bluuebunny/crossref_metadata_2025_split huggingface dataset:
Vis‐NIR Light‐Responsive Photocatalytic Activity of C3N4−Ag−Ag2O Heterojunction‐Decorated Carbon‐fiber Cloth as Efficient Filter‐Membrane‐Shaped Photocatalyst
Authors: Shen Xiaofeng , Zhang Yan , Duoerkun Gumila , Shi Zhun , Liu Jianshe , Chen Zhigang , Keung Wong Po , Zhang Lisha 
Published: January 2019

AbstractC3N4‐decorated carbon‐fiber (CF) cloth has been demonstrated to be a filter‐membrane‐shaped photocatalyst for degrading flowing wastewater, but it can be excited only by visible light (λ<450 nm). To extend the photoresponse range to NIR region, herein we have designed and prepared C3N4−Ag−Ag2O heterojunctions on CF cloth. The growth of C3N4 nanosheets (thickness: 20–30 nm) on CF cloth is realized by a thermal condensation method, and then Ag/Ag2O nanoparticles (10–20 nm) are deposited on CF/C3N4 cloth by a chemical precipitation method. CF/C3N4/Ag/Ag2O cloth exhibits excellent flexibility and strong photoabsorption in a broad Vis‐NIR region (400–1400 nm), wider than CF/C3N4 (absorption edge: 450 nm). Under the irradiation of 808 nm or 980 nm laser, CF/C3N4/Ag/Ag2O cloth can remove 83 %/41 % AO7 and 72 %/38 % 4‐CP in 140 min respectively, significantly higher than those (33 %/13 % AO7 and 31 %/10 % 4‐CP) by CF/Ag/Ag2O cloth and those (3 %/1 % AO7 and 0 %/1 % 4‐CP) by CF/C3N4 cloth. Interestingly, when CF/C3N4/Ag/Ag2O cloth is used as the filter‐membrane to photo‐degrade the flowing wastewater (AO7, 20 mg L−1, rate: 1.5 L h−1), the removal efficiency of AO7 reaches up 97 % after 8 grade reactors. Therefore, CF/C3N4/Ag/Ag2O cloth can be used as an efficient filter‐membrane‐shaped photocatalyst with NIR photoresponse.
Hierarchical Zn‐Doped CoO Nanoflowers for Electrocatalytic Oxygen Evolution Reaction
Authors: Huo Meiling , Yang Zhiyuan , Yang Chenxi , Gao Zhong , Qi Jing , Liang Zuozhong , Liu Kaiqiang , Chen Heyin , Zheng Haoquan , Cao Rui 
Published: January 2019

AbstractHierarchical Zn‐doped CoO nanoflowers have been prepared using their hydroxides as precursors. The nanoflowers are assembled by dozens of 2D nanoplates. Each nanoplate is formed by numerous Zn‐doped CoO nanoparticles. Zn‐doped CoO catalyst is highly efficient for electrocatalytic water oxidation with a low overpotential (η=293 mV at j=10 mA cm−2) and long‐term stability, which is comparable to the commercial RuO2 catalysts in alkaline media. The 3D hierarchical structure provides abundant surface catalytic sites, while the density functional theory (DFT) calculations show that the Zn doping is also beneficial for the enhanced oxygen evolution reaction (OER) activities. This series of novel hierarchical porous nanoflowers is a promising anode material for water oxidation.
Review on Metal Sulphide‐based Z‐scheme Photocatalysts
Authors: Di Tingmin , Xu Quanlong , Ho WingKei , Tang Hua , Xiang Quanjun , Yu Jiaguo 
Published: January 2019

