bluuebunny/crossref_metadata_2025_split huggingface dataset:
Poly‐Hydride [AuI7(PPh3)7H5](SbF6)2 cluster complex: Structure, Transformation, and Electrocatalytic CO2 Reduction Properties
Authors: Tang Li , Luo Yuting , Ma Xiaoshuang , Wang Bin , Ding Mei , Wang Ru , Wang Pu , Pei Yong , Wang Shuxin 
Published: January 2023

AbstractHydride AuI bonds are labile due to the mismatch in electric potential of an oxidizing metal and reducing ligand, and therefore the structure and structure–activity relationships of nanoclusters that contain them are seldom studied. Herein, we report the synthesis and characterization of [Au7(PPh3)7H5](SbF6)2 (abbrev. Au7H52+), an Au cluster complex containing five hydride ligands, which decomposed to give [Au8(PPh3)7]2+ (abbrev. Au82+) upon exposure to light (300 to 450 nm). The valence state of AuI and H− was verified by density functional theory (DFT) calculations, NMR, UV/Vis and XPS. The two nanoclusters behaved differently in the electrocatalytic CO2 reduction reaction (CO2RR): Au7H52+ exhibited 98.2 % selectivity for H2, whereas Au82+ was selective for CO (73.5 %). Further DFT calculations showed that the H− ligand inhibited the CO2RR process compared with the electron‐donor H.
Chemomechanically Stable Small Single‐crystal Mo‐doped LiNi0.6Co0.2Mn0.2O2 Cathodes for Practical 4.5 V‐class Pouch‐type Li‐ion Batteries
Authors: Liang Longwei , Li Xiaoying , Su Maoshui , Wang Lixian , Sun Jinfeng , Liu Yang , Hou Linrui , Yuan Changzhou 
Published: January 2023

AbstractHigh voltage can cost‐effectively boost energy density of Ni‐rich cathodes based Li‐ion batteries (LIBs), but compromises their mechanical, electrochemical and thermal‐driven stability. Herein, a collaborative strategy (i.e., small single‐crystal design and hetero‐atom doping) is devised to construct a chemomechanically reliable small single‐crystal Mo‐doped LiNi0.6Co0.2Mn0.2O2 (SS‐MN6) operating stably under high voltage (≥4.5 V vs. Li/Li+). The substantially reduced particle size combined with Mo6+ doping absorbs accumulated localized stress to eradicate cracks formation, subdues the surface side reactions and lattice oxygen missing meanwhile, and improves thermal tolerance at highly delithiated state. Consequently, the SS‐MN6 based pouch cells are endowed with striking deep cycling stability and wide‐temperature‐tolerance capability. The contribution here provides a promising way to construct advanced cathodes with superb chemomechanical stability for next‐generation LIBs.
Electroreduction of CO2 on Au(310)@Cu High‐index Facets
Authors: Liang Liang , Feng Quanchen , Wang Xingli , Hübner Jessica , Gernert Ulrich , Heggen Marc , Wu Longfei , Hellmann Tim , Hofmann Jan P. , Strasser Peter 
Published: January 2023

AbstractThe chemical selectivity and faradaic efficiency of high‐index Cu facets for the CO2 reduction reaction (CO2RR) is investigated. More specifically, shape‐controlled nanoparticles enclosed by Cu {hk0} facets are fabricated using Cu multilayer deposition at three distinct layer thicknesses on the surface facets of Au truncated ditetragonal nanoprisms (Au DTPs). Au DTPs are shapes enclosed by 12 high‐index {310} facets. Facet angle analysis confirms DTP geometry. Elemental mapping analysis shows Cu surface layers are uniformly distributed on the Au {310} facets of the DTPs. The 7 nm Au@Cu DTPs high‐index {hk0} facets exhibit a CH4 : CO product ratio of almost 10 : 1 compared to a 1 : 1 ratio for the reference 7 nm Au@Cu nanoparticles (NPs). Operando Fourier transform infrared spectroscopy spectra disclose reactive adsorbed *CO as the main intermediate, whereas CO stripping experiments reveal the high‐index facets enhance the *CO formation followed by rapid desorption or hydrogenation.
Correlating the Experimentally Determined CO Adsorption Enthalpy with the Electrochemical CO Reduction Performance on Cu Surfaces
Authors: Xiong Haocheng , Sun Qiwen , Chen Kedang , Xu Yifei , Chang Xiaoxia , Lu Qi , Xu Bingjun 
Published: January 2023

AbstractCO binding energy has been widely employed as a descriptor for effective catalysts in the electrochemical CO2and CO reduction reactions (CO(2)RR), however, it has yet to be determined experimentally at electrochemical interfaces due to the lack of suitable techniques. In this work, we developed a method to determine the standard adsorption enthalpy of CO on Cu surfaces with quantitative surface enhanced infrared absorption spectroscopy. On dendritic Cu at −0.75 V vs. SHE, the standard adsorption enthalpy, entropy and Gibbs free energy were determined to 1.5±0.5 kJ mol−1, ≈37.9±13.4 J/(mol K), and ≈−9.8±4.0 kJ mol−1, respectively. Comparison of the standard adsorption enthalpy of oxide‐derived Cu and dendritic Cu, as well as their CORR activities, suggests the presence of stronger binding sites on OD Cu, which could favor multicarbon products. The method developed in this work will help establish the correlation between the CO binding energy and the CO(2)RR activity.
Biased Borate Esterification during Nucleoside Phosphorylase‐Catalyzed Reactions: Apparent Equilibrium Shifts and Kinetic Implications**
Authors: Kaspar Felix , Brandt Felix , Westarp Sarah , Eilert Lea , Kemper Sebastian , Kurreck Anke , Neubauer Peter , Jacob Christoph R. , Schallmey Anett 
Published: January 2023

AbstractBiocatalytic nucleoside (trans‐)glycosylations catalyzed by nucleoside phosphorylases have evolved into a practical and convenient approach to the preparation of modified nucleosides, which are important pharmaceuticals for the treatment of various cancers and viral infections. However, the obtained yields in these reactions are generally determined exclusively by the innate thermodynamic properties of the nucleosides involved, hampering the biocatalytic access to many sought‐after target nucleosides. We herein report an additional means for reaction engineering of these systems. We show how apparent equilibrium shifts in phosphorolysis and glycosylation reactions can be effected through entropically driven, biased esterification of nucleosides and ribosyl phosphates with inorganic borate. Our multifaceted analysis further describes the kinetic implications of this in situ reactant esterification for a model phosphorylase.
Glycine Imine—The Elusive α‐Imino Acid Intermediate in the Reductive Amination of Glyoxylic Acid
Authors: Paczelt Viktor , Wende Raffael C. , Schreiner Peter R. , Eckhardt André K. 
Published: January 2023

AbstractSimple unhindered aldimines tend to hydrolyze or oligomerize and are therefore spectroscopically not well characterized. Herein we report the formation and spectroscopic characterization of the simplest imino acid, namely glycine imine, by cryogenic matrix isolation IR and UV/Vis spectroscopy. Glycine imine forms after UV irradiation of 2‐azidoacetic acid by N2 extrusion in anti‐(E,E)‐ and anti‐(Z,Z)‐conformation that can be photochemically interconverted. In matrix isolation pyrolysis experiments with 2‐azidoacetic acid, glycine imine cannot be trapped as it further decarboxylates to aminomethylene. In aqueous solution glycine imine is hydrolyzed to hydroxy glycine and hydrated glyoxylic acid. At higher concentrations or in the presence of FeIISO4 as a reducing agent glycine imine undergoes self‐reduction by oxidative decarboxylation chemistry. Glycine imine may be seen as one of the key reaction intermediates connecting prebiotic amino acid and sugar formation chemistry.
One‐Dimensional Covalent Organic Frameworks for the 2e− Oxygen Reduction Reaction
Authors: An Shuhao , Li Xuewen , Shang Shuaishuai , Xu Ting , Yang Shuai , Cui Cheng‐Xing , Peng Changjun , Liu Honglai , Xu Qing , Jiang Zheng , Hu Jun 
Published: January 2023

AbstractTwo‐dimensional covalent organic frameworks (2D COFs) are often employed for electrocatalytic systems because of their structural diversity. However, the efficiency of atom utilization is still in need of improvement, because the catalytic centers are located in the basal layers and it is difficult for the electrolytes to access them. Herein, we demonstrate the use of 1D COFs for the 2e− oxygen reduction reaction (ORR). The use of different four‐connectivity blocks resulted in the prepared 1D COFs displaying good crystallinity, high surface areas, and excellent chemical stability. The more exposed catalytic sites resulted in the 1D COFs showing large electrochemically active surface areas, 4.8‐fold of that of a control 2D COF, and thus enabled catalysis of the ORR with a higher H2O2 selectivity of 85.8 % and activity, with a TOF value of 0.051 s−1 at 0.2 V, than a 2D COF (72.9 % and 0.032 s−1). This work paves the way for the development of COFs with low dimensions for electrocatalysis.
Preparation of fluorinated epoxy‐phthalonitrile resins with excellent thermal stability and low dielectric constant
Authors: Dong Jinghui , Sang Xiaoming , Yin Weihao , Chen Xinggang 
Published: January 2023

