bluuebunny/crossref_metadata_2025_split huggingface dataset:
Evaluation of the advantage of surgeons certified by the endoscopic surgical skill qualification system participating in laparoscopic low anterior rectal resection
Authors: Sawada Naruhiko , Akagi Tomonori , Shimomura Manabu , Todate Yukitoshi , Nagakari Kunihiko , Takeshita Hiroaki , Maruyama Satoshi , Takata Manabu , Ichikawa Nobuki , Hida Koya , Iijima Hiroaki , Yamaguchi Shigeki , Taketomi Akinobu , Naitoh Takeshi ,   The EnSSURE Study Group Collaboratives in Japan Society of Laparoscopic Colorectal Surgery.
Published: December 2023

AbstractBackgroundA technical qualification system was developed in 2004 by the Japan Society for Endoscopic Surgery. An analysis of the EnSSURE study on 3188 stage II–III rectal cancer patients, which was performed by including the participation of qualified surgeons as assistants and advisers without restricting their participation as operators, revealed that the participation of technically qualified surgeons in surgery improved the technical and oncological safety of laparoscopic rectal resection.AimThis secondary retrospective analysis of the EnSSURE study examined the advantage of qualified surgeons participating in laparoscopic low anterior resection (LAR).MethodsThe outcomes of low anterior resection were compared between groups with and without the participation of surgeons qualified by the Endoscopic Surgical Skill Qualification System (Q and non‐Q groups, respectively). We used propensity score matching to generate paired cohorts at a one‐to‐one ratio. The postoperative complication rate, short‐term results (hemorrhage volume, operative time, number of dissected lymph nodes, open conversion rate, intraoperative complication rate, and R0 resection rate), and long‐term results (disease‐free survival rate, local recurrence rate, and overall survival rate) were evaluated.ResultsThe frequencies of postoperative complications, anastomotic bleeding, and intraperitoneal abscess were significantly lower, the operative time was significantly shorter, the postoperative hospital stay was significantly shorter, and the number of dissected lymph nodes was higher in the Q group. No significant differences were observed in disease‐free survival, local recurrence, or overall survival rate rates between the groups.ConclusionThe participation of qualified surgeons in LAR is technically advantageous.
Risk of Multiple Sclerosis in People Living with HIV: An International Cohort Study
Authors: McKay Kyla A. , Wijnands José M. A. , Manouchehrinia Ali , Zhu Feng , Sereda Paul , Li Jenny , Ye Monica , Trigg Jason , Kooij Katherine , Ekström Anna Mia , Gisslén Magnus , Hillert Jan , Hogg Robert S. , Tremlett Helen , Kingwell Elaine 
Published: December 2023

ObjectiveThere has been interest in a possible negative association between HIV and multiple sclerosis (MS). We aimed to compare the risk of MS in a cohort of individuals living with HIV to that in the general population.MethodsPopulation‐based health data were accessed for 2 cohorts of HIV‐positive persons from Sweden and British Columbia, Canada. Incident MS was identified using MS registries or a validated algorithm applied to administrative data. Individuals with HIV were followed from 1 year after the first clinical evidence of HIV or the first date of complete administrative health data (Canada = April 1, 1992 and Sweden = January 1, 2001) until the earliest of incident MS, emigration, death, or study end (Canada = March 31, 2020 and Sweden = December 31, 2018). The observed MS incidence rate in the HIV‐positive cohort was compared to the expected age‐, sex‐, calendar year‐, income‐specific, and region of birth‐specific rates in a randomly selected sample of >20% of each general population. The standardized incidence ratio (SIR) for MS following the first antiretroviral therapy exposure (“ART‐exposed”) was also calculated.ResultsThe combined Sweden‐Canada cohort included 29,163 (75% men) HIV‐positive persons. During 242,248 person‐years of follow‐up, 14 incident MS cases were observed in the HIV‐positive cohort, whereas 26.19 cases were expected. The SIR for MS in the HIV‐positive population was 0.53 (95% confidence interval [CI] = 0.32–0.90). The SIR for MS following the first ART exposure was 0.55 (95% CI = 0.31–0.96).InterpretationThis international population‐based study demonstrated a lower risk of MS among HIV‐positive individuals, and HIV‐positive ART‐exposed individuals. These findings provide support for further exploration into the relationship among HIV, ART, and MS. ANN NEUROL 2024;95:487–494
Asymmetric Cu−N−La Species Enabling Atomic‐Level Donor‐Acceptor Structure and Favored Reaction Thermodynamics for Selective CO2 Photoreduction to CH4
Authors: Xie Wenke , Liu Yushen , Zhang Xing , Yan Huijuan , Liu Xuan‐He , Zhang Xiaoyu , Zhao Qinglan , Huang Hongwei 
Published: December 2023

AbstractPhotocatalytic CO2 reduction into ideal hydrocarbon fuels, such as CH4, is a sluggish kinetic process involving adsorption of multiple intermediates and multi‐electron steps. Achieving high CH4 activity and selectivity therefore remains a great challenge, which largely depends on the efficiency of photogenerated charge separation and transfer as well as the intermediate energy levels in CO2 reduction. Herein, we construct La and Cu dual‐atom anchored carbon nitride (LaCu/CN), with La‐N4 and Cu‐N3 coordination bonds connected by Cu−N−La bridges. The asymmetric Cu−N−La species enables the establishment of an atomic‐level donor‐acceptor structure, which allows the migration of electrons from La atoms to the reactive Cu atom sites. Simultaneously, intermediates during CO2 reduction on LaCu/CN demonstrate thermodynamically more favorable process for CH4 formation based on theoretical calculations. Eventually, LaCu/CN exhibits a high selectivity (91.6 %) for CH4 formation with a yield of 125.8 μmol g−1, over ten times of that for pristine CN. This work presents a strategy for designing multi‐functional dual‐atom based photocatalysts.
Boosting the Catalase‐Like Activity of SAzymes via Facile Tuning of the Distances between Neighboring Atoms in Single‐Iron Sites
Authors: Zhang Hao , Wang Pengbo , Zhang Jingru , Sun Qingdi , He Qian , He Xiaohui , Chen Hongyu , Ji Hongbing 
Published: December 2023

AbstractA nanozyme with neighboring single‐iron sites (Fe2‐SAzyme) was introduced as a bioinspired catalase mimic, featuring excellent activity under varied conditions, twice as high as that of random Fe1‐SAzyme and ultrahigh H2O2 affinity as that of bioenzymes. Surprisingly, the interatomic spacing tuning between adjacent iron sites also suppressed the competitive peroxidase pathway, remarkably increasing the catalase/peroxidase selectivity up to ~6 times compared to Fe1‐SAzyme. This dramatically switched the catalytic activity of Fe‐SAzymes from generating (i.e. Fe1‐SAzymes, preferably mimicking peroxidase) to scavenging ROS (i.e. Fe2‐SAzymes, dominantly mimicking catalase). Theoretical and experimental investigations suggested that the pairwise single‐iron sites may serve as a robust molecular tweezer to efficiently trap and decompose H2O2 into O2, via cooperative hydrogen‐bonding induced end‐bridge adsorption. The versatile mechano‐assisted in situ MOF capsulation strategy enabled facile access to neighboring M2‐SAzyme (M=Fe, Ir, Pt), even up to a 1000 grams scale, but with no obvious scale‐up effect for both structures and performances.
Signalverstärkung und Nah‐Infrarot Übersetzung von Enzymatischen Reaktionen mit Nanosensoren**
Authors: Metternich Justus T. , Hill Björn , Wartmann Janus A. C. , Ma Chen , Kruskop Rebecca M. , Neutsch Krisztian , Herbertz Svenja , Kruss Sebastian 
Published: December 2023

AbstractEnzymatische Reaktionen kommen in zahlreichen biochemischen Verfahren zum Nachweis von Analyten zum Einsatz. Um das Vorhandensein eines Analyten zu messen, werden die Enzyme an eine Erkennungseinheit konjugiert und wandeln ein Substrat in ein (farbiges) Produkt um, das im sichtbaren Bereich (VIS) des Spektrums nachgewiesen werden kann. Der niedrigste nachweisbare enzymatische Umsatz stellt somit eine Grenze für die Empfindlichkeit dar. Hier zeigen wir, dass Substrate und Produkte der Meerrettichperoxidase (HRP) und der β‐Galaktosidase die Fluoreszenz im nahen Infrarot (NIR) von einwandigen Kohlenstoffnanoröhren (SWCNTs) verändern, wenn diese mit (Bio−)Polymeren modifiziert sind. Durch die Fluoreszenz im NIR übersetzen die SWCNTs ein VIS‐Signal in ein NIR‐Signal. Zudem führt die Affinität der Nanosensoren zu einer höheren effektiven lokalen Konzentration der Reaktanten. Dies bewirkt eine nichtlineare sensorbasierte Signalverstärkung und ‐übersetzung (SENSAT). Für das HRP‐Substrat p‐Phenylendiamin (PPD) ergibt sich eine bis zu ≈120‐fache Signalverstärkung, die es erlaubt, Reaktionen unterhalb der VIS Nachweisgrenze im NIR (≈1000 nm) zu verfolgen. Der Ansatz ist auch auf andere Substrate wie 3,3‐5,5′‐Tetramethylbenzidin (TMB) anwendbar. Ein Adsorptionsmodell erklärt die beobachteten Signaländerung und bestätigt den Verstärkungsmechanismus. Mit Hilfe dieses Ansatzes lassen sich Signale von chromogenen enzymatischen Reaktionsprodukten verstärken, in den NIR‐Bereich übertragen und die Empfindlichkeit biochemischer Assays erhöhen.
Two‐Electron Redox Reactivity of Thorium Supported by Redox‐Active Tripodal Frameworks
Authors: Hsueh Fang‐Che , Chen Damien , Rajeshkumar Thayalan , Scopelliti Rosario , Maron Laurent , Mazzanti Marinella 
Published: December 2023