AbstractSemiconductor‐based Z‐scheme heterojunction photocatalysts have received considerable attention for solar energy conversion and environmental purification due to their spatially separated reduction and oxidation sites, effective separation and transportation of photo‐excited charge carriers and strong redox ability. With their wide visible‐light responsive range and high photocatalytic activity, metal sulphide is an important material in developing photocatalysts. This review summarizes and highlights recent research progress in sulphide‐based direct Z‐scheme photocatalysts, followed by analysis on the limitations over all‐solid‐state Z‐scheme photocatalyst. Furthermore, the applications and characterization methods of sulphide‐based direct Z‐scheme photocatalyst are summarized. Finally, the challenges and perspectives of sulphide‐based Z‐scheme photocatalyst are discussed.
All Fiber Based Electrochemical Capacitor towards Wearable AC Line Filters with Outstanding Rate Capability
Authors: Gao Kaifei , Wang Siliang , Liu Weijie , Yue Yang , Rao Jiangyu , Su Jun , Li Luying , Zhang Zhi , Liu Nishuang , Xiong Lun , Gao Yihua 
Published: January 2019

AbstractDue to their high spatial utilization, excellent flexibility and good adaptability, fiber‐shaped devices have promising potential for applications in wearable electronics. However, the fiberization process of the component with alternate current (AC) line filtering function is still far from being satisfactory, since it is difficult to arrange an ordered structure in a fiber shape in large‐scale manufacturing. This leads to a slow frequency response. Herein, a weavable fiber‐shaped electrochemical capacitor (SC) for AC line filtering is made of reduced graphene oxide (rGO) fibers with a highly oriented porous structure by wet‐spinning method. The highly consistent orientations of the rich pores greatly improve the ionic accessible sites, ion mobility and the electron transport pathways. As a result, the all‐fiber‐based SC revealing a high rate performance (500 V s−1) and a fast frequency response (RC time constant ∼0.241 ms, phase angle ∼−80°) is successfully applied to filter ±1.5 V AC to 1.04 V direct current (DC). Notably, the highly flexible SC exhibits an outstanding consistency during the performance test at bending and folding states. This work shows a potential substitution for aluminium electrolytic capacitors (AEC) towards wearable electronic.
Cyanohydridoborate Anions: Synthesis, Salts, and Low‐Viscosity Ionic Liquids
Authors: Bischoff Lisa A. , Drisch Michael , Kerpen Christoph , Hennig Philipp T. , Landmann Johannes , Sprenger Jan A. P. , Bertermann Rüdiger , Grüne Matthias , Yuan Qinqin , Warneke Jonas , Wang Xue‐Bin , Ignat'ev Nikolai V. , Finze Maik 
Published: January 2019

AbstractHigh‐yield syntheses up to molar scales for salts of [BH(CN)3]− (2) and [BH2(CN)2]− (3) starting from commercially available Na[BH4] (Na5), Na[BH3(CN)] (Na4), BCl3, (CH3)3SiCN, and KCN were developed. Direct conversion of Na5 into K2 was accomplished with (CH3)3SiCN and (CH3)3SiCl as a catalyst in an autoclave. Alternatively, Na5 is converted into Na[BH{OC(O)R}3] (R=alkyl) that is more reactive towards (CH3)3SiCN and thus provides an easy access to salts of 2. Some reaction intermediates were identified, for example, Na[BH(CN){OC(O)Et}2] (Na7 b) and Na[BH(CN)2{OC(O)Et}] (Na8 b). A third entry to 2 and 3 uses ether adducts of BHCl2 or BH2Cl such as the commercial 1,4‐dioxane adducts that react with KCN and (CH3)3SiCN. Alkali metal salts of 2 and 3 are convenient starting materials for organic salts, especially for low viscosity ionic liquids (ILs). [EMIm]3 has the lowest viscosity and highest conductivity with 10.2 mPa s and 32.6 mS cm−1 at 20 °C known for non‐protic ILs. The ILs are thermally, chemically, and electrochemically robust. These properties are crucial for applications in electrochemical devices, for example, dye‐sensitized solar cells (Grätzel cells).
New Casbanes and the First trans‐Cyclopropane seco‐Casbane from the Australian Rainforest Plant Croton insularis
Authors: Maslovskaya Lidiya A. , Savchenko Andrei I. , Pierce Carly J. , Boyle Glen M. , Gordon Victoria A. , Reddell Paul W. , Parsons Peter G. , Williams Craig M. 
Published: January 2019

