bluuebunny/crossref_metadata_2025_split huggingface dataset:
Exploring Self‐Healing Liquid Na–K Alloy for Dendrite‐Free Electrochemical Energy Storage
Authors: Zhang Liyuan , Xia Xinhui , Zhong Yu , Xie Dong , Liu Sufu , Wang Xiuli , Tu Jiangping 
Published: October 2018

AbstractThe development of high‐performance dendrite‐free liquid‐metal anodes at room temperature is of great importance for the advancement of alkali metal batteries. Herein an intriguing self‐healing liquid dendrite‐free Na–K alloy, fabricated by a facile room‐temperature alloying process, aiming for application in potassium‐ion batteries is reported. Through extensive investigation, its self‐healing characteristics are rooted upon a thin solid K2O layer (KOL) coated on the liquid Na–K alloy. The KOL not only acts as a protective layer to prevent the Na–K alloy from making contact with the electrolyte, but also greatly improves the wetting capability and adhesion between the liquid alloy and the carbon matrix (e.g., carbon fiber cloth (CFC)) to form a stable interface. Consequently, the as‐prepared CFC/KOL@Na–K alloy anode exhibits prominent electrochemical performance with smaller hysteresis (less than 0.3 V beyond 140 cycles at 0.4 mA cm−2), better capacity retention, and higher Coulombic efficiency than the CFC/bare Na–K alloy counterpart. When coupled with a potassium Prussian blue (PPB) cathode, the full cell manifests higher capability retention and improved cycling stability. This research deepens the understanding of self‐healing Na–K alloys and opens a new way to achieve high‐performance dendrite‐free alkali metal anodes for application in rechargeable batteries.
Unveiling the Roles of Formation Process in Improving Cycling Performance of Magnesium Stannide Composite Anode for Magnesium‐Ion Batteries
Authors: Nguyen Giang Thi Huong , Nguyen Dan‐Thien , Song Seung‐Wan 
Published: October 2018

AbstractThe combination of Mg2+‐insertion type anodes with various Mg‐free cathode counterparts and electrolytes enables Mg‐ion batteries. Microsized magnesium stannide (Mg2Sn) active material for a potential Mg2+‐insertion anode has shown extremely low capacity and low Coulombic efficiency in the early cycles, due to not yet a full participation of active material and an irreversible capacity loss by anode–electrolyte interfacial reactions. An activation process, i.e., formation cycle, is necessary to mitigate those issues and to improve the cycling performance. Herein, the application of formation process to the Mg2Sn composite anode that includes graphite as an electrochemically inactive but electronically conductive component, the condition optimization of formation process, and the systematic studies of the effects of formation process on the cycling performance and anode–electrolyte interfacial reactions are reported. A basic understanding of the early cycling behavior and interfacial phenomena of Mg2Sn anode is provided, which gives insight into improvement of performance of alloy anodes in Mg‐ion batteries.
Synergistic Cu/Pd Catalysis for Enantioselective Allylation of Ketimine Esters: The Direct Synthesis of α‐Substituted α‐Amino Acids and 2H‐Pyrrols
Authors: Wei Liang , Xiao Lu , Wang Chun‐Jiang 
Published: October 2018

AbstractAn efficient synergistic Cu/Pd catalyzed enantioselective α‐allylation of acyclic ketimine esters has been reported, which provides an entry to nonproteinogenic α‐allyl α‐amino acids in high yield, exclusive regioselectivity, and excellent enantioselectivity. Moreover, the more challenging cyclic ketimine ester could also be employed as a nucleophile for the construction of 3,4‐dihydro‐2H‐pyrrole derivatives bearing a quaternary stereogenic center using the same catalytic system.magnified image
Rh‐Catalyzed Hydrogenation of CO2 to Formic Acid in DMSO‐based Reaction Media: Solved and Unsolved Challenges for Process Development
Authors: Jens Christian M. , Scott Martin , Liebergesell Bastian , Westhues Christian G. , Schäfer Pascal , Franciò Giancarlo , Leonhard Kai , Leitner Walter , Bardow André 
Published: October 2018

