CO2-mediated organocatalytic chlorine evolution under industrial conditions.

During the chlor-alkali process, in operation since the nineteenth century, electrolysis of sodium chloride solutions generates chlorine and sodium hydroxide that are both important for chemical manufacturing1-4. As the process is very energy intensive, with 4% of globally produced electricity (about 150 TWh) going to the chlor-alkali industry5-8, even modest efficiency improvements can deliver substantial cost and energy savings. A particular focus in this regard is the demanding chlorine evolution reaction, for which the state-of-the-art electrocatalyst is still the dimensionally stable anode developed decades ago9-11. New catalysts for the chlorine evolution reaction have been reported12,13, but they still mainly consist of noble metal14-18. Here we show that an organocatalyst with an amide functional group enables the chlorine evolution reaction; and that in the presence of CO2, it achieves a current density of 10 kA m-2 and a selectivity of 99.6% at an overpotential of only 89 mV and thus rivals the dimensionally stable anode. We find that reversible binding of CO2 to the amide nitrogen facilitates formation of a radical species that plays a critical role in Cl2 generation, and that might also prove useful in the context of Cl- batteries and organic synthesis19-21. Although organocatalysts are typically not considered promising for demanding electrochemical applications, this work demonstrates their broader potential and the opportunities they offer for developing industrially relevant new processes and exploring new electrochemical mechanisms.

Visible light-driven photocatalytic sulfonative oxidation of benzyl secondary amines.

A method for the α-oxidation and sulfonation of benzyl secondary amines was developed utilizing Ir(III) or Eosin Y as the photocatalyst in the presence of O2 as a green oxidant. Using commercial substrates, 37 products from cyclic and acyclic benzylamines were achieved with good functional group compatibility in 48-87% yields. Furthermore, tetrahydroisoquinoline protected by an Ac or a Boc group was oxidized under standard conditions.

KCNQ2 mutations cause unique neonatal behavior arrests without motor seizures: Functional characterization.

OBJECTIVE: KCNQ2 gene mutation usually manifests as neonatal seizures in the first week of life. Nonsense mutations cause a unique self-limited familial neonatal epilepsy (SLFNE), which is radically different from developmental epileptic encephalopathy (DEE). However, the exact underlying mechanisms remain unclear. METHODS: The proband, along with their mother and grandmother, carried the c.1342C > T (p.Arg448Ter) mutation in the KCNQ2 gene. The clinical phenotypes, electroencephalography (EEG) findings, and neurodevelopmental outcomes were comprehensively surveyed. The mutant variants were transfected into HEK293 cells to investigate functional changes. RESULTS: The proband exhibited behavior arrests, autonomic and non-motor neonatal seizures with changes in heart rate and respiration. EEG exhibited focal sharp waves. Seizures were remitted after three months of age. The neurodevelopmental outcomes at three years of age were unremarkable. A functional study demonstrated that the currents of p.Arg448Ter were non-functional in homomeric p.Arg448Ter compared with that of the KCNQ2 wild type. However, the current density and V1/2 exhibited significant improvement and close to that of the wild-type after transfection with heteromeric KCNQ2 + p.Arg448Ter and KCNQ2 + KCNQ3 + p.Arg448Ter respectively. Channel expression on the cell membrane was not visible after homomeric transfection, but not after heteromeric transfection. Retigabine did not affect homomeric p.Arg448Ter but improved heteromeric p. Arg448Ter + KCNQ2 and heteromeric KCNQ2 + Arg448Ter + KCNQ3. CONCLUSIONS: The newborn carrying the p. Arg448Ter mutation presented frequent behavioral arrests, autonomic, and non-motor neonatal seizures. This unique pattern differs from KCNQ2 seizures, which typically manifest as motor seizures. Although p.Arg448Ter is a non-sense decay, the functional study demonstrated an almost-full compensation mechanism after transfection of heteromeric KCNQ2 and KCNQ3.

Correlation of meniscus tear type with synovial inflammation and the therapeutic potential of docosapentaenoic acid.