AbstractInvestigation of the Australian rainforest plant Croton insularis revealed seven new cis‐, two new trans‐cyclopropane casbanes, and the first trans‐cyclopropane seco‐casbane. The relative configuration of the cyclopropane moiety for all compounds (EBC‐182, 217, 218, 220, 343, 357, 358, 361, 365, 373; EBC=EcoBiotics Compound) was assigned using 13C NMR data. Comparison of the experimental electronic circular dichroism (ECD) spectra with the theoretical curves, calculated by TD‐DFT at the B3LYP/6‐31+G**//B3LYP/6‐31+G** level, in conjunction with NOE data afforded the absolute configuration. EBC‐180, 181 and 220 displayed potent activity against cervical carcinoma (HeLa cells).
Ensemble Effects in the Temperature‐Dependent Photoluminescence of Silicon Nanocrystals
Authors: Jakob Matthias , Javadi Morteza , Veinot Jonathan G. C. , Meldrum Al , Kartouzian Aras , Heiz Ulrich 
Published: January 2019

AbstractIn this work the temperature‐dependent photoluminescence of alkyl‐capped silicon nanocrystals with mean diameters of between 3 and 9 nm has been investigated. The nanocrystals were characterized extensively by FTIR, TEM, powder XRD, and X‐ray photoelectron spectroscopy prior to low‐temperature and time‐resolved photoluminescence spectroscopy experiments. The photoluminescence (PL) properties were evaluated in the temperature range of 41–300 K. We found that the well‐known temperature‐dependent blueshift of the PL maximum decreases with increasing nanocrystal diameter and eventually becomes a redshift for nanocrystal diameters larger than 6 nm. This implies that the observed shifts cannot be explained solely by band‐gap widening, as is commonly assumed. We propose that the luminescence of drop‐cast silicon nanocrystals is affected by particle ensemble effects, which can explain the otherwise surprising temperature dependence of the luminescence peak.
Direct Measurement of Through‐Bond Effects in Molecular Multivalent Interactions
Authors: Feng Xueyan , Yu Chanchan , Feng Feng , Lu Pan , Chai Yahong , Li Qilong , Zhang Di , Wang Xiuyu , Yao Li 
Published: January 2019

AbstractMultivalent interactions occur throughout biology, and have a number of characteristics that monovalent interactions do not. However, it remains challenging to directly measure the binding force of molecular multivalent interactions and identify the mechanism of interactions. In this study, the specific interaction between bivalent aptamer and thrombin has been measured directly and quantitatively by force‐induced remnant magnetization spectroscopy to investigate the binding force and through‐bond effects of the multivalent interactions. The measured differential binding forces enable through‐bond effects in thrombin–aptamer complexes to be identified, where aptamer binding at exosite II produces visible effects on their binding at exosite I and vice versa. This method might be suitable for practical applications in the design of high‐performance ligands.
A Fluorescence Light‐Up Silver Nanocluster Beacon Modulated by Metal Ions and Its Application in Telomerase‐Activity Detection
Authors: Peng Manshu , Na Na , Ouyang Jin 
Published: January 2019

AbstractDNA‐templated silver nanoclusters (DNA‐AgNCs) have been extensively studied in recent years. The enhancement of fluorescence emission from DNA‐AgNCs is still being explored. Herein, a study on the fluorescence enhancement of DNA‐AgNCs induced by metal ions is reported. The enhancement is greatly dependent on the primary sequence and secondary structure of the DNA strands. Thus, a label‐free AgNCs‐based molecular beacon (MB) was explored for the detection of telomerase activity. Nonfluorescent MB‐AgNCs in phosphate buffer emit dramatic red fluorescence when Mg2+ is introduced, whereas Mg2+ has a limited effect on the weak fluorescence of DNA‐AgNCs when the hairpin structure of MB is opened. Telomerase primer can be elongated by telomerase, which results in unfolding of MB in a strand‐displacement reaction. On the basis of the different brightnesses of AgNCs produced by the two DNA templates, telomerase activity can be detected. The MB‐AgNCs sensing platform provides a simple and low‐cost method to detect telomerase activity and shows great potential in the construction of cost‐effective probes for biomolecular detection.
Oxygen‐Deficient Dumbbell‐Shaped Anatase TiO2−x Mesocrystals with Nearly 100 % Exposed {101} Facets: Synthesis, Growth Mechanism, and Photocatalytic Performance
Authors: Li Yongjun , Ye Xiaozhou , Cao Shengxin , Yang Chujing , Wang Yun , Ye Jianfeng 
Published: January 2019

