bluuebunny/crossref_metadata_2025_split huggingface dataset:
Highly Stable Co Single Atom Confined in Hierarchical Carbon Molecular Sieve as Efficient Electrocatalysts in Metal–Air Batteries
Authors: Liang Shuang , Zou Lian‐Chun , Zheng Li‐Jun , Li Fei , Wang Xiao‐Xue , Song Li‐Na , Xu Ji‐Jing 
Published: February 2022

AbstractSingle atoms catalysts’ (SACs) applications in the energy storage field are hindered by their insufficient stability and poor recyclability due to their oxidation and agglomeration. To address this challenge, herein, a Co‐CMS composite material is synthesized by confining Co SACs into the highly ordered pores of the carbon molecular sieve (CMS). Related theoretical and experimental methods prove that the microporous trapping and hydroxyl doping of CMS are favorable for synergistically stabilizing the precursor and contributing to the subsequent conversion of single atoms with strong interactions between Co, O, and N. The unique 3D spiral pore structure of CMS facilitates the mass transfer of reactants and the highly dispersed Co single atoms confined in CMS increase the active sites. These properties are ideal for oxygen reduction reaction catalysts. Benefiting from the above‐mentioned superiority, the Co‐CMS cathode exhibits superior performance in a rechargeable Zn–air battery with a lower charge–discharge voltage gap of 0.77 V and a power density of 219 mW cm−2. The applications of Co‐CMS catalysts are also extended to other metal–air batteries in this work, which further highlights the advantages of carbon molecular sieves in stabilizing SACs materials.
Oxidative Addition von C−F‐Bindungen an das Silanid‐Anion [Si(C2F5)3]−
Authors: Tiessen Natalia , Keßler Mira , Neumann Beate , Stammler Hans‐Georg , Hoge Berthold 
Published: February 2022

AbstractVerbindungen von Hauptgruppenelementen in niedrigen Oxidationsstufen sind in der Lage, die Reaktivität von Übergangsmetallkomplexen nachzuahmen. Wie Letztere neigen niedervalente Hauptgruppenelementverbindungen zur Änderung ihrer Oxidationsstufe und Koordinationszahl um +2, wodurch sie die wesentlichen Voraussetzungen für oxidative Additionen erfüllen. Prominente Beispiele für Hauptgruppenelementverbindungen, die mit Organohalogeniden R−X (R=Alkyl, Aryl, X=F, Cl, Br, I) oxidative Additionen eingehen, sind Carbene und ihre höheren Analoga. Kürzlich wurde auch über Aluminyl‐Anionen berichtet, die wie Carbene und Silylene starke σ‐Bindungen von R−X‐Spezies oxidativ addieren können. Hier stellen wir nun mit dem Tris(pentafluorethyl)silanid‐Anion, [Si(C2F5)3]−, das erste Anion aus der 14. Gruppe vor, welches C−F‐Bindungen im Sinne einer oxidativen Addition zu spalten vermag. Dies ermöglichte die Isolierung von nicht‐chelatierten Tetraorganofluorosilicat‐Salzen, die unseres Wissens bisher nur als reaktive Zwischenstufen nachgewiesen wurden.
Drastische Ereignisse und langsame Transformation definieren die Struktur eines aktiven Kupfer‐Zink‐Aluminiumoxid‐Katalysators für die Methanol Synthese
Authors: Beck Arik , Newton Mark A. , Zabilskiy Maxim , Rzepka Przemyslaw , Willinger Marc G. , van Bokhoven Jeroen A. 
Published: February 2022