BACKGROUND: Synovitis, characterized by inflammation of the synovial membrane, is commonly induced by meniscus tears. However, significant differences in inflammatory responses and the key inflammatory mediators of synovium induced by different types of meniscal tears remain unclear. METHODS: Magnetic resonance imaging (MRI) was employed to identify the type of meniscus tear, and the quantification of synovial inflammation was assessed through H&E staining assay. Transcription and expression levels of IL-1ß and IL-6 were evaluated using bioinformatics, ELISA, RT-qPCR, and IHC of CD68 staining assays. The therapeutic potential of Docosapentaenoic Acid (DPA) was determined through network pharmacology, ELISA, and RT-qPCR assays. The safety of DPA was assessed using colony formation and EdU staining assays. RESULTS: The results indicate that both IL-1ß and IL-6 play pivotal roles in synovitis pathogenesis, with distinct expression levels across various subtypes. Among tested meniscus tears, oblique tear and bucket handle tear induced the most severe inflammation, followed by radial tear and longitudinal tear, while horizontal tear resulted in the least inflammation. Furthermore, in synovial inflammation induced by specific meniscus tears, the anterior medial tissues exhibited significantly higher local inflammation than the anterior lateral and suprapatellar regions, highlighting the clinical relevance and practical guidance of anterior medial tissues' inflammatory levels. Additionally, we identified the essential omega-3 fatty acid DPA as a potential therapeutic agent for synovitis, demonstrating efficacy in blocking the transcription and expression of IL-1ß and IL-6 with minimal side effects. CONCLUSION: These findings provide valuable insights into the nuanced nature of synovial inflammation induced by various meniscal tear classifications and contribute to the development of new adjunctive therapeutic agents in the management of synovitis.

Single-Atom Manganese-Catalyzed Oxygen Evolution Drives the Electrochemical Oxidation of Silane to Silanol.

The oxygen evolution reaction (OER), characterized by a four-electron transfer kinetic process, represents a significant bottleneck in improving the efficiency of hydrogen production from water electrolysis. Consequently, extensive research efforts have been directed towards identifying single-atom electrocatalysts with exceptional OER performance. Despite the comprehensive understanding of the OER mechanism, its application to other valuable synthetic reactions has been limited. Herein, we leverage the MOOH intermediate, a key species in the Mn-N-C single-atom catalyst (Mn-SA@NC), which can be cyclically delivered in the OER. We exploit this intermediate' s capability to facilitate electrophilic transfer with silane, enabling efficient silane oxidation under electrochemical conditions. The SAC electrocatalytic system exhibits remarkable performance with catalyst loadings as low as 600 ppm and an exceptional turnover number of 9132. Furthermore, the catalytic method demonstrates stability under a 10 mmol flow chemistry setup. By serving as an OER electrocatalyst, the Mn-SA@NC drives the entire reaction, establishing a practical Mn SAC-catalyzed organic electrosynthesis system. This synthesis approach not only presents a promising avenue for the utilization of electrocatalytic OER but also highlights the potential of SACs as an attractive platform for organic electrosynthesis investigations.

Single-Atom Iron Catalyst as an Advanced Redox Mediator for Anodic Oxidation of Organic Electrosynthesis.

Homogeneous electrocatalysts can indirect oxidate the high overpotential substrates through single-electron transfer on the electrode surface, enabling efficient operation of organic electrosynthesis catalytic cycles. However, the problems of this chemistry still exist such as high dosage, difficult recovery, and low catalytic efficiency. Single-atom catalysts (SACs) exhibit high atom utilization and excellent catalytic activity, hold great promise in addressing the limitations of homogeneous catalysts. In view of this, we have employed Fe-SA@NC as an advanced redox mediator to try to change this situation. Fe-SA@NC was synthesized using an encapsulation-pyrolysis method, and it demonstrated remarkable performance as a redox mediator in a range of reported organic electrosynthesis reactions, and enabling the construction of various C-C/C-X bonds. Moreover, Fe-SA@NC demonstrated a great potential in exploring new synthetic method for organic electrosynthesis. We employed it to develop a new electro-oxidative ring-opening transformation of cyclopropyl amides. In this new reaction system, Fe-SA@NC showed good tolerance to drug molecules with complex structures, as well as enabling flow electrochemical syntheses and gram-scale transformations. This work highlights the great potential of SACs in organic electrosynthesis, thereby opening a new avenue in synthetic chemistry.