AbstractThe development of hierarchical TiO2 superstructures with new morphologies and intriguing photoelectric properties for utilizing solar energy is known to be an effective approach to alleviate the serious problems of environmental pollution. Herein, unique oxygen‐deficient dumbbell‐shaped anatase TiO2−x mesocrystals (DTMCs) enclosed by nearly 100 % {101} facets were readily synthesized by mesoscale transformation in TiCl3/acetic acid (HAc) mixed solution, followed by calcination under vacuum. These mesocrystals exhibited much higher photoreactivity toward removing the model pollutants methyl orange and CrVI than truncated tetragonal bipyramidal anatase nanocrystals (TNCs), anatase mesocrystals built from truncated tetragonal bipyramidal anatase nanocrystals (TTMCs), and anatase mesocrystals constructed by anatase nanocrystals with nearly 100 % exposed {101} facets (TMCs), revealing that both the oxidation and reduction abilities of anatase TiO2 were simultaneously enhanced upon fabricating an oxygen‐deficient mesocrystalline architecture with about 100 % exposed {101} facets. Further characterization illustrated that such an enhancement of photoreactivity was mainly due to the strengthened light absorption, boosted charge carrier separation, and nearly 100 % exposed {101} facets of the oxygen‐deficient dumbbell‐shaped anatase mesocrystals. This work will be useful for guiding the synthesis of oxygen‐deficient ordered superstructures of metal oxides with desired morphologies and exposed facets for promising applications in environmental remediation.
Selective Carbanion–Pyridine Coordination of a Reactive P,N Ligand to RhI
Authors: Devillard Marc , Ehlers Andreas , Siegler Maxime A. , van der Vlugt Jarl Ivar 
Published: January 2019

AbstractLigands with reactive carbon sites in the periphery of a metal center have emerged as a powerful approach for metal–ligand bond activation. These reactive carbon sites are commonly generated by deprotonation strategies. Carbon–silicon bond cleavage is a potential alternative to access such constructs. Herein, the monodesilylation of bis‐silyl‐substituted P,N scaffold PNSi2 in the coordination sphere of [RhI(Cl)(CO)(PNSi2)] (1) with sodium azide is disclosed. This affords a unique dinucleating anionic κ2‐C,N‐κ1‐P ligand with a carbanionic methine carbon atom directly bound to rhodium as part of a four‐membered Rh‐N‐C‐C rhodacycle. This dimer undergoes meta‐pyridine C−H activation facilitated by weak bases, which leads to a desymmetrization of the system and provides a σ,π‐bridging 3‐pyridyl fragment bound to RhI. The facile Si−C cleavage strategy may pave the way to studying the reactivity and functionalization of a variety of κ2‐C,N‐coordinated pyridine scaffolds for selective transformations.
Nanowire‐Templated Synthesis of FeNx‐Decorated Carbon Nanotubes as Highly Efficient, Universal‐pH, Oxygen Reduction Reaction Catalysts
Authors: Li Yanqiang , Huang Huiyong , Chen Siru , Wang Chao , Ma Tingli 
Published: January 2019

AbstractIt is of increasing importance to develop highly active and economical oxygen reduction reaction (ORR) electrocatalysts, which have great significance for the large‐scale implementation of various energy conversion systems, including metal–air batteries and fuel cells. Herein, a novel method to synthesize FeNx‐decorated carbon nanotubes as a high‐efficiency ORR catalyst, by utilizing ZnO nanowires as a sacrificial template and a Fe–polydopamine complex as metal and carbon sources, is reported. The obtained catalyst shows great potential for replacing Pt/C as the ORR catalyst under various pH conditions, from alkaline to acidic electrolytes. The high conductivity, large surface area of the carbon nanotube, and highly active FeNx species contributed greatly to the high performance of the catalyst. The work presented herein paves a new way for the synthesis of 1D porous nanomaterials for a broad range of energy‐related applications.
Towards the Design of Optically Active Thiophene S‐Oxides using Quantum Chemistry
Authors: Verlinden Steven , Woller Tatiana , De Proft Frank , Verniest Guido , Alonso Mercedes 
Published: January 2019

