bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ag Thin Film Dewetting Prevention by Ion Implantation
Authors: Chi Longxing , Bassim Nabil 
Published: May 2019

AbstractIon implantation is applied here to prevent metallic silver (Ag) thin films from dewetting on a sapphire substrate during annealing. In these experiments, silicon (Si) and indium (In) atoms are implanted into Ag thin films grown directly on sapphire, which are then annealed for different time periods to introduce film dewetting. It is observed that trace amounts of 1014 cm−2 dopants significantly retard the film grain growth, alter the film surface wetting features, and trivially influence the electrical and optical performance of the original film. A grain growth model with the presence of solute species is introduced here, combined with a thermodynamic simulation of film dewetting. It is found that doping ions introduce solute drag into Ag grains thereby significantly retarding the grain growth by generating a limiting grain size. The shrunken grains then alter the film surface energy distribution, transferring the most stable state from the dewetting phase to the wetting phase. The approach provides a novel strategy to suppress metallic thin films from dewetting with high stability, durability, and insignificant impact on the film performance without using an adhesion layer and also potentially expands the thermal processing window for metallic thin films.
WNT10B variants in split hand/foot malformation: Report of three novel families and review of the literature
Authors: Brunelle Perrine , Jourdain Anne‐Sophie , Escande Fabienne , Martinovic Jelena , Dupont Juliette , Busa Tiffany , Moncla Anne , Frénois Frédéric , Stichelbout Morgane , Manouvrier‐Hanu Sylvie , Petit Florence 
Published: May 2019

AbstractSplit‐hand/foot malformation (SHFM) is a genetically heterogeneous congenital limb malformation typically limited to a defect of the central rays of the autopod, presenting as a median cleft of hands and feet. It can be associated with long bone deficiency or included in more complex syndromes. Among the numerous genetic causes, WNT10B homozygous variants have been recently identified in consanguineous families, but remain still rarely described (SHFM6; MIM225300). We report on three novel SHFM families harboring WNT10B variants and review the literature, allowing us to highlight some clinical findings. The feet are more severely affected than the hands and there is a frequent asymmetry without obvious side‐bias. Syndactyly of third–fourth fingers was a frequent finding (62%). Polydactyly, which was classically described in SHFM6, was only present in 27% of patients. No genotype–phenotype correlation is delineated but heterozygous individuals might have mild features of SHFM, suggesting a dose‐effect of the WNT10B loss‐of‐function.
Training in clinical genetics and genetic counseling in Asia
Authors: Cutiongco‐de la Paz Eva Maria , Chung Brian Hon‐Yin , Faradz Sultana M. H. , Thong Meow‐Keong , David‐Padilla Carmencita , Lai Poh San , Lin Shuan‐Pei , Chen Yin‐Hsiu , Sura Thanyachai , Laurino Mercy 
Published: May 2019

AbstractThe status of training in clinical genetics and genetic counseling in Asia is at diverse stages of development and maturity. Most of the training programs are in academic training centers where exposure to patients in the clinics or in the hospital is a major component. This setting provides trainees with knowledge and skills to be competent geneticists and genetic counselors in a variety of patient care interactions. Majority of the training programs combine clinical and research training which provide trainees a broad and integrated approach in the diagnosis and management of patients while providing opportunities for research discoveries that can be translated to better patient care. The background on how the training programs in clinical genetics and genetic counseling in Asia evolved to their current status are described. Each of these countries can learn from each other through sharing of best practices and resources.
Boosting Solid‐State Diffusivity and Conductivity in Lithium Superionic Argyrodites by Halide Substitution
Authors: Adeli Parvin , Bazak J. David , Park Kern Ho , Kochetkov Ivan , Huq Ashfia , Goward Gillian R. , Nazar Linda F. 
Published: May 2019