AbstractFluoropolymers find applications in heat‐resistant cables, chemical‐resistant linings, electronic components, cladding materials, and weather‐resistant films. Therefore, it is imperative to improve their temperature resistance level and dielectric properties. In this study, a series of new fluorinated epoxy‐phthalonitrile resins with different mass ratios were prepared by adding phthalonitrile to the epoxy resin matrix, followed by a two‐step reaction of the amine with the epoxy resin at low temperature, and then by the reaction of the nitrile with the epoxy resin and the nitrile group at high temperature. The thermal stability and thermal oxidation stability of the cured products were improved; the initial decomposition temperature for 5% weight loss in air was 375.3°C, indicating good heat resistance performance. In addition, the glass transition temperature and storage modulus of the fluorinated epoxy‐phthalonitrile resins cured products increased with an increase in phthalonitrile content. The storage modulus remained above 1500 MPa until 150°C. The glass transition temperature of fluorinated epoxy‐phthalonitrile resins (at a mass ratio of 5:5) was 180°C, much higher than that of the epoxy resin (which was 140°C). Moreover, the dielectric constant of fluorinated phthalonitrile‐epoxy resin (5:5 mass ratio) was 2.01, which was 39.63% lower than that of fluorinated epoxy resin. The thermoset matrix has potential applications in the fabrication of a variety of low dielectric constant composites for electronic device related industries.
Identification and expression analyses of the olfactory‐related genes in different tissues' transcriptome of a predacious soldier beetle,Podabrus annulatus(Coleoptera, Cantharidae)
Authors: Wang Xiaoxiao , Liu Haoyu , Xie Guanglin , Wang Wenkai , Yang Yuxia 
Published: January 2023

AbstractWe sequenced and analyzed the transcriptomes from different tissues of the soldier beetle,Podabrus annulatus(Coleoptera: Cantharidae), and obtained 75.74 Gb clean reads which were assembled into 95,274 unigenes. Among these transcripts, 25,484 unigenes of highly quality were annotated. Based on annotation and tBLASTn results, we identified a total of 101 candidate olfactory‐related genes for the first time, including 11 putative odorant‐binding proteins (OBPs), 6 chemosensory proteins (CSP), 50 olfactory receptors (ORs), 25 gustatory receptors (GRs), 6 ionotropic receptors (IRs), and 3 sensory neuron membrane proteins (SNMPs). BLASTX best‐hit results indicated that these chemosensory genes were most identical to their respective orthologs fromPhotinus pyralis. Phylogenetic analyses also revealed that the ORs, GRs, and IRs ofPodabrus annulatusare closely related to those ofPhotinus pyralis. The fragment per kilobase per million mapped fragments (FPKM) values showed that the PannOBP2, PannOBP3, and PannOBP10 were predominantly expressed in the antennae, PannOBP1 in the abdomen–thorax, while others were not identified to be tissue‐specific. These olfactory‐related differentially expressed genes (DEGs) demonstrated different roles in the olfactory system ofPodabrus annulatus. This study establishes the groundwork for future research into the molecular mechanism of olfactory recognition inPodabrus annulatus.
Retracted: Pan‐neuronal knockdown of Ras GTPase‐activating protein 1 alters Drosophila activity and sleep behavior
Authors: Lagunas‐Rangel Francisco Alejandro 
Published: January 2023

AbstractThe above article, published online on 18 January 2023 in Wiley Online Library (https://onlinelibrary.wiley.com/doi/abs/10.1002/arch.22001), has been retracted by agreement between the author, the journal Editor in Chief, Yonggyun Kim and Wiley Periodicals, LLC.The retraction has been agreed due to errors identified in the research methodology. The author confirms that repeating the research with corrected methodology has yielded significantly different results; therefore, the results and conclusions of the published article must be considered invalid.
Novel Approach for the Isolation and Immobilization of a Recombinant Transaminase: Applying an Advanced Nanocomposite System
Authors: Koplányi Gábor , Bell Evelin , Molnár Zsófia , Katona Gábor , Lajos Neumann Péter , Ender Ferenc , Balogh György T. , Žnidaršič‐Plazl Polona , Poppe László , Balogh‐Weiser Diána 
Published: January 2023

