bluuebunny/crossref_metadata_2025_split huggingface dataset:
Plasmon‐Induced Hot Carrier Separation across Dual Interface in Gold–Nickel Phosphide Heterojunction for Photocatalytic Water Splitting
Authors: Mondal Indranil , Lee Hyunhwa , Kim Heeyoung , Park Jeong Young 
Published: December 2019

AbstractPrecise control of the topology of metal nanocrystals and appropriate modulation of the metal–semiconductor heterostructure is an important way to understand the relationship between structure and material properties for plasmon‐induced solar‐to‐chemical energy conversion. Here, a bottom‐up wet chemical approach to synthesize Au/Ni2P heterostructures via Pt‐catalyzed quasi‐epitaxial overgrowth of Ni on Au nanorods (NR) is presented. The structural motif of the Ni2P is controlled using the aspect ratio of the Au NR and the effective micelle concentration of the C16TAB capping agent. Highly ordered Au/Pt/Ni2P nanostructures are employed as the photoelectrocatalytic anode system for water splitting. Electrochemical and ultrafast absorption spectroscopy characterization indicates that the structural motif of the Ni2P (controlled by the outer‐shell deposition of Ni) helps to manipulate hot electron transfer during surface plasmon decay. With optimized Ni2P thickness, Pt‐tipped Au NR with an aspect ratio of 5.2 exhibits a geometric current density of 10 mA cm−2 with an overpotential of 140 mV. The photoanode displays unprecedented long‐term stability with continuous chronoamperometric performance of 50 h at an input potential of 1.5 V with over 30 days. This work provides definitive guidance for designing plasmonic–catalytic nanomaterials for enhanced solar‐to‐chemical energy conversion.
Charge‐Transfer Exciton Manipulation Based on Hydrogen Bond for Efficient White Thermally Activated Delayed Fluorescence
Authors: Sun Jianan , Zhang Jing , Liang Qianqian , Wei Ying , Duan Chunbo , Han Chunmiao , Xu Hui 
Published: December 2019

AbstractDespite the success of thermally activated delayed fluorescence (TADF) emitters in monochromatic organic light‐emitting diodes (OLED), only few efficient full‐TADF white OLEDs (WOLED) are reported because of the challenge in rational exciton allocation between blue and other color emitters. Herein, it is demonstrated that the appropriate exciton delocalization in blue TADF matrixes can simultaneously support the sufficient blue emission and the energy loss–free charge and exciton transfer to yellow TADF emitters. Through introducing steric hindrance–modulated intermolecular hydrogen bond networks, a fluorinated carbazole‐phosphine oxide hybrid realizes the balance of exciton localization and delocalization, giving rise to state‐of‐the‐art external quantum efficiency beyond 20% from its simple trilayer full‐TADF WOLEDs, accompanied by excellent spectral stability. The correlation between the efficiencies of the blue TADF matrixes and their intermolecular interactions reveals that the exciton delocalization is crucial for the exciton allocation optimization in multicomponent emission systems.
Fabrication of Bio‐Inspired 2D MOFs/PAA Hybrid Membrane for Asymmetric Ion Transport
Authors: Wang Chen , Liu Fei‐Fei , Tan Zheng , Chen Yu‐Ming , Hu Wen‐Chao , Xia Xing‐Hua 
Published: December 2019

AbstractBiological ion channels are known as membrane proteins which can turn on and off under environmental stimulus to regulate ion transport and energy conversion. Rapid progress made in biological ion channels provides inspiration for developing artificial nanochannels to mimic the structures and functions of ion transport systems and energy conversion in biological ion channels. Due to the advantages of abundant pore channels, metal–organic frameworks (MOFs) have become competitive materials to control the nanofluidic transport. Herein, a facile in situ synthesis method is developed to prepare hybrid nanochannels constructed by 2D MOFs and porous anodic aluminum (PAA). The introduction of asymmetries in the chemical composition and surface charge properties gives the hybrid outstanding ion current rectification properties and excellent ion selectivity. A power density of 1.6 W m−2 is achieved by integrating it into a salinity‐gradient‐driven device. With advantages of facile fabrication method and high ion selectivity, the prepared 2D MOFs/PAA hybrid membrane offers a promising candidate for power conversion and water desalination.
Hierarchical NiS@CoS with Controllable Core‐Shell Structure by Two‐Step Strategy for Supercapacitor Electrodes
Authors: Miao Yidong , Zhang Xuping , Zhan Jiang , Sui Yanwei , Qi Jiqiu , Wei Fuxiang , Meng Qingkun , He Yezeng , Ren Yaojian , Zhan Zhenzhen , Sun Zhi 
Published: December 2019