AbstractDeveloping high‐performance all‐solid‐state batteries is contingent on finding solid electrolyte materials with high ionic conductivity and ductility. Here we report new halide‐rich solid solution phases in the argyrodite Li6PS5Cl family, Li6−xPS5−xCl1+x, and combine electrochemical impedance spectroscopy, neutron diffraction, and 7Li NMR MAS and PFG spectroscopy to show that increasing the Cl−/S2− ratio has a systematic, and remarkable impact on Li‐ion diffusivity in the lattice. The phase at the limit of the solid solution regime, Li5.5PS4.5Cl1.5, exhibits a cold‐pressed conductivity of 9.4±0.1 mS cm−1 at 298 K (and 12.0±0.2 mS cm−1 on sintering)—almost four‐fold greater than Li6PS5Cl under identical processing conditions and comparable to metastable superionic Li7P3S11. Weakened interactions between the mobile Li‐ions and surrounding framework anions incurred by substitution of divalent S2− for monovalent Cl− play a major role in enhancing Li+‐ion diffusivity, along with increased site disorder and a higher lithium vacancy population.
Size‐Independent Fast Ion Intercalation in Two‐Dimensional Titania Nanosheets for Alkali‐Metal‐Ion Batteries
Authors: Yang Jinlin , Xiao Xu , Gong Wenbin , Zhao Liang , Li Guohui , Jiang Kun , Ma Renzhi , Rummeli Mark H. , Li Feng , Sasaki Takayoshi , Geng Fengxia 
Published: May 2019

AbstractCompared to lithium ions, the fast redox intercalation of large‐radius sodium or potassium ions into a solid lattice in non‐aqueous electrolytes is an elusive goal. Herein, by regulating the interlayer structure of stacked titania sheets through weakened layer‐to‐layer interactions and a robustly pillared gallery space, the two‐dimensional channel between neighboring sheets was completely open to guest intercalation, allowing fast intercalation that was practically irrespective of the carrier‐ion sizes. Regardless of employing regular Li or large‐radius Na and K ions, the material manifested zero strain‐like behavior with no significant change in both host structure and interlayer space, enabling comparable capacities for all tested ions along with excellent rate behaviors and extraordinarily long lifetimes, even with 80‐μm‐thick electrodes. The result highlights the importance of interlayer structural features for unlocking the electrochemical activity of a layered material.
Semi‐heterogene duale Nickel‐/Photokatalyse mit Kohlenstoffnitriden: Veresterung von Carbonsäuren mit Arylhalogeniden
Authors: Pieber Bartholomäus , Malik Jamal A. , Cavedon Cristian , Gisbertz Sebastian , Savateev Aleksandr , Cruz Daniel , Heil Tobias , Zhang Guigang , Seeberger Peter H. 
Published: May 2019

AbstractKreuzkupplungen durch duale Nickel‐/Photokatalyse sind aus Synthesesicht vielversprechend, jedoch werden meist teure, nicht wiederverwendbare Edelmetallkomplexe als Photokatalysatoren verwendet. Heterogene Halbleiter bieten hier eine nachhaltige Alternative. Graphitische Kohlenstoffnitride sind eine Klasse metallfreier Halbleiter mit großem Potenzial für photokatalytische organische Umwandlungen. Wir zeigen, dass graphitische Kohlenstoffnitride im Zusammenspiel mit Nickelkatalyse selektive C‐O‐Kreuzkupplungen von Carbonsäuren mit Arylhalogeniden induzieren können und die jeweiligen Arylester in hervorragender Ausbeute und Selektivität liefern. Dieser eingesetzte organische Halbleiter ist kompatibel mit einem breiten Substratspektrum, in der Lage, grünes Licht zu nutzen, und kann mehrfach wiederverwendet werden. Um die Kupplung bei verschiedenen Wellenlängen und Ansatzgrößen zu untersuchen, wurde zur Aufzeichnung des Reaktionsverlaufes eine In‐situ‐FTIR‐Methode entwickelt.
Catechol Oxidase versus Tyrosinase Classification Revisited by Site‐Directed Mutagenesis Studies
Authors: Prexler Sarah M. , Frassek Martin , Moerschbacher Bruno M. , Dirks‐Hofmeister Mareike E. 
Published: May 2019

