Single-Cell RNA Sequencing Identifies WARS1+ Mesenchymal Stem Cells with Enhanced Immunomodulatory Capacity and Improved Therapeutic Efficacy.

Psoriasis is a common inflammatory skin disorder with no cure. Mesenchymal stem cells (MSCs) have immunomodulatory properties for psoriasis, but the therapeutic efficacies varied, and the molecular mechanisms were unknown. In this study, we improved the efficacy by enhancing the immunomodulatory effects of umbilical cord-derived MSCs (UC-MSCs). UC-MSCs stimulated by TNF-α and IFN-γ exhibited a better therapeutic effect in a mouse model of psoriasis. Single-cell RNA sequencing revealed that the stimulated UC-MSCs overrepresented a subpopulation expressing high tryptophanyl-tRNA synthetase 1 (WARS1). WARS1-overexpressed UC-MSCs treat psoriasis-like skin inflammation more efficiently than control UC-MSCs by restraining the proinflammatory macrophages. Mechanistically, WARS1 maintained a RhoA-Akt axis and governed the immunomodulatory properties of UC-MSCs. Together, we identify WARS1 as a master regulator of UC-MSCs with enhanced immunomodulatory capacities, which paves the way for the directed modification of UC-MSCs for escalated therapeutic efficacy.

Synergistic Catalytic Performance of Pt-Au Bimetallic Catalysts on High-Crystallinity ZSM-23 Zeolite for Hexadecane Hydroisomerization: Metal-Acid Balance and Enhanced Isomerization Selectivity.

Highly crystalline ZSM-23 zeolite, exhibiting a distinctive dumbbell morphology, was synthesized via a hydrothermal method. Bifunctional catalysts, comprising single metals (Pt or Au) and bimetals (Pt-Au), were successfully prepared by using a positional precipitation method. The hydroisomerization of hexadecane served as a model reaction to assess the catalytic performance arising from the synergistic effects of bimetallic active sites. In comparison to single-metal catalysts, 0.3Au0.7Pt/ZSM-23 demonstrated increased n-C16 conversion, while 0.5Au0.5Pt/ZSM-23 exhibited enhanced i-C16 selectivity, achieving the highest i-C16 yield. The bimetallic catalyst not only finely tuned the metal site activity through bimetallic synergy but also achieved a superior balance between metal and acid catalysis, resulting in improved catalytic performance in the n-C16 hydroisomerization. The Pt-Au bimetallic catalyst approached the ideal requirements for a hydroisomerization catalyst, achieving a harmonious balance of metal and acid catalysis.

Population pharmacokinetics of imetelstat, a first-in-class oligonucleotide telomerase inhibitor.

Imetelstat is a novel, first-in-class, oligonucleotide telomerase inhibitor in development for the treatment of hematologic malignancies including lower-risk myelodysplastic syndromes and myelofibrosis. A nonlinear mixed-effects model was developed to characterize the population pharmacokinetics of imetelstat and identify and quantify covariates that contribute to its pharmacokinetic variability. The model was developed using plasma concentrations from 7 clinical studies including 424 patients with solid tumors or hematologic malignancies who received single-agent imetelstat via intravenous infusion at various dose levels (0.4-11.7 mg/kg) and schedules (every week to every 4 weeks). Covariate analysis included factors related to demographics, disease, laboratory results, renal and hepatic function, and antidrug antibodies. Imetelstat was described by a two-compartment, nonlinear disposition model with saturable binding/distribution and dose- and time-dependent elimination from the central compartment. Theory-based allometric scaling for body weight was included in disposition parameters. The final covariates included sex, time, malignancy, and dose on clearance; malignancy and sex on volume of the central compartment; and malignancy and spleen volume on concentration of target. Clearance in females was modestly lower, resulting in nonclinically relevant increases in predicted exposure relative to males. No effects on imetelstat pharmacokinetics were identified for mild-to-moderate hepatic or renal impairment, age, race, and antidrug antibody status. All model parameters were estimated with adequate precision (relative standard error < 29%). Visual predictive checks confirmed the capacity of the model to describe the data. The analysis supports the imetelstat body-weight-based dosing approach and lack of need for dose individualizations for imetelstat-treated patients.

