bluuebunny/crossref_metadata_2025 huggingface dataset:
σ‐Cyclopropyl to π‐Allyl Rearrangement at AuIII
Authors: Holmsen Marte S. M. , Vesseur David , García‐Rodeja Yago , Miqueu Karinne , Bourissou Didier
Published: June 2023

The possibility for AuIII σ‐cyclopropyl complexes to undergo ring‐opening and give π‐allyl complexes was interrogated. The transformation was first evidenced within (P,C)‐cyclometalated complexes, it occurs within hours at −50 °C. It was then generalized to other ancillary ligands. With (N,C)‐cyclometalated complexes, the rearrangement occurs at room temperature while it proceeds already at −80 °C with a dicationic (P,N)‐chelated complex. Density Functional Theory (DFT) calculations shed light on the mechanism of the transformation, a disrotatory electrocyclic ring‐opening. Intrinsic Bond Orbital (IBO) analysis along the reaction profile shows the cleavage of the distal σ(CC) bond to give a π‐bonded allyl moiety. Careful inspection of the structure and bonding of cationic σ‐cyclopropyl complexes support the possible existence of C−C agostic interactions at AuIII.
Quantifying Degradation Parameters of Single‐Crystalline Ni‐Rich Cathodes in Lithium‐Ion Batteries
Authors: Zhao Wengao , Wang Kuan , Fan Xinming , Ren Fucheng , Xu Xieyu , Liu Yangyang , Xiong Shizhao , Liu Xiangsi , Zhang Zhengfeng , Si Mayan , Zhang Ruizhuo , van den Bergh Wessel , Yan Pengfei , Battaglia Corsin , Brezesinski Torsten , Yang Yong
Published: June 2023

Single‐crystal LiNixCoyMnzO2 (SC‐NCM, x+y+z=1) cathodes are renowned for their high structural stability and reduced accumulation of adverse side products during long‐term cycling. While advances have been made using SC‐NCM cathode materials, careful studies of cathode degradation mechanisms are scarce. Herein, we employed quasi single‐crystalline LiNi0.65Co0.15Mn0.20O2 (SC‐NCM65) to test the relationship between cycling performance and material degradation for different charge cutoff potentials. The Li/SC‐NCM65 cells showed >77 % capacity retention below 4.6 V vs. Li+/Li after 400 cycles and revealed a significant decay to 56 % for 4.7 V cutoff. We demonstrate that the SC‐NCM65 degradation is due to accumulation of rock‐salt (NiO) species at the particle surface rather than intragranular cracking or side reactions with the electrolyte. The NiO‐type layer formation is also responsible for the strongly increased impedance and transition‐metal dissolution. Notably, the capacity loss is found to have a linear relationship with the thickness of the rock‐salt surface layer. Density functional theory and COMSOL Multiphysics modeling analysis further indicate that the charge‐transfer kinetics is decisive, as the lower lithium diffusivity of the NiO phase hinders charge transport from the surface to the bulk.
Ribozyme‐Catalyzed Late‐Stage Functionalization and Fluorogenic Labeling of RNA
Authors: Scheitl Carolin P. M. , Okuda Takumi , Adelmann Juliane , Höbartner Claudia
Published: June 2023

Site‐specific introduction of bioorthogonal handles into RNAs is in high demand for decorating RNAs with fluorophores, affinity labels or other modifications. Aldehydes represent attractive functional groups for post‐synthetic bioconjugation reactions. Here, we report a ribozyme‐based method for the synthesis of aldehyde‐functionalized RNA by directly converting a purine nucleobase. Using the methyltransferase ribozyme MTR1 as an alkyltransferase, the reaction is initiated by site‐specific N1 benzylation of purine, followed by nucleophilic ring opening and spontaneous hydrolysis under mild conditions to yield a 5‐amino‐4‐formylimidazole residue in good yields. The modified nucleotide is accessible to aldehyde‐reactive probes, as demonstrated by the conjugation of biotin or fluorescent dyes to short synthetic RNAs and tRNA transcripts. Upon fluorogenic condensation with a 2,3,3‐trimethylindole, a novel hemicyanine chromophore was generated directly on the RNA. This work expands the MTR1 ribozyme's area of application from a methyltransferase to a tool for site‐specific late‐stage functionalization of RNA.
Two‐Dimensional Conjugated Metal‐Organic Frameworks with Large Pore Apertures and High Surface Areas for NO2 Selective Chemiresistive Sensing
Authors: Chen Pei , Su Xi , Wang Chuanzhe , Zhang Guang , Zhang Ting , Xu Gang , Chen Long
Published: June 2023

The emergence of two‐dimensional conjugated metal–organic frameworks (2D c‐MOFs) with pronounced electrical properties (e.g., high conductivity) has provided a novel platform for efficient energy storage, sensing, and electrocatalysis. Nevertheless, the limited availability of suitable ligands restricts the number of available types of 2D c‐MOFs, especially those with large pore apertures and high surface areas are rare. Herein, we develop two new 2D c‐MOFs (HIOTP‐M, M=Ni, Cu) employing a large p‐π conjugated ligand of hexaamino‐triphenyleno[2,3‐b:6,7‐b′:10,11‐b′′]tris[1,4]benzodioxin (HAOTP). Among the reported 2D c‐MOFs, HIOTP‐Ni exhibits the largest pore size of 3.3 nm and one of the highest surface areas (up to 1300 m2 g−1). As an exemplary application, HIOTP‐Ni has been used as a chemiresistive sensing material and displays high selective response (405 %) and a rapid response (1.69 min) towards 10 ppm NO2 gas. This work demonstrates significant correlation linking the pore aperture of 2D c‐MOFs to their sensing performance.
Transformation of Type III to Type II Porous Liquids by Tuning Surface Rigidity of Rhodium(II)‐Based Metal‐Organic Polyhedra for CO2 Cycloaddition
Authors: Dinker Manish Kumar , Li Meng‐Meng , Zhao Kan , Zuo Mingrui , Ding Lifeng , Liu Xiao‐Qin , Sun Lin‐Bing
Published: June 2023