AbstractCatechol oxidases (COs) and tyrosinases (TYRs) are both polyphenol oxidases (PPOs) that catalyze the oxidation of ortho‐diphenols to the corresponding quinones. By the official classification, only TYRs can also catalyze the hydroxylation of monophenols to ortho‐diphenols. Researchers have been trying to find the molecular reason for the mono‐/diphenolase specificity for decades. However, the hypotheses for the lack of monophenolase activity of plant COs are only based on crystal structures so far. To test these hypotheses, we performed site‐directed mutagenesis studies and phylogenetic analyses with dandelion PPOs offering high phylogenetic diversity, the results of which refute the structure‐based hypotheses. While plant PPOs of phylogenetic group 2 solely exhibit diphenolase activity, plant PPOs of phylogenetic group 1 unexpectedly also show monophenolase activity. This finding sheds new light upon the molecular basis for mono‐/diphenol substrate specificity and challenges the current practice of generally naming plant PPOs as COs.
A Rutile TiO2 Electron Transport Layer for the Enhancement of Charge Collection for Efficient Perovskite Solar Cells
Authors: Wang Yongling , Wan Jiawei , Ding Jie , Hu Jin‐Song , Wang Dan 
Published: May 2019

AbstractInterfacial charge collection efficiency has demonstrated significant effects on the power conversion efficiency (PCE) of perovskite solar cells (PSCs). Herein, crystalline phase‐dependent charge collection is investigated by using rutile and anatase TiO2 electron transport layer (ETL) to fabricate PSCs. The results show that rutile TiO2 ETL enhances the extraction and transportation of electrons to FTO and reduces the recombination, thanks to its better conductivity and improved interface with the CH3NH3PbI3 (MAPbI3) layer. Moreover, this may be also attributed to the fact that rutile TiO2 has better match with perovskite grains, and less trap density. As a result, comparing with anatase TiO2 ETL, MAPbI3 PSCs with rutile TiO2 ETL delivers significantly enhanced performance with a champion PCE of 20.9 % and a large open circuit voltage (VOC) of 1.17 V.
Viskoelastische konjugierte polymere Fluide
Authors: Shinohara Akira , Pan Chengjun , Guo Zhenfeng , Zhou Liyang , Liu Zhonghua , Du Lei , Yan Zhichao , Stadler Florian J. , Wang Lei , Nakanishi Takashi 
Published: May 2019

AbstractOptoelektronische Funktionen in viskoelastischen Polymeren öffnet den Zugang zu neuartigen, hochentwickelten weichen Materialien, die für biomedizinische und robotische Anwendungen erforderlich sind. Es ist jedoch schwierig, sowohl viskoelastisches Verhalten als auch hervorragende optoelektronische Eigenschaften zu erreichen, da eine große Konzentration von π‐konjugierten Anteilen in der Hauptkette diese drastisch versteift. Hier führen wir ein neuen Konzept zur Herstellung von additivfreien viskoelastischen konjugierten Polymeren (VE‐CPs) bei Raumtemperatur ein, das über voluminöse, flexible Alkylseitenketten als “interne Weichmacher” bei intakter π‐konjugierter Hauptkette erreicht wird. Je nach genauer chemischer Struktur der Haupt‐ und Seitenketten dieser Polymere zeigen diese ein gel‐ und elastomerähnliches rheologisches Verhalten ohne Vernetzung oder Verschlaufung. Außerdem zeigen binäre Mischungen dieser VE‐CPs eine neuartige dynamische Mischbarkeit mit selbstheilenden und mechanisch induzierten Fluoreszenzfarbänderungen.
Porphyrin Nanocage‐Embedded Single‐Molecular Nanoparticles for Cancer Nanotheranostics
Authors: Yu Guocan , Cen Tian‐Yong , He Zhimei , Wang Shu‐Ping , Wang Zhantong , Ying Xin‐Wen , Li Shijun , Jacobson Orit , Wang Sheng , Wang Lei , Lin Li‐Sen , Tian Rui , Zhou Zijian , Ni Qianqian , Li Xiaopeng , Chen Xiaoyuan 
Published: May 2019

AbstractSingle molecular nanoparticles (SMNPs) integrating imaging and therapeutic capabilities exhibit unparalleled advantages in cancer theranostics, ranging from excellent biocompatibility, high stability, prolonged blood lifetime to abundant tumor accumulation. Herein, we synthesize a sophisticated porphyrin nanocage that is further functionalized with twelve polyethylene glycol arms to prepare SMNPs (porSMNPs). The porphyrin nanocage embedded in porSMNPs can be utilized as a theranostic platform. PET imaging allows dynamic observation of the bio‐distribution of porSMNPs, confirming their excellent circulation time and preferential accumulation at the tumor site, which is attributed to the enhanced permeability and retention effect. Moreover, the cage structure significantly promotes the photosensitizing effect of porSMNs by inhibiting the π–π stacking interactions of the photosensitizers, ablating of the tumors without relapse by taking advantage of photodynamic therapy.
Phosphazenylphosphine: Die elektronenreichsten ungeladenen Brønsted‐ und Lewis‐Phosphor‐Basen
Authors: Ullrich Sebastian , Kovačević Borislav , Xie Xiulan , Sundermeyer Jörg 
Published: May 2019

AbstractWir entdeckten, dass Phosphazenylphosphine (PAPs) stärkere P‐Superbasen darstellen als ihre korrespondierenden Schwesinger‐Phosphazen‐N‐Superbasen. Ein einfacher synthetischer Zugang zu diesen PR3‐Derivaten sowie ihre Homologisierung, XRD‐Strukturen, Protonenaffinitäten (PA) und Gasphasenbasizitäten (GB), berechnete wie auch experimentelle pK
‐Werte werden beschrieben. Im Gegensatz zu ihren N‐basischen Verwandten entpuppen PAPs sich darüber hinaus als privilegierte Liganden in der Übergangsmetallchemie. Tatsächlich stellen sie die stärksten bislang bekannten P‐Donorliganden dar und überragen sowohl etablierte als auch kürzlich eingeführte Liganden, wie PtBu3 oder Imidazolin‐2‐ylidenaminophosphine (IAPs), hinsichtlich niedrigerer elektronischer Tolman‐Parameter (TEP) und größerer Kegelwinkel.
Highly Reproducible Formation of a Polymer Single‐Molecule Junction for a Well‐Defined Current Signal
Authors: Harashima Takanori , Hasegawa Yusuke , Kaneko Satoshi , Kiguchi Manabu , Ono Tomoya , Nishino Tomoaki 
Published: May 2019

AbstractSingle‐molecule devices attract much interest in the development of nanoscale electronics. Although a variety of functional single molecules for single‐molecule electronics have been developed, there still remains the need to implement sophisticated functionalization toward practical applications. Given its superior functionality encountered in macroscopic materials, a polymer could be a useful building block in the single‐molecule devices. Therefore, a molecular junction composed of polymer has now been created. Furthermore, an automated algorithm was developed to quantitatively analyze the tunneling current through the junction. Quantitative analysis revealed that the polymer junction exhibits a higher formation probability and longer lifetime than its monomer counterpart. These results suggest that the polymer provides a unique opportunity to design both stable and highly functional molecular devices for nanoelectronics.
Spatial Positioning and Chemical Coupling in Coacervate‐in‐Proteinosome Protocells
Authors: Booth Richard , Qiao Yan , Li Mei , Mann Stephen 
Published: May 2019

AbstractThe integration of molecularly crowded microenvironments into membrane‐enclosed protocell models represents a step towards more realistic representations of cellular structure and organization. Herein, the membrane diffusion‐mediated nucleation of either negatively or positively charged coacervate microdroplets within the aqueous lumen of individual proteinosomes is used to prepare nested hybrid protocells with spatially organized and chemically coupled enzyme activities. The location and reconfiguration of the entrapped droplets are regulated by tuning the electrostatic interactions between the encapsulated coacervate and surrounding negatively charged proteinosome membrane. As a consequence, alternative modes of a cascade reaction involving membrane‐ and coacervate‐segregated enzymes can be implemented within the coacervate‐in‐proteinosome protocells.
Fabrication of Photoactuators: Macroscopic Photomechanical Responses of Metal–Organic Frameworks to Irradiation by UV Light
Authors: Shi Yi‐Xiang , Zhang Wen‐Hua , Abrahams Brendan F. , Braunstein Pierre , Lang Jian‐Ping 
Published: May 2019

