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Unveiling the Catalytic Potential of Facet Heterojunctions in Platinum Alloys for Oxygen Reduction Reaction
Abstract Ensuring high‐quality activity of proton exchange membrane fuel cells (PEMFCs) while mitigating the degradation of Pt‐based alloy catalysts remains challenging. A platinum‐skinned truncated octahedral PtNi alloy with (100)/(111) facet heterostructures is synthesized through a low‐temperature thermally driven etching strategy, demonstrating exceptional oxygen reduction reaction (ORR) activity and stability. The heterostructure of the Pt skin ‐PtNi(111) facet destabilizes the *OOH intermediate and promotes the preferential O─O bond cleavage, leading to the optimization of ORR pathway. A linear correlation between the generalized coordination number () and Δ G *OH demonstrates that the facet hetero‐sites optimize the adsorption of *OH to the theoretically optimal state through ligand and geometric effects. The optimized PNZC‐5A160 catalyst exhibits enhanced ORR activity (2.97 A mg Pt −1 at 0.9 V vs. RHE) and superior H 2 ‐O 2 single PEMFC performance [mass activity (MA) of 0.5 A mg Pt −1 at 0.9 V iR‐free ; peak power density of 1.42 W cm −2 , exceeding the U.S. Department of Energy 2025 targets. After accelerated stress tests, the loss in MA at 0.9 V iR‐free and in potential at 0.8 A cm −2 is only 8% and 3.7 mV, respectively, due to the enhanced binding of subsurface Pt and Ni to surface Pt atoms through Pt skin, thereby inhibiting the dissolution of Pt and Ni.
A Donor–Acceptor‐Type Two‐Dimensional Poly(Arylene Vinylene) for Efficient Electron Transport and Sensitive Chemiresistors
Abstract Two‐dimensional (2D) conjugated polymers and their layer‐stacked 2D conjugated covalent organic frameworks, such as 2D poly(arylene vinylene)s (2D PAVs), are emerging as promising polymer semiconductors for electronics and photocatalysis. However, achieving narrow optical band gaps and efficient electron transport remains a significant challenge for this class of materials to enhance the device's performance. Here, we report a donor‐acceptor‐type 2D PAV ( 2DPAV‐TBDT‐IT , where TBDT = thienyl‐benzodithiophene and IT = s ‐indacene‐1,3,5,7(2 H ,6 H )‐tetraone) synthesized via an Aldol‐type 2D polycondensation approach. Notably, 2DPAV‐TBDT‐IT benefits from an effective intralayer donor–acceptor effect, exhibiting an optical band gap of 1.15 eV, the smallest among the reported 2D conjugated polymers. Density functional theory calculations reveal a unique electron‐dominating transport for 2DPAV‐TBDT‐IT , with a strongly dispersive conduction band minimum and, thus, a small effective mass for electrons half that for holes. Additionally, terahertz spectroscopy measurements indicate a high charge mobility of 26 cm 2 V −1 s −1 at room temperature for the powder sample. Given the high electron‐deficiency of 2DPAV‐TBDT‐IT for facile electron injection from hazardous gases and the high‐mobility electron‐dominating transport in the material, we further fabricate chemiresistors from 2DPAV‐TBDT‐IT , showing ultrasensitive SO 2 analyte detection with limit of detection of 0.088 ppb, significantly surpassing the reported chemiresistive SO 2 sensors.
Oligoether Chain Engineering in Covalent Organic Frameworks: Enhancing Transport Pathways and Oxygen Reduction Activity for Efficient Electrocatalytic Hydrogen Peroxide Production
Abstract Oligoethers with various numbers of ethylene oxide (EO) units, known for their flexibility, electronegativity, and hydrophilicity, can be leveraged to construct complex molecular architectures with broad applicability. In this study, we present the synthesis of two‐dimensional (2D) covalent organic frameworks (COFs) incorporating oligoethers with EO segments of varying lengths (2D‐COF‐EOs) to explore the role of EO units in modulating the two‐electron (2e − ) oxygen reduction reaction (ORR) pathway for electrocatalytic hydrogen peroxide (H 2 O 2 ) production. By embedding hydrophilic EO side chains into the hydrophobic frameworks, intermolecular interactions are promoted through hydrogen bonding, leading to the self‐assembly and spatial aggregation of these side chains. The high crystallinity of the COFs facilitates orderly stacking of the skeleton, creating hydrophilic nanoscale transport channels that enhance ORR kinetics. Among the synthesized COFs, 2D‐COF‐EO 1 , which contains one EO group, exhibits a remarkable H 2 O 2 production rate of 5820 mmol g cat −1 h −1 and a 2e − ORR selectivity of 89.2%. Theoretical calculations and in situ electrocatalytic experiments reveal that the elongation of the EO units significantly alters the electronic structure of carbon atoms adjacent to oxygen atoms, lowering the energy barriers associated with the formation of OOH* intermediates and thus promoting the 2e − ORR pathway. This work offers valuable insights into optimizing COFs with different EO units for efficient 2e − ORR‐based electrocatalytic processes.
Self‐Compartmented Electrolyte Design for Stable Cycling of Lithium Metal Batteries under Extreme Conditions
Abstract Electrolyte is the key component dictating lithium battery performance, especially under extreme conditions such as fast cycling and low temperatures. However, conventional electrolyte design principles, which generally rely on a homogeneous mixture of solvents, salts, and functional additives, fail to simultaneously meet the requirements for both anodic/cathodic interfacial stability and bulk ion‐transport kinetics in lithium metal batteries. Herein, we present a self‐compartmented electrolyte design methodology. Lithium 4,5‐dicyano‐2‐(trifluoromethyl)imidazol‐1‐ide (LiTDI), featuring the ability to selectively self‐assemble on the cathode/electrolyte interface, compartmented the electrolyte into a heterogonous one. Close to the cathode side, LiTDI could induce an interfacial high‐concentration region, where the anion‐rich solvation structure facilitates the formation of a stable cathode–electrolyte interphase (CEI). In the bulk, the electrolyte maintains a low concentration with low viscosity, ensuring fast ion transport and superior rate performance. Li||NCM811 cells achieve over 500 stable cycles with 80.3% capacity retention and deliver 169.3 mAh g −1 at a 10C discharge rate. Under low‐temperature conditions (−20 °C), the cells maintained outstanding stability over 700 cycles at 0.5C charge/discharge, achieving capacity retention of 96.6% and an average Coulombic efficiency of 99.2%. This work provides a new electrolyte design paradigm, addressing the critical challenges of LMBs for high‐voltage and low‐temperature applications.
A Powerful Regulator to Enhance Electrocatalytic Reaction Kinetics and Thermodynamics: The Ordered Hetero‐Nanowire
Abstract Optimizing the thermodynamics of electrode reactions is a valid strategy for achieving superior electrocatalysts for direct methanol fuel cells (DMFCs). However, as the catalyst downsizes to the nanoscale, the influence of mass transfer kinetics is pronounced in improving electrocatalytic activity. Herein, an ordered hetero‐nanowire (NW) regulator that couples the virtues of kinetics and thermodynamics is reported. Finite element analysis demonstrates that the periodic arrangement of hetero‐NWs could construct a uniform electric field, promoting the precise mass transfer of reactant molecules and accelerating the electrode reaction kinetics for the methanol oxidation reaction (MOR). In addition, the microscopic electronic structure effect of the well‐defined catalyst weakens the bonding interaction toward toxic carbonaceous intermediates, which meanwhile strengthens the adsorption of hydroxyl species, critically contributing to enhanced MOR durability. The wide generality of this regulator has been confirmed by a series of as‐prepared ordered hetero‐NW catalysts, which show prominent electrocatalytic performance, including relatively high mass activity, superior CO resistance, and long‐term stability. Therefore, this work reveals the importance of the tandem effect of kinetics and thermodynamics in electrocatalysis, which provides valuable insights for developing customized and highly efficient catalysts for extensive applications.
Nitrogen Insertion via Asymmetric Condensation and Chirality Transfer: A Stereodivergent Entry to Cyanocyclopropanes
Abstract The condensation of prochiral cyclobutanones and diphenylphosphinyl hydroxylamine is achieved under Brønsted acid catalysis. Interestingly, the competing aza‐Baeyer–Villiger reaction is completely suppressed and the axially chiral oxime esters can be isolated in excellent yield and selectivity (up to 96% yield, up to 97:3 er). Computational analysis highlights the crucial role of the Brønsted acid in facilitating a successful condensation. Building on the inherent reactivity of the corresponding oxime esters, a one‐pot protocol toward cyanocyclopropanes was discovered, which establishes two consecutive stereocenters. This unusual ring contraction is triggered by strong base and permits an axial‐to‐point chirality transfer with good enantiospecificity (up to 98% es). Fine‐tuning the reaction parameters enables stereodivergent access to both diastereomers of the cyanocyclopropanes, and the utility of this method is demonstrated through the formal synthesis of the drug tasimelteon.
Antibacterial Siderophores of <i>Pandoraea</i> Pathogens and Their Impact on the Diseased Lung Microbiota
Abstract Antibiotic‐resistant bacteria of the genus Pandoraea , frequently acquired from the environment, are an emerging cause of opportunistic respiratory infections, especially in cystic fibrosis (CF) patients. However, their specialized metabolites, including niche and virulence factors, remained unknown. Through genome mining of environmental and clinical isolates of diverse Pandoraea species, we identified a highly conserved biosynthesis gene cluster ( pan ) that codes for a nonribosomal peptide synthetase (NRPS) assembling a new siderophore. Using bioinformatics‐guided metabolic profiling of wild type and a targeted null mutant, we discovered the corresponding metabolites, pandorabactin A and B. Their structures and chelate (gallium) complexes were elucidated by a combination of chemical degradation, derivatization, NMR, and MS analysis. Metagenomics and bioinformatics of sputum samples of CF patients indicated that the presence of the pan gene locus correlates with the prevalence of specific bacteria in the lung microbiome. Bioassays and mass spectrometry imaging showed that pandorabactins have antibacterial activities against various lung pathogens ( Pseudomonas , Mycobacterium , and Stenotrophomonas ) through depleting iron in the competitors. Taken together, these findings offer first insight into niche factors of Pandoraea and indicate that pandorabactins shape the diseased lung microbiota through the competition for iron.
Spherical Nucleic Acids‐Directed Cryosynthesis of Manganese Nanoagents for Tumor Imaging and Therapy
Abstract DNAzyme‐based theranostic nanotechnologies that can respond to specific tumor pathophysiological parameters hold great promise for tumor diagnostics and effective treatments. However, their clinical translation is hindered by insufficient intracellular availability of essential metal cofactors required for DNAzyme activation. To overcome this limitation, we developed a temperature‐controlled synthesis strategy for fabricating multifunctional DNA‐templated manganese carbonate nanoparticles (DtMnP). The process involves three critical phases: (i) spherical nucleic acid hybrids, DNAzyme‐functionalized AuNPs, serve as scaffolds for spatially controlled Mn 2+ deposition through phosphate coordination, initiating heterogeneous nucleation of MnCO 3 ; (ii) rapid liquid nitrogen freezing induces nanoparticle growth along DNA templates; and (iii) lyophilization‐mediated structural stabilization enables convenient long‐term storage. The DtMnP exhibits pH‐responsive dissolution, releasing 90% of Mn 2+ within 60 min under tumor microenvironment conditions (pH 5.5). The released Mn 2+ ion enables dual functionality: (i) superior magnetic resonance imaging (MRI) contrast of MCF‐7 xenograft models with enhanced biosafety, and (ii) synergistic therapeutic efficacy through DNAzyme‐mediated EGR‐1 gene silencing (60% mRNA downregulation) combined with Mn 2+ ‐catalyzed Fenton reactions generating cytotoxic hydroxyl radicals (45% apoptosis in MCF‐7 cells). The cryo‐encapsulated DtMnP exemplifies a flexible and efficient approach for integrating various functional components into a single nanoparticle for tumor theranostic applications.
Engineering Bodipy‐Based Metal–Organic Frameworks for Efficient Full‐Spectrum Photocatalysis in Amide Synthesis
Abstract Developing photocatalysts that can efficiently utilize the full solar spectrum is a crucial step toward transforming sustainable energy solutions. Due to their light absorption limitations, most photo‐responsive metal–organic frameworks (MOFs) are constrained to the ultraviolet (UV) and blue light regions. Expanding their absorption to encompass the entire solar spectrum would unlock their full potential, greatly enhancing efficiency and applicability. Here, we report the design and synthesis of a series of highly stable boron‐dipyrromethene (bodipy)‐based MOFs (BMOFs) by reacting dicarboxyl‐functionalized bodipy ligands with Zr‐oxo clusters. Leveraging the acidity of the methyl groups on the bodipy backbone, we expanded the conjugation system through a solid‐state condensation reaction with various aldehydes, achieving full‐color absorption, thereby extending the band edge into the near‐infrared (NIR) and infrared (IR) regions. These BMOFs demonstrated exceptional reactivity and recyclability in heterogeneous photocatalytic activities, including C─H bond activation of saturated aza‐heterocycles and C─N bond cleavage of N , N ‐dimethylanilines to produce amides under visible light. Our findings highlight the transformative potential of BMOFs in photocatalysis, marking a significant leap forward in the design of advanced photocatalytic materials with tunable properties.
Decoding the Chemical Language of Ribosomally Synthesized and Post‐Translationally Modified Peptides from the Untapped Archaea Domain
Abstract Chemical communication is crucial in ecosystems with complex microbial communities. However, the difficulties inherent to the cultivation of archaea have led to a limited understanding of their chemical language, especially regarding the structure diversity and function of secondary metabolites (SMs). Our in‐depth exploration into the biosynthetic potential of archaea has unveiled the previously unexplored biosynthetic capabilities and chemical diversity of archaeal ribosomally synthesized and post‐translationally modified peptides (RiPPs). Through the first application of heterologous expression in archaeal SM discovery, we have identified 24 lanthipeptides, including a distinctive type featuring diamino‐dicarboxylic termini. It highlights the uniqueness of archaeal biosynthetic pathways and significantly expands the chemical landscape of archaeal SMs. Additionally, archaeal lanthipeptides demonstrate antagonistic activity against haloarchaea, mediating the unique biotic interaction in the halophilic niche. They showcase a new ecological role of RiPPs in enhancing the host's motility by inducing the rod‐shaped cell morphology and upregulating the archaellin gene expression, facilitating the archaeal interaction with abiotic environments. These discoveries broaden our understanding of archaeal chemical language and provide promising prospects for future exploration of SM‐mediated interaction.
Ligand‐Controlled Regiodivergent Carbosilylation of 1,3‐Dienes via Nickel‐Catalyzed Three‐Component Coupling Reactions
Abstract The regiodivergent carbosilylation of 1,3‐dienes presents a formidable challenge due to inherently complex selectivity control over multiple potential reaction pathways. Here, we report a ligand‐controlled, regiodivergent carbosilylation of 1,3‐dienes with aldehydes and silylboranes, achieving unprecedented site‐selectivity using nickel catalysts with distinct phosphine ligands. The use of triethylphosphine promotes 4,3‐addition selectivity, while employing (2‐biphenyl)dicyclohexylphosphine facilitates 4,1‐addition selectivity. This method displays excellent regio‐ and diastereoselectivity, as well as a broad substrate scope and substantial functional group tolerance. Mechanistic studies indicate that the ligand choice is crucial for directing the reaction pathway and stabilizing π‐allyl‐nickel intermediates. Our protocol provides a practical and efficient approach to synthesizing valuable functionalized allylsilanes, which are important in various synthetic applications.
Electrostatic Potential Matching in an Anion‐Pillared Framework for Benchmark Hexafluoroethane Purification from Ternary Mixture
Abstract One‐step purification of CF 3 CF 3 from ternary CF 3 CH 2 F/CF 3 CHF 2 /CF 3 CF 3 mixture is crucial since its vital role in the semiconductor industry. However, efficient separation of chemically inert CF₃CF₃ remains challenging due to the difficulty in creating specific recognition sites in porous materials. In this work, we report the first example of anion‐pillared MOFs to the separation of fluorinated electronic specialty gases, utilizing the unique electrostatic potential matching in the bipolar pores of SIFSIX‐1‐Cu to realize a benchmark CF 3 CH 2 F/CF 3 CHF 2 /CF 3 CF 3 separation. SIFSIX‐1‐Cu exhibits the highest CF 3 CH 2 F and CF 3 CHF 2 adsorption capacity at 0.01 bar, as well as the highest CF 3 CH 2 F/CF 3 CF 3 and CF 3 CHF 2 /CF 3 CF 3 IAST selectivity. Additionally, high‐purity (≥ 99.995%) CF 3 CF 3 with record productivity (882.9 L kg −1 ) can be acquired through one‐step breakthrough experiment of CF 3 CH 2 F/CF 3 CHF 2 /CF 3 CF 3 (5/5/90). Theoretical calculations further reveal that the coexistence of electronegative SiF 6 2− and partially electropositive H sites promotes SIFSIX‐1‐Cu to effectively anchor CF 3 CH 2 F and CF 3 CHF 2 through multiple supramolecular interactions.
A Method for Constructing Nucleosome Arrays with Spatially Defined Histone PTMs and DNA Damage
Abstract DNA damage repair mechanisms, such as base excision repair (BER), safeguard cells against genotoxic agents that cause genetic instability and diseases, including cancer. In eukaryotic nuclei, DNA within nucleosome arrays is less accessible to repair factors than naked DNA owing to the structural constraints of chromatin. Histone acetylation is crucial for loosening the chromatin structure and facilitating access to damaged DNA, yet its effects—particularly in histone globular domains—on BER in nucleosome arrays remain unexplored. Herein, we employ an abiotic/enzymatic hybrid catalyst system (ABEHCS) and a plug‐and‐play strategy to regioselectively introduce histone acetylation and deoxycytidine‐to‐deoxyuridine DNA damage. This approach enables the construction of nucleosome arrays with diverse spatial configurations of histone acetylation and DNA lesions, similar to those found in living organisms. Our findings reveal that H3K56 acetylation in the histone globular domain enhances BER efficiency mediated by UDG and APE1 in nucleosome arrays, contingent upon the spatial relationship between H3K56Ac and the DNA damage site.
Bleating, growling, barking, and spitting: Metaphorical extensions and valency patterns of verbs of speaking
This corpus-based and qualitative study examines the valency patterns of Croatian verbs that encode verbal activity and belong to the semantic field of verbs of speaking through metaphorical and metonymic extensions, using a cognitive linguistics framework, specifically the usage-based model. The analysis focuses on examples such as the metaphoric use of animal sounds (e.g., blejati ‘to bleat’) and verbs associated with bodily processes (e.g., srati ‘to shit’), which often convey negative or stereotypical attitudes towards speakers or messages, or even extreme disdain. This paper contributes to the understanding of cross-domain figurative extensions of verb meanings and their valency adaptations. A dataset of 438 example sentences containing 152 verbs with figurative extensions targeting the domain of speaking was meticulously compiled from Croatian corpora. This dataset enabled a manual annotation and analysis of the transfer and adaptation of valency patterns across domains. The study addresses the following key questions: 1. What source domains are used for verbs of speaking as targets? 2. Do verbs retain the valency patterns of the source domain or adopt those of the target domain? 3. Is the passivization of transitive verbs possible in metaphorical contexts? The findings indicate that with a metaphorical shift in meaning, verbs often adopt new valency patterns from the target domain. Our examples of valency pattern change as a result of a metaphorical meaning shift demonstrate that verbs can appear with arguments not explicitly subcategorized by the verb itself.