AbstractConstructing hierarchical core‐shell configuration from well‐known metal sulfides is one way to further tune and utilize unique species. Herein, a novel core‐shell structure is developed based on CoS deposited on NiS nanosheets, which involves hydrothermal and electrodeposition method. The micromorphology of the composite electrode can be optimized by adjusting the cycles of electrodeposition. Taking advantages of the highly conductive, open framework of the core‐shell nanolayer, the 5‐NiS@CoS electrode shows a specific capacitance of 1210 F g−1 at a current density of 1 A g−1 (retaining 82% from 1 to 10 A g−1, while NiS substrate is only 39%). The specific capacitance retention rate is 80.94% at 10 A g−1 after 2000 cycles (NiS substrate is 59.6%). Moreover, NiS@CoS//AC asymmetric supercapacitor device delivers an energy density of 24.1 Wh kg−1 at a power density of 752.15 W kg−1 and remarkable stability (over 80% retention after 5000 cycles). This work may prompt the exploration of the synthesis of inexpensive compounds incorporating highly reactive components for supercapacitors.
Surface/Interface Structure Degradation of Ni‐Rich Layered Oxide Cathodes toward Lithium‐Ion Batteries: Fundamental Mechanisms and Remedying Strategies
Authors: Liang Longwei , Zhang Wenheng , Zhao Fei , Denis Dienguila Kionga , Zaman Fakhr uz , Hou Linrui , Yuan Changzhou 
Published: December 2019

AbstractNickel‐rich layered transition‐metal oxides with high‐capacity and high‐power capabilities are established as the principal cathode candidates for next‐generation lithium‐ion batteries. However, several intractable issues such as the poor thermal stability and rapid capacity fade as well as the air‐sensitivity particularly for the Ni content over 80% have seriously restricted their broadly practical applications. The properties and nature of the stable surface/interface, where the Li+ shuttles back and forth between the cathode and electrolyte, play a significant role in their ultimate lithium‐storage performance and industrial processability. Thus, tremendous efforts are made to in‐depth understanding of the essential origins of surface/interface structure degradation and efficient surface modification methodologies are intensively explored. The purpose of the contribution is first to provide a comprehensive review of the up‐to‐date mechanisms proposed to rationally elucidate the surface/interface behaviors, and then, focus on recent developed strategies to optimize the surface/interface structure and chemistry including synthetic condition regulation, surface doping, surface coating, dual doping‐coating modification, and concentration‐gradient structure as well as electrolyte additives. Finally, the perspective on future research trends and feasible approaches toward advanced Ni‐rich cathodes with stable surface/interface is presented briefly.
Disentangling phylogenetic and functional components of shape variation among shoot apical meristems of a wide range of herbaceous angiosperms
Authors: Schnablová Renáta , Neustupa Jiří , Woodard Kateřina , Klimešová Jitka , Herben Tomáš 
Published: December 2019