AbstractProcess concepts have been conceived and evaluated for the amine‐free homogeneous catalyzed hydrogenation of CO2 to formic acid (FA). Base‐free DMSO‐mediated production of FA has been shown to avoid the formation of stable intermediates and presumably the energy‐intensive FA recovery strategies. Here, we address the challenges in the development of an overall process: from catalyst immobilization to the FA isolation. The immobilization of the homogeneous catalyst was achieved using a multiphasic approach (n‐heptane/DMSO) ensuring high retention of the catalyst (>99%) and allowing facile separation of the catalyst‐free product phase. We show that the strong molecular interactions between DMSO and FA on the one hand shift the equilibrium towards the product side, on the other hand, lead to the formation of an azeotrope preventing a simple isolation step by distillation. Thus, we devised an isolation strategy based on the use of co‐solvents and computed the energy demands. Acetic acid was identified as best co‐solvent and its compatibility with the catalyst system was experimentally verified. Overall, the outlined process involving DMSO and acetic acid as co‐solvent has a computed energy demand on a par with state‐of‐the art amine‐based processes. However, the insufficient chemical stability of DMSO poses major limitations on processes based on this solvent.magnified image
Graphdiyne: Recent Achievements in Photo‐ and Electrochemical Conversion
Authors: Zhao Yasong , Tang Hongjie , Yang Nailiang , Wang Dan 
Published: October 2018

AbstractAs a rising star of carbon allotropes, graphynes (GYs) merely consist of sp‐ and sp2‐hybridized carbon atoms, which endow them a large conjugated network and expanded 2D porous structure. With unique topological structure, GYs display unusual semiconducting properties, especially in the aspects of charge mobility and electron transport. Among the members of the GY family, only graphdiyne (GD) can be successfully synthesized in large quantities. The advanced properties of GD make it promising in various applications. Here, the recent progress in the synthesis of GD and GD‐based composites is reviewed as well as their applications in photorelated and electrocatalytic applications. It is hoped that this Review will promote the development and applications of carbon chemistry.
Flash‐Induced Stretchable Cu Conductor via Multiscale‐Interfacial Couplings
Authors: Park Jung Hwan , Seo Jeongmin , Kim Cheolgyu , Joe Daniel J. , Lee Han Eol , Im Tae Hong , Seok Jae Young , Jeong Chang Kyu , Ma Boo Soo , Park Hyung Kun , Kim Taek‐Soo , Lee Keon Jae 
Published: October 2018

AbstractHerein, a novel stretchable Cu conductor with excellent conductivity and stretchability is reported via the flash‐induced multiscale tuning of Cu and an elastomer interface. Microscale randomly wrinkled Cu (amplitude of ≈5 µm and wavelength of ≈45 µm) is formed on a polymer substrate through a single pulse of a millisecond flash light, enabling the elongation of Cu to exceed 20% regardless of the stretching direction. The nanoscale interlocked interface between the Cu nanoparticles (NPs) and the elastomer increases the adhesion force of Cu, which contributes to a significant improvement of the Cu stability and stretchability under harsh yielding stress. Simultaneously, the flash‐induced photoreduction of CuO NPs and subsequent Cu NP welding lead to outstanding conductivity (≈37 kS cm−1) of the buckled elastic electrode. The 3D structure of randomly wrinkled Cu is modeled by finite element analysis simulations to show that the flash‐activated stretchable Cu conductors can endure strain over 20% in all directions. Finally, the wrinkled Cu is utilized for wireless near‐field communication on the skin of human wrist.
New Generation Hole Transporting Materials for Perovskite Solar Cells: Amide‐Based Small‐Molecules with Nonconjugated Backbones
Authors: Petrus Michiel L. , Schutt Kelly , Sirtl Maximilian T. , Hutter Eline M. , Closs Anna C. , Ball James M. , Bijleveld Johan C. , Petrozza Annamaria , Bein Thomas , Dingemans Theo J. , Savenije Tom J. , Snaith Henry , Docampo Pablo 
Published: October 2018