AbstractThe increasing application of recombinant enzymes demands not only effective and sustainable fermentation, but also highly efficient downstream processing and further stabilization of the enzymes by immobilization. In this study, a novel approach for the isolation and immobilization of His‐tagged transaminase fromChromobacterium violaceum(CvTA) has been developed. A recombinant ofCvTA was simultaneously isolated and immobilized by binding on silica nanoparticles (SNPs) with metal affinity linkers and additionally within poly(lactic acid) (PLA) nanofibers. The linker length and the nature of the metal ion significantly affected the enzyme binding efficiency and biocatalytic activity ofCvTA‐SNPs. The formation of PLA nanofibers by electrospinning enabled rapid embedding ofCvTA‐SNPs biocatalysts and ensured enhanced stability and activity. The developed advanced immobilization method reduces the time required for enzyme isolation, purification and immobilization by more than fourfold compared to a classical stepwise technique.
Imatinib suppresses activation of hepatic stellate cells by targeting STAT3/IL‐6 pathway through miR‐124
Authors: Alavifard Helia , Mazhari Sogol , Meyfour Anna , Tokhanbigli Samaneh , Ghavami Saeid , Zali Mohammad Reza , Aghdaei Hamid Asadzadeh , Hatami Behzad , Baghaei Kaveh 
Published: January 2023

AbstractThe activation of hepatic stellate cells is the primary function of facilitating liver fibrosis. Interfering with the coordinators of different signaling pathways in activated hepatic stellate cells (aHSCs) could be a potential approach in ameliorating liver fibrosis. Regarding the illustrated anti‐fibrotic effect of imatinib in liver fibrosis, we investigated the imatinib′s potential role in inhibiting HSC activation through miR‐124 and its interference with the STAT3/hepatic leukemia factor (HLF)/IL‐6 circuit. The anti‐fibrotic effect of imatinib was investigated in the LX‐2 cell line and carbon tetrachloride (CCl4)‐induced Sprague‐Dawley rat. The expression of IL‐6, STAT3, HLF, miR‐124, and α‐smooth muscle actin (α‐SMA) were quantified by quantitative real‐time PCR (qRT‐PCR) and the protein level of α‐SMA and STAT3 was measured by western blot analysis both in vitro and in vivo. The LX‐2 cells were subjected to immunocytochemistry (ICC) for α‐SMA expression. After administering imatinib in the liver fibrosis model, histopathological examinations were done, and hepatic function serum markers were checked. Imatinib administration alleviated mentioned liver fibrosis markers. The expression of miR‐124 was downregulated, while IL‐6/HLF/STAT3 circuit agents were upregulated in vitro and in vivo. Notably, imatinib intervention decreased the expression of IL‐6, STAT3, and HLF. Elevated expression of miR‐124 suppressed the expression of STAT3 and further inhibited HSCs activation. Our results demonstrated that imatinib not only ameliorated hepatic fibrosis through tyrosine kinase inhibitor (TKI) activity but also interfered with the miR‐124 and STAT3/HLF/IL‐6 pathway. Considering the important role of miR‐124 in regulating liver fibrosis and HSCs activation, imatinib may exert its anti‐fibrotic activity through miR‐124.
PCI for late STEMI: Better late than never?
Authors: Davis Monique G. , Blankenship James C. 
Published: January 2023

Key Points
Management of patients presenting with late STEMI (>12 hours) remains controversial.
In this study, outcomes of early and late STEMI were similar despite more critical cardiovascular risk profiles among late presenters, potentially supporting a strategy of PCI in late STEMI presenters.
An algorithm for the management of late STEMI is presented
Nothing to do does not mean any consequences
Authors: Aranzulla Tiziana Claudia , Musumeci Giuseppe 
Published: January 2023

Key Points
Post‐TAVR new‐onset left bundle branch block (nLBBB) has clinical and echocardiographic prognostic implications, being associated with higher rates of permanent pacemaker (PPM) implantation and hospitalization for heart failure, and with worse left ventricular ejection fraction and remodeling.
Close monitoring of patients who developed post‐TAVR nLBBB is needed, and predefined clinical, electrocardiographic and echocardiographic follow‐up should be scheduled at discharge
Future studies aimed at identifying predictors of post‐TAVR nLBBB occurrence and regression, as well as the time windows in which it is likely will help in targeting patients at higher risk of PPM
A novel RAD51 variant resulting in Fanconi anemia identified in an infant with multiple congenital anomalies
Authors: Geilmann Shelby , Solstad Rachel , Palmquist Rachel , Flores Daboub Josue , Botto Lorenzo D. , Grubb Peter H. , Bonkowsky Josh L. , Longo Nicola , Malone Jenkins Sabrina 
Published: January 2023

AbstractFanconi anemia, FA, is a rare, multi‐system disease caused by pathogenic variants in DNA repair genes. We report a novel RAD51 variant in an infant with FA whose tracheobronchomalacia has not been described in FA. His severe presentation expands the phenotype of RAD51‐associated FA, reported only in three patients previously.
Nonketotic hyperglycemic hemichorea‐hemiballismus in a pediatric patient: A case report
Authors: Saroufim Rita , Hannon Tamara 
Published: January 2023