AbstractDer Kupfer‐Zink‐Aluminiumoxid‐Katalysator (CZA) ist einer der wichtigsten industriellen Katalysatoren. Jedoch versteht man die komplexe CZA‐Struktur nur teilweise und das bremst seine Weiterentwicklung. Um einen sehr aktiven und stabilen Katalysator zu erzeugen sind optimale Aktivierungsbedingungen in Wasserstoff essentiell. In dieser Arbeit folgen wir mithilfe von operando Röntgenadsorptionspektroskopie und ‐diffraktion der Entwicklung eines industriellen CZA‐Katalysatorvorläufer zum arbeitenden Katalysator. Zwei Ereignisse während der Aktivierung führen zu drastischen Veränderung in den kupfer‐ und zinkhaltigen Komponenten des CZA‐Katalysators und bestimmen die Struktur des fertigen Katalysators: Erstens, die Reduktion des ursprünglichen Kupfer(II)oxids und, zweitens, das Kristallwachstum und Reoxidierung von Zinkoxid während des Wechsels zu katalytischen Bedingungen. Diese drastischen Ereignisse werden von anderen graduellen Transformationen begleitet. Um maßgeschneiderte Aktivierungsprotokolle, die die maximale Lebensdauer und Aktivität des Katalysators erzielen, zu entwickeln, müssen wir diesen Transformationen verstehen.
Access to a Labile Monomeric Magnesium Radical by Ball‐Milling
Authors: Jędrzkiewicz Dawid , Mai Jonathan , Langer Jens , Mathe Zachary , Patel Neha , DeBeer Serena , Harder Sjoerd 
Published: February 2022

AbstractIn order to isolate a monometallic Mg radical, the precursor (Am)MgI⋅(CAAC) (1) was prepared (Am=tBuC(N‐DIPP)2, DIPP=2,6‐diisopropylphenyl, CAAC=cyclic (alkyl)(amino)carbene). Reduction of a solution of 1 in toluene with the reducing agent K/KI led to formation of a deep purple complex that rapidly decomposed. Ball‐milling of 1 with K/KI gave the low‐valent MgI complex (Am)Mg⋅(CAAC) (2) which after rapid extraction with pentane and crystallization was isolated in 15 % yield. Although a benzene solution of 2 decomposes rapidly to give Mg(Am)2 (3) and unidentified products, the radical is stable in the solid state. Its crystal structure shows planar trigonal coordination at Mg. The extremely short Mg−C distance of 2.056(2) Å indicates strong Mg−CAAC bonding. Calculations and EPR measurements show that most of the spin density is in a π* orbital located at the C−N bond in CAAC, leading to significant C−N bond elongation. This is supported by calculated NPA charges in 2: Mg +1.73, CAAC −0.82. Similar metal‐to‐CAAC charge transfer was calculated for M0(CAAC)2 and [MI(CAAC)2+] (M=Be, Mg, Ca) complexes in which the metal charges range from +1.50 to +1.70. Although the spin density of the radical is mainly located at the CAAC ligand, complex 2 reacts as a low‐valent MgI complex: reaction with a I2 solution in toluene gave (Am)MgI⋅(CAAC) (1) as the major product.
A Highly Fluorescent Dinuclear Aluminium Complex with Near‐Unity Quantum Yield**
Authors: Portwich Flavio L. , Carstensen Yves , Dasgupta Anindita , Kupfer Stephan , Wyrwa Ralf , Görls Helmar , Eggeling Christian , Dietzek Benjamin , Gräfe Stefanie , Wächtler Maria , Kretschmer Robert 
Published: February 2022

AbstractThe high natural abundance of aluminium makes the respective fluorophores attractive for various optical applications, but photoluminescence quantum yields above 0.7 have yet not been reported for solutions of aluminium complexes. In this contribution, a dinuclear aluminium(III) complex featuring enhanced photoluminescence properties is described. Its facile one‐pot synthesis originates from a readily available precursor and trimethyl aluminium. In solution, the complex exhibits an unprecedented photoluminescence quantum yield near unity (Φabsolute 1.0±0.1) and an excited‐state lifetime of 2.3 ns. In the solid state, J‐aggregation and aggregation‐caused quenching are noted, but still quantum yields of 0.6 are observed. Embedding the complex in electrospun non‐woven fabrics yields a highly fluorescent fleece possessing a quantum yield of 0.9±0.04.
In Situ Hydrogen Evolution Monitoring During the Electrochemical Formation and Cycling of Pressed‐Plate Carbonyl Iron Electrodes in Alkaline Electrolyte
Authors: Weinrich Henning , Pleie Jan , Schmid Bernhard , Tempel Hermann , Kungl Hans , Eichel Rüdiger‐A. 
Published: February 2022

AbstractThe hydrogen evolution reaction (HER) on iron is a parasitic side reaction for the reduction of iron (hydr)oxide in alkaline electrolyte, which lowers the Coulombic efficiency of iron‐based batteries. Tackling this issue, here we investigate the HER on iron electrodes by in situ gas chromatography, allowing for a quantitative correlation of the applied electrode potential and the resulting hydrogen evolution. As a result, it is shown that the HER follows a distinctive profile corresponding to the electrode potential and changes depending on the state of the iron electrode formation. Moreover, it is shown that the charging efficiency of the iron electrode can be increased by an alteration of the charging procedure, i. e., a more negative cut‐off potential for the discharge and a potential limitation for the recharge. In this study, a charging efficiency of 96.7 % is achieved, using an optimized charging procedure for a formed carbonyl iron electrode containing 8.5 wt.% of Bi2S3.
Nucleic acids movement and its relation to genome dynamics of repetitive DNA
Authors: Kejnovsky Eduard , Jedlicka Pavel 
Published: February 2022

AbstractThere is growing evidence of evolutionary genome plasticity. The evolution of repetitive DNA elements, the major components of most eukaryotic genomes, involves the amplification of various classes of mobile genetic elements, the expansion of satellite DNA, the transfer of fragments or entire organellar genomes and may have connections with viruses. In addition to various repetitive DNA elements, a plethora of large and small RNAs migrate within and between cells during individual development as well as during evolution and contribute to changes of genome structure and function. Such migration of DNA and RNA molecules often results in horizontal gene transfer, thus shaping the whole genomic network of interconnected species. Here, we propose that a high evolutionary dynamism of repetitive genome components is often related to the migration/movement of DNA or RNA molecules. We speculate that the cytoplasm is probably an ideal compartment for such evolutionary experiments.
Involvement of the BDNF–TrkB–KCC2 pathway in neuropathic pain after brachial plexus avulsion
Authors: Zhao Shuo , Wang Fengyu , Wang Li , Xu Yali , Lv Li , Duan Wenxu , Bai Runze , Meng Zhao , Shao Xinzhong 
Published: February 2022

AbstractIntroductionBrachial plexus avulsion significantly increased brain‐derived neurotrophic factor (BDNF) release in the spinal cord. Here we investigated the involvement of the BDNF–TrkB–KCC2 pathway in neuropathic pain caused by BPA injury. We hypothesized that activation of BDNF–TrkB may inhibit neuronal excitability by downregulating KCC2 to maintain a high intracellular Cl‐concentration. We established a neuropathic pain rat model by avulsion of the lower trunk brachial plexus, and investigated the effects of the TrkB‐specific antibody K‐252a on the expression of BDNF, TrkB, and KCC2.MethodsWe randomly divided 40 male SD rats into four groups. In the brachial plexus avulsion group, C8‐T1 roots were avulsed from the spinal cord at the lower trunk level. In the K252a group, 5uL K252a was applied intrathecally daily for three days after avulsion. In the sham surgery group, expose only and without damage. The control group did not undergo any treatment. Mechanical hyperalgesia and cold allodynia were analyzed by electronic pain measuring instrument and acetone spray method at different time points on days 1, 3, 7, 10, 14, and 21 after surgery. At 21 days after surgery, the expression of BDNF and TrkB in dorsal horn neurons and GFAP in astrocytes were detected by immunohistochemistry at the C5‐T1 segment of the spinal cord. The expression levels of BDNF, TrkB, and KCC2 in the C5‐T1 spinal cord were measured by Western Blot at 7 and 21 days.ResultsMechanical hyperalgesia and cold allodynia were significantly reduced in the K252a group compared with the brachial plexus avulsion group. Compared with the BPA group, BDNF, TrkB and GFAP were significantly decreased in the K252a group at 21 days after treatment by immunohistochemical test. In the WB test, the expressions of BDNF and TrkB in the K252a group were quantitatively detected to be decreased, while the expression of KCC2 was increased, which was obvious at 7 and 21 days.ConclusionBDNF‐TrkB‐KCC2 pathway can significantly relieve neuropathic pain after BPA, and is a potential target for the treatment of neuropathic pain.
Dissemination of validated health literacy videos: A tailored approach
Authors: Blee Shannon M. , Facdol Jamil , Dixon Margie D. , Master Viraj , Switchenko Jeffrey M. , Pentz Rebecca D. 
Published: February 2022