AbstractThe high stability of the + IVoxidation state limits thorium redox reactivity. Here we report the synthesis and the redox reactivity of two Th(IV) complexes supported by the arene‐tethered tris(siloxide) tripodal ligands [(KOSiR2Ar)3‐arene)]. The two‐electron reduction of these Th(IV) complexes generates the doubly reduced [KTh((OSi(OtBu)2Ar)3‐arene)(THF)2] (2OtBu) and [K(2.2.2‐cryptand)][Th((OSiPh2Ar)3‐arene)(THF)2](2Ph‐crypt) where the formal oxidation state of Th is +II. Structural and computational studies indicate that the reduction occurred at the arene anchor of the ligand. The robust tripodal frameworks store in the arene anchor two electrons that become available at the metal center for the two‐electron reduction of a broad range of substrates (N2O, COT, CHT, Ph2N2, Ph3PS and O2) while retaining the ligand framework. This work shows that arene‐tethered tris(siloxide) tripodal ligands allow implementation of two‐electron redox chemistry at the thorium center while retaining the ligand framework unchanged.
Precise Methylation Yields Acceptor with Hydrogen‐Bonding Network for High‐Efficiency and Thermally Stable Polymer Solar Cells
Authors: Wei Weifei , Zhang Cai'e , Chen Zhanxiang , Chen Wei , Ran Guangliu , Pan Guangjiu , Zhang Wenkai , Müller‐Buschbaum Peter , Bo Zhishan , Yang Chuluo , Luo Zhenghui 
Published: December 2023

AbstractUtilizing intermolecular hydrogen‐bonding interactions stands for an effective approach in advancing the efficiency and stability of small‐molecule acceptors (SMAs) for polymer solar cells. Herein, we synthesized three SMAs (Qo1, Qo2, and Qo3) using indeno[1,2‐b]quinoxalin‐11‐one (Qox) as the electron‐deficient group, with the incorporation of a methylation strategy. Through crystallographic analysis, it is observed that two Qox‐based methylated acceptors (Qo2 and Qo3) exhibit multiple hydrogen bond‐assisted 3D network transport structures, in contrast to the 2D transport structure observed in gem‐dichlorinated counterpart (Qo4). Notably, Qo2 exhibits multiple and stronger hydrogen‐bonding interactions compared with Qo3. Consequently, PM6 : Qo2 device realizes the highest power conversion efficiency (PCE) of 18.4 %, surpassing the efficiencies of devices based on Qo1 (15.8 %), Qo3 (16.7 %), and Qo4 (2.4 %). This remarkable PCE in PM6 : Qo2 device can be primarily ascribed to the enhanced donor‐acceptor miscibility, more favorable medium structure, and more efficient charge transfer and collection behavior. Moreover, the PM6 : Qo2 device demonstrates exceptional thermal stability, retaining 82.8 % of its initial PCE after undergoing annealing at 65 °C for 250 hours. Our research showcases that precise methylation, particularly targeting the formation of intermolecular hydrogen‐bonding interactions to tune crystal packing patterns, represents a promising strategy in the molecular design of efficient and stable SMAs.
Signal Amplification and Near‐Infrared Translation of Enzymatic Reactions by Nanosensors**
Authors: Metternich Justus T. , Hill Björn , Wartmann Janus A. C. , Ma Chen , Kruskop Rebecca M. , Neutsch Krisztian , Herbertz Svenja , Kruss Sebastian 
Published: December 2023