AbstractNonketotic hyperglycemic hemichorea‐hemiballismus (NHHH) is an infrequent complication of diabetes mellitus, and rarely occurs in children. We present an adolescent boy with recent diagnosis of type 1 diabetes who presented with hemichorea and brain imaging findings consistent with NHHH. His symptoms resolved with euglycemia and valproic acid after few weeks.
Understanding the Impact of Fe‐Doping on the Structure and Battery Performance of a Co‐Free Li‐Rich Layered Cathodes
Authors: Celeste Arcangelo , Paolacci Matteo , Schiavi Pier Giorgio , Brutti Sergio , Navarra Maria Assunta , Silvestri Laura 
Published: January 2023

AbstractA series of Co‐free Li‐rich layered oxides, Li1.24Mn0.62‐xNi0.14FexO2 (x=0, 0.01, 0.02 and 0.03) has been synthetized by a self‐combustion reaction. Fe doping affects either lattice structure and bonding as shown by the changes in the size of unit cell calculated from diffraction patterns and in the vibrational frequencies observed in Raman spectra. The electrochemical performance has been evaluated in a lithium cell by galvanostatic cycling: Doped samples show better capacity retention and minor decreases in the specific capacity (i. e., Li1.24Mn0.60Ni0.14Fe0.02O2 can supply a specific capacity of 235 mAhg−1 with 94 % of capacity retention after 150 cycles). These positive effects originated by alterations in the point defectivity (Ni3+ concentration, anionic and cationic vacancies), changes in the transport properties, as showed by Cyclic Voltammetry; as well as an improved structural resilience compared to the un‐doped material in postmortem analyses.
Ions Dynamics and Diffusion in Self‐Healing Chemical Gel Electrolytes for Li‐ion Batteries
Authors: Quartarone Eliana , Davino Stefania , Lufrano Ernestino , Coppola Luigi , Simari Cataldo , Nicotera Isabella 
Published: January 2023

AbstractA successful strategy for improving the safety issues of new‐generation lithium‐ion batteries is to replace liquid electrolytes with solid or quasi‐solid membranes, a procedure that ensures adequate ionic conductions and are mechanical strengths.
Liquid Dynamics Determine Transition Metal‐N‐Heterocyclic Carbene Complex Formation
Authors: Zaby Paul , Blasius Jan , Müller Anna K. , Nolan Steven P. , Hollóczki Oldamur 
Published: January 2023

AbstractThe mechanism of metal‐N‐heterocyclic carbene (NHC) complex formation from imidazolium salts in the presence of weak bases was investigated through theoretical methods. Quantum chemical calculations revealed that the two bases considered here, sodium acetate and trimethylamine, both facilitate complex formation. In contrast to previous experiments, these calculations indicated a slightly lower barrier with the amine. Molecular dynamics simulations showed that the ionic nature of the [AuCl2]− and imidazolium ions, as well as the sodium acetate base keep these species associated in the reaction mixture through ion pairing. This pre‐association of the components produces those clusters that are essential for the metal complex formation reaction. The neutral amine, however, remains mostly separated from the other reaction partners, making it a significantly less effective base.
Light‐triggered Modulation of Supramolecular Chirality
Authors: Yang Fan , Yue Bingbing , Zhu Liangliang 
Published: January 2023

AbstractDynamically controlling the supramolecular chirality is of great significance in development of functional chiral materials, which is thus essential for the specific function implementation. As an external energy input, light is remote and accurate for modulating chiral assemblies. In non‐polarized light control, some photochemically reactive units (e. g., azobenzene, ɑ‐cyanostilbene, spiropyran, anthracene) or photo‐induced directionally rotating molecular motors were designed to drive chiral transfer or amplification. Besides, photoexcitation induced assembly based physical approach was also explored recently to regulate supramolecular chirality beyond photochemical reactions. In addition, circularly polarized light was applied to induce asymmetric arrangement of organic molecules and asymmetric photochemical synthesis of inorganic metallic nanostructures, in which both wavelength and handedness of circularly polarized light have effects on the induced supramolecular chirality. Although light‐triggered chiral assemblies have been widely applied in photoelectric materials, biomedical fields, soft actuator, chiral catalysis and chiral sensing, there is a lack of systematic review on this topic. In this review, we summarized the recent studies and perspectives in the constructions and applications of light‐responsive chiral assembled systems, aiming to provide better knowledge for the development of multifunctional chiral nanomaterials.