Porous liquids (PLs), a summation of porous hosts and bulky solvents bestowing permanent cavities, are the prominent emerging materials. Despite great efforts, exploration of porous hosts and bulky solvents is still needed to develop new PL systems. Metal‐organic polyhedra (MOPs) with discrete molecular architectures can be considered as porous hosts; however, many of them are insoluble entities. Here we report the transformation of type III PL to type II PLs by tuning the surface rigidity of insoluble MOP, Rh24L24, in a bulky ionic liquid (IL). Functionalization of N‐donor molecules on Rh−Rh axial sites ensue their solubilization in bulky IL which confer type II PLs. Experimental and theoretical studies reveal the bulkiness of IL as per the cage apertures, and the cause of their dissolution as well. The obtained PLs, capturing more CO2 than neat solvent, have depicted higher catalytic activity for CO2 cycloaddition compared to individual MOPs and IL.
Ligand‐Free Ultrasmall Recyclable Iridium(0) Nanoparticles for Regioselective Aromatic Hydrogenation of Phosphine Oxide Scaffolds: An Easy Access to New Phosphine Ligands
Authors: Hedouin Gaspard , Sharma Sudripet , Kaur Karanjeet , Choudhary Ramesh Hiralal , Jasinski Jacek B. , Gallou Fabrice , Handa Sachin
Published: June 2023

Herein, we developed the recyclable ligand‐free iridium (Ir)‐hydride based Ir0 nanoparticles (NPs) for the first regioselective partial hydrogenation of PV‐substituted naphthalenes. Both the isolated and in situ generated NPs are catalytically active. A control nuclear magnetic resonance (NMR) study revealed the presence of metal‐surface‐bound hydrides, most likely formed from Ir0 species. A control NMR study confirmed that hexafluoroisopropanol as a solvent was accountable for substrate activation via hydrogen bonding. High‐resolution transmission electron microscopy of the catalyst supports the formation of ultrasmall NPs, and X‐ray photoelectron spectroscopy confirmed the dominance of Ir0 in the NPs. The catalytic activity of NPs is broad as showcased by highly regioselective aromatic ring reduction in various phosphine oxides or phosphonates. The study also showcased a novel pathway toward preparing bis(diphenylphosphino)‐5,5′,6,6′,7,7′,8,8′‐octahydro‐1,1′‐binaphthyl (H8‐BINAP) and its derivatives without losing enantioselectivity during catalytic events.
Multiple Heteroatom‐Hydrogen Bonds Bridging Electron Transport in Covalent Organic Framework‐Based Supramolecular System for Photoreduction of CO2
Authors: He Yajun , Zhao Yun , Wang Xiaofeng , Liu Zheyuan , Yu Yan , Li Liuyi
Published: June 2023

Supramolecular systems consisting of covalent organic frameworks (COFs) and Ni complex are designed for robust photocatalytic reduction of CO2. Multiple heteroatom‐hydrogen bonding between the COF and Ni complex is identified to play a decisive role in the photoexcited electron transfer across the liquid‐solid interface. The diminution of steric groups on COF or metal complex can optimize catalytic performance, which is more attributable to the enhanced hydrogen‐bond interaction rather than their intrinsic activity. The photosystem with relatively strong strength of hydrogen bonds exhibits remarkable photocatalytic CO2‐to‐CO conversion, far superior to photosystems with supported atomic Ni or metal complex alone in the absence of hydrogen‐bond effect. Such heteroatom‐hydrogen bonds bridging electron transport pathway confers supramolecular system with high photocatalytic performance, providing an avenue to rationally design efficient and steadily available photosystems.
Dual Photosensitizer Coupled Three‐Dimensional Metal‐Covalent Organic Frameworks for Efficient Photocatalytic Reactions
Authors: Lu Meng , Zhang Shuai‐Bing , Yang Ming‐Yi , Liu Yu‐Fei , Liao Jia‐Peng , Huang Pei , Zhang Mi , Li Shun‐Li , Su Zhong‐Min , Lan Ya‐Qian
Published: June 2023

In this work, we innovatively assembled two types of traditional photosensitizers, that is pyridine ruthenium/ferrum (Ru(bpy)32+/Fe(bpy)32+) and porphyrin/metalloporphyrin complex (2HPor/ZnPor) by covalent linkage to get a series of dual photosensitizer‐based three‐dimensional metal‐covalent organic frameworks (3D MCOFs), which behaved strong visible light‐absorbing ability, efficient electron transfer and suitable band gap for highly efficient photocatalytic hydrogen (H2) evolution. Rubpy‐ZnPor COF achieved the highest H2 yield (30 338 μmol g−1 h−1) with apparent quantum efficiency (AQE) of 9.68 %@420 nm, which showed one of the best performances among all reported COF based photocatalysts. Furthermore, the in situ produced H2 was successfully tandem used in the alkyne hydrogenation with ≈99.9 % conversion efficiency. Theoretical calculations reveal that both the two photosensitizer units in MCOFs can be photoexcited and thus contribute optimal photocatalytic activity. This work develops a general strategy and shows the great potential of using multiple photosensitive materials in the field of photocatalysis.
Lyophilized mixed micelles of exemestane: A novel paradigm to improve its absorption and anticancer activity
Authors: Singh Gurdeep , Kaur Prabhjot , Singh Davinder , Tiwary Ashok K. , Arora Saroj , Bedi Neena
Published: June 2023