Boosting Formate Electrooxidation by Heterostructured PtPd Alloy and Oxides Nanowires.

Direct formate fuel cells (DFFCs) receive increasing attention as promising technologies for the future energy mix and environmental sustainability, as formate can be made from carbon dioxide utilization and is carbon neutral. Herein, heterostructured platinum-palladium alloy and oxides nanowires (PtPd-ox NWs) with abundant defect sites are synthesized through a facile self-template method and demonstrated high activity toward formate electrooxidation reaction (FOR). The electronic tuning arising from the heterojunction between alloy and oxides influence the work function of PtPd-ox NWs. The sample with optimal work function reveals the favorable adsorption behavior for intermediates and strong interaction in the d-p orbital hybridization between Pt site and oxygen in formate, favoring the FOR direct pathway with a low energy barrier. Besides the thermodynamic regulation, the heterostructure can also provide sufficient hydroxyl species to facilitate the formation of carbon dioxide due to the ability of combining absorbed hydrogen and carbon monoxide at adjacent active sites, which contributes to the improvement of FOR kinetics on PtPd-ox NWs. Thus, heterostructured PtPd-ox NWs achieve dual regulation of FOR thermodynamics and kinetics, exhibiting remarkable performance and demonstrating potential in practical systems.

Modulating the Electronic Structure of Cobalt in Molecular Catalysts via Coordination Environment Regulation for Highly Efficient Heterogeneous Nitrate Reduction.

Ammonia (NH3) is pivotal in modern industry and represents a promising next-generation carbon-free energy carrier. Electrocatalytic nitrate reduction reaction (eNO3RR) presents viable solutions for NH3 production and removal of ambient nitrate pollutants. However, the development of eNO3RR is hindered by lacking the efficient electrocatalysts. To address this challenge, we synthesized a series of macrocyclic molecular catalysts for the heterogeneous eNO3RR. These materials possess different coordination environments around metal centers by surrounding subunits. Consequently, electronic structures of the active centers can be altered, enabling tunable activity towards eNO3RR. Our investigation reveals that metal center with an N2(pyrrole)-N2(pyridine) configuration demonstrates superior activity over the others and achieves a high NH3 Faradaic efficiency (FE) of over 90 % within the tested range, where the highest FE of approximately 94 % is obtained. Furthermore, it achieves a production rate of 11.28 mg mgcat -1 h-1, and a turnover frequency of up to 3.28 s-1. Further tests disclose that these molecular catalysts with diverse coordination environments showed different magnetic moments. Theoretical calculation results indicate that variated coordination environments can result in a d-band center variation which eventually affects rate-determining step energy and calculated magnetic moments, thus establishing a correlation between electronic structure, experimental activity, and computational parameters.

Spin-related Cu-Co pair to increase electrochemical ammonia generation on high-entropy oxides.

The electrochemical conversion of nitrate to ammonia is a way to eliminate nitrate pollutant in water. Cu-Co synergistic effect was found to produce excellent performance in ammonia generation. However, few studies have focused on this effect in high-entropy oxides. Here, we report the spin-related Cu-Co synergistic effect on electrochemical nitrate-to-ammonia conversion using high-entropy oxide Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O. In contrast, the Li-incorporated MgCoNiCuZnO exhibits inferior performance. By correlating the electronic structure, we found that the Co spin states are crucial for the Cu-Co synergistic effect for ammonia generation. The Cu-Co pair with a high spin Co in Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O can facilitate ammonia generation, while a low spin Co in Li-incorporated MgCoNiCuZnO decreases the Cu-Co synergistic effect on ammonia generation. These findings offer important insights in employing the synergistic effect and spin states inside for selective catalysis. It also indicates the generality of the magnetic effect in ammonia synthesis between electrocatalysis and thermal catalysis.