AbstractBackgroundPreviously, we showed that chemotherapy terminology is difficult for patients to understand. Therefore, we developed short videos explaining key terminology and though proven effective, they will only be helpful if appropriately disseminated. Therefore, we aimed to determine the best dissemination method at three different healthcare settings.MethodsWith consent, we interviewed healthcare workers from (1) an academic cancer center, Winship Cancer Institute (Winship) serving higher SES patients, (2) an inner‐city, safety‐net hospital Grady Memorial (GMH), (3) clinics serving rural Georgia, from the Winship Community Network (Network). All interviews were transcribed and analyzed using a semantic content analysis method. Suggested dissemination plans were then implemented.ResultsTwenty‐two Winship, 11 GMH, and 4 Network healthcare workers were interviewed. Seventy‐two percent (n = 8) of the GMH and 100% (n = 4) of Network healthcare workers felt that the best place for patients to view the videos was in the clinic, compared to 27% (n = 6) of the Winship clinicians. 68% (n = 15) of the Winship clinicians stated an app would be the most useful format, compared to 27% (n = 3) at GMH, and 0% at Network sites. Video viewing increased after dissemination plans were implemented.CONCLUSIONEducational materials explaining oncology treatment terminology enhance patient understanding, yet without proper dissemination, these tools may never reach the intended patient population. Our study shows that dissemination plans need to be tailored to each individual patient population, with rural and lower SES patients needing to view the videos during clinic visits, and patients of more means viewing them using technology at home.
Primary mucoepidermoid carcinoma of the intrahepatic bile duct: A case report
Authors: Kato Kenichi , Hara Yasuyuki , Nishida Akiko , Suzuki Shuhei , Sato Hidenori , Chin Masahiro , Hashizume Eiji 
Published: February 2022

AbstractMucoepidermoid carcinoma (MEC) is the most common salivary gland carcinoma; however, hepatobiliary MEC is extremely rare. A 74‐year‐old patient was diagnosed with hepatobiliary MEC after hepatectomy. We considered its origin could be the peribiliary glands. Its genome profile was similar to salivary MEC rather than standard biliary tract carcinoma.
MELAS with multiple stroke‐like episodes due to the variant m.13513G>A in MT‐ND5
Authors: Ghosh Ritwik , Dubey Souvik , Bhuin Subhas , Lahiri Durjoy , Ray Biman Kanti , Finsterer Josef 
Published: February 2022

AbstractMitochondrial encephalopathy, lactic acidosis, and stroke‐like episodes (MELAS) is characterized by metabolic stroke, seizures, cognitive decline, lactic acidosis, ragged‐red fibers, headache, and vomiting, and in 80% of cases due to the mtDNA variant m.3243A>G. We report the case of a MELAS patient carrying a variant in subunit‐5 of the respiratory chain (MT‐ND5), rarely reported in MELAS. The patient is a 33‐year‐old male, who experienced a series of stroke‐like episodes (StLEs) since age 23 years, which manifested clinically as seizures transient sensory disturbances, weakness, and visual or cognitive impairment. Over 9 years, these StLEs were misinterpreted as ischemic strokes, respectively, as cerebral vasculitis. He presented with mild, recurrent elevations of the creatine kinase. Initially, anti‐seizure drugs and steroids appeared to be beneficial. Despite good recovery of each single StLE, the patient experienced a progressive decline of cognitive functions and activities of daily living. Cerebral imaging showed corresponding stroke‐like lesions in changing locations. At age 32y, genetic work‐up revealed the variant m.13513G>A in MT‐ND5. The patient profited significantly from a cocktail with anti‐oxidants/cofactors. This case shows that the variant m.13513G>A in MT‐ND5 can manifest as MELAS that StLEs recover spontaneously and that the course of MELAS is slowly progressive.
A Study on the Binary and Ternary CuZnAl Catalysts without Additives for Efficient CO Hydrogenation to Ethanol
Authors: Liu Jing , Fan Jinchuan , Li Fang , Gong Jie , Wang Sen , Yang Denghui , Huang Wei 
Published: February 2022

AbstractSynthesis of ethanol from syngas on CuZnAl catalyst without additives has attracted substantial interest. However, the active sites and the reaction mechanism are still not fully understood due to the complexity of the ternary system. Herein, a series of binary (CuZn, CuAl, ZnAl) and ternary CuZnAl catalysts were prepared using complete liquid method for CO hydrogenation to ethanol. The results show that CAT‐CZ and CAT‐ZA possess much higher ability for ethanol synthesis than CAT‐CA, which is attributed to the presence of the key species Zn and the strong interaction at the interface. In situ DRIFTS measurements reveal the intermediate species of each catalyst, indicating that there are different carbon chain growth paths in CAT‐CZ and CAT‐ZA. The desirable catalytic CO hydrogenation performance (10.87 % of CO conversion and 57.18 % proportion of ethanol in total alcohol) on CAT‐CZA can be attributed the existence of multiple mechanisms for the ethanol production process.
Tuning the C/N Ratio of C‐Rich Graphitic Carbon Nitride (g‐C3N4) Materials by the Melamine/Carboxylic Acid Adduct Route
Authors: Gashi Arianit , Parmentier Julien , Fioux Philippe , Marsalek Roman 
Published: February 2022

AbstractC‐rich graphitic carbonitride materials (CNx) with a large range of compositions have been prepared thanks to the self‐assembly, in different ratios, of melamine (M) and a panel of polycarboxylic acids (A) such as oxalic, tartaric and citric acid. The thermal conversion of the formed adducts (MAy), led to CNx phases, with x ranging from 0.66 to 1.4 (x=1.33 for g‐C3N4 for comparison). The properties of these materials were examined by different techniques (XRD, Raman spectroscopy, TEM, TGA, XPS and DRIFT). It appears that the increase in the C content is associated with the disappearance of the long‐range order of heptazine units and an increase in the sub‐nanometer carbon‐rich cluster size within the graphitic g‐C3N4 structure. This trend is followed by a significant increase in the interlayer spacing and a lower proportion of N=C−N bonds compared to C=C bonds. The thermal stability under an inert atmosphere of these phases and their UV‐Visible absorbance properties were also investigated.
Parasitic Light Absorption, Rate Laws and Heterojunctions in the Photocatalytic Oxidation of Arsenic(III) Using Composite TiO2/Fe2O3
Authors: Bullen Jay C. , Heiba Hany F. , Kafizas Andreas , Weiss Dominik J. 
Published: February 2022

AbstractComposite photocatalyst‐adsorbents such as TiO2/Fe2O3 are promising materials for the one‐step treatment of arsenite contaminated water. However, no previous study has investigated how coupling TiO2 with Fe2O3 influences the photocatalytic oxidation of arsenic(III). Herein, we develop new hybrid experiment/modelling approaches to study light absorption, charge carrier behaviour and changes in the rate law of the TiO2/Fe2O3 system, using UV‐Vis spectroscopy, transient absorption spectroscopy (TAS), and kinetic analysis. Whilst coupling TiO2 with Fe2O3 improves total arsenic removal by adsorption, oxidation rates significantly decrease (up to a factor of 60), primarily due to the parasitic absorption of light by Fe2O3 (88 % of photons at 368 nm) and secondly due to changes in the rate law from disguised zero‐order kinetics to first‐order kinetics. Charge transfer across this TiO2‐Fe2O3 heterojunction is not observed. Our study demonstrates the first application of a multi‐adsorbate surface complexation model (SCM) towards describing As(III) oxidation kinetics which, unlike Langmuir‐Hinshelwood kinetics, includes the competitive adsorption of As(V). We further highlight the importance of parasitic light absorption and catalyst fouling when designing heterogeneous photocatalysts for As(III) remediation.
Beamforming design with fully connected analog beamformer using deep learning
Authors: P. Jeyakumar , M. Tharanitaran N. , E. Malar , P. Muthuchidambaranathan 
Published: February 2022