AbstractPhotoreactive olefinic species are incorporated into a metal–organic framework (MOF), [Zn(bdc)(3‐F‐spy)] (1). Single crystals of 1 are shown to undergo three types of photomechanical macroscopic deformation upon illumination by UV light. To demonstrate the practical potential of this system, the inclusion of 1 in a PVA (polyvinyl alcohol) composite membrane, by exploiting hydrogen‐bonding interactions, is presented. Using this composite membrane, the amplification of mechanical stress to achieve macroscopic actuation behavior is demonstrated. These results pave the way for the generation of MOF‐based soft photoactuators that produce clearly defined mechanical responses upon irradiation with light. Such systems are anticipated to have considerable potential in photomechanical energy harvesting and conversion systems.
Photoswitchable Dissipative Two‐Dimensional Colloidal Crystals
Authors: Vialetto Jacopo , Anyfantakis Manos , Rudiuk Sergii , Morel Mathieu , Baigl Damien 
Published: May 2019

AbstractControl over particle interactions and organization at fluid interfaces is of great importance both for fundamental studies and practical applications. Rendering these systems stimulus‐responsive is thus a desired challenge both for investigating dynamic phenomena and realizing reconfigurable materials. Here, we describe the first reversible photocontrol of two‐dimensional colloidal crystallization at the air/water interface, where millimeter‐sized assemblies of microparticles can be actuated through the dynamic adsorption/desorption behavior of a photosensitive surfactant added to the suspension. This allows us to dynamically switch the particle organization between a highly crystalline (under light) and a disordered (in the dark) phase with a fast response time (crystallization in ≈10 s, disassembly in ≈1 min). These results evidence a new kind of dissipative system where the crystalline state can be maintained only upon energy supply.
Endlich homoleptisch: Synthese und vollständige Charakterisierung stabiler Salze des Mangantetranitrosylkations
Authors: Bohnenberger Jan , Derstine Brandon , Daub Michael , Krossing Ingo 
Published: May 2019

AbstractTrotz der Ähnlichkeit zu Kohlenmonoxid ist die Chemie von homoleptischen Stickstoffmonoxidkomplexen im Unterschied zu ihren Carbonylanaloga bislang grundlegend unerforscht. Hier beschreiben wir die Synthese des ersten echten homoleptischen Übergangsmetallnitrosylkomplexes als Salz der schwach koordinierenden Anionen (WCAs) [Al(ORF)4]− und [F{Al(ORF)3}2]− (RF=C(CF3)3). Diese Salze sind in guten Ausbeuten phasenrein zugänglich und wurden vollständig durch IR/Raman‐, NMR‐ und UV/Vis‐Spektroskopie sowie mittels Einkristallstrukturanalyse und Pulverdiffraktometrie charakterisiert. Sie könnten als bisher beispiellose Modellsysteme für theoretische und experimentelle Studien zu Nitrosylkomplexen fungieren.
Optimierung der Größe von Platin‐Nanopartikeln für eine erhöhte Massenaktivität der elektrochemischen Sauerstoffreduktion
Authors: Garlyyev Batyr , Kratzl Kathrin , Rück Marlon , Michalička Jan , Fichtner Johannes , Macak Jan M. , Kratky Tim , Günther Sebastian , Cokoja Mirza , Bandarenka Aliaksandr S. , Gagliardi Alessio , Fischer Roland A. 
Published: May 2019