The objective of the present investigation was to prepare and optimize lyophilized mixed micelles (Lyp‐EXE‐MMs) of exemestane (EXE) with improved solubility, bioavailability, in vivo anticancer activity, and physical stability, by using various cryoprotectants. The prepared lyophilized mixed micelles were characterized by various techniques, including dynamic light scattering, zeta potential, powdered X‐ray diffraction, differential scanning calorimetry (DSC), nuclear magnetic resonance (1H NMR), transmission electron microscopy (TEM), and so on. Thereafter, the lyophilized micelles were evaluated for ex vivo permeation, in vitro drug release and gene/protein expression (RT‐PCR and Western blot analysis) in MCF‐7 breast cancer cells. The developed formulation was also investigated for its in vivo anticancer study in BALB/c mice with induced breast cancer. The use of trehalose (10% w/w) was proven to be a suitable cryoprotectant for these micelles. Lyp‐EXE‐MMs were spherical, with a particle size of 42.9 ± 3.8 nm and a polydispersity index of 0.307 ± 0.122. Furthermore, % drug loading and % entrapment efficiency were found to be 5.8 ± 1.4 and 89.1 ± 1.1, respectively. Lyp‐EXE‐MMs showed sustained release behavior as compared to EXE‐suspensions in SGF/SIF (pH 1.2 and 6.8) and phosphate buffer saline (pH 7.4). The micelles induced apoptosis through the regulation of BAX, BCL2, Caspase‐3, p53, and CYP19A1 in MCF‐7 cells, which was correlated to enhanced ex vivo drug permeation. Animals receiving EXE micelle formulations showed reduced tumor volume and improved survivability and pharmacokinetic parameters as compared to pure EXE. Lyp‐EXE‐MMs were found to withstand simulated harsh conditions of SGF/SIF during stability studies. The fabricated EXE micellar preparations hold a promising approach for breast cancer treatment.
Electrochemical aptasensors for pathogenic detection toward point‐of‐care diagnostics
Authors: Kizilkurtlu Ahmet Akif , Demirbas Erhan , Agel Hatice Esra
Published: June 2023

A biosensor system refers to a biomedical device, which detects biological, chemical, or biochemical components by converting those signals to an electrical signal by utilizing and uniting physical or chemical transducer with biorecognition elements. An electrochemical biosensor is generally based on the reaction of either production or consumption of electrons under a three‐electrode system. Biosensor systems are exploited in a wide range of areas, such as medicine, agriculture, husbandry, food, industry, environment protection, quality control, waste disposal, and the military. Pathogenic infections are the third leading cause of death worldwide after cardiovascular diseases and cancer. Therefore, there is an urgent need for effective diagnostic tools to control food, water, and soil contamination result in protecting human life and health. Aptamers are peptide or oligonucleotide‐based molecules that show very high affinity to their targets that are produced from large pools of random amino acid or oligonucleotide sequences. Generally, aptamers have been utilized for fundamental sciences and clinical implementations for their target‐specific affinity and have been intensely exploited for different kinds of biosensor applications for approximately 30 years. The convergence of aptamers with biosensor systems enabled the construction of voltammetric, amperometric, and impedimetric biosensors for the detection of specific pathogens. In this review, electrochemical aptamer biosensors were evaluated by discussing the definition, types, and production techniques of aptamers, the advantages of aptamers as a biological recognition element against their alternatives, and a wide range of aptasensor examples from literature in the detection of specific pathogens.
Rare‐Earth Doped Configurational Entropy Stabilized High Entropy Spinel Oxide as an Efficient Anchoring/Catalyst Functional Interlayer for High‐Performance Lithium‐Sulfur Battery
Authors: Chatterjee Arindam , Ganguly Dipsikha , Sundara Ramaprabhu , Bhattacharya Subramshu S.
Published: June 2023

Lithium‐sulfur batteries (LSBs) are one of the most promising and potential modern‐day energy storage devices due to the low‐cost sulfur‐based cathode and remarkably high energy density (∼2600 Wh kg−1). However, the detrimental shuttle effect of lithium polysulfide (LiPS) and the sluggish electrochemical redox kinetics of lithium sulfide (Li2S) formation restrict its commercial viability. Herein, we design a novel transition metal‐rare earth high entropy oxide (TM‐RE HEO) Co0.08Mn0.08Ni0.08Fe1.96Mg0.08Nd0.01Gd0.01Sm0.01Pr0.01O4 as a polysulfide adsorbent and catalyst for the redox reactions of sulfur species in Li−S battery. TM‐RE HEO interlayer exhibits an excellent discharge capacity of 1146 mAh g−1 at 0.1 C rate, high rate capability, and reasonable long‐term cycling stability at 0.5 C rate with a low capacity decay of 0.08 % per cycle after 300 cycles. High degree of chemical confinement of soluble polysulfides, as demonstrated by the strong bonding between TM‐RE HEO and Li2S6, and expedited catalytic conversion to insoluble Li2S, result from strong polar catalytically active multiple metal sites and abundant oxygen vacancies. This work demonstrates the potential of high entropy oxide in developing high‐efficiency LSB technology.
CHOmpact: A reduced metabolic model of Chinese hamster ovary cells with enhanced interpretability
Authors: Jiménez del Val Ioscani , Kyriakopoulos Sarantos , Albrecht Simone , Stockmann Henning , Rudd Pauline M. , Polizzi Karen M. , Kontoravdi Cleo
Published: June 2023

Metabolic modeling has emerged as a key tool for the characterization of biopharmaceutical cell culture processes. Metabolic models have also been instrumental in identifying genetic engineering targets and developing feeding strategies that optimize the growth and productivity of Chinese hamster ovary (CHO) cells. Despite their success, metabolic models of CHO cells still present considerable challenges. Genome‐scale metabolic models (GeMs) of CHO cells are very large (>6000 reactions) and are difficult to constrain to yield physiologically consistent flux distributions. The large scale of GeMs also makes the interpretation of their outputs difficult. To address these challenges, we have developed CHOmpact, a reduced metabolic network that encompasses 101 metabolites linked through 144 reactions. Our compact reaction network allows us to deploy robust, nonlinear optimization and ensure that the computed flux distributions are physiologically consistent. Furthermore, our CHOmpact model delivers enhanced interpretability of simulation results and has allowed us to identify the mechanisms governing shifts in the anaplerotic consumption of asparagine and glutamate as well as an important mechanism of ammonia detoxification within mitochondria. CHOmpact, thus, addresses key challenges of large‐scale metabolic models and will serve as a platform to develop dynamic metabolic models for the control and optimization of biopharmaceutical cell culture processes.
Longitudinal study of gut microbiome in obsessive–compulsive disorder
Authors: Chen Long Long , Abbaspour Afrouz , Aspvall Kristina , Rück Christian , Bulik Cynthia M. , Pascal Diana
Published: June 2023

Introduction

Patients with obsessive–compulsive disorder (OCD) often have limited exposure to a diverse environment and perform repetitive compulsions such as excessive cleaning and washing, which could lead to altered gut microbiome. Therefore, longitudinal studies that investigate changes in gut microbiome before and after cognitive behavioral therapy based on exposure and response prevention (ERP) are warranted.

Methods

All study participants (N = 64) underwent a structured psychiatric diagnostic interview prior to inclusion. Nutritional intake was assessed with a comprehensive food frequency questionnaire. Stool samples were collected from OCD patients before ERP (n = 32) and 1 month after completion of ERP (n = 15), as well as from healthy controls (HCs; n = 32). Taxonomic and functional analyses were performed using data from microbiome whole genome sequencing.

Results

Patients with OCD at baseline reported consuming significantly less fiber than HCs (R2 = .12, F(2, 59) = 5.2, p ≤ .01). There were no significant differences in α‐ and β‐diversity indices, or taxonomic dissimilarities at the species level between patients with OCD and HCs, or within patients before and after ERP. Functional profiling based on gut microbial gene expression was grouped into 56 gut–brain modules with neuroactive potential. None of the gut–brain modules differed significantly in expression between patients with OCD at baseline and HCs or within patients before and after ERP.

Conclusions

The diversity, composition, and functional profile of the gut microbiome in patients with OCD did not differ significantly from HCs and remained stable over time, despite behavioral changes.
Failure analysis of lead‐acid batteries at extreme operating temperatures
Authors: Prasad Umesh , Prakash Jyoti , Kannan Arunachala Nadar M. , Kamavaram Venkat , Arumugam Ganesh K.
Published: June 2023

The lead‐acid battery system is designed to perform optimally at ambient temperature (25°C) in terms of capacity and cyclability. However, varying climate zones enforce harsher conditions on automotive lead‐acid batteries. Hence, they aged faster and showed lower performance when operated at extremity of the optimum ambient conditions. In this work, a systematic study was conducted to analyze the effect of varying temperatures (−10°C, 0°C, 25°C, and 40°C) on the sealed lead acid. Enersys® Cyclon (2 V, 5 Ah) cells were cycled at C/10 rate using a battery testing system. Environmental aging results in shorter cycle life due to the degradation of electrode and grid materials at higher temperatures (25°C and 40°C), while at lower temperatures (−10°C and 0°C), negligible degradation was observed due to slower kinetics and reduced available capacity. Electrochemical impedance spectroscopy, X‐ray diffraction, and energy‐dispersive X‐ray spectroscopy analysis were used to evaluate the degradation mechanism and chemical and morphological changes.
Reactive Mass Transfer around Isolated Bubbles Rising in a Thin‐Gap Cell
Authors: Laurini Larissa , Béteille Arthur , Fink Gerhard , Herres-Pawlis Sonja , Loubière Karine
Published: June 2023

The reactive mass transfer around isolated bubbles of pure oxygen rising in a thin‐gap cell filled with acetonitrile at rest is investigated. A colorimetric technique based on the bio‐inspired copper(I) complex [Cu(TMG2tol)]OTf is used. The gap‐ and time‐averaged dissolved oxygen concentration fields can be measured in the far‐wake of the bubbles with 3 < d < 47 mm. The variations of the Sherwood numbers with the Péclet numbers indicate that the mass transfer results obtained are identical with the ones measured earlier with the copper(I) complex [Cu(btmgp)I]. This demonstrates the independency of mass transfer from the properties of the chemical system used. The results significantly enlarge the existing database, which is of great importance to establish robust scaling laws.
Operating Behavior of Pulse Jet‐Cleaned Filters Regarding Energy Demand and Particle Emissions – Part 1: Experimental Parameter Study
Authors: Bächler Peter , Meyer Jörg , Dittler Achim
Published: June 2023

Filter operation of a pilot‐scale baghouse filter was evaluated under energy and particle emission criteria. Evaluation of the required total power for filter operation takes into account the fan power as well as the consumption of pressurized air. Filter face velocity, raw‐gas concentration, and tank pressure for regeneration were varied for several cycle time settings to identify the minimum power. Cycle times shorter than at minimum power are not feasible due to increased dust emissions and no additional energetic benefit. Cycle times longer than at minimum power may lower the dust emissions at the cost of increased power consumption. Lowering filter face velocity can greatly lower the power consumption of baghouse filters, having implications on filter layout.
Chemodivergent Tandem Radical Cyclization of Alkene‐Substituted Quinazolinones: Rapid Access to Mono‐ and Di‐Alkylated Ring‐Fused Quinazolinones
Authors: Wu Hong‐Li , Zhang Wei‐Kang , Zhang Can‐Can , Wang Ling‐Tao , Yang Wen‐Hui , Tian Wen‐Chan , Ge Guo‐Ping , Xie Long‐Yong , Yi Rongnan , Wei Wen‐Ting
Published: June 2023