Nurses’ perspectives and experience in caring for patients undergoing hemodialysis at Benjamin Mkapa hospital in Dodoma, Tanzania: A qualitative study
Background Caring for patients undergoing hemodialysis is a challenge for nurses. Poor quality of care in hemodialysis is reported to have a significant contribution to the high mortality rate among patients. Improving the health outcomes of the patient requires an in-depth exploration of the perspectives and views of nurses working in the hemodialysis unit. However, there is a paucity of information regarding the perspectives and experiences of nurses working in Hemodialysis units, particularly in resource-constrained countries like Tanzania. This study aimed to explore the perspectives and experiences of nurses caring for patients undergoing hemodialysis. Materials and Methods An explorative qualitative study was conducted among nurses working in Hemodialysis units at Benjamin Mkapa Hospital in Dodoma, Tanzania. A purposive sampling method was used to select the participants. Ten in-depth interviews were conducted using a semi-structured interview guide and an audio recorder as the main data collection tools. A thematic analysis approach was used to analyze the data. Findings Three themes and the associated subthemes emerged from this study. 1) Conducive environments for the provision of nursing care 2) Challenges affecting hemodialysis care, and 3) Strategies for improving hemodialysis care. A good nurse-patient relationship, financial incentives, and availability of equipment facilitate the provision of care among patients. Treatment costs, problems in adhering to dialysis prescriptions, and staff shortages were the challenges affecting hemodialysis care. On the other hand, increasing dialysis centres, training nurses, and free health insurance coverage were strategies for improving hemodialysis care. Conclusion The findings highlighted several key aspects related to the perspectives and experiences of providing nursing care for patients undergoing hemodialysis. The conducive working environment, coupled with financial incentives, is an important factor in improving nurses’ care for patients undergoing hemodialysis. However, the high costs related to the utilization of hemodialysis services are the challenge to achieving better outcomes.
Bis(pinacolato)Diboron‐Enabled Nickel‐Catalyzed Regio‐ and Enantioselective Reductive [3 + 2] Annulation of β‐Bromoenones with Alkynes
Abstract Chiral five‐membered cyclic tertiary alcohols are important structural motifs in functional materials, pharmaceuticals, and bioactive molecules. Hence, developing efficient methodologies for synthesizing compounds featuring these privileged scaffolds represents a crucial pursuit within synthetic chemistry. Herein, we present a regio‐ and enantioselective Ni‐catalyzed strategy for the reductive [3 + 2] annulation of β‐bromoenones with alkynes, providing convenient access to chiral five‐membered cyclic tertiary alcohols with high levels of regio‐, and enantioselectivity via axial chirality transfer to central chirality. The utilization of an environmentally sustainable bis(pinacolato)diboron (B 2 pin 2 ) is crucial for the success of this asymmetric reductive cyclization reaction. Simultaneously, the mild reaction environment greatly enhances functional group compatibility. This has been demonstrated by the broad substrate scope, late‐stage functionalizations of bioactive compounds or drug molecules, and subsequent transformations. Amongst, it is worth emphasizing that these functionally enriched chiral five‐membered cyclic tertiary alcohols can efficiently participate in Diels–Alder reactions to synthesize enantioenriched polycyclic and heterocyclic molecules, thereby further validating the significance of introducing a cyclopentadiene skeleton. The preliminary mechanistic studies revealed the mode of action of B 2 pin 2 in mononuclear Ni‐catalyzed asymmetric reductive [3 + 2] annulation reactions and density functional theory (DFT) calculations clarified the origin of the experimentally observed regio‐ and enantioselectivity.
Clinical study outcomes in IgA nephropathy: A systematic literature review and narrative synthesis
Introduction IgA nephropathy (IgAN) is an inflammatory kidney disease which, if left untreated, often progresses to kidney failure (KF). This systematic literature review identifies, collates, summarizes, and assesses the quality of clinical trial data describing the efficacy of therapies used for IgAN. Methods Ovid Embase, PubMed, CENTRAL, and the Cochrane database of systematic reviews were searched on October 18th, 2021, and updated on December 12th, 2023. Electronic searches were supplemented with manual searches of key conferences, clinical trial registries, and bibliography screening. PRISMA and Cochrane guidelines were followed. Results A total of 6710 references were identified (electronic and manual searches), of which 6483 were excluded. This resulted in 254 references reporting 183 studies which met our inclusion criteria. The majority of these IgAN studies (98/183 studies [60%]) had a non-randomized or single-arm design and/or a small population size or focused on dietary and traditional medicine, resulting in a high risk of bias and necessitated additional filtering to prioritize larger (n>30) randomized assessment of pharmacological interventions reporting key clinical outcomes. This additional filtering resulted in 76 randomized controlled trials (100 references) selected for narrative synthesis; 60 reported proteinuria outcomes and 18 reported estimated glomerular filtration rate (eGFR) outcomes. Conclusions Until recently, the evidence has been mixed or inconsistent across studies for the efficacy of IgAN treatments in reducing proteinuria or slowing eGFR decline due to a high risk of bias in many included studies. The latest large, phase 3 NefIgArd (NCT03643965) and PROTECT (NCT03762850) clinical trials have demonstrated a meaningful reduction in proteinuria and eGFR decline for patients with IgAN receiving targeted-release formulation budesonide (TRF-B) or sparsentan. Results from other high-quality randomized controlled trials with a follow-up period of at least 2 years are still required to better support advancements in the management of IgAN.
Rhodium‐Catalyzed Atroposelective Synthesis of Axially Chiral 1‐Aryl Isoquinolines via De Novo Isoquinoline Formation
Abstract Axially chiral heterobiaryl moieties serve as core skeletons for bioactive molecules, chiral ligands, and organocatalysts. Enantioselective de novo formation of the heteroaromatic ring is one of the most straightforward approaches to access enantioenriched heterobiaryls. Herein, an enantioselective de novo construction of isoquinolines by rhodium‐catalyzed C─H activation/annulation of aromatic imines with alkynes is disclosed. This approach is operationally simple, allowing for rapid access to a variety of axially chiral 1‐aryl isoquinolines in excellent yields and enantioselectivity (up to 98% yield and 99:1 er). The synthetic application of the current method was demonstrated by functional group transformations and suitability for millimolar‐scale reactions. Detailed experimental and theoretical studies revealed the turnover‐limiting step and provided insight into the origin of the enantioselectivity for this reaction.
The diagnostic accuracy of nanopore sequencing in Tuberculous Lymphadenitis: Systematic review and meta-analysis protocol
Background Tuberculous lymphadenitis (TL) is a common case of extrapulmonary tuberculosis caused by Mycobacterium tuberculosis (MTB). The current use of nanopore sequencing in TL is limited. The aim of our study is to complete a systematic review and meta-analysis protocol to assess the performance of nanopore sequencing in TL. Methods English databases (including Medline via PubMed, Cochrane Library, and Embase) and Chinese databases (including Wanfang Database and China National Knowledge Infrastructure) will be searched for literature related to the research topic. We designed eligibility criteria based on PICT (Population, Index Test, Comparator Test and Target Condition). We will extract relevant data from the included articles when they have been identified. The quality of the studies will be assessed using the Quality Assessment of Diagnostic Accuracy Studies (QUADAS-2) tool. We will use midas package in STATA for the calculation of the pooled effect values and the corresponding forest plots when the final number of included studies is more than four, and Meta-DiSc for the calculation of the pooled effect values and the forest plots when the number of included studies is less than four. When the results of different reference gold standards are reported simultaneously in the same literature, we will extract the corresponding TP, FP, FN, and TN values according to the different reference gold standards and analyze them independently. I2 statistic will be used to quantify inter-study heterogeneity. If substantial heterogeneity (I² > 50%) is detected, potential sources will be investigated through subgroup, meta-regression, and sensitivity analysis. Conclusion We conducted this protocol according to the guidelines and submitted it to a peer-reviewed journal to improve our protocol through peer review and ultimately better guide the completion of the systematic review and meta-analysis. Systematic review registration PROSPERO Registration number: CRD42024595521
Photovoltaic Absorber “Glues” for Efficient Bifacial Selenium Photovoltaics
Abstract Bifacial solar cells hold great potential for achieving higher power output than conventional monofacial devices by harvesting solar irradiance from both their front and rear surfaces. However, almost all currently reported bifacial devices typically require a sputtered rear transparent conducting oxide electrode, which can damage the underlying layers due to plasma effects during the deposition process. Here, we report a glue‐bonding strategy that uses a high‐viscosity photovoltaic absorber slurry—in the case of molten selenium (Se)—as the adhesive to bond two charge‐transport layer‐deposited commercial fluorine‐doped tin oxide glasses, directly creating bifacial solar cells without the use of magnetron sputtering. We find that molten Se exhibits relatively high viscosity, high stability, and Newtonian fluid characteristics, facilitating film formation using this strategy. The resulting bifacial Se solar cells exhibit a bifaciality factor of 90.1%, surpassing all types of conventional thin‐film solar cells. These cells achieve efficiencies of 8.61% under 1‐sun illumination with an albedo of 0.3 and 26.17% under 1000‐lux indoor illumination with an albedo of 0.8, with no efficiency loss after 1000 h of ambient storage.