A lncRNA Dleu2-encoded peptide relieves autoimmunity by facilitating Smad3-mediated Treg induction.

Micropeptides encoded by short open reading frames (sORFs) within long noncoding RNAs (lncRNAs) are beginning to be discovered and characterized as regulators of biological and pathological processes. Here, we find that lncRNA Dleu2 encodes a 17-amino-acid micropeptide, which we name Dleu2-17aa, that is abundantly expressed in T cells. Dleu2-17aa promotes inducible regulatory T (iTreg) cell generation by interacting with SMAD Family Member 3 (Smad3) and enhancing its binding to the Foxp3 conserved non-coding DNA sequence 1 (CNS1) region. Importantly, the genetic deletion of Dleu2-17aa in mice by start codon mutation impairs iTreg generation and worsens experimental autoimmune encephalomyelitis (EAE). Conversely, the exogenous supplementation of Dleu2-17aa relieves EAE. Our findings demonstrate an indispensable role of Dleu2-17aa in maintaining immune homeostasis and suggest therapeutic applications for this peptide in treating autoimmune diseases.

Relationship between STAP1 methylation in peripheral blood T cells and the clinicopathological characteristics and prognosis of patients within 5-cm diameter HCC.

BACKGROUND: The aim of this study is to explore the methylation of signal transduction adaptor protein 1 (STAP1) in peripheral blood T cells as a prognostic marker for hepatocellular carcinoma (HCC) ≤5 cm. METHODS: A total of 66 HCC patients who visited our hospital from November 2012 to June 2016 were retrospectively analyzed, and 55 patients who met the inclusion and exclusion criteria were studied. Clinical and pathological data were collected from all patients to detect STAP1 methylation. STAP1 methylation expression was analyzed in HCC patients ≤5 cm with different clinicopathological features; univariate and independent prognostic factors were analyzed in HCC patients; and the relationship between STAP1 methylation expression and prognosis was analyzed in HCC patients. RESULTS: There was no significant difference in STAP1 methylation expression between patients with different gender, age, history of alcoholism, history of liver cirrhosis, recurrence, 3-year OS, 5-year OS, treatment, number of tumors, tumor diameter, HBV-DNA, HBSAg, Hbe-Ag expression, and AFP level (P>0.05); however, there was significant difference in STAP1 methylation expression between patients with different survival, 3-year DFS, and 5-year DFS (P<0.05). Multivariate Cox regression analysis showed that recurrence and STAP1 methylation were independent factors for OS and DFS (P<0.05). Kaplan-Meier survival curve results showed that the median survival time, OS, and DFS of STAP1 hypermethylation expression were shorter than those of hypomethylation (P<0.05). CONCLUSIONS: STAP1 methylation in peripheral blood T cells serves as a potential prognostic marker for HCC ≤5 cm.

Imetelstat in patients with lower-risk myelodysplastic syndromes who have relapsed or are refractory to erythropoiesis-stimulating agents (IMerge): a multinational, randomised, double-blind, placebo-controlled, phase 3 trial.

