bluuebunny/crossref_metadata_2025_split huggingface dataset:
A human lower third molar from the Acheulean site of Cueva del Ángel (Lucena, Córdoba, Spain)
Authors: Bermúdez Francisco J. , Martínez de Pinillos Marina , Medina‐Lara Francisca , Barroso‐Medina Cecilia , Cabral‐Mesa Antonio L. , Santiago‐Pérez Antonio , Ortiz José Eugenio , Sánchez‐Palencia Yolanda , Saos Thibaud , Grégoire Sophie , Pois Véronique , Vialet Amélie , Monge Guadalupe , Moigne Anne‐Marie , Caparrós Miguel , de Torres Trinidad , Bermúdez de Castro José María , Barroso‐Ruiz Cecilio 
Published: December 2022

AbstractObjectivesTo present a new dental specimen that will provide additional evidence for a better understanding of early European Upper Pleistocene hominin morphological variability.Materials and MethodsWe described the morphology of this human right lower third molar at both the outer enamel surface and the enamel–dentine junction by means of micro‐computed tomography. In order to better understand hominin diversity, our morphological and metrical results were compared with those of other hominins obtained from published research. We provide a direct aspartic acid racemization dating of the molar.ResultsThe direct dating (104.3 ka) situates the molar within the Marine isotopic stage 5d. The crown dimensions are comparable to those of the Sima de los Huesos sample and modern humans. The combination of a continuous middle trigonid crest and a well‐developed anterior fovea lies within the range of morphological variation reported for Neanderthal lower molars. The distal portion of the molar has a prominent protostylid.DiscussionCrown and root morphology of this molar fits within the Neanderthal morphological pattern. However, both its dimensions and the absence of a hypoconulid tend to position this specimen away from contemporaneous Neanderthals and rather relate it more closely to some Middle Pleistocene populations.ConclusionsA new dental specimen is added to the Iberian Peninsula fossil record from the Marine isotopic stage 5, attesting to some degree of dental variability in the early Upper Pleistocene.
Contextualizing pandemics: Respiratory survivorship before, during, and after the 1918 influenza pandemic in Newfoundland
Authors: van Doren Taylor P. , Kelmelis Saige 
Published: December 2022

AbstractBackgroundResearch on the 1918 influenza pandemic often focuses exclusively on pandemic years, reducing the potential long‐term insights about the pandemic. It is critical to frame the 1918 pandemic within the underlying population dynamics, health, and sociocultural context to understand what factors contributed to pandemic mortality and survivorship, with respect to observed inequality, and consequences of the pandemic.Materials & MethodsIndividual death records and censuses from The Rooms Provincial Archives and Memorial University of Newfoundland Digital Archives for three major causes of death—influenza and pneumonia; tuberculosis; and pooled bronchitis, measles, and whooping cough—were collected for three periods in the early 20th century: pre‐pandemic (1909–11), pandemic (March 1918–Janaury 1919), and post‐pandemic (1933–1935). We calculated pooled age‐standardized mortality rates and changes in pre‐ to post‐pandemic mortality rates by region. We fit Kaplan–Meier and Cox proportional hazards models to each period, controlling for age, cause of death, and region.ResultsPandemic mortality was higher than that of pre‐ and post‐pandemic periods. Post‐pandemic mortality was significantly lower than pre‐pandemic mortality in all regions, except Western Newfoundland. Survival was lowest during the pandemic and increased significantly post‐pandemic (p < 0.0001), with no significant differences among regions during the pandemic (p = 0.32). Significant differences in survivorship in 1933–1935 were driven by increasing differences in survivorship for P&I among the regions more than other causes of death.DiscussionMyopic perspectives of pandemics can obscure our understanding of observed outcomes. Inequalities in respiratory disease mortality are evident in pre‐ and post‐pandemic periods, but these would have been missed in investigations of the pandemic period alone.
Quantitative Single‐Molecule Electrochemiluminescence Bioassay
Authors: Zhu Wenxin , Dong Jinrun , Ruan Guoxiang , Zhou Yuan , Feng Jiandong 
Published: December 2022

AbstractA single‐molecule electrochemiluminescence bioassay is developed here which allows imaging and direct quantification of single biomolecules. Imaging single biomolecules is realized by localizing the electrochemiluminescence events of the labeled molecules. Such an imaging system allows mapping the spatial distribution of biomolecules with electrochemiluminescence and contains quantitative single‐molecule insights. We further quantify biomolecules by spatiotemporally merging the repeated reactions at one molecule site and then counting the clustered molecules. The proposed single‐molecule electrochemiluminescence bioassay is used to detect carcinoembryonic antigen, showing a limit of detection of 67 attomole concentration which is 10 000 times better than conventional electrochemiluminescence bioassays. This spatial resolution and sensitivity enable single‐molecule electrochemiluminescence bioassay a new toolbox for both specific bioimaging and ultrasensitive quantitative analysis.
Bio‐Inspired Bimetallic Cooperativity Through a Hydrogen Bonding Spacer in CO2 Reduction
Authors: Zhang Chanjuan , Gotico Philipp , Guillot Regis , Dragoe Diana , Leibl Winfried , Halime Zakaria , Aukauloo Ally 
Published: December 2022

AbstractAt the core of carbon monoxide dehydrogenase (CODH) active site two metal ions together with hydrogen bonding scheme from amino acids orchestrate the interconversion between CO2 and CO. We have designed a molecular catalyst implementing a bimetallic iron complex with an embarked second coordination sphere with multi‐point hydrogen‐bonding interactions. We found that, when immobilized on carbon paper electrode, the dinuclear catalyst enhances up to four fold the heterogeneous CO2 reduction to CO in water with an improved selectivity and stability compared to the mononuclear analogue. Interestingly, quasi‐identical catalytic performances are obtained when one of the two iron centers was replaced by a redox inactive Zn metal, questioning the cooperative action of the two metals. Snapshots of X‐ray structures indicate that the two metalloporphyrin units tethered by a urea group is a good compromise between rigidity and flexibility to accommodate CO2 capture, activation, and reduction.
Kupferkatalysierte, hochgradig enantioselektive Addition eines Siliciumnukleophils an 3‐substituierte 2H‐Azirine unter Verwendung eines Si‐B‐Reagenzes
Authors: Zhao Zhi‐Yuan , Cui Ming , Irran Elisabeth , Oestreich Martin 
Published: December 2022

Abstract3‐Substituierte 2H‐Azirine können als gespannte cyclische Ketimine angesehen werden, und hochgradig enantioselektive Additionsreaktionen von Siliciumnukleophilen an acyclische und auch cyclische Ketimine sind bislang nicht erreicht worden. Die vorliegende Arbeit schließt diese Lücke für jene Azirine mit Hilfe einer kupferkatalysierten Silylierung unter Verwendung eines Silylboronsäureesters als ein latentes Siliciumnukleophil. Die daraus hervorgehenden C‐silylierten, ungeschützten (N−H) Aziridine werden in hohen Ausbeuten und mit hervorragenden Enantioselektivitäten erhalten und können danach ohne nennenswerten Verlust des Enantiomerenüberschusses in nützliche Verbindungen überführt werden.
Superlattice‐based Plasmonic Catalysis: Concentrating Light at the Nanoscale to Drive Efficient Nitrogen‐to‐Ammonia Fixation at Ambient Conditions
Authors: Boong Siew Kheng , Chong Carice , Lee Jinn‐Kye , Ang Zhi Zhong , Li Haitao , Lee Hiang Kwee 
Published: December 2022

AbstractPlasmonic catalysis promises green ammonia synthesis but is limited by the need for co‐catalysts and poor performances due to weak electromagnetic field enhancement. Here, we use two‐dimensional plasmonic superlattices with dense electromagnetic hotspots to boost ambient nitrogen‐to‐ammonia photoconversion without needing co‐catalyst. By organizing Ag octahedra into a square superlattice to concentrate light, the ammonia formation is enhanced by ≈15‐fold and 4‐fold over hexagonal superlattice and disorganized array, respectively. Our unique catalyst achieves superior ammonia formation rate and apparent quantum yield up to ≈15‐fold and ≈103‐fold, respectively, better than traditional designs. Mechanistic investigations reveal the abundance of intense plasmonic hotspots is crucial to promote hot electron generation and transfer for nitrogen reduction. Our work offers valuable insights to design electromagnetically hot plasmonic catalysts for diverse chemical and energy applications.
Strain‐Release Driven Epoxidation and Aziridination of Bicyclo[1.1.0]butanes via Palladium Catalyzed σ‐Bond Nucleopalladation
Authors: Wölfl Bernhard , Winter Nils , Li Jiajing , Noble Adam , Aggarwal Varinder K. 
Published: December 2022

AbstractThe development of preparative methods for the synthesis of four‐membered carbocycles is gaining increasing importance due to the widespread utility of cyclic compounds in medicinal chemistry. Herein, we report the development of a new methodology for the production of spirocyclic epoxides and aziridines containing a cyclobutane motif. In a two‐step one‐pot process, a bicyclo[1.1.0]butyl sulfoxide is lithiated and added to a ketone, aldehyde or imine, and the resulting intermediate is cross‐coupled with an aryl triflate through C−C σ‐bond alkoxy‐ or aminopalladation with concomitant epoxide or aziridine formation. After careful optimization, a remarkably efficient reaction was conceived that tolerated a broad variety of both aromatic and aliphatic substrates. Lastly, through several high yielding ring‐opening reactions, we demonstrated the excellent applicability of the products as modular building blocks for the introduction of three‐dimensional structures into target molecules.
Hydroxocobalamin to treat refractory vasoplegia following phaeochromocytoma resection in a child
Authors: Giustini A. J. , Rowe E. V. , Perez F. D. , Mihm F. G. 
Published: December 2022

SummaryPhaeochromocytomas and paragangliomas are rare neuroendocrine tumours that often secrete catecholamines, which can cause dramatic swings in blood pressure and end‐organ damage. During surgical resection of these tumours, antihypertensive drug infusions are often required, but after resection patients may become vasoplegic, in part due to cessation of catecholamine secretion by the tumour in the context of pre‐operative α1 adrenoceptor antagonism. Numerous medications have been used to treat vasoplegia in this setting, including noradrenaline, vasopressin and, more recently, angiotensin II. We report the case of a patient who experienced vasoplegia after phaeochromocytoma resection which was refractory to vasopressin and angiotensin II infusions but was successfully treated with high dose hydroxocobalamin.
Accelerated aging of 18 years rejuvenated polylactide bottles by fast scanning calorimetry
Authors: Vashchuk Alina , Missaoui Tasnim , Delpouve Nicolas , Dargent Eric 
Published: December 2022

AbstractThis study focuses on the accelerated physical aging kinetics of rejuvenated polylactide (PLA) that has previously been processed and stored during 18 years under ambient conditions. The finish of a conditioned PLA bottle is subjected to structural relaxation for times varying between 0.001 and 1000.0 min at 45°C, that is, 15°C below its calorimetric glass transition temperature. The recovery of in‐situ aged PLA is monitored by fast scanning calorimetry and it is observed that the thermodynamic equilibrium is reached within the experimental aging time. Moreover, the time evolution of the enthalpy of recovery finds consistency with results obtained for PLA granules which did not undergo additional processing neither prolonged storage nor service life conditions. Thus, it is deduced that both processing and storage do not induce major degradation reactions that could affect the aging kinetics. Therefore, the behavior of a structurally rejuvenated amorphous PLA is depicted through the one of an unaged PLA.
Synergy of MoO2with Pt as Unilateral Dual Cocatalyst for Improving Photocatalytic Hydrogen Evolution over g‐C3N4
Authors: Su Fengyun , Wang Zhishuai , Tian Mengzhen , Yang Chunxia , Xie Haiquan , Ding Chenghua , Jin Xiaoli , Chen Jiaqi , Ye Liqun 
Published: December 2022

AbstractPt is usually used as cocatalyst for g‐C3N4to produce H2by photocatalytic splitting of water. However, the photocatalytic performance is still limited by the fast recombination of photo‐generated electrons and holes, as well as the poor absorption of visible light. In this work, MoO2/g‐C3N4composites were prepared, in which MoO2synergetic with Pt photo‐deposited during H2evolution reaction worked as unilateral dual cocatalyst to improve the photocatalytic activity. Within 4 hours of irradiation, the hydrogen production rate of MoO2‐Pt dual cocatalyst modified g‐C3N4reached 3804.89 μmol/g/h, which was 120.18 times of that of pure g‐C3N4(GCN, 31.66 μmol/g/h), 10.98 times of that of MoO2modified g‐C3N4(346.39 μmol/g/h), and 9.18 times of that of Pt modified g‐C3N4(413.64 μmol/g/h). Characterization results demonstrate that the deficient MoO2not only promoted visible light absorption of g‐C3N4, but also worked as a “electron pool” to capture and transfer electrons to Pt.
Room‐Temperature ZnBr2‐Catalyzed Regioselective 1,6‐Hydroarylation of Electron‐Rich Arenes to para‐Quinone Methides: Synthesis of Unsymmetrical Triarylmethanes
Authors: Xiong Biquan , Si Lulu , Zhu Longzhi , Wu Rong , Liu Yu , Xu Weifeng , Zhang Fan , Tang Ke‐Wen , Wong Wai‐Yeung 
Published: December 2022

AbstractA mild and efficient Zn(II)‐catalyzed regioselective 1,6‐hydroarylation of para‐quinone methides (p‐QMs) with electron‐rich arenes protocol is reported. A variety of electron‐rich arenes and para‐quinone methides are well tolerated under mild conditions, delivering a broad range of triarylmethanes in good to excellent yields. The present method also works well for the hydroarylation of p‐QMs with other nucleophiles, such as aniline, indole and phenol derivatives, offering the corresponding triarylmethanes with good yields under the standard conditions. The possible mechanism for the formation of C(sp3)−C(sp2) bonds in hydroarylation reactions has been explored by step‐by‐step control experiments, and the reaction may follow a second‐order manner in a chemical kinetic study.
Allograft rejection following immune checkpoint inhibitors in solid organ transplant recipients: A safety analysis from a literature review and a pharmacovigilance system
Authors: Cui Xiangli , Yan Cilin , Xu Ye , Li Dandan , Guo Mingxing , Sun Liying , Zhu Zhijun 
Published: December 2022

AbstractAimThis study aimed to systematically characterize transplant rejection after immune checkpoint inhibitors (ICIs) initiation in solid organ transplant recipients (SOTRs).MethodsData were extracted from the US FDA Adverse Event Reporting System (FAERS) database and case reports in the literature. Disproportionality analysis including information component and reported odds ratio (ROR) was performed to access potential risk signals.ResultsA total of 168 patients with transplant rejection after ICIs usage were identified in the FAERS database, and 89 cases were identified in the literature review. ICIs were significantly associated with transplant rejection (ROR025: 2.2). A strong risk signal was found for combination therapy with pembrolizumab and ipilimumab compared to monotherapy.ConclusionImmune checkpoint inhibitors were significantly associated with transplant rejection in SOTRs.
Autosomal recessive cutis laxa type Ib—Successful redo aortic root and arch replacement
Authors: Pees Christiane , Zimpfer Daniel , Radakovic Sonja , Beitzke Dietrich , Michel‐Behnke Ina , Laccone Franco A. 
Published: December 2022

AbstractWe present an adolescent girl with a highly stenotic ascending aortic conduit of her former during infancy corrected giant aneurysm. Genetic testing determined autosomal recessive cutis laxa type‐Ib as the underlying connective tissue disorder. Re‐do valve sparing root and arch replacement gained excellent restoration of the aorta; 1‐year‐follow‐up was uneventful.
A laser‐assisted endoscopic approach to pyriform sinus fistula via fibrin glue cauterization
Authors: Momii Manami , Kawano Toshiaki , Takakura Sonoka , Hirano Takashi , Tateyama Kaori , Suzuki Masashi 
Published: December 2022

AbstractIn the past, the general treatment method for pyriform sinus fistula was its removal by open surgery; however, in recent years, endoscopic surgery has become more common. We report two cases where laser surgery was performed using an endoscope and recurrence was prevented using fibrin glue. Both cases involved 3‐year‐old girls who underwent laser ablation of a pyriform sinus fistula under an endoscope, after which the site was closed with fibrin glue. No recurrence was observed in either case, and the postoperative course was uneventful. This approach is presented as a non‐invasive and effective treatment for pyriform sinus fistula.
Pituitary metastasis as the first manifestation of lung carcinoma
Authors: Amaral Sara , Matias Alexandra , Bouça Bruno , Manique Inês , Palha Ana , Cortez Luísa , Cerqueira Luís , Forte Dalila , Sagarribay Amets , Dutra Eduardo , Cristóvão Miguel , Pontinha Carlos , Mafra Manuela , Silva‐Nunes José 
Published: December 2022

AbstractPituitary metastases are rare. Clinical presentation could range from asymptomatic to panhypopituitarism or local symptoms. We present a case report of a 43‐year‐old male patient with a new onset headache, visual disturbances, and panhypopituitarism. The investigation led to the diagnosis of pituitary metastasis as the first manifestation of underlying lung cancer.
First‐Principles Investigation of Charged Germagraphene as a Cathode Material for Dual‐Carbon Batteries
Authors: Yilmaz Burcu , Otani Minoru , Ishihara Tatsumi , Akbay Taner 
Published: December 2022