AbstractEnzymatic reactions are used to detect analytes in a range of biochemical methods. To measure the presence of an analyte, the enzyme is conjugated to a recognition unit and converts a substrate into a (colored) product that is detectable by visible (VIS) light. Thus, the lowest enzymatic turnover that can be detected sets a limit on sensitivity. Here, we report that substrates and products of horseradish peroxidase (HRP) and β‐galactosidase change the near‐infrared (NIR) fluorescence of (bio)polymer modified single‐walled carbon nanotubes (SWCNTs). They translate a VIS signal into a beneficial NIR signal. Moreover, the affinity of the nanosensors leads to a higher effective local concentration of the reactants. This causes a non‐linear sensor‐based signal amplification and translation (SENSAT). We find signal enhancement up to ≈120x for the HRP substrate p‐phenylenediamine (PPD), which means that reactions below the limit of detection in the VIS can be followed in the NIR (≈1000 nm). The approach is also applicable to other substrates such as 3,3′‐5,5′‐tetramethylbenzidine (TMB). An adsorption‐based theoretical model fits the observed signals and corroborates the sensor‐based enhancement mechanism. This approach can be used to amplify signals, translate them into the NIR and increase sensitivity of biochemical assays.
Asymmetric Synthesis of Chiral 1,2‐Bis(Boronic) Esters Featuring Acyclic, Non‐Adjacent 1,3‐Stereocenters
Authors: Jiang Xia‐Min , Ji Chong‐Lei , Ge Jian‐Fei , Zhao Jia‐Hui , Zhu Xin‐Yuan , Gao De‐Wei 
Published: December 2023

AbstractThe construction of acyclic, non‐adjacent 1,3‐stereogenic centers, prevalent motifs in drugs and bioactive molecules, has been a long‐standing synthetic challenge due to acyclic nucleophiles being distant from the chiral environment. In this study, we successfully synthesized highly valuable 1,2‐bis(boronic) esters featuring acyclic and nonadjacent 1,3‐stereocenters. Notably, this reaction selectively produces migratory coupling products rather than alternative deborylative allylation or direct allylation byproducts. This approach introduces a new activation mode for selective transformations of gem‐diborylmethane in asymmetric catalysis. Additionally, we found that other gem‐diborylalkanes, previously challenging due to steric hindrance, also successfully participated in this reaction. The incorporation of 1,2‐bis(boryl)alkenes facilitated the diversification of the alkenyl and two boron moieties in our target compounds, thereby enabling access to a broad array of versatile molecules. DFT calculations were performed to elucidate the reaction mechanism and shed light on the factors responsible for the observed excellent enantioselectivity and diastereoselectivity. These were determined to arise from ligand‐substrate steric repulsions in the syn‐addition transition state.
Non‐invasive and Sensitive Fluorescence Detection of Phenylpyruvic Acid via a Guanidinomethyl‐modified Calixarene
Authors: Wang Huan‐Yu , Hu Zong‐Ying , Tian Han‐Wen , Hu Xin‐Yue , Pan Yu‐Chen , Guo Dong‐Sheng 
Published: December 2023

AbstractDetection of phenylpyruvic acid (PPA) is important for the diagnosis of phenylketonuria (PKU). In this study, we designed a guanidinomethyl‐modified calix[5]arene that can strongly and selectively bind with PPA. Via indicator displacement assay, we set up a calibration line for accurately determining PPA concentration down to the μM range in artificial urine based on the linear relationship between the fluorescence intensity and PPA concentration. This work provides a low‐cost, easy‐to‐operate, rapid, and sensitive method for PPA detection, and may offer an alternative for PKU diagnosis in clinical study.
Poly[(2‐methacryloyloxy)Ethyl]Trimethylammonium Chloride Supported Cobalt Oxide Nanoparticles as an Active Electrocatalyst for Efficient Oxygen Evolution Reaction
Authors: Islam Santa , Abu Nayem S. M. , Sultana Nasrin , Shaheen Shah Syed , Awal Abdul , Anjum Ahtisham , Jafar Mazumder Mohammad A. , Nasiruzzaman Shaikh M. , Abdul Aziz Md. , Saleh Ahammad A. J. 
Published: December 2023