BACKGROUND: Unmet medical needs remain in patients with red blood cell transfusion-dependent (RBC-TD) lower-risk myelodysplastic syndromes (LR-MDS) who are not responding to or are ineligible for erythropoiesis-stimulating agents (ESAs). Imetelstat, a competitive telomerase inhibitor, showed promising results in a phase 2 trial. We aimed to compare the RBC transfusion independence (RBC-TI) rate with imetelstat versus placebo in patients with RBC-TD LR-MDS. METHODS: In phase 3 of IMerge, a double-blind, placebo-controlled trial conducted in 118 sites including university hospitals, cancer centres, and outpatient clinics in 17 countries, patients (aged ≥18 years) with ESA-relapsed, ESA-refractory, or ESA-ineligible LR-MDS (low or intermediate-1 risk disease as per International Prognostic Scoring System [IPSS] criteria) were randomly assigned via a computer-generated schedule (2:1) to receive imetelstat 7·5 mg/kg or placebo, administered as a 2-h intravenous infusion, every 4 weeks until disease progression, unacceptable toxic effects, or withdrawal of consent. Randomisation was stratified by previous RBC transfusion burden and IPSS risk group. Patients, investigators, and those analysing the data were masked to group assignment. The primary endpoint was 8-week RBC-TI, defined as the proportion of patients without RBC transfusions for at least 8 consecutive weeks starting on the day of randomisation until subsequent anti-cancer therapy, if any. Primary efficacy analyses were performed in the intention-to-treat population, and safety analyses were conducted in patients who received at least one dose of trial medication or placebo. This trial is registered with ClinicalTrials.gov (NCT02598661; substudy active and recruiting). FINDINGS: Between Sept 11, 2019, and Oct 13, 2021, 178 patients were enrolled and randomly assigned (118 to imetelstat and 60 to placebo). 111 (62%) were male and 67 (38%) were female. 91 (77%) of 118 patients had discontinued treatment by data cutoff in the imetelstat group versus 45 (75%) in the placebo group; a further one patient in the placebo group did not receive treatment. Median follow-up was 19·5 months (IQR 12·0-23·4) in the imetelstat group and 17·5 months (12·1-22·7) in the placebo group. In the imetelstat group, 47 (40% [95% CI 30·9-49·3]) patients had an RBC-TI of at least 8 weeks versus nine (15% [7·1-26·6]) in the placebo group (rate difference 25% [9·9 to 36·9]; p=0·0008). Overall, 107 (91%) of 118 patients receiving imetelstat and 28 (47%) of 59 patients receiving placebo had grade 3-4 treatment-emergent adverse events. The most common treatment-emergent grade 3-4 adverse events in patients taking imetelstat were neutropenia (80 [68%] patients who received imetelstat vs two [3%] who received placebo) and thrombocytopenia (73 [62%] vs five [8%]). No treatment-related deaths were reported. INTERPRETATION: Imetelstat offers a novel mechanism of action with durable transfusion independence (approximately 1 year) and disease-modifying activity for heavily transfused patients with LR-MDS who are not responding to or are ineligible for ESAs. FUNDING: Janssen Research & Development before April 18, 2019, and Geron Corporation thereafter.

Identification of a Necroptosis-Related Prognostic Signature and Associated Regulatory Axis in Lung Adenocarcinoma.

Background: Lung cancer is considered to be the second most aggressive and rapidly fatal cancer after breast cancer. Necroptosis, a novel discovered pattern of cell death, is mediated by Receptor-interacting serine/threonine-protein kinase 1 (RIPK1), Receptor-interacting serine/threonine-protein kinase 3 (RIPK3), and Mixed Lineage Kinase Domain Like Pseudokinase (MLKL). Methods: For the purpose of developing a prognostic model, Least absolute shrinkage and selection operator (LASSO) Cox regression analysis was conducted. Using Pearson's correlation analysis, we evaluated the correlation between necroptosis-related markers and tumor immune infiltration. A bioinformatics analysis was conducted to construct a necroptosis-related regulatory axis. Results: There was a downregulation of most of necroptosis-related genes in lung adenocarcinoma (LUAD) versus lung tissues but an increase in PGAM5, HMGB1, TRAF2, EZH2 levels. We also summarized the Single Nucleotide Variant (SNV) and copy number variation (CNV) of necroptosis-related genes in LUAD. Consensus clustering identified two clusters in LUAD with distinct immune cell infiltration and ESTIMATEScore. Genes related to necroptosis were associated with necroptosis, Tumor necrosis factor (TNF) signaling pathway, and apoptosis according to Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathways. Four prognostic genes (ALDH2, HMGB1, NDRG2, TLR2) were combined to develop a prognostic gene signature for LUAD patients, which was highly accurate in predicting prognosis. Univariate and multivariate analysis identified HMGB1, pT stage, and pN stage as independent factors impacting on LUAD patients' prognosis. A significant correlation was found between the level of TLR2 and NDRG2 and clinical stage, immunity infiltration, and drug resistance. Additionally, the progression of LUAD might be regulated by lncRNA C5orf64/miR-582-5p/NDRG2/TLR2. Conclusion: The current bioinformatics analysis identified a necroptosis-related prognostic signature for LUAD and their relation to immunity infiltration. This result requires further investigation.