AbstractThe importance of axially chiral biaryls has risen steeply in the recent decades. This structural motif proved to be successful in catalytic asymmetric synthesis and the configuration of the biaryl axis is decisive for the biological activity. A new approach for the atroposelective synthesis of biaryls would be through a cycloaddition between an enantiopure phenyl‐substituted thiophene S‐oxide and an alkyne. Importantly, the chiral center of the thiophene S‐oxide needs to be stable enough to avoid pyramidal inversion during the cycloaddition. Considering that the racemization of thiophene monoxides has been scarcely investigated so far, we perform a thorough quantum chemical study on the inversion barriers of a large number of chiral thiophene S‐oxide derivatives. Our main goal is to identify substitution patterns leading to stable atropisomers at room temperature. Appealingly, the role of stereoelectronic effects and the position of the substituents as well as the importance of aromaticity on the pyramidal inversion barrier are elucidated for the first time.
Metal–Organic Frameworks Harness Cu Chelating and Photooxidation Against Amyloid β Aggregation in Vivo
Authors: Yu Dongqin , Guan Yijia , Bai Fuquan , Du Zhi , Gao Nan , Ren Jinsong , Qu Xiaogang 
Published: January 2019

AbstractRecently, photooxygenation of amyloid β (Aβ) has emerged as an effective way to inhibit Aβ aggregation in Alzheimer's disease (AD) treatment. However, their further application has been highly obstructed by self‐aggregation, no metal chelating ability, and poor protein‐enrichment capacity. Herein, porphyrinic metal–organic frameworks (PMOFs) are utilized as a superior CuII chelating and photooxidation agent for inhibiting Aβ aggregation. We selected only four classical kinds of POMFs (Zr–MOF, Al–MOF, Ni–MOF, Hf–MOF) for further investigation in our study, which are stable in physiological conditions and exhibit excellent biocompatibility. Among them, Hf–MOF was the most efficient Aβ photooxidant. A possible explanation about the difference in capacity of 1O2 generation of these four PMOFs has been provided according to the experimental results and DFT calculations. Furthermore, Hf–MOFs are modified with Aβ‐targeting peptide, LPFFD. This can not only enhance Hf–MOFs targeting cellular Aβ to decrease Aβ‐induced cytotoxicity, but also improve Aβ photooxidation in the complicated living environment. More intriguingly, in vivo studies indicate that the well‐designed LPFFD modified Hf–MOFs can decrease Aβ‐induced neurotoxicity and extend the longevity of the commonly used transgenic AD model Caenorhabditis elegans CL2006. Our work may open a new avenue for using MOFs as neurotoxic‐metal‐chelating and photo‐therapeutic agents for AD treatment.
Synthesis of Polycyclic and Cage Siloxanes by Hydrolysis and Intramolecular Condensation of Alkoxysilylated Cyclosiloxanes
Authors: Sugiyama Tomoaki , Shiba Hiroya , Yoshikawa Masashi , Wada Hiroaki , Shimojima Atsushi , Kuroda Kazuyuki 
Published: January 2019

AbstractThe controlled synthesis of oligosiloxanes with well‐defined structures is important for the bottom‐up design of siloxane‐based nanomaterials. This work reports the synthesis of various polycyclic and cage siloxanes by the hydrolysis and intramolecular condensation of monocyclic tetra‐ and hexasiloxanes functionalized with various alkoxysilyl groups. An investigation of monoalkoxysilylated cyclosiloxanes revealed that intramolecular condensation occurred preferentially between adjacent alkoxysilyl groups to form new tetrasiloxane rings. The study of dialkoxy‐ and trialkoxysilylated cyclotetrasiloxanes revealed multistep intramolecular condensation reactions to form cubic octasiloxanes in relatively high yields. Unlike conventional methods starting from organosilane monomers, intramolecular condensation enables the introduction of different organic substituents in controlled arrangements. So‐called Janus cubes have been successfully obtained, that is, Ph4R4Si8O12, in which R=Me, OSiMe3, and OSiMe2Vi (Vi=vinyl). These findings will enable the creation of siloxane‐based materials with diverse functions.
Assembly of the Entire Carbon Backbone of a Stereoisomer of the Antitumor Marine Natural Product Hemicalide
Authors: Lecourt Camille , Dhambri Sabrina , Yamani Khalil , Boissonnat Guillaume , Specklin Simon , Fleury Etienne , Hammad Karim , Auclair Eric , Sablé Serge , Grondin Antonio , Arimondo Paola B. , Sautel François , Massiot Georges , Meyer Christophe , Cossy Janine , Sorin Geoffroy , Lannou Marie‐Isabelle , Ardisson Janick 
Published: January 2019

