bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bioinspired Structural Hierarchy within Macroscopic Volumes of Synthetic Composites
Authors: Rajasekharan Anand K. , Lotsari Antiope , Lutz‐Bueno Viviane , Liebi Marianne , Andersson Martin 
Published: July 2018

AbstractA key challenge in developing bioinspired composites is the fabrication of well‐defined 3D hierarchical structures ranging from nano to the macroscale. Herein, the development of a synthetic polymer–apatite composite realized by integrating bottom‐up self‐assembly and additive manufacturing (AM) is described. The resulting composite exhibits a bioinspired hierarchical structure over its 3D macroscopic volume. The composite is assembled in a bottom‐up manner, where periodic nanoscale assemblies of organic micellar fibrils and inorganic apatite nanocrystals are organized as bundles of mineralized microstructures. These microstructural bundles are preferentially oriented throughout the macroscopic volume of the material via extrusion based AM. The obtained structural hierarchy is investigated in 3D using electron microscopy and small angle X‐ray scattering tensor tomography and correlated to the structural hierarchy and anisotropy observed in biological tissues such as bone and the bone–cartilage interface. This work demonstrates the possibility to form polymer–apatite composites with a well‐defined hierarchical structure throughout its macroscopic volume, which is crucial for the development of mechanically optimized materials for applications such as bone and osteochondral implants.
Flexible VOx Nanosphere@SWCNT Hybrid Films with Dual‐Confinement Function of Polysulfides for High‐Performance Lithium–Sulfur Batteries
Authors: Zhang Miao , Yang Yang , Zhang Xinghua , Cheng Meng , Yuan Hongxin , Amin Kamran , Ahmad Aziz , Mao Lijuan , Yan Wei , Wei Zhixiang 
Published: July 2018

AbstractWith the rapid development of flexible electronics, a binder‐free, flexible sulfur composite material is required to fabricate a cathode for high energy density lithium–sulfur (Li–S) batteries. Here, a facile hydrothermal method is reported to control the synthesis of VOx hollow nanospheres (VHS) of different sizes. The sulfur‐loaded VHSs are further mixed with single‐walled carbon nanotubes (SWCNTs) to obtain a flexible binder‐free composite. SWCNTs intertwine around the VOx nanospheres and form an interconnective network to provide conductivity and structural integrity, whereas the small VOx nanospheres offer strong confinement and excellent adsorption ability for polysulfides, thus yielding good cyclability. Results illustrate that VHS with diameters of ≈200 nm (VHS‐200) show an outstanding capacity of 1069 mAh g−1 at 1 C, which is higher than that of VHS with diameters of ≈400 and 900 nm (VHS‐400 and VHS‐900). Notably, the electrode shows rate performance of 614 mAh g−1 at a high current rate of 20 C. Finally, the assembled flexible Li–S batteries show good bending and cycling stabilities in various bending angles, which is promising for potential applications in flexible electronics.
Plasma Enabled Synthesis and Processing of Materials for Lithium‐Ion Batteries
Authors: Joseph Jickson , Murdock Adrian T. , Seo Dong Han , Han Zhao Jun , O'Mullane Anthony P. , Ostrikov Kostya (Ken) 
Published: July 2018

AbstractLi‐ion batteries (LIBs) dominate the energy storage market owing to their versatility and efficient energy storage. Also, for electric vehicle applications, batteries with better power, safety, and cyclability are needed. To address the issues related to lower power density, lesser cyclability, low capacity retention, safety, cost, etc., several modifications like nanostructuring, 3D and 2D architectures, doping, core shell particles, binder free electrodes, modified electrolytes, and separators are employed. Plasma technologies can reduce the number of steps and time required for the synthesis of nanoarchitectures and material modifications, hence a reduction in the cost required to produce LIBs against the high initial investment required. This review paper aims at emphasizing plasma enabled modification and synthesis techniques for LIB electrodes, separators, electrolytes, and for recent advances like solid state and flexible batteries.
High‐Quality Indium Phosphide Films and Nano‐Network Grown Using Low‐Cost Metal‐Catalyzed Vapor–Liquid–Solid Method for Photovoltaic Applications
Authors: Hashemi Amiri Seyed Ebrahim , Gan Lin , Fan Fan , Ranga Praneeth , Ning Cun‐Zheng 
Published: July 2018

AbstractGrowth of high‐quality InP film is demonstrated by directly co‐evaporating elemental In and P in a simple low‐cost chemical vapor deposition (CVD) reactor. By exploring the interplay between the metal‐assisted vapor–liquid–solid and vapor–solid mechanisms, the authors present the growth of highly stoichiometric InP thin films or nano‐network in a wide range of growth temperature from 560 to 720 °C. Photoluminescence (PL) measurements reveal high optical quality of the as‐grown InP film with PL bandwidth (≈49 meV) comparable to commercial InP wafer (≈41 meV). The versatility of this approach is demonstrated through successful growth of thin films on diverse substrates such as silicon, InP, and fused quartz. The effects of catalysts are also studied by comparing growths based on Au‐catalyst with In‐self‐catalyst (without Au). The temperature dependence study of Au‐catalyzed growth shows that higher growth temperature results in formation of larger grain sizes and continuous void‐free polycrystalline InP films. Preliminary solar cell devices are fabricated on a p‐type silicon with an indium‐tin‐oxide contact layer. It is believed that the new growth strategy provides a simpler, lower cost (both precursors and substrates) approach for producing high‐quality InP thin film for the fabrication of high efficiency, low‐cost solar cells.
Shaping High‐Q Planar Fano Resonant Metamaterials toward Futuristic Technologies
Authors: Lim Wen Xiang , Manjappa Manukumara , Pitchappa Prakash , Singh Ranjan 
Published: July 2018

AbstractAdvances in plasmonic metamaterials have been rapidly evolving with innovations aimed at developing metadevices for real‐world applications. In reality, energy losses in plasmonic systems are prevalent and it is of paramount importance to come up with solutions that could overcome the limitations that impede further advancements toward the miniaturization of optoelectronic metadevices. High‐Q Fano resonance as a scattering phenomenon can be easily triggered by introducing asymmetry into plasmonic systems, and thus it offers a simple approach for reducing radiative losses through lineshape engineering. High‐Q Fano resonance possesses narrow linewidth and intensely confined electromagnetic fields, which makes it viable for widespread applications. The purpose of this review is to consolidate the current advances and contributions that high‐Q Fano resonance has made in the metamaterial community. Two general modes of energy loss including radiative and nonradiative losses are introduced and possible ways to overcome these challenges are examined. Furthermore, applications based on high‐Q Fano resonance including sensors, lasing spasers, and optical switches are discussed, embracing the future of Fano resonance based high performance photonic technologies.
Structural Color Sensors with Thermal Memory: Measuring Functional Properties of Ti‐Based Nitrides by Eye
Authors: Schnabