bridges, and 6 Agm(SR)n motif units. The 12 hydride ligands in Au16Ag43 have been confirmed by both 2H NMR and ESI-MS measurements, and their positions have been theoretically evaluated, located at the interlayer between the Au16Ag3 kernel and the Ag-SR shell. The metastable [Au16Ag43H12(SPhCl2)34]5- can convert to [Au12Ag32(SPhCl2)30]4- spontaneously. Structurally, the Au16Ag3 kernel of [Au16Ag43H12(SPhCl2)34]5- could be regarded as the overlapping of two hollow Au8Ag3 cages via sharing an Ag3 line, which is in contrast to the solely icosahedral Au12 kernel of [Au12Ag32(SPhCl2)30]4-. Besides, the overall construction of Au16Ag43 or Au12Ag32 follows a complementing or overlapping assembly mode, respectively. Overall, the structural anatomy of Au16Ag43H12(SPhCl2)34 sheds some new insight into the structural evolution of metal nanoclusters.

Integration of a low-cost electronic nose and a voltammetric electronic tongue for red wines identification.

The purpose of this present study was to develop a rapid and effective approach for identification of red wines that differ in geographical origins, brands, and grape varieties, a multi-sensor fusion technology based on a novel cost-effective electronic nose (E-nose) and a voltammetric electronic tongue (E-tongue) was proposed. The E-nose sensors was created using porphyrins or metalloporphyrins, pH indicators and Nile red printed on a C2 reverse phase silica gel plate. The voltammetric E-Tongue with six metallic working electrodes, namely platinum, gold, palladium, tungsten, titanium, and silver was employed to sense the taste of red wines. Principal component analysis (PCA) was utilized for dimensionality reduction and decorrelation of the raw sensors datasets. The fusion models derived from extreme learning machine (ELM) were built with PCA scores of E-nose and tongue as the inputs. Results showed superior performance (100% recognition rate) using combination of odor and taste sensors than individual artificial systems. The results suggested that fusion of the novel cost-effective E-nose created and voltammetric E-tongue coupled with ELM has a powerful potential in rapid quality evaluation of red wine.

Downregulation of GATS gene inhibits proliferation, clonogenicity and migration in triple negative breast cancer cells MDA-MB-231 by cell autophagy.

The triple negative breast cancer (TNBC) accounts for 15% to 20% of the total number of breast cancer diagnosed. A number of clinical studies have shown that TNBC has a high risk of early recurrence and distant metastasis, and a low rate of disease free survival and total survival. The premise of TNBC deterioration was abnormal proliferation and migration of tumor cells, and this study firstly showed that GATS gene could promote proliferation of MDA-MB-231 breast cancer cells. Through lentiviral expression system, the GATS gene was konckdown by shGATS lentivirus infection in the MDA-MB-231 cells, and the result indicated it could remarkably decrease the ability of cell proliferation and migration. Real-time PCR, western blot and immunofluorescence experiments showed the expressions of protein LC3, and p-Akt in shGATS cell group were lower than the shCtrl group. Therefore, we suggest the GATS could promote the MDA-MB-231 cell proliferation, migration and clonogenicity through cell autophagy by the PI3K/Akt pathway, which paved the way for further study the function of GATS in TNBC, and GATS may potentially be a target for gene therapy against triple negative breast cancer.

Phosphorus and short-chain fatty acids recovery from waste activated sludge by anaerobic fermentation: Effect of acid or alkali pretreatment.

Waste activated sludge (WAS) was pretreated by acid or alkali to enhance the anaerobic fermentation (AF) for phosphorus (P) and short-chain fatty acids (SCFAs) release into the liquid simultaneously. With acid pretreatment, the released total P concentration achieved 120mg/L, which was 71.4% higher than that with alkali pretreatment. In addition, alkali pretreatment enhanced organic P release with about 35.3% of organic P in the solid being converted to inorganic P, while little had changed with acid pretreatment. The results also showed that acid and alkali pretreatment enhanced SCFAs production by 15.3 and 12.5times, respectively. Acid pretreatment could be preferred for simultaneous recovery of P and SCFAs by AF.