AbstractA strategy for the assembly of the entire carbon backbone of a stereoisomer of the antitumor marine natural product hemicalide has been investigated. The devised convergent approach relies on Horner–Wadsworth–Emmons and Julia–Kocienski olefination reactions for the construction of the C6=C7 and C34=C35 double bonds, respectively, an aldol reaction to create the C27−C28 bond, and a Suzuki–Miyaura cross‐coupling as the endgame to form the C15−C16 bond.
Imidazolidinones and Imidazolidine‐2,4‐diones as Antiviral Agents
Authors: Swain Sharada Prasanna , Mohanty Sandeep 
Published: January 2019

AbstractImidazolidinones and imidazolidine‐2,4‐diones are important classes of heterocyclic compounds that possess potent activities against several viruses such as dengue virus, enterovirus, hepatitis C virus (HCV), and human immunodeficiency virus (HIV). The first imidazolidinone derivative as an anti‐HIV agent was reported in 1996. Imidazolidinones inhibit HIV aspartic protease activity, and also act as CCR5 co‐receptor antagonists. Significant effort has been devoted to the design of various imidazolidinone analogues that are active against drug‐resistant HIV strains, with fewer side effects. Different scaffolds have been designed through both rational drug design strategies and computer‐aided drug design. Imidazolidinones have been found to be potent against HIV, and preclinical studies are currently in progress. There are some reports of imidazolidinones as having both anti‐HCV and anti‐dengue virus activity, and more research has yet to be done along these lines. These compounds inhibit NS3 serine protease of HCV, and NS2B‐NS3 protease of dengue virus. Pyridyl‐imidazolidinones possess very specific and potent activity against human enterovirus 71 (EV71) by targeting the EV71 capsid protein VP1, and inhibiting viral adsorption and/or viral RNA uncoating.
TAS‐120 Cancer Target Binding: Defining Reactivity and Revealing the First Fibroblast Growth Factor Receptor 1 (FGFR1) Irreversible Structure
Authors: Kalyukina Maria , Yosaatmadja Yuliana , Middleditch Martin J. , Patterson Adam V. , Smaill Jeff B. , Squire Christopher J. 
Published: January 2019

Abstract1‐[(3S)‐3‐[4‐Amino‐3‐[2‐(3,5‐dimethoxyphenyl)ethynyl]‐1H‐pyrazolo[3,4‐d]pyrimidin‐1‐yl]‐1‐pyrrolidinyl]‐2‐propen‐1‐one (TAS‐120) is an irreversible inhibitor of the fibroblast growth factor receptor (FGFR) family, and is currently under phase I/II clinical trials in patients with confirmed advanced metastatic solid tumours harbouring FGFR aberrations. This inhibitor specifically targets the P‐loop of the FGFR tyrosine kinase domain, forming a covalent adduct with a cysteine side chain of the protein. Our mass spectrometry experiments characterise an exceptionally fast chemical reaction in forming the covalent complex. The structural basis of this reactivity is revealed by a sequence of three X‐ray crystal structures: a free ligand structure, a reversible FGFR1 structure, and the first reported irreversible FGFR1 adduct structure. We hypothesise that the most significant reactivity feature of TAS‐120 is its inherent ability to undertake conformational sampling of the FGFR P‐loop. In designing novel covalent FGFR inhibitors, such a phenomenon presents an attractive strategy requiring appropriate positioning of an acrylamide group similarly to that of TAS‐120.