Chemodivergent tandem radical cyclization offers exciting possibilities for the synthesis of structurally diverse cyclic compounds. Herein, we revealed a chemodivergent tandem cyclization of alkene‐substituted quinazolinones under metal‐ and base‐free conditions, this transformation is initiated by alkyl radicals produced from oxidant‐induced α‐C(sp3)−H functionalization of alkyl nitriles or esters. The reaction resulted in the selective synthesis of a series of mono‐ and di‐alkylated ring‐fused quinazolinones by modulating the loading of oxidant, reaction temperature, and reaction time. Mechanistic investigations show that the mono‐alkylated ring‐fused quinazolinones is constructed by the key process of 1,2‐hydrogen shift, whereas the di‐alkylated ring‐fused quinazolinones is mainly achieved through crucial steps of resonance and proton transfer. This protocol is the first example of remote second alkylation on the aromatic ring via α‐C(sp3)−H functionalization and difunctionalization achieved by association of two unsaturated bonds in radical cyclization.
Chiral Diketopyrrolo[3,4‐c]pyrrole‐1,2,3‐1H‐triazole Dyes with Highly Tuneable Properties in Solution and Thin Films
Authors: Albano Gianluigi , Zinna Francesco , Taddeucci Andrea , Capozzi Maria Annunziata M. , Pescitelli Gennaro , Punzi Angela , Di Bari Lorenzo , Farinola Gianluca M.
Published: June 2023

Invited for the cover of this issue are the research groups of Lorenzo Di Bari at the University of Pisa and Gianluca Maria Farinola at the University of Bari Aldo Moro. The image depicts three diketopyrrolo[3,4‐c]pyrrole–1,2,3‐1H‐triazole dyes with the same chiral appendage R* but different achiral substituent groups Y showing profoundly different features in their aggregated form. Read the full text of the article at 10.1002/chem.202300291.
Acidic CO2 Electrolysis Addressing the “Alkalinity Issue” and Achieving High CO2 Utilization
Authors: Zhang Ting , Zhou Jinlei , Luo Ting , Lu Ji‐Qing , Li Zhengquan , Weng Xuexiang , Yang Fa
Published: June 2023

Electrochemical CO2 reduction reaction (CO2RR) provides a promising approach for sustainable chemical fuel production of carbon neutrality. Neutral and alkaline electrolytes are predominantly employed in the current electrolysis system, but with striking drawbacks of (bi)carbonate (CO32−/HCO3−) formation and crossover due to the rapid and thermodynamically favourable reaction between hydroxide (OH−) with CO2, resulting in low carbon utilization efficiency and short‐lived catalysis. Very recently, CO2RR in acidic media can effectively address the (bi)carbonate issue; however, the competing hydrogen evolution reaction (HER) is more kinetically favourable in acidic electrolytes, which dramatically reduces CO2 conversion efficiency. Thus, it is a big challenge to effectively suppress HER and accelerate acidic CO2RR. In this review, we begin by summarizing the recent progress of acidic CO2 electrolysis, discussing the key factors limiting the application of acidic electrolytes. We then systematically discuss addressing strategies for acidic CO2 electrolysis, including electrolyte microenvironment modulation, alkali cations adjusting, surface/interface functionalization, nanoconfinement structural design, and novel electrolyzer exploitation. Finally, the new challenges and perspectives of acidic CO2 electrolysis are suggested. We believe this timely review can arouse researchers′ attention to CO2 crossover, inspire new insights to solve the “alkalinity problem” and enable CO2RR as a more sustainable technology.
Regioselective Iridium‐Catalyzed C8‐H Borylation of 4‐Quinolones via Transient O‐Borylated Quinolines
Authors: Al Mamari Hamad H. , Borel Julie , Hickey Aobha , Courtney Eimear , Merz Julia , Zhang Xiaolei , Friedrich Alexandra , Marder Todd B. , McGlacken Gerard P.
Published: June 2023

The quinolone–quinoline tautomerization is harnessed to effect the regioselective C8‐borylation of biologically important 4‐quinolones by using [Ir(OMe)(cod)]2 as the catalyst precursor, the silica‐supported monodentate phosphine Si‐SMAP as the ligand, and B2pin2 as the boron source. Initially, O‐borylation of the quinoline tautomer takes place. Critically, the newly formed 4‐(pinBO)‐quinolines then undergo N‐directed selective Ir‐catalyzed borylation at C8. Hydrolysis of the OBpin moiety on workup returns the system to the quinolone tautomer. The C8‐borylated quinolines were converted to their corresponding potassium trifluoroborate (BF3K) salts and to their C8‐chlorinated quinolone derivatives. The two‐step C‐H borylation‐chlorination reaction sequence resulted in various C8‐Cl quinolones in good yields. Conversion to C8‐OH‐, C8‐NH2‐, and C8‐Ar‐substituted quinolones was also feasible by using this methodology.
Acidic Properties of Known and New COOH‐Functionalized M(IV) Metal‐Organic Frameworks
Authors: Poschmann Mirjam Patricia Margarete , Lillerud Karl Petter , Stock Norbert
Published: June 2023

Herein, we report two new COOH‐functionalized metal‐organic frameworks (MOFs) of composition [M6O4(OH)6(PMA)2(H2PMA)]×H2O, M=Zr, Hf), denoted CAU‐61, synthesized by using pyromellitic acid (H4PMA), a tetracarboxylic acid, as the linker and acetic acid as the solvent. The structure was determined from powder X‐ray diffraction data and one‐dimensional inorganic building units are connected through tetracarboxylate as well as dicarboxylate linker molecules, resulting in highly stable microporous framework structures with limiting and maximum pore diameter of ∼3.6 and ∼5.0 Å, respectively, lined with −COOH groups. Thermal stabilities of up to 400 °C in air, chemical stability in water at pH 1 to 12 and water uptake of 17 mol/mol prompted us to study the proton exchange of the μ2‐OH, μ3‐OH of the IBU and −COOH groups of the linker by titration with LiOH. Comparison of the pKa values with three UiO‐66 derivatives confirms distinct pKa value ranges and trends for the different acidic protons. Furthermore, the preparation of Zr−CAU‐61 membranes and first results on permeation of dyes and ions in aqueous solutions are presented.
Association between the beta‐blockers, calcium channel blockers, all‐cause mortality and length of hospitalization in patients with heart failure with preserved ejection fraction: A meta‐analysis of randomized controlled trials
Authors: Wu Mingming , Ni Dan , Huang Lin‐ling , Qiu Shengjun
Published: June 2023

Purpose

To establish an association between beta‐blockers (BBs), calcium channel blockers (CCBs), all‐cause mortality, and hospitalization in patients with Heart failure with preserved Ejection Fraction (HFpEF).