AbstractState‐of‐the‐art perovskite‐based solar cells employ expensive, organic hole transporting materials (HTMs) such as Spiro‐OMeTAD that, in turn, limits the commercialization of this promising technology. Herein an HTM (EDOT‐Amide‐TPA) is reported in which a functional amide‐based backbone is introduced, which allows this material to be synthesized in a simple condensation reaction with an estimated cost of <$5 g−1. When employed in perovskite solar cells, EDOT‐Amide‐TPA demonstrates stabilized power conversion efficiencies up to 20.0% and reproducibly outperforms Spiro‐OMeTAD in direct comparisons. Time resolved microwave conductivity measurements indicate that the observed improvement originates from a faster hole injection rate from the perovskite to EDOT‐Amide‐TPA. Additionally, the devices exhibit an improved lifetime, which is assigned to the coordination of the amide bond to the Li‐additive, offering a novel strategy to hamper the migration of additives. It is shown that, despite the lack of a conjugated backbone, the amide‐based HTM can outperform state‐of‐the‐art HTMs at a fraction of the cost, thereby providing a novel set of design strategies to develop new, low‐cost HTMs.
Organic Semiconductor Based Devices for Solar Water Splitting
Authors: Yao Liang , Rahmanudin Aiman , Guijarro Néstor , Sivula Kevin 
Published: October 2018

AbstractSolution processable organic semiconductors are well‐established as high‐performance materials for inexpensive and scalable solar energy conversion in organic photovoltaic (OPV) devices, but their promise in the economic conversion of solar energy into chemical energy (solar fuels) has only recently been recognized. Herein, the main approaches employing organic semiconductor‐based devices toward solar H2 generation via water splitting are compared and performance demonstrations are reviewed. OPV‐biased water electrolysis is seen to advance significantly with the development of the tandem OPV device and the optimization of operating potential and redox catalysts. This approach now exceeds 6% solar‐to‐hydrogen conversion efficiency while over 10% is reasonably feasible. By contrast, while the direct water splitting by an organic semiconductor in a photo‐electrochemical cell has attractive advantages, increasing the performance remains a challenge. Photocathodes employing a bulk‐heterojunction have been optimized to give 7–8 mA cm−2 water reduction photocurrent under standard conditions, but photoanodes remain <1 mA cm−2, and robustness remains a critical issue. However, recent investigations into the direct organic semiconductor/electrolyte interface have brought important insights into free charge generation, the nature of the semiconductor/catalyst interface, and the stability of organic photoelectrodes. Outlooks toward advancing both approaches are discussed.
Point‐of‐care screening for sickle cell disease in low‐resource settings: A multi‐center evaluation of HemoTypeSC, a novel rapid test
Authors: Steele Cindy , Sinski Annette , Asibey Jacqueline , Hardy‐Dessources Marie‐Dominique , Elana Gisèle , Brennan Colleen , Odame Isaac , Hoppe Carolyn , Geisberg Mark , Serrao Erik , Quinn Charles T. 
Published: October 2018