AbstractTo combat with energy crisis considering clean energy, oxygen evolution reaction (OER) is crucial to implement electrolytic hydrogen fuel production in real life. Here, straightforward chemical synthesis pathways are followed to prepare cobalt tetraoxide nanoparticles (Co3O4NPs) in an alkaline OER process using poly[(2‐methacryloyloxy)ethyl]trimethylammonium chloride (Co3O4NPs@PMTC) as support to prevent aggregation. In material characterization, the X‐ray diffraction (XRD) pattern confirms the crystallinity of the synthesized Co3O4NPs@PMTC, and Raman spectroscopy indicates that the Co3O4NPs contain cubic close‐packed oxides. The morphological analysis reveals the wrinkle‐like disruption which is distributed evenly owing to the folded nanosheet arrays. Energy‐dispersive X‐ray spectroscopy indicates the presence of a significant number of cobalt atoms in the Co3O4NPs, and elemental mapping analysis demonstrates the composition of the NPs. At a current density of 10 mA cm−2, oxygen is emitted at 1.67 V delivering an overpotential of 440 mV. This unique structure of Co3O4NPs@PMTC provides beneficial functions that are responsible for a large number of active sites and the rapid release of oxygen gas with long‐term stability. Through kinetic study, we found a Tafel slope of 48.9 mV dec−1 which proves the catalytic behavior of Co3O4NPs@PMTC is promising toward the OER process.
Modified Electrochemical Sensors for the Detection of Selected Food Azo Dyes: A Review
Authors: Cardenas‐Riojas Andy A. , Calderon‐Zavaleta Sandy L. , Quiroz‐Aguinaga Ulises , Muedas‐Taipe Golfer , Carhuayal‐Alvarez Saira M. , Ascencio‐Flores Yeshy F. , Ponce‐Vargas Miguel , Baena‐Moncada Angélica M. 
Published: December 2023

AbstractThere are plenty of evidence that consuming high levels of azo dyes, such as Tartrazine, Sunset Yellow, Allura Red, Ponceau 4R, Amaranth, Sudan, and Azorubine, is associated with serious health problems. Therefore, electrochemical sensors have been developed for their effective detection, also offering low cost, portability, and the fact that they do not require harmful solvents. They are customarily employed in several electrochemical techniques, including cyclic voltammetry, differential pulse voltammetry, and square wave voltammetry. The most commonly employed materials in the manufacturing of electrochemical sensors are carbonaceous materials given their high stability, surface area, and conductivity. Employing these carbonaceous materials results in an enhanced sensitivity of electrochemical sensors when detecting azo dyes. To further improve the sensors, these materials are modified with metal oxides, polymers, polysaccharide, ionic liquids, and metal nanoparticles, allowing the detection of ultra‐sensitive traces of azo dyes. Therefore, this review provides an overview of the characteristics of modified carbonaceous materials and their applications for the detection of food azo dyes, along with a summary of the currently employed electroanalytical detection methods. Additionally, this review discusses the development of novel nanomaterials and their technological advances, while exploring their potential environmental and health impacts within the food industry.
Defective Carbon for Next‐Generation Stationary Energy Storage Systems: Sodium‐Ion and Vanadium Flow Batteries
Authors: McArdle Sophie , Bauer Felix , Granieri Simone Fiorini , Ast Marius , Di Fonzo Fabio , Marshall Aaron T. , Radinger Hannes 
Published: December 2023

AbstractThis review examines the role of defective carbon‐based electrodes in sodium‐ion and vanadium flow batteries. Methods for introducing defects into carbon structures are explored and their effectiveness in improving electrode performance is demonstrated. In sodium‐based systems, research focuses primarily on various precursor materials and heteroatom doping to optimise hard carbon electrodes. Defect engineering increases interlayer spacing, porosity, and changes the surface chemistry, which improves sodium intercalation and reversible capacities. Heteroatom functionalisation and surface modification affect solid electrolyte interface formation and coulombic efficiencies. For flow batteries, post‐fabrication electrode enhancement methods produce defects to improve electrode kinetics, although these methods often introduce oxygen functional groups as well, making isolation of defect effects difficult. Continued research efforts are key to developing carbon‐based electrodes that can meet the unique challenges of future battery systems.
High Temperature Solid Oxide Electrolysis – Technology and Modeling
Authors: Mueller Marius , Klinsmann Markus , Sauter Ulrich , Njodzefon Jean-Claude , Weber André 
Published: December 2023

AbstractIn the global quest to renounce from fossil fuels, a large demand for the renewable production of hydrogen via water electrolysis exists. In this context, the solid oxide electrolyzer (SOE) is an interesting technology due to its high efficiency resulting from elevated operating temperatures of up to 900 °C. Physical modeling plays a vital role in the development of SOEs, as it lowers experimental costs and provides insight where measurements reach limits. A main challenge for modeling SOEs is the multitude of physical effects, occurring and interacting on various spatial and temporal scales. This requires assumptions and simplifications, particularly when increasing scope and dimensions of a model. In this review, we discuss the different approaches currently available in literature.