Methods

The present meta‐analysis has been performed as per the guidelines of (PRISMA). An inclusive literature search was made without any limitations on language using the electronic databases Cochrane Library, EMBASE, and PubMed up to November 2022. The outcomes evaluated in this meta‐analysis involved all‐cause mortality and hospitalization due to heart failure. The number of patients with HFpEF and their positive outcomes was extracted and analyzed using RevMan software.

Results

In total, 10 articles were included in the present meta‐analysis, with a pooled sample size of 12 940 HFpEF patients. In comparison with placebo, both BB and CCB substantially reduced the risk of all‐cause mortality and hospitalization. However, BB are more effective because they provide a significant reduction in all‐cause mortality (risk ratio (RR) = 0.60; 95% confidence interval [CI] = 0.43–0.83; p = .002] and hospitalization (RR = 0.54; 95% CI = 0.37–0.80; p = .002) as compared with CCB with a risk ratio of all‐cause mortality (RR = 0.77; 95% CI = 0.60–0.98; p = .03) and hospitalization (RR = 0.63; 95% CI = 0.44–0.90; p < .00001). A random‐effects model was used because of high heterogeneity between the studies (I2 > 70%).

Conclusions

The current meta‐analysis suggests that BBs were more beneficial than CCB in reducing all‐cause mortality and hospitalization duration in patients with HFpEF.
Homogeneous Gold Catalysis for Regioselective Carbocyclization of Alkynyl Precursors
Authors: Praveen Chandrasekar , Szafert Sławomir
Published: June 2023

π‐Activation of alkynyl precursors possessing an endogenous carbon nucleophile is one of the imperative topics in homogeneous gold catalysis as it offers Csp3‐Csp2 and Csp2‐Csp2 linked carbocycles. However, the exo‐dig and endo‐dig cyclization modes unlocks the possibility of both small and large rings respectively, thereby losing regioselectivity. Nevertheless, several gold‐catalyzed carbocyclizations which permits one isomer by controlling or avoiding the formation of other went largely unnoticed. Hence, this review is an attempt to summarize such approaches reported from early 2000’s to till date along with our viewpoint on contributing parameters for regioselectivity. This review covers only unimolecular reactions with classifications primarily based on the type of endogenous nucleophiles such as silyloxyenols, enamides/enamines, benzenoids, heteroaromatics and alkyls/alkenyls. From an application perspective, these reactions are significant in total synthesis and materials science. Therefore, those reactions that finds application in natural product synthesis and π‐functional materials are highlighted in appropriate places.
Organic Thermoelectric Materials from n‐Type Polymer Semiconductors
Authors: Li Mingwei , Shi Yongqiang
Published: June 2023

Organic thermoelectric (OTE) materials have garnered increasing attention due to their potential application in wearable/flexible TE generator for energy harvesting. To meet the practical application of thermoelectric device, high‐performance p‐ and n‐type OTE materials are both necessary. In the past few years, improved n‐type polymer semiconductors have developed rapidly in the OTE field; however, their thermoelectric performance is still lagging behind p‐type counterparts. Therefore, more efforts should be made to enhance n‐type polymer TE performance, including development of novel molecule structure, synthesis of new dopants and optimization of device engineering. In this Review, we highlight the effects of molecular structure and side chain length and polarity of n‐type polymer semiconductors on the TE performance such as electron transport, electrical conductivity, and power factor. Finally, further perspectives and challenges are also discussed to provide useful guidelines for the design of high‐performance n‐type OTE materials.
A Peculiar Photo‐Induced Transformation Exalted in Nanometric Size CoFe Prussian Blue Analogs
Authors: Balthazar Grégory , Bordage Amélie , Fornasieri Giulia , Altenschmidt Laura , Zitolo Andrea , Bleuzen Anne
Published: June 2023

The discovery of a photomagnetic effect in a CoFe Prussian blue analog (PBA) has triggered a growing interest for photo‐switchable bimetallic cyanide‐bridged systems. Nevertheless, in between cyanide‐bridged extended coordination polymers and discrete molecules, the photo‐switching phenomena are much less well known in nano‐sized materials. A photo‐induced transformation, specific to the nanometric size, is evidenced by magnetometry and by X‐ray absorption spectroscopy at the Co and Fe K‐edges in an alkali cation free Prussian blue analog. The nanoparticles before irradiation can be described as having a core‐shell structure, the core being made of the well‐known fcc‐CoII(HS)FeIII structure of CoFe PBAs while the shell contains CoII ions in octahedral geometry and significantly distorted Fe(CN)6 entities. Irradiation induces a change of the local structures around the transition metal ions, which remain in the same oxidation state, with different behaviors of the Co and Fe sub‐lattices.
Differentiation, Transcriptomic Profiling, and Calcium Imaging of Human Hypothalamic Neurons
Authors: Chen Hsiao‐Jou Cortina , Mazzaferro Simone , Tian Tian , Mali Iman , Merkle Florian T.
Published: June 2023

Neurons in the hypothalamus orchestrate homeostatic physiological processes and behaviors essential for life. Human pluripotent stem cells (hPSCs) can be differentiated into many types of hypothalamic neurons, progenitors, and glia. This updated unit includes published studies and protocols with new advances in the differentiation, maturation, and interrogation by transcriptomic profiling and calcium imaging of human hypothalamic cell populations. Specifically, new methods to freeze and thaw hypothalamic progenitors after they have been patterned and before substantial neurogenesis has occurred are provided that will facilitate experimental flexibility and planning. Also included are updated recipes and protocols for neuronal maturation, with details on the equipment and methods for examining their transcriptomic response and cell‐autonomous properties in culture in the presence of synaptic blockers. Together, these protocols facilitate the adoption and use of this model system for fundamental biological discovery and therapeutic translation to human diseases such as obesity, diabetes, sleep disorders, infertility, and chronic stress. © 2023 The Authors. Current Protocols published by Wiley Periodicals LLC.