SummaryBeamforming (BF) architecture, an emerging approach for large‐scale antenna arrays, is a key task for the next decade's communication systems. The proposed approach in millimeter wave transmission is a fully connected analog phase‐shifter‐based BF architecture with limited radio frequency chains and imperfect channel state information (CSI). Deep learning (DL) is a powerful method for channel estimation and signal identification in wireless communications. Hence, this research proposes a DL‐enabled beamforming neural network (BFNN) which can be programmed to optimize the beamformer to attain better spectral efficiency. Simulation findings reveal that the proposed BFNN achieves significant performance gain and high robustness to imperfect CSI. The proposed BFNN greatly decreases the computational complexity by 0.16 million floating point operations (FLOPs) over 0.26 million FLOPs by conventional BF algorithms.
An adult case of congenital duodenal diaphragm that was successfully treated by endoscopic resection using a grasping‐type scissor forceps
Authors: Fukuda Shin‐ichiro , Ichida Kaoru , Kitagawa Yusuke , Nakano Kayoko , Tomohito Chaen , Yoshimura Daisuke , Ochiai Toshiaki , Ihara Eikichi , Ogawa Yoshihiro 
Published: February 2022

AbstractCongenital duodenal diaphragm (CDD) is a rare disease that is usually diagnosed in the neonatal period; however, it is sometimes diagnosed later in the adult period. A 39‐year‐old woman was referred to our hospital due to tarry stool and anemia. Emergent esophagogastroduodenoscopy (EGD) revealed an obstructing membranous structure with a small orifice in the second portion of the duodenum, together with dilatation of the bulbar part. The membranous structure was accompanied by a Dieulafoy‐like vessel on the backside, which was considered to have caused tarry stool and anemia. The Dieulafoy‐like vessel was successfully treated by endoscopic hemostasis. Based on the computed tomographic gastrography and barium duodenography findings, it was diagnosed as CDD. Later, endoscopic resection of the diaphragm was conducted by an endoscopic submucosal dissection (ESD)‐based procedure, with the use of an electrosurgical grasping‐type scissor forceps (ClutchCutter [CC]). There were no procedure‐related complications. The definite diagnosis of CDD was made based on the observation of typical structures in a pathological examination. This is the first case report of adult CDD that was successfully treated by endoscopic resection using ESD‐based techniques with a CC.
The long and the short of it: Mechanisms of synchronous and compensatory dynamics across temporal scales
Authors: Shoemaker Lauren G. , Hallett Lauren M. , Zhao Lei , Reuman Daniel C. , Wang Shaopeng , Cottingham Kathryn L. , Hobbs Richard J. , Castorani Max C. N. , Downing Amy L. , Dudney Joan C. , Fey Samuel B. , Gherardi Laureano A. , Lany Nina , Portales‐Reyes Cristina , Rypel Andrew L. , Sheppard Lawrence W. , Walter Jonathan A. , Suding Katharine N. 
Published: February 2022

AbstractSynchronous dynamics (fluctuations that occur in unison) are universal phenomena with widespread implications for ecological stability. Synchronous dynamics can amplify the destabilizing effect of environmental variability on ecosystem functions such as productivity, whereas the inverse, compensatory dynamics, can stabilize function. Here we combine simulation and empirical analyses to elucidate mechanisms that underlie patterns of synchronous versus compensatory dynamics. In both simulated and empirical communities, we show that synchronous and compensatory dynamics are not mutually exclusive but instead can vary by timescale. Our simulations identify multiple mechanisms that can generate timescale‐specific patterns, including different environmental drivers, diverse life histories, dispersal, and non‐stationary dynamics. We find that traditional metrics for quantifying synchronous dynamics are often biased toward long‐term drivers and may miss the importance of short‐term drivers. Our findings indicate key mechanisms to consider when assessing synchronous versus compensatory dynamics and our approach provides a pathway for disentangling these dynamics in natural systems.