AbstractAs part of the concerted effort for development of energy storage technologies, dual‐ion batteries (DIBs) or dual‐carbon batteries (DCBs) are attracting interest, owing primarily to their eco‐friendly active materials. The use of carbon as the active materials of DCBs brings about several challenges involving capacity and stability. This contribution aims to provide an in‐depth understanding of the structural and electronic properties of Ge‐doped graphene (Germagraphene) as a novel cathode material for DCBs. Density functional theory (DFT) calculations are combined with the effective screening medium (ESM) method for analyzing the electronic and band structure of PF6−anion‐adsorbed Germagraphene under a potential bias. These theoretical investigations indicate that the use of Ge as a dopant for graphene has a positive impact on the adsorption of the anion on the cathode under both neutral and electrically biased conditions.
Probing the Kinetic Origin of Varying Oxidative Stability of Ethyl‐ vs. Propyl‐spaced Amines for Direct Air Capture
Authors: Li Sichi , Cerón Maira R. , Eshelman Hannah V. , Varni Anthony J. , Maiti Amitesh , Akhade Sneha , Pang Simon H. 
Published: December 2022

AbstractAmine‐based adsorbents are promising for direct air capture of CO2, yet oxidative degradation remains a key unmitigated risk hindering wide‐scale deployment. Borrowing wisdom from the basic auto‐oxidation scheme, insights are gained into the underlying degradation mechanisms of polyamines by quantum chemical, advanced sampling simulations, adsorbent synthesis, and accelerated degradation experiments. The reaction kinetics of polyamines are contrasted with that of typical aliphatic polymers and they elucidate for the first time the critical role of aminoalkyl hydroperoxide decomposition in the oxidative degradation of amino‐oligomers. The experimentally observed variation in oxidative stability of polyamines with different backbone structures is explained by the relationship between the local chemical structure and the free energy barrier of aminoalkyl hydroperoxide decomposition, suggesting that its energetics can be used as a descriptor to screen and design new polyamines with improved stability. The developed computational capability sheds light on radical‐induced degradation chemistry of other organic functional materials.
Tailored Solvation and Interface Structures by Tetrahydrofuran‐Derived Electrolyte Facilitates Ultralow Temperature Lithium Metal Battery Operations
Authors: Kim Soohwan , Pol Vilas G. 
Published: December 2022

AbstractIneffectiveness of Li‐ion batteries (LIBs) in cold climates hinders electronics to work in various conditions including frigid environments, despite high demands. Given that intrinsic properties of LIB materials cause this problem, optimized cell chemistries ultimately are required for low‐temperature usage. In this study, Li‐metal batteries (LMBs) composed of a Li‐metal anode (LMA) stabilized by a localized high‐concentration electrolyte (LHCE) are found to significantly enhance low‐temperature performance. The LHCE allows the LMA to have compact and regular deposition and excellent plating/stripping efficiency at sub‐zero temperatures. The LHCE produces an inorganic‐rich solid‐electrolyte interphase with larger amounts of Li2O/LiF interfaces, dominance of ion aggregates in Li+solvation, and enhanced Li+transport, which can greatly improve the LMA stability. LMB full cells based on LiNi0.8Co0.1Mn0.1O2cathodes with the tailored electrolyte show high retentions of 75 and 64 % at −20 and −40 °C, respectively. Furthermore, the LMB configuration retains its charge−discharge capability even at −60 °C.
In‐silico generation of high‐dimensional immune response data in patients using a deep neural network
Authors: Fallahzadeh Ramin , Bidoki Neda H. , Stelzer Ina A. , Becker Martin , Marić Ivana , Chang Alan L. , Culos Anthony , Phongpreecha Thanaphong , Xenochristou Maria , De Francesco Davide , Espinosa Camilo , Berson Eloise , Verdonk Franck , Angst Martin S. , Gaudilliere Brice , Aghaeepour Nima 
Published: December 2022

AbstractTechnologies for single‐cell profiling of the immune system have enabled researchers to extract rich interconnected networks of cellular abundance, phenotypical and functional cellular parameters. These studies can power machine learning approaches to understand the role of the immune system in various diseases. However, the performance of these approaches and the generalizability of the findings have been hindered by limited cohort sizes in translational studies, partially due to logistical demands and costs associated with longitudinal data collection in sufficiently large patient cohorts. An evolving challenge is the requirement for ever‐increasing cohort sizes as the dimensionality of datasets grows. We propose a deep learning model derived from a novel pipeline of optimal temporal cell matching and overcomplete autoencoders that uses data from a small subset of patients to learn to forecast an entire patient's immune response in a high dimensional space from one timepoint to another. In our analysis of 1.08 million cells from patients pre‐ and post‐surgical intervention, we demonstrate that the generated patient‐specific data are qualitatively and quantitatively similar to real patient data by demonstrating fidelity, diversity, and usefulness.