Conjugated Nickel Phthalocyanine Derivatives for Heterogeneous Electrocatalytic H2 O2 Synthesis.

Electrocatalytic hydrogen peroxide (H2 O2 ) production has emerged as a promising alternative to the chemical method currently used in industry, due to its environmentally friendly conditions and potential for higher activity and selectivity. Heterogeneous molecular catalysts are promising in this regard, as their active site configurations can be judiciously designed, modified, and tailored with diverse functional groups, thereby tuning the activity and selectivity of the active sites. In this work, nickel phthalocyanine derivatives with various conjugation degrees are synthesized and identified as effective pH-universal electrocatalysts for H2 O2 production after heterogenized on nitrogen-decorated carbon, with increased conjugation degrees leading to boosted selectivity. This is explained by the regulated d-band center, which optimized the binding energy of the reaction intermediate, reducing the energy barrier for oxygen reduction and leading to optimized H2 O2 selectivity. The best catalyst, NiPyCN/CN, exhibits a high H2 O2  electrosynthesis activity with ≈95% of H2 O2 faradic efficiency in an alkaline medium, demonstrating its potential for H2 O2 production.

Small RNA sequencing identified miR-3180 as a potential prognostic biomarker for Chinese hepatocellular carcinoma patients.

MicroRNAs (miRNAs) and their target genes are aberrantly expressed in many cancers and are linked to carcinogenesis and metastasis, especially among hepatocellular carcinoma (HCC) patients. This study sought to identify new biomarkers related to HCC prognosis using small RNA sequencing from the tumor and matched normal adjacent tissue of 32 patients with HCC. Eight miRNAs were downregulated and 61 were upregulated more than twofold. Of these, five miRNAs, hsa-miR-3180, hsa-miR-5589-5p, hsa-miR-490-5p, hsa-miR-137, and hsa-miR-378i, were significantly associated with 5-year overall survival (OS) rates. Differential upregulation of hsa-miR-3180 and downregulation of hsa-miR-378i in tumor samples supported the finding that low and high concentrations of hsa-miR-3180 (p = 0.029) and hsa-miR-378i (p = 0.047), respectively, were associated with higher 5-year OS. Cox regression analyses indicated that hsa-miR-3180 (HR = 0.08; p = 0.013) and hsa-miR-378i (HR = 18.34; p = 0.045) were independent prognostic factors of poor survival. However, high hsa-miR-3180 expression obtained larger AUCs for OS and progression-free survival (PFS) and had better nomogram prediction than hsa-miR-378i. These findings indicate that hsa-miR-3180 may be associated with HCC progression and could serve as a potential biomarker for this disease.

Tenascin C+ papillary fibroblasts facilitate neuro-immune interaction in a mouse model of psoriasis.

Dermal fibroblasts and cutaneous nerves are important players in skin diseases, while their reciprocal roles during skin inflammation have not been characterized. Here we identify an inflammation-induced subset of papillary fibroblasts that promotes aberrant neurite outgrowth and psoriasiform skin inflammation by secreting the extracellular matrix protein tenascin-C (TNC). Single-cell analysis of fibroblast lineages reveals a Tnc+ papillary fibroblast subset with pro-axonogenesis and neuro-regulation transcriptomic hallmarks. TNC overexpression in fibroblasts boosts neurite outgrowth in co-cultured neurons, while fibroblast-specific TNC ablation suppresses hyperinnervation and alleviates skin inflammation in male mice modeling psoriasis. Dermal γδT cells, the main producers of type 17 pathogenic cytokines, frequently contact nerve fibers in mouse psoriasiform lesions and are likely modulated by postsynaptic signals. Overall, our results highlight the role of an inflammation-responsive fibroblast subset in facilitating neuro-immune synapse formation and suggest potential avenues for future therapeutic research.