Basic Protocol 1: hPSC maintenance

Basic Protocol 2: Hypothalamic neuron differentiation

Support Protocol 1: Cortical neuron (control) differentiation

Basic Protocol 3: Neuronal maturation

Support Protocol 2: Cryopreservation and thawing of neuronal progenitors

Support Protocol 3: Quality control: Confirmation of hypothalamic patterning and neurogenesis

Support Protocol 4: Bulk RNA sequencing of hypothalamic cultures

Basic Protocol 4: Calcium imaging of hypothalamic neurons using Fura‐2 AM

Alternate Protocol: Calcium imaging of green fluorescent hypothalamic neurons using Rhod‐3 AM
A bidirectional single‐phase Z‐source AC‐AC converter with reduced voltage stress on switches and safe commutation strategy
Authors: Mousavi Seyyed Mohammad Javad , Babaei Ebrahim , Alizadeh Darioush , Bahador Asghar
Published: June 2023

In this paper, a bidirectional single‐phase Z‐source ac‐ac converter is proposed. Common features between the proposed converter and its counterparts are the capability of boost in‐phase, buck out‐of‐phase, and common ground. The output voltage gain of the proposed converter is improved compared with previous Z‐source ac‐ac converters, while the total standing voltage (TSV) of the switches has also been significantly reduced. Owing to the reduction of voltage stress of semiconductor elements, the switching device power (SDP) of the proposed converter is reduced. As a result, the cost of the converter is also reduced. A bidirectional switch is replaced instead of the output filter inductor to reduce the volume and weight of the converter. A safe commutation strategy is applied to eliminate voltage spikes on switches. Furthermore, the proposed converter can transfer power in both directions. By evaluating the converter in different operating modes, the key relationships and parametric design of the converter are presented. A laboratory prototype is made to confirm the proposed converter performance.
Standardized naming convention and classification system for critical loads of nitrogen and sulfur deposition
Authors: Phelan Jennifer , Bell Michael D. , Lynch Jason A. , Geiser Linda H.
Published: June 2023

Critical loads (CLs) of atmospheric deposition have been used for multiple decades to assess the impacts of air pollutants on terrestrial and aquatic ecosystems. However, these CLs have been developed by different researchers, at different times, using different methods, and are named in different ways with varying levels of information and levels of specificity. In this study, we identified the elements that describe CLs and used them to develop and test a standardized CL naming convention and a complementary CL classification system applicable to all CLs. The CL naming convention consists of: the form of deposition; the biological receptor, response, and threshold; and chemical criterion and threshold, thereby clearly communicating what the CL is and what it protects. The CL classification system contains all the elements that define and describe a CL, but the CL classes are not fixed and are therefore, defined by the user. The application of the CL naming convention and classification system to an existing US CL database and national forest was successful, demonstrating not only the utility of the naming convention and classification system, but how both can also be used to guide future CL science.
Spatial modeling of the relative abundance of wading birds in peninsular Florida using citizen science data
Authors: Lee Veronica , Skripnikov Andrey
Published: June 2023

Recent literature has shown citizen science data that include reported counts, such as observations from the eBird database, can be used to model the relative abundance of selected species. The objective of our study was to extend on both the methodology and the range of species considered by previous research on relative abundance modeling; we selected the Floridian peninsula as our geographical area of interest. We confirmed that, much like for other bird species and geographical areas, modeling such data with a classic Poisson generalized linear model was not appropriate due to overdispersion. Moreover, assuming linearity for the effects of all environmental and observer effort covariates on relative abundance was shown to be overly simplistic. These concerns led us to consider a variety of potentially suitable modeling techniques; the quasi‐Poisson generalized additive model displayed the best combination of flexibility, strong predictive performance, and ease of interpretation. Expanding on previous research for eBird data, we chose to explicitly incorporate spatial dependence into the modeling task by performing hierarchical generalized additive modeling with a spatial conditional autoregressive structure for random effects. This practice allows us to account for spatial factors not represented by model covariates, such as species dispersal patterns or colonial breeding habits. After conducting appropriate testing procedures and fitting spatially explicit models, we found that our data contain moderate spatial dependence and that spatially explicit models have overall superior predictive performance to models that do not account for spatial dependence. Upon closer inspection, spatially explicit models perform especially well compared with their nonspatial counterparts in identifying situations with low abundance, with a negligible trade‐off in prediction accuracy for situations with high abundance. We conclude that quasi‐Poisson hierarchical generalized additive models with spatial random effects provide the best representation of the relative abundance of bird populations. Moreover, our spatially explicit models are more realistic based on domain knowledge when regarding the impact of environmental covariates, which is important when considering conservation implications and future projections.
Preparing 3D Perovskite Li0.33La0.557TiO3 Nanotubes Framework Via Facile Coaxial Electro‐Spinning Towards Reinforced Solid Polymer Electrolyte
Authors: Zhao Yichun , Fan Lin , Xiao Biao , Cai Shaojun , Chai Jingchao , Liu Xueqing , Liu Jiyan , Liu Zhihong
Published: June 2023