Polymerization Based on Modified ß-Cyclodextrin Achieves Efficient Phosphorescence Energy Transfer for Anti-Counterfeiting.

Supramolecular polymerization can not only activate guest phosphorescence, but also promote phosphorescence Förster resonance energy transfer and induce effective delayed fluorescence. Herein, the solid supramolecular assemblies of ternary copolymers based on acrylamide, modified ß-cyclodextrin (CD), and carbazole (CZ) are reported. After doping with polyvinyl alcohol (PVA) and dyes, a NIR luminescence supramolecular composite with a lifetime of 1.07 s, an energy transfer efficiency of up to 97.4% is achieved through tandem phosphorescence energy transfer. The ternary copolymers can realize macrocyclic enrichment of dyes in comparison to CZ and acrylamide copolymers without CD, which can facilitate energy transfer between triplet and singlet with a high donor-acceptor ratio. Additionally, the flexible polymeric films exhibit regulable lifetime, tunable luminescence color, and repeatable switchable afterglow by adjusting the excitation wavelength, donor-acceptor ratio, and wet/dry stimuli. The luminescence materials are successfully applied to information encryption and anti-counterfeiting.

Orbital Fulde-Ferrell Pairing State in Moiré Ising Superconductors.

In this Letter, we study superconducting moiré homobilayer transition metal dichalcogenides where the Ising spin-orbit coupling (SOC) is much larger than the moiré bandwidth. We call such noncentrosymmetric superconductors, moiré Ising superconductors. Because of the large Ising SOC, the depairing effect caused by the Zeeman field is negligible and the in-plane upper critical field (B_{c2}) is determined by the orbital effects. This allows us to study the effect of large orbital fields. Interestingly, when the applied in-plane field is larger than the conventional orbital B_{c2}, a finite-momentum pairing phase would appear which we call the orbital Fulde-Ferrell (FF) state. In this state, the Cooper pairs acquire a net momentum of 2q_{B}, where 2q_{B}=eBd is the momentum shift caused by the magnetic field B and d denotes the layer separation. This orbital field-driven FF state is different from the conventional FF state driven by Zeeman effects in Rashba superconductors. Remarkably, we predict that the FF pairing would result in a giant superconducting diode effect under electric gating when layer asymmetry is induced. An upturn of the B_{c2} as the temperature is lowered, coupled with the giant superconducting diode effect, would allow the detection of the orbital FF state.

Josephson Diode Effect Induced by Valley Polarization in Twisted Bilayer Graphene.

Recently, the Josephson diode effect (JDE), in which the superconducting critical current magnitudes differ when the currents flow in opposite directions, has attracted great interest. In particular, it was demonstrated that gate-defined Josephson junctions based on magic-angle twisted bilayer graphene showed a strong nonreciprocal effect when the weak-link region is gated to a correlated insulating state at half filling (two holes per moiré cell). However, the mechanism behind such a phenomenon is not yet understood. In this Letter, we show that the interaction-driven valley polarization, together with the trigonal warping of the Fermi surface, induce the JDE. The valley polarization, which lifts the degeneracy of the states in the two valleys, induces a relative phase difference between the first and the second harmonics of the supercurrent and results in the JDE. We further show that the nontrivial current phase relation, which is responsible for the JDE, also generates the asymmetric Shapiro steps.

Gate-Defined Topological Josephson Junctions in Bernal Bilayer Graphene.

Recent experiments on Bernal bilayer graphene (BLG) deposited on monolayer WSe_{2} revealed robust, ultraclean superconductivity coexisting with sizable induced spin-orbit coupling. Here, we propose BLG/WSe_{2} as a platform to engineer gate-defined planar topological Josephson junctions, where the normal and superconducting regions descend from a common material. More precisely, we show that if superconductivity in BLG/WSe_{2} is gapped and emerges from a parent state with intervalley coherence, then Majorana zero-energy modes can form in the barrier region upon applying weak in-plane magnetic fields. Our results spotlight a potential pathway for "internally engineered" topological superconductivity that minimizes detrimental disorder and orbital-magnetic-field effects.

Lifetime risk, life expectancy, loss-of-life expectancy and lifetime healthcare expenditure for Stevens-Johnson syndrome/toxic epidermal necrolysis in Taiwan: follow-up of a nationwide cohort from 2008 to 2019.

BACKGROUND: Stevens-Johnson syndrome (SJS) and toxic epidermal necrolysis (TEN) not only cause acute, devastating mucocutaneous reactions but also have long-lasting implications on survivors' lives. OBJECTIVES: To quantify the lifetime burden of SJS/TEN. METHODS: The cumulative incidence rate (CIR), life expectancy (LE), loss-of-life expectancy (LoLE) and lifetime healthcare expenditure (HE) for SJS/TEN were estimated over the period from 2008 to 2019 using data from the National Health Insurance Research Database of Taiwan and life tables of vital statistics. RESULTS: In this nationwide cohort of 6552 incident SJS/TEN cases, a trend towards a decrease in the CIR was observed between 2008 and 2019. Compared with the general population, patients with SJS/TEN experience a tremendous loss of 9.43 (1.06) [mean (SEM)] years of LE after diagnosis of SJS/TEN. Male patients with SJS/TEN had higher LoLE [10.74 (1.22) vs. 7.69 (1.43) years] and annual HE than females. Younger age at diagnosis of SJS/TEN was associated with longer LE but greater LoLE and higher lifetime HE. Patients with intensive care unit admission on diagnosis, malignancy, diabetes mellitus, end-stage renal disease and SJS/TEN-associated sequelae experienced substantially greater LoLE and HE per life year. CONCLUSIONS: Patients with SJS/TEN suffer substantial loss-of-LE and HE, particularly young patients, compared with the general population. These data provide a reference estimate of the lifetime burden of SJS/TEN to help health authorities evaluate the cost-effectiveness of future preventive and treatment strategies to minimize the burden of SJS/TEN.

Three-Component Electrochemical Aminoselenation of 1,3-Dienes.

Azoles and organoselenium compounds are pharmacologically important scaffolds in medicinal chemistry and natural products. We developed an efficient regioselective electrochemical aminoselenation reaction of 1,3-dienes, azoles, and diselenide derivatives to access selenium-containing allylazoles skeletons. This protocol is more economical and environmentally friendly and features a broad substrate scope; pyrazole, triazole, and tetrazolium were all tolerated under the standard conditions, which could be applied to the expedient synthesis of bioactive molecules and in the pharmaceutical industry.

Electrocatalytic ring-opening dihydroalkoxylation of N-aryl maleimides with alcohols under metal- and oxidant-free conditions.

The electrocatalytic ring-opening dihydroalkoxylation of N-aryl maleimides with alcohols under metal- and oxidant-free conditions is described. This electrochemical process consists of anodic single-electron transfer oxidation, cathodic radical reduction, rearrangement-ring cleavage and nucleophilic addition cascade, which employs tetrabutylammonium bromide not only as a redox catalyst but also as an efficient supporting electrolyte, and offers a practical and environmentally friendly route to ring-opening difunctionalization products.

In-situ construction of fluorescent probes for hydrogen peroxide detection in mitochondria and lysosomes with on-demand modular assembling and double turn-on features.

Due to the diverse H2O2 distribution in organelles, fluorescent probes were usually required to be prepared separately, which limited the convenience and practicability. Herein, we reported a flexible strategy to in-situ construct H2O2 fluorescent probes in different organelles. A tetrazine fused probe TP was developed with rapid click reaction capacity and sensitive H2O2 response. When treated with H2O2, the turn-on fluorescence was effectively quenched by the tetrazine part. Only after click reaction with dienophiles, the fluorescence resumed. In application, cells were firstly treated with triphenylphosphorus tagged norbornene (TPP-NB) to label mitochondria, which was followed by the introduction of probe TP to trigger click reaction. The in-situ constructed probe P1 served as a local H2O2 sensor. In a similar way, probe P2 was in-situ constructed in lysosomes via probe TP and morpholine tagged norbornene (MP-NB). With this on-demand modular assembling and double turn-on features, our strategy to construct fluorescent probes presented high flexibility and anti-interference performance, which was expected to inspired more applications in biological studies.

Daidzein promotes the proliferation and osteogenic differentiation of periodontal ligament stem cell.

CONTEXT: Daidzein is a kind of isoflavone compound with many biological functions. However, the specific mechanism regarding the treatment of periodontitis with daidzein is still unclear. OBJECTIVE: To investigate the effect of daidzein on the proliferation and osteogenic differentiation of human periodontal ligament stem cells (hPDLSCs) and its mechanism. MATERIALS AND METHODS: Human periodontal ligament stem cells from clinical samples were isolated in vitro and identified by flow cytometry. hPDLSCs were treated with different concentrations of daidzein. Cell proliferation ability and viability were measured by MTT assay and cell colony formation assay. Osteogenic differentiation and calcification of hPDLSCs were observed by alkaline phosphatase (ALP) staining and alizarin red staining. Western blot was used to detect the expression of c-myc, CyclinD1, osteogenic differentiation-related proteins, and Wnt/ß-catenin signaling pathway proteins in hPDLSCs. RESULTS: human periodontal ligament stem cells were positive for surface antigens CD146, STRO-1, and CD90 expression, but negative for CD45 expression, indicating the successful isolation of hPDLSCs. In addition, daidzein could significantly promote the proliferation, cell viability, ALP activity, and osteogenic differentiation of hPDLSC. At the same time, daidzein could notably increase the expression levels of c-myc, CyclinD1, osteogenic differentiation-related proteins, and Wnt/ß-catenin signaling pathway proteins, while an inhibitor of Wnt/ ß-catenin pathway, XAV-939, could reverse the effect caused by daidzein. DISCUSSION AND CONCLUSION: Daidzein promotes the proliferation and osteogenic differentiation of hPDLSCs by activating Wnt/ß-catenin signaling pathway.

Performance measurement of nonhomogeneous Hong Kong hospitals using directional distance functions.

Cook et al. (Oper Res 61(3):666-676, 2013) propose a DEA-based model for the performance evaluation of non-homogeneous decision making units (DMUs) based on constant returns to scale (CRS), extended by Li et al. (Health Care Manag Sci 22(2):215-228, 2019) to variable returns to scale (VRS). This paper locates these models into more general DDF models to deal with nonhomogeneous DMUs and applies these to Hong Kong hospitals. The production process of each hospital is divided into subunits which have the same inputs and outputs and hospital performance is measured using the subunits. The paper provides CRS and VRS versions of DDF models and compares them with Cook et al. (Oper Res 61(3):666-676, 2013) and Li et al. (Health Care Manag Sci 22(2):215-228, 2019). A kernel-based method is used to estimate the distributions as well as a DEA-based efficiency analysis adapted by Simar and Zelenyuk to test the distributions. Both DDF CRS and VRS versions produce results similar to Cook et al. (Oper Res 61(3):666-676, 2013) and Li et al. (Health Care Manag Sci 22(2):215-228, 2019) respectively. However, the statistical tests find differences for the different technologies assumed as would be expected. For hospital managers, the more generalised DDF models expand their range of options in terms of directional improvements and priorities as well as dealing with non-homogeneity.

Spectroscopic fingerprint of chiral Majorana modes at the edge of a quantum anomalous Hall insulator/superconductor heterostructure.

With the recent discovery of the quantum anomalous Hall insulator (QAHI), which exhibits the conductive quantum Hall edge states without external magnetic field, it becomes possible to create a topological superconductor (SC) by introducing superconductivity into these edge states. In this case, 2 distinct topological superconducting phases with 1 or 2 chiral Majorana edge modes were theoretically predicted, characterized by Chern numbers (N) of 1 and 2, respectively. We present spectroscopic evidence from Andreev reflection experiments for the presence of chiral Majorana modes in an Nb/(Cr0.12Bi0.26Sb0.62)2Te3 heterostructure with distinct signatures attributed to 2 different topological superconducting phases. The results are in qualitatively good agreement with the theoretical predictions.