Highly Crystalline Polyimide Covalent Organic Framework as Dual-Active-Center Cathode for High-Performance Lithium-Ion Batteries.

Polyimide covalent organic framework (PI-COF) materials that can realize intrinsic redox reactions by changing the charge state of their electroactive sites are considered as emerging electrode materials for rechargeable devices. However, the highly crystalline PI-COFs with hierarchical porosity are less reported due to the rapid reaction between monomers and the poor reversibility of the polyimidization reaction. Here, we developed a water-assistant synthetic strategy to adjust the reaction rate of polyimidization, and PI-COF (COFTPDA-PMDA) with kgm topology consisting of dual active centers of N,N,N',N'-tetrakis(4-aminophenyl)-1,4-benzenediamine (TPDA) and pyromellitic dianhydride (PMDA) ligands was successfully synthesized with high crystallinity and porosity. The COFTPDA-PMDA possesses hierarchical micro-/mesoporous channels with the largest surface area (2669 m2/g) in PI-COFs, which can promote the Li+ ions and bulky bis(trifluoromethanesulfonyl)imide (TFSI-) ions in organic electrolyte to sufficiently interact with the dual active sites on COF skeleton to increase the specific capacity of cathode materials. As a cathode material for lithium-ion batteries, COFTPDA-PMDA@50%CNT which integrated high surface area and dual active center of COFTPDA-PMDA with carbon nanotubes via π-π interactions gave a high initial charge capacity of 233 mAh/g (0.5 A/g) and maintains at 80 mAh/g even at a high current density of 5.0 A/g after 1800 cycles.

AHNAK Contributes to Hepatocellular Carcinoma Growth by Interacting with IGF-1R.

Neuroblast differentiation-associated protein AHNAK, a large structural scaffold protein, remains mysterious in biological processes. AHNAK plays a suppressive or progressive role in different types of cancers. To investigate the role of the AHNAK in hepatocellular carcinoma (HCC), cell viability assays were performed to determine the cell proliferation of the stable AHNAK-knockdown HepG2 cell line; co-immunoprecipitation (Co-IP) and liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) were performed on HCC and matched paracancerous (MPC) tissues. The Metascape platform was used for enrichment analyses; the "ComplexHeatmap" package was applied for cluster analyses and visualization. Co-IP, Western botting and immunofluorescence double staining were performed to assess the interactions between AHNAK and insulin-like growth factor 1 receptor (IGF-1R). AHNAK silencing reduced the viability of HepG2 cells; the interactome in HCC and MPC tissues enriched 204 pathways and processes, which partially reflected the signature of HCC field cancerization. AHNAK could co-localize and interact with IGF-1R. These results suggested that the AHNAK complex contributes to HCC growth, potentially by interacting with IGF-1R.

Targeting the transcription factor HES1 by L-menthol restores protein phosphatase 6 in keratinocytes in models of psoriasis.

Protein Phosphatase 6 down-regulation in keratinocytes is a pivotal event that amplifies the inflammatory circuits in psoriasis, indicating that restoration of protein phosphatase 6 can be a rational strategy for psoriasis treatment. Through the phenotypic screen, we here identify L-menthol that ameliorates psoriasis-like skin inflammation by increasing protein phosphatase 6 in keratinocytes. Target identification approaches reveal an indispensable role for the transcription factor hairy and enhancer of split 1 in governing the protein phosphatase 6-upregulating function of L-menthol in keratinocytes. The transcription factor hairy and enhancer of split 1 is diminished in the epidermis of psoriasis patients and imiquimod-induced mouse model, while L-menthol upregulates the transcription factor hairy and enhancer of split 1 by preventing its proteasomal degradation. Mechanistically, the transcription factor hairy and enhancer of split 1 transcriptionally activates the expression of immunoglobulin-binding protein 1 which promotes protein phosphatase 6 expression and inhibits its ubiquitination. Collectively, we discover a therapeutic compound, L-menthol, for psoriasis, and uncover the dysfunctional the transcription factor hairy and enhancer of split 1- immunoglobulin-binding protein 1- protein phosphatase 6 axis that contributes to psoriasis pathology by using L-menthol as a probe.