PremiseThe shoot apical meristem (SAM) is the basic determinant of plant body organization, but interspecific variation inSAMshape and its relationship to stem and leaf morphological traits is not well known. Here we tested the hypothesis that differentSAMshapes are associated with specific shoot traits of the plant body and examined the phylogenetic conservatism of these relationships.MethodsWe used geometric morphometrics ofSAMoutlines for a phylogenetically representative set of 110 herbaceous angiosperms and examined their relationship to a number of shoot traits.ResultsWe found large variations inSAMshapes across angiosperm lineages, but covering only a subset of geometrically possible shapes. Part of this variation was allometric (due toSAMsize), but the dominant shape variation (dome‐shaped vs. flat surface) was size‐independent and strongly phylogenetically conserved.SAMshapes were largely independent of their cell size and therefore of the number of cells involved. Different patterns in shape variation of outer and innerSAMboundaries were associated with stem thickness, leaf area, and leafiness of the stem.ConclusionsThe findings show that geometric interdependence of meristem zones gives rise to correlations among organ numbers, sizes, and their proportions. Phylogenetic conservatism in these correlations indicates conservatism in regulatory processes that underlie the correlations, or the individual traits, that give rise to plant architecture.
Tunable Periodically Ordered Mesoporosity in Palladium Membranes Enables Exceptional Enhancement of Intrinsic Electrocatalytic Activity for Formic Acid Oxidation
Authors: Ding Jia , Liu Zhi , Liu Xiaorui , Liu Bin , Liu Jie , Deng Yida , Han Xiaopeng , Hu Wenbin , Zhong Cheng 
Published: December 2019

AbstractDeveloping superior electrocatalysts for formic acid oxidation (FAO) is the most crucial step in commercializing direct formic acid fuel cells. Herein, we electrodeposited palladium membranes with periodically ordered mesoporosity obtained by asymmetrically replicating the bicontinuous cubic phase structure of a lyotropic liquid‐crystal template. The Pd membrane with the largest periodicity and highest degree of order delivered up to 90.5 m2 g−1 of electrochemical active surface area and 3.34 A mg−1 electrocatalysis capability towards FAO, 3.8 and 7.8 times the values of the commercial Pd/C catalyst, respectively. By controlling the temperature and potential of the electrodeposition procedure, the periodicity area and order degree of the mesoporosity are highly tunable. These Pd membranes gave prototype formic acid fueled cells with 4.3 and 2.4 times the maximum current and power density of the commercial Pd/C catalyst.
Ribosomal Incorporation of Aromatic Oligoamides as Peptide Sidechain Appendages
Authors: Tsiamantas Christos , Kwon Sunbum , Rogers Joseph M. , Douat Céline , Huc Ivan , Suga Hiroaki 
Published: December 2019

AbstractDerivatives of 4‐aminomethyl‐l‐phenylalanine with aromatic oligoamide foldamers as sidechain appendages were successfully charged on tRNA by means of flexizymes. Their subsequent incorporation both at the C‐terminus of, and within, peptide sequences by the ribosome, was demonstrated. These results expand the registry of chemical structures tolerated by the ribosome to sidechains significantly larger and more structurally defined than previously demonstrated.
Access to Hydroxy‐Functionalized Polypropylene through Coordination Polymerization
Authors: Zhong Yuanhao , Douair Iskander , Wang Tiantian , Wu Chunji , Maron Laurent , Cui Dongmei 
Published: December 2019

AbstractPreparation of polyethylenes containing hydroxy groups has been already industrialized through radical copolymerization under harsh conditions followed by alcoholysis. By contrast, hydroxy‐functionalized polypropylene has proven a rather challenging goal in polymer science. Propylene can't be polymerized through a radical mechanism, and its coordination copolymerization with polar monomers is frustrated by catalyst poisoning. Herein, we report a new strategy to reach this target. The coordination polymerization of allenes by rare‐earth‐metal precursors affords pure 1,2‐regulated polyallenes, which are facilely transformed into poly(allyl alcohol) analogues by subsequent hydroboration/oxidation. Strikingly, the copolymerization of allenes and propylene gives unprecedented hydroxy‐functionalized polypropylene after post‐polymerization modification. Mechanistic elucidation by DFT simulation suggests kinetic rather than thermodynamic control.
Exploiting the Bulk Photovoltaic Effect in a 2D Trilayered Hybrid Ferroelectric for Highly Sensitive Polarized Light Detection
Authors: Peng Yu , Liu Xitao , Sun Zhihua , Ji Chengmin , Li Lina , Wu Zhenyue , Wang Sasa , Yao Yunpeng , Hong Maochun , Luo Junhua 
Published: December 2019

AbstractPolarized light detection is attracting increasing attention for its wide applications ranging from optical switches to high‐resolution photodetectors. Two‐dimensional (2D) hybrid perovskite‐type ferroelectrics combining inherent light polarization dependence of bulk photovoltaic effect (BPVE) with excellent semiconducting performance present significant possibilities. Now, the BPVE‐driven highly sensitive polarized light detection in a 2D trilayered hybrid perovskite ferroelectric, (allyammonium)2(ethylammonium)2Pb3Br10 (1), is presented. It shows a superior BPVE with near‐band gap photovoltage of ca. 2.5 V and high on/off switching ratio of current (ca. 104). Driven by the superior BPVE, 1 exhibits highly sensitive polarized light detection with a polarization ratio as high as ca. 15, which is far more beyond than those of structural anisotropy‐based monocomponent devices. This is the first realization of BPVE‐driven polarized light detection in hybrid perovskite ferroelectrics.
Synthese von gem‐Difluorolefinen durch C‐H‐Funktionalisierung und β‐Fluorideliminierungsreaktionen
Authors: Yang Zhen , Möller Mieke , Koenigs Rene M. 
Published: December 2019

AbstractIn diesem Artikel berichten wir über die palladiumkatalysierte Reaktion von Indolen mit fluorierten Diazoalkanen. Dieser Ansatz bietet nun erstmalig eine einfache Methode für die effiziente Synthese von gem‐Difluorolefinen unter milden Reaktionsbedingungen mit fluorierten Diazoalkane. Diese reagieren mit N‐alkylierten Indolen in einer C‐H‐Funktionalisierung gefolgt von einer β‐Fluorideliminierungsreaktion. Die entsprechenden Cyclopropanierungsprodukte werden erhalten, wenn in dieser Reaktion N‐arylierte Indole eingesetzt werden. In mechanistischen Studien können wir zeigen, dass eine β‐Fluorideliminierung einen zentralen Reaktionsschritt darstellt. Diese Methode ist damit ein neuartiges Konzept, das den einfachen und direkten Transfer einer 1‐Aryl‐(2,2‐difluorvinyl)‐Gruppe für die Synthese von gem‐Difluorolefinen ermöglicht.
Exploiting a C–N Bond Forming Cytochrome P450 Monooxygenase for C–S Bond Formation
Authors: Morita Iori , Mori Takahiro , Mitsuhashi Takaaki , Hoshino Shotaro , Taniguchi Yoshimasa , Kikuchi Takashi , Nagae Kei , Nasu Norihiro , Fujita Makoto , Ohwada Tomohiko , Abe Ikuro 
Published: December 2019

AbstractC–S bond formation reactions are widely distributed in the biosynthesis of biologically active molecules, and thus have received much attention over the past decades. Herein, we report intramolecular C–S bond formation by a P450 monooxygenase, TleB, which normally catalyzes a C−N bond formation in teleocidin biosynthesis. Based on the proposed reaction mechanism of TleB, a thiol‐substituted substrate analogue was synthesized and tested in the enzyme reaction, which afforded the unprecedented sulfur‐containing thio‐indolactam V, in addition to an unusual indole‐fused 6/5/8‐tricyclic product whose structure was determined by the crystalline sponge method. Interestingly, conformational analysis revealed that the SOFA conformation is stable in thio‐indolactam V, in sharp contrast to the major TWIST form in indolactam V, resulting in differences in their biological activities.
Direct C−H Bond Borylation of (Hetero)Arenes: Evolution from Noble Metal to Metal Free
Authors: Li Yahui , Wu Xiao‐Feng 
Published: December 2019

AbstractOrganoboron compounds are among the most versatile and useful building blocks in modern synthetic chemistry. The past decades have seen impressive developments in the direct C−H bond borylation of (hetero)arenes in which the applied catalysts are shifting from noble metals to metal‐free systems. This Highlight gives a brief summary on this evolution and focuses on recent elegant work in this field.
Synthesis of gem‐Difluoro Olefins through C−H Functionalization and β‐fluoride Elimination Reactions
Authors: Yang Zhen , Möller Mieke , Koenigs Rene M. 
Published: December 2019

AbstractA palladium catalyzed C−H functionalization and consecutive β‐fluoride elimination reaction between indole heterocycles and fluorinated diazoalkanes is reported. This approach provides for the first time a facile method for the rapid synthesis of gem‐difluoro olefins using fluorinated diazoalkanes under mild reaction conditions. Cyclopropanation products were obtained when N‐arylated rather than N‐alkylated indoles were applied in this reaction. Mechanistic studies reveal the importance of the β‐fluoride elimination step in this transformation. This method presents a new concept for the simple and direct transfer of a 1‐aryl‐(2,2‐difluorovinyl) group to access gem‐difluoro olefins.
Synthesis and investigation of desalinating, antibacterial, and mechanical properties of tetraethylorthosilicate crosslinked chitosan/polyethylene glycol (PEG‐300) membranes for reverse osmosis
Authors: Raza Arsalan , Kayani Anum , Sabir Aneela , Ahmad Adnan , Hussain Tajamal , Raza Muhammad Hamid , Bano Shehr , Islam Atif , Khan Rafi Ullah 
Published: December 2019

ABSTRACTSolution casting method was used to synthesize chitosan (CS)‐based membranes for reverse osmosis (RO) using PEG‐300 and tetraethylorthosilicate as a crosslinker. Their salt rejection (%) and permeate flux (mL/h.m2) was measured by using lab scale RO plant. FTIR spectroscopy reveals interactions between CS and PEG by shifting of OH peak from 3237 cm−1 to lower wavenumber in modified membranes. SEM results showed pores in modified membranes while pure CS membranes had uniform nonporous and dense microstructure. DMA results demonstrated that the addition of PEG lowers the Tg value up to 6.5%. Water content of membranes increases up to 82.63% as the amount of PEG increases owing to its hydrophilic nature. The bacterial killing ability showed that the modified membranes possess good antibacterial activity against Escherichia coli in comparison to the control film. The permeation results revealed that salt rejection and flux of the modified membranes increased up 60% and 86.36 mL/h.m2, respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48870.
The Effect of Stereoscopic Augmented Reality Visualization on Learning Anatomy and the Modifying Effect of Visual‐Spatial Abilities: A Double‐Center Randomized Controlled Trial
Authors: Bogomolova Katerina , van der Ham Ineke J.M. , Dankbaar Mary E.W. , van den Broek Walter W. , Hovius Steven E.R. , van der Hage Jos A. , Hierck Beerend P. 
Published: December 2019

Monoscopically projected three‐dimensional (3D) visualization technology may have significant disadvantages for students with lower visual‐spatial abilities despite its overall effectiveness in teaching anatomy. Previous research suggests that stereopsis may facilitate a better comprehension of anatomical knowledge. This study evaluated the educational effectiveness of stereoscopic augmented reality (AR) visualization and the modifying effect of visual‐spatial abilities on learning. In a double‐center randomized controlled trial, first‐ and second‐year (bio)medical undergraduates studied lower limb anatomy with stereoscopic 3D AR model (n = 20), monoscopic 3D desktop model (n = 20), or two‐dimensional (2D) anatomical atlas (n = 18). Visual‐spatial abilities were tested with Mental Rotation Test (MRT), Paper Folding Test (PFT), and Mechanical Reasoning (MR) Test. Anatomical knowledge was assessed by the validated 30‐item paper posttest. The overall posttest scores in the stereoscopic 3D AR group (47.8%) were similar to those in the monoscopic 3D desktop group (38.5%; P = 0.240) and the 2D anatomical atlas group (50.9%; P = 1.00). When stratified by visual‐spatial abilities test scores, students with lower MRT scores achieved higher posttest scores in the stereoscopic 3D AR group (49.2%) as compared to the monoscopic 3D desktop group (33.4%; P = 0.015) and similar to the scores in the 2D group (46.4%; P = 0.99). Participants with higher MRT scores performed equally well in all conditions. It is instrumental to consider an aptitude–treatment interaction caused by visual‐spatial abilities when designing research into 3D learning. Further research is needed to identify contributing features and the most effective way of introducing this technology into current educational programs.
DyF3: An Efficient Electrocatalyst for N2 Fixation to NH3 under Ambient Conditions
Authors: Li Yuanfang , Li Tingshuai , Zhu Xiaojuan , Alshehri Abdulmohsen Ali , Alzahrani Khalid Ahmed , Lu Siyu , Sun Xuping 
Published: December 2019