CircRRAS2 promotes myogenic differentiation of bovine MuSCs and is a novel regulatory molecule of muscle development.

The proliferation and myogenic differentiation of muscle stem cells (MuSCs) are important factors affecting muscle development and beef quality. There is increasing evidence that circRNAs can regulate myogenesis. We found a novel circRNA, named circRRAS2 that is significantly upregulated in the differentiation phase of bovine MuSCs. Here, we aimed to determine its roles in the proliferation and myogenic differentiation of these cells. The results showed that circRRAS2 was expressed in several bovine tissues. CircRRAS2 inhibited MuSCs proliferation and promoted myoblast differentiation. In addition, chromatin isolation by using RNA purification and mass spectrometry in differentiated muscle cells identified 52 RNA-binding proteins that could potentially bind to circRRAS2, in order to regulate their differentiation. The results suggest that circRRAS2 could be a specific regulator of myogenesis in bovine muscle.HighlightsCircRRAS2 expression is higher in DM cells than in GM cells.CircRRAS2 could significantly inhibit the proliferation and apoptosis of bovine MuSCs.CircRRAS2 promotes the differentiation of bovine MuSCs into myotubes.CircRRAS2 may exert regulatory effects through multiple RNA binding proteins.

A Blockchain and IPFS-Based Anticounterfeit Traceable Functionality of Car Insurance Claims System.

Due to frequent traffic accidents around the world, people often take out car insurance to mitigate their losses and receive compensation in a traffic accident. However, in the existing car insurance claims process, there are problems such as insurance fraud, inability to effectively track and transmit insurance data, cumbersome insurance procedures, and high insurance data storage costs. Since the immutability and traceability features of blockchain technology can prevent data manipulation and trace past data, we have used the Elliptic Curve Digital Signature Algorithm (ECDSA) to sign and encrypt car insurance data, ensuring both data integrity and security. We propose a blockchain and IPFS-based anticounterfeiting and traceable car insurance claims system to improve the above problems. We incorporate the Interplanetary File System (IPFS) to reduce the cost of storing insurance data. This study also attempts to propose an arbitration mechanism in the event of a car insurance dispute.

CircUBE2Q2 promotes differentiation of cattle muscle stem cells and is a potential regulatory molecule of skeletal muscle development.

BACKGROUND: The growth and development of muscle stem cells (MuSCs) are significant events known to affect muscle plasticity, disease, meat production, and meat quality, which involves the types and functions of mRNA and non-coding RNA. Here, MuSCs were cultured from Guangxi fetal cattle. RNA sequencing was used to analyze the RNA expression of mRNA and non-coding RNAs during the cell proliferation and differentiation phases. RESULTS: Two thousand one hundred forty-eight mRNAs and 888 non-coding RNAs were differentially expressed between cell proliferation and differentiation phases, including 113 miRNAs, 662 lncRNAs, and 113 circRNAs. RT-qPCR verified the differential expression levels of mRNAs and non-coding RNAs, and the differentially expressed circUBE2Q2 was subsequently characterized. Expression profile analysis revealed that circUBE2Q2 was abundant in muscle tissues and intramuscular fat. The expression of cricUBE2Q2 was also significantly upregulated during MuSCs myogenic differentiation and SVFs adipogenic differentiation and decreased with age in cattle muscle tissue. Finally, the molecular mechanism of circUBE2Q2 regulating MuSCs function that affects skeletal muscle development was investigated. The results showed that circUBE2Q2 could serve as a sponge for miR-133a, significantly promoting differentiation and apoptosis of cultured MuSCs, and inhibiting proliferation of MuSCs. CONCLUSIONS: CircUBE2Q2 is associated with muscle growth and development and induces MuSCs myogenic differentiation through sponging miR-133a. This study will provide new clues for the mechanisms by which mRNAs and non-coding RNAs regulate skeletal muscle growth and development, affecting muscle quality and diseases.