It is of significance to construct continuous multiphase percolation channels with fast lithium‐ion pathway in hybrid solid electrolytes. 3D ceramic nanostructure frameworks have attracted great attention in this field. Herein, the three‐dimensional perovskite Li0.33La0.557TiO3 nanotubes framework (3D‐LLTO‐NT) is fabricated via a facile coaxial electro‐spinning process followed by a calcination process at 800 °C. The hybrid polymer electrolyte of 3D‐LLTO‐NT framework and poly (ethylene carbonate) (3D‐LLTO‐NT@PEC) shows improved ionic conductivity of 1.73 × 10−4 S cm−1 at ambient temperature, higher lithium‐ion transference number (tLi+) of 0.78 and electrochemical stability window up to 5.0 V vs Li/Li+. The all‐solid‐state cell of LiFePO4/3D‐LLTO‐NT@PEC/Li delivers a high specific capacity of 140.2 mAh g−1 at 0.1 C at ambient temperature. This outstanding performance is attributed to the 3D ceramic nanotubes frameworks which provide fast lithium ion transfer pathway and stable interfaces.
Diagnostic yield and predictive value on left ventricular remodelling of genetic testing in dilated cardiomyopathy
Authors: Bertero Edoardo , Fracasso Giulia , Eustachi Virginia , Coviello Domenico , Cecconi Massimiliano , Giovinazzo Stefano , Toma Matteo , Merlo Marco , Sinagra Gianfranco , Porto Italo , Ameri Pietro , Canepa Marco
Published: June 2023

Aims

We assessed the diagnostic yield of genetic testing and the relationship of left ventricular (LV) reverse remodelling (LVRR) with the presence of DNA pathogenic (P) or likely pathogenic (LP) variants in patients with dilated cardiomyopathy (DCM).

Methods and results

From 680 outpatients followed at the Heart Failure Outpatient Clinic of our institution, we selected subjects with a diagnosis of DCM as defined by LV ejection fraction (LVEF) ≤40% and LV dilatation not explained by coronary artery disease or other causes. All patients were offered genetic investigation of 42 disease‐associated DCM genes with next‐generation sequencing. Seventy patients fulfilled the definition of DCM and 66 underwent genetic investigation. We identified 18 P/LP variants in 16 patients, with a diagnostic yield of 24%. The most common variants were truncating TTN variants (n = 7), followed by LMNA (n = 3), cytoskeleton Z‐disc (n = 3), ion channel (n = 2), motor sarcomeric (n = 2), and desmosomal (n = 1) genes. After a median follow‐up of 53 months (inter‐quartile range 20–111), patients without P/LP variants exhibited higher systolic and diastolic blood pressure, lower plasma brain natriuretic peptide levels, and a larger extent of LVRR, as reflected by the increase in LVEF (+14% vs. +1%, P = 0.0008) and decrease in indexed LV end‐diastolic diameter (−6.5 vs. −2 mm/m2, P = 0.03) compared with patients with P/LP variants.

Conclusions

Our results confirm the high diagnostic yield of genetic testing in selected DCM patients and suggest that identification of P/LP variants in DCM portends poorer LVRR in response to guideline‐directed medical therapy.
Dioxygen Reduction in Acetonitrile with Copper Pyridylalkylamine Complexes: The Influence of Acid Strength on the Catalytic Performance
Authors: Langerman Michiel , van Dorth Micha , Hetterscheid Dennis G. H.
Published: June 2023

The pyridylalkylamine copper complex [Cu(tmpa)(L)]2+ has previously been proposed to reduce dioxygen via a dinuclear resting state, based on experiments in organic aprotic solvents using chemical reductants. Conversely, a mononuclear reaction mechanism was observed under electrochemical conditions in a neutral aqueous solution. We have investigated the electrochemical oxygen and hydrogen peroxide reduction reaction catalyzed by [Cu(tmpa)(L)]2+ in acetonitrile, using several different acids over a range of pKa. We demonstrate that strong acids lead to the loss of redox reversibility and to the destabilization of the copper complex under non‐catalytic conditions. Under milder conditions, the electrochemical oxygen reduction reaction (ORR) was shown to proceed via a mononuclear catalytic intermediate, similar to what we have previously observed in water. However, in acetonitrile the catalytic rate constants of the ORR are dramatically lower by a factor 105, which is caused by the unfavorable equilibrium of formation of [CuII(O2⋅−)(tmpa)]+ in acetonitrile. This results in higher catalytic rates for the reduction of hydrogen peroxide than for the ORR.
Collective Total Synthesis of 4‐Azafluorenone Alkaloids
Authors: Jourjine Ilya A. P. , Bracher Franz
Published: June 2023

4‐Azafluorenones are typically obtained by acid‐mediated cyclization of 2‐arylnicotinates. However, this approach fails to give 5‐oxygenated 4‐azafluorenones due to lactonization of 2‐(2‐alkoxy)phenylnicotinate intermediates. Herein, we report two modifications of established approaches to 4‐azafluorenone synthesis that, either in combination or by themselves, enable the flexible preparation of 4‐azafluorenones with diverse oxygenation patterns in the benzenoid ring. Undesired lactonization was circumvented via tert‐butyl hydroperoxide (TBHP)‐mediated radical cyclization of 2‐aryl‐3‐(hydroxymethyl)pyridines. In the absence of suitable protecting groups for phenolic intermediates, bromide substituents were regioselectively introduced as latent hydroxy groups and later converted under palladium catalysis. We present the first total syntheses of five 4‐azafluorenone alkaloids muniranine, darienine, 5,8‐dimethoxy‐7‐hydroxyonychine, 5,6,7,8‐tetramethoxyonychine, and 6,8‐dihydroxy‐7‐methoxyonychine in addition to new total syntheses of six 4‐azafluorenone alkaloids and one related pyridocoumarin alkaloid.