AbstractEine Aktivitätserhöhung der Sauerstoffreduktion (ORR) gilt als der Schlüssel zu zahlreichen Energieanwendungen. Durch die Kombination von Theorie und Experiment werden Pt‐Nanopartikel mit optimaler Größe für die effiziente ORR in Protonenaustauschmembran‐Brennstoffzellen hergestellt. Optimale Nanopartikelgrößen werden durch rechnergestütztes Screening in der Nähe von 1, 2 und 3 nm vorhergesagt. Um die Ergebnisse der Rechnungen zu bestätigen, synthetisierten wir ca. 1 nm große Pt‐Nanopartikel mit einem Templatansatz basierend auf Metall‐organischen Gerüsten. Der Elektrokatalysator wurde durch HR‐TEM und XPS charakterisiert, und seine Aktivität in der ORR wurde unter Verwendung einer rotierenden Scheibenelektrode gemessen. Die beobachtete Massenaktivität liegt nahe an der rechnerischen Vorhersage. Wir verzeichnen die aktuell höchste Massenaktivität unter reinen Pt‐Katalysatoren für die ORR im vergleichbaren Größenbereich. Die Massen‐ sowie die spezifische Aktivität waren zweimal so hoch wie die des kommerziellen Tanaka‐Katalysators.
Carboxylate‐Assisted Oxidative Addition to Aminoalkyl PdII Complexes: C(sp3)−H Arylation of Alkylamines by Distinct PdII/PdIV Pathway
Authors: Whitehurst William G. , Blackwell J. Henry , Hermann Gary N. , Gaunt Matthew J. 
Published: May 2019

AbstractReported is the discovery of an approach to functionalize secondary alkylamines using 2‐halobenzoic acids as aryl‐transfer reagents. These reagents promote an unusually mild carboxylate‐assisted oxidative addition to alkylamine‐derived palladacycles. In the presence of AgI salts, a decarboxylative C(sp3)−C(sp2) bond reductive elimination leads to γ‐aryl secondary alkylamines and renders the carboxylate motif a traceless directing group. Stoichiometric mechanistic studies were effectively translated to a Pd‐catalyzed γ‐C(sp3)−H arylation process for secondary alkylamines.
Visualizing Microglia with a Fluorescence Turn‐On Ugt1a7c Substrate
Authors: Kim Beomsue , Fukuda Masahiro , Lee Jung‐Yeol , Su Dongdong , Sanu Srikanta , Silvin Aymeric , Khoo Audrey T. T. , Kwon Taejoon , Liu Xiao , Chi Weijie , Liu Xiaogang , Choi Sejong , Wan Diana S. Y. , Park Sung‐Jin , Kim Jin‐Soo , Ginhoux Florent , Je H. Shawn , Chang Young‐Tae 
Published: May 2019

AbstractMicroglia, the brain‐resident macrophage, are involved in brain development and contribute to the progression of neural disorders. Despite the importance of microglia, imaging of live microglia at a cellular resolution has been limited to transgenic mice. Efforts have therefore been dedicated to developing new methods for microglia detection and imaging. Using a thorough structure–activity relationships study, we developed CDr20, a high‐performance fluorogenic chemical probe that enables the visualization of microglia both in vitro and in vivo. Using a genome‐scale CRISPR‐Cas9 knockout screen, the UDP‐glucuronosyltransferase Ugt1a7c was identified as the target of CDr20. The glucuronidation of CDr20 by Ugt1a7c in microglia produces fluorescence.
Synergy between Plasmonic and Electrocatalytic Activation of Methanol Oxidation on Palladium–Silver Alloy Nanotubes
Authors: Huang Lin , Zou Jiasui , Ye Jin‐Yu , Zhou Zhi‐You , Lin Zhang , Kang Xiongwu , Jain Prashant K. , Chen Shaowei 
Published: May 2019

AbstractLocalized surface plasmon resonance (LSPR) excitation of noble metal nanoparticles has been shown to accelerate and drive photochemical reactions. Here, LSPR excitation is shown to enhance the electrocatalysis of a fuel‐cell‐relevant reaction. The electrocatalyst consists of PdxAg alloy nanotubes (NTs), which combine the catalytic activity of Pd toward the methanol oxidation reaction (MOR) and the visible‐light plasmonic response of Ag. The alloy electrocatalyst exhibits enhanced MOR activity under LSPR excitation with significantly higher current densities and a shift to more positive potentials. The modulation of MOR activity is ascribed primarily to hot holes generated by LSPR excitation of the PdxAg NTs.