AbstractNH3 synthesis by the Haber–Bosch method is regarded as the dominant method in industry. Such a process is energy‐intensive, accompanied by a large amount of CO2 emission. Electrocatalytic N2 reduction is a sustainable avenue for NH3 production at ambient conditions. However, it needs a catalyst to boost the N2 reduction reaction. Here, we demonstrate that DyF3 is an efficient electrocatalyst. In 0.1 m Na2SO4, DyF3 attains a large NH3 yield of 10.9 μg h−1 mg−1cat. at −0.45 V vs. the reversible hydrogen electrode, with the corresponding Faradaic efficiency of 8.8 %. Furthermore, this catalyst exhibits high electrochemical stability.
Photoswitchable Adhesives Using Azobenzene‐Containing Materials
Authors: Xu Guofeng , Li Shuxiu , Liu Chengwei , Wu Si 
Published: December 2019

AbstractPhotoinduced reversible solid‐to‐liquid transitions of azobenzene‐containing materials can control adhesion. Photoswitchable adhesives based on azobenzene‐containing small molecules and polymers are under intense investigation. The melting points or glass transition temperatures of such azobenzene‐containing materials intransandcisforms are above and below room temperature, respectively. Photoswitching of these materials results in reversibletrans‐cisisomerization and solid‐to‐liquid transitions. The solidtransazobenzene‐containing materials have strong adhesion and the liquidcisazobenzene‐containing materials have weaker adhesion. In this Minireview, we introduce adhesives based on azobenzene‐containing small molecules and polymers. The remaining challenges and perspectives in the field of photoswitchable adhesives using azobenzene‐containing materials are also discussed.
Design and Synthesis of ZnII‐Coordination Polymers Anchored with NSAIDs: Metallovesicle Formation and Multi‐drug Delivery
Authors: Bera Sourabh , Chowdhury Abhinanda , Sarkar Koushik , Dastidar Parthasarathi 
Published: December 2019

AbstractA series of coordination polymers synthesized from a bis‐pyridyl linker, namely 4,4′‐azopyridine (L), selected non‐steroidal‐anti‐inflammatory drugs (NSAIDs), namely diclofenac (Dic), ibuprofen (Ibu), flurbiprofen (Flu), mefenamic acid (Mefe), and naproxen (Nap), and Zn(NO3)2 were characterized by single crystal X‐ray diffraction. One of the coordination polymers, namely CP3 derived from Flu, was able to form metallovesicles in DMSO, DMSO/H2O and DMSO/DMEM (biological media) as revealed by TEM, AFM and DLS. Metallovesicle formation by CP3 was further supported by loading a fluorescent dye, namely calcein, as well as an anti‐cancer drug, doxorubicin hydrochloride (DOX), as revealed by UV‐vis and emission spectra, and fluorescence microscopy. DOX‐loaded metallovesicles of CP3 (DOX@CP3‐vesicle) could be delivered in vitro to a highly aggressive human breast cancer cell line, namely MDA‐MB‐231, as revealed by MTT and cell migration assays, and also cell imaging performed under laser scanning confocal microscope (LSCM). Thus, a proof of concept for developing a multi‐drug delivery system derived from a metallovesicle for delivering an anti‐cancer drug to cancer cells is demonstrated for the first time.