Multi-atom cluster catalysts for efficient electrocatalysis.

Multi-atom cluster catalysts have turned out to be novel heterogeneous catalysts with atomic dispersion for electrochemical energy applications. Beyond a simple combination of single-atom catalysts, they could offer boosted activity as a result of the synergistic effects between adjacent atoms. Meanwhile, the multiple active sites in the catalytic center may render them versatile binding modes toward adsorbates and provide an opportunity for catalyzing complex reactions with diverse products. Herein, a comprehensive review of the recent development of multi-atom cluster catalysts for electrochemical energy applications is provided. Specifically, the origin of synergistic effects in multi-atom cluster catalysts and related modulation methods are illustrated and summarized. The introduction of multi-atom cluster catalysts to circumvent the scaling relationships as well as their potential for developing new descriptors is then discussed. Subsequently, the methods for fabricating multi-atom cluster catalysts and related characterization techniques are reviewed. This is followed by the discussion of their application in key electrochemical reactions such as water splitting, oxygen reduction, and carbon dioxide/monoxide reduction, as well as the real-time techniques for their mechanistic study. Finally, the future challenges and opportunities concerning the improvement of multi-atom cluster catalysts are outlined, which are essential to make such electrocatalysts viable for electrochemical energy conversion.

The effect of the hydroxyl group position on the electrochemical reactivity and product selectivity of butanediol electro-oxidation.

This article presents a study on the effect of the hydroxyl group position on the electro-oxidation of butanediols, including 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, and 1,4-butanediol. The effect of the hydroxyl group position in butanediols on their electro-oxidation reactivities is investigated by cyclic voltammetry, linear sweep voltammetry, chronopotentiometry and chronoamperometry in 1.0 M KOH. The results show that the closer the two hydroxyl groups are, the higher the reactivity, and the lower the anodic potential butanediol has. Moreover, the oxidation products from chronoamperometry are analyzed by means of HPLC and NMR. Some value-added products, such as 3-hydroxypropionic acid/3-hydroxypropionate, are produced. The DFT calculation indicates that the oxidation of vicinal diols responds to the conversion from a hydroxyl group to a carboxylate group, followed by C-C bond cleavage, where the carbon charge decreases. These results provide an insight into reactant selection for the electrochemical synthesis of value-added chemicals.

Near infrared optically responsive Ag-Cu bimetallic 2D nanocrystals with controllable spatial structures.

The optical properties of cost-effective Ag-Cu bimetallic nanocrystals, with synergistically enhanced catalytic and biological activities, are limited within ultraviolet-visible region due to lack of morphology control. In order to overcome this constraint, two-dimensional (2D) Ag-Cu bimetallic heterostructures were designed and synthesized by a seed-mediated colloidal growth method. The conformal Cu domain was epitaxially deposited on Ag nanoplates with different spatial configuration under retention of their 2D shape. Both of the 2D Ag-Cu core@shell and Janus structures display tunable localized surface plasmon resonance from visible to near infrared regions. The results of catalytic reduction of 4-nitrophenol show that the 2D Ag-Cu core@shell structure has better synergistic catalytic performance than Janus structure and Ag plates. In addition to surface-related synergistically enhanced bactericidal performance, their antibacterial effect can also be significantly enhanced by near infrared light irradiation. These results indicate that 2D Ag-Cu heterostructures can benefit from both synergistically improved surface activity and great optical responsive characteristics.