AbstractSickle cell disease (SCD) is a common, life‐threatening genetic disorder that is best managed when diagnosed early by newborn screening. However, SCD is most prevalent in low‐resource regions of the world where newborn screening is rare and diagnosis at the point‐of‐care is challenging. In many such regions, the majority of affected children die, undiagnosed, before the age of 5 years. A rapid and affordable point‐of‐care test for SCD is needed. The diagnostic accuracy of HemoTypeSC, a point‐of‐care immunoassay, for SCD was evaluated in individuals who had SCD, hemoglobin C disease, the related carrier (trait) states, or a normal hemoglobin phenotype. Children and adults participated in low‐, medium‐ and high‐resource environments (Ghana [n = 383], Martinique [n = 46], and USA [n = 158]). Paired blood specimens were obtained for HemoTypeSC and a reference diagnostic assay. HemoTypeSC testing was performed at the site of blood collection, and the reference test was performed in a laboratory at each site. In 587 participants, across all study sites, HemoTypeSC had an overall sensitivity of 99.5% and specificity of 99.9% across all hemoglobin phenotypes. The test had 100% sensitivity and specificity for sickle cell anemia. Sensitivity and specificity for detection of normal and trait states were >99%. HemoTypeSC is an inexpensive (<$2 per test), accurate, and rapid point‐of‐care test that can be used in resource‐limited regions with a high prevalence of SCD to provide timely diagnosis and support newborn screening programs.
Synthesis of ArSe‐Substituted Aniline Derivatives by C(sp2)‐H Functionalization
Authors: Ren Yaokun , Xu Baojun , Zhong Zijian , Pittman Charles U. , Zhou Aihua 
Published: October 2018

AbstractC−Se is an important bond in organic chemistry and organoselenium derivatives are associated with various biological, pharmaceutical, and material applications. Here, two synthetic methods to construct ArSe‐substituted aniline analogs using KSeCN or selenium powder as selenium sources with aromatic halides or arylboronic acid as reactants by C(sp2)‐H functionalization were developed. These two types of reactions proceeded with high efficiency and broad functional group tolerance, giving ArSe‐substituted anilines in good yields. These two new methods enrich existing C−Se construction methods.
Fingolimod enhances the efficacy of delayed alteplase administration in acute ischemic stroke by promoting anterograde reperfusion and retrograde collateral flow
Authors: Tian De‐Cai , Shi Kaibin , Zhu Zilong , Yao Jia , Yang Xiaoxia , Su Lei , Zhang Sheng , Zhang Meixia , Gonzales Rayna J. , Liu Qiang , Huang DeRen , Waters Michael F. , Sheth Kevin N. , Ducruet Andrew F. , Fu Ying , Lou Min , Shi Fu‐Dong 
Published: October 2018

ObjectiveThe present study was undertaken to determine the efficacy of coadministration of fingolimod with alteplase in acute ischemic stroke patients in a delayed time window.MethodsThis was a prospective, randomized, open‐label, blinded endpoint clinical trial, enrolling patients with internal carotid artery or middle cerebral artery proximal occlusion within 4.5 to 6 hours from symptom onset. Patients were randomly assigned to receive alteplase alone or alteplase with fingolimod. All patients underwent pretreatment and 24‐hour noncontrast computed tomography (CT)/perfusion CT/CT angiography. The coprimary endpoints were the decrease of National Institutes of Health Stroke Scale scores over 24 hours and the favorable shift of modified Rankin Scale score (mRS) distribution at day 90. Exploratory outcomes included vessel recanalization, anterograde reperfusion, and retrograde reperfusion of collateral flow.ResultsEach treatment group included 23 patients. Compared with alteplase alone, patients receiving fingolimod plus alteplase exhibited better early clinical improvement at 24 hours and a favorable shift of mRS distribution at day 90. In addition, patients who received fingolimod and alteplase exhibited a greater reduction in the perfusion lesion accompanied by suppressed infarct growth by 24 hours. Fingolimod in conjunction with alteplase significantly improved anterograde reperfusion of downstream territory and prevented the failure of retrograde reperfusion from collateral circulation.InterpretationFingolimod may enhance the efficacy of alteplase administration in the 4.5‐ to 6‐hour time window in patients with a proximal cerebral arterial occlusion and salvageable penumbral tissue by promoting both anterograde reperfusion and retrograde collateral flow. These findings are instructive for the design of future trials of recanalization therapies in extended time windows. Ann Neurol 2018;84:725–736
A Single Extracellular Vesicle (EV) Flow Cytometry Approach to Reveal EV Heterogeneity
Authors: Shen Wen , Guo Kaizhu , Adkins Gary Brent , Jiang Qiaoshi , Liu Yang , Sedano Sabrina , Duan Yaokai , Yan Wei , Wang Shizhen Emily , Bergersen Kristina , Worth Danielle , Wilson Emma H. , Zhong Wenwan 
Published: October 2018

AbstractExtracellular vesicles (EVs) actively participate in intercellular communication and pathological processes. Studying the molecular signatures of EVs is key to reveal their biological functions and clinical values, which, however, is greatly hindered by their sub‐100 nm dimensions, the low quantities of biomolecules each EV carries, and the large population heterogeneity. Now, single‐EV flow cytometry analysis is introduced to realize single EV counting and phenotyping in a conventional flow cytometer for the first time, enabled by target‐initiated engineering (TIE) of DNA nanostructures on each EV. By illuminating multiple markers on single EVs, statistically significant differences are revealed among the molecular signatures of EVs originating from several breast cancer cell lines, and the cancer cell‐derived EVs among the heterogeneous EV populations are successfully recognized. Thus, our approach holds great potential for various biological and biomedical applications.
Alkyl‐C‐C‐Bindungsbildung durch Nickel/Photoredox‐Kreuzkupplung
Authors: Milligan John A. , Phelan James P. , Badir Shorouk O. , Molander Gary A. 
Published: October 2018

AbstractDie Verbindung von Photoredox‐ und Nickel‐Katalyse führte zu einer Renaissance in der Radikalchemie und bei nickelkatalysierten Umsetzungen, insbesondere für die Kohlenstoff‐Kohlenstoff‐Bindungsbildung. Gemeinsam unterstützen diese Entwicklungen die Lösung des seit langem bestehenden Problems der Kreuzkupplung funktionalisierter Alkylfragmente in späten Synthesestadien. Basierend auf der Vorstellung, dass photokatalytisch erzeugte Alkylradikale leicht von Ni‐Komplexen eingefangen werden können, sind gänzlich neue Ausgangsstoffe für die Kreuzkupplung denkbar. In diesem Kurzaufsatz werden die neuesten Entwicklungen für mehrere Arten von Alkyl‐Kreuzkupplungen beleuchtet, die ausschließlich durch diesen Ansatz verwirklicht werden können.
Synthesis of BCP Benzylamines From 2‐Azaallyl Anions and [1.1.1]Propellane
Authors: Shelp Russell A. , Walsh Patrick J. 
Published: October 2018

AbstractFor bioactive molecules, bicyclo[1.1.1]pentanes (BCPs) are an emerging isostere of rigid spacer groups that have shown potential to improve drug‐like qualities. As BCPs become an increasingly popular motif for evaluation in drug candidates, organic chemists must meet the demand to reliably incorporate them into new targets. To provide access to BCP analogues of diaryl methanamines, a ubiquitous scaffold in medicinal chemistry, we report the synthesis of BCP benzylamines through reactivity of [1.1.1]propellane with 2‐azaallyl anions, which are generated in situ from N‐benzyl ketimines. The reaction proceeds rapidly at room temperature and tolerates a broad substrate scope, providing straightforward access to 23 new BCP benzylamine derivatives. Initial experiments support the intermediacy of a BCP anion. Additionally, the reaction can be promoted by substoichiometric loadings of base, highlighting an unusual reactivity of both 2‐azaallyls and [1.1.1]propellane.
Schnelle, quantitative und hochempfindliche patientennahe Labordiagnostik: ein tragbares Raman‐Lesegerät für seitliche Flusstests in der klinischen Chemie
Authors: Tran Vi , Walkenfort Bernd , König Matthias , Salehi Mohammad , Schlücker Sebastian 
Published: October 2018

AbstractIm Folgenden wird über die Entwicklung eines tragbaren Raman‐Lesegerätes für seitliche Flusstests (“lateral flow assay”, LFA) mit einer speziellen, maßgeschneiderten optischen Fasersonde für die Linienbeleuchtung zur schnellen, quantitativen und hochempfindlichen patientennahen Labordiagnostik (“point‐of‐care testing”, POCT) berichtet. Das Schwangerschaftshormon humanes Choriongonadotropin (HCG) ist in klinischen Proben innerhalb von 2–5 s bis zu einer Konzentration von 1.6 mIU mL−1 detektierbar. Die Akquisitionszeit ist um mehrere Größenordnungen kürzer als bei den aktuell existierenden Raman‐Geräten. Die Empfindlichkeit des kommerziell erhältlichen seitlichen Flusstests wird mit dem Lesegerät um das 15‐fache übertroffen. Die Raman/SERS‐LFA‐Technologie ermöglicht kostengünstiges, quantitatives und hochempfindliches POCT mit Multiplexing‐Potential für praktische Anwendungen, unter anderem in der klinischen Chemie, der Lebensmittel‐ und Umweltanalytik, sowie für den Nachweis von Drogen und Biowaffen.
Surface‐Enhanced Raman Spectroscopy for the Detection of a Metabolic Product in the Headspace Above Live Bacterial Cultures
Authors: Kelly Jessica , Patrick Robin , Patrick Sheila , Bell Steven E. J. 
Published: October 2018

AbstractIn situ surface‐enhanced Raman spectra of the headspace above cultures of six bacterial species showed strong characteristic bands from chemisorbed methyl sulfide. This marker compound is created by dissociation of dimethyl disulfide (DMDS), a fermentative metabolite of bacteria, on the surface of the enhancing Au or Ag nanoparticle films. Kinetic binding plots of media spiked with DMDS and of live cultures showed that the Au‐based substrates were more suitable for the rapid detection of bacteria than Ag‐based substrates. For E. coli DH5α, the sensitivity limit for headspace SERS detection was 1.5×107 CFU mL−1, which corresponded to detection 15 min after inoculation of the growth medium. Since the metabolites are only produced by viable bacteria, antibiotic (gentamicin) treatment stopped the normal signal growth of the marker peak. This work is a promising step towards rapid bedside detection of bacterial infections and rapid screening of antibiotics against bacteria.
Kernel Homology in Gold Nanoclusters
Authors: Zhuang Shengli , Liao Lingwen , Yuan Jinyun , Wang Chengming , Zhao Yan , Xia Nan , Gan Zibao , Gu Wanmiao , Li Jin , Deng Haiteng , Yang Jinlong , Wu Zhikun 
Published: October 2018

AbstractHomology is well known in organic chemistry; however, it has not yet been reported in nanochemistry. Herein, we introduce the concept of kernel homology to describe the phenomenon of metal nanoclusters sharing the same “functional group” in kernels with some similar properties. To illustrate this point, we synthesized two novel gold nanoclusters, Au44(TBBT)26 and Au48(TBBT)28 (TBBTH=4‐tert‐butylbenzenethiol), and solved their total structures by X‐ray crystallography, which reveals that they have the same Au23 bi‐icosahedron capped with a similar bottom cap (Au6 and Au8, respectively) in the kernels. The two novel gold nanoclusters, together with the existing Au38(PET)24 nanocluster (PETH=phenylethanethiol), have the same “functional group”—Au23—in their kernels and have some similar properties (e.g., electrochemical properties); therefore, they are comparable to the homologues in organic chemistry.
Alkyl Carbon–Carbon Bond Formation by Nickel/Photoredox Cross‐Coupling
Authors: Milligan John A. , Phelan James P. , Badir Shorouk O. , Molander Gary A. 
Published: October 2018

AbstractThe union of photoredox and nickel catalysis has resulted in a renaissance in radical chemistry as well as in the use of nickel‐catalyzed transformations, specifically for carbon–carbon bond formation. Collectively, these advances address the longstanding challenge of late‐stage cross‐coupling of functionalized alkyl fragments. Empowered by the notion that photocatalytically generated alkyl radicals readily undergo capture by Ni complexes, wholly new feedstocks for cross‐coupling have been realized. Herein, we highlight recent developments in several types of alkyl cross‐couplings that are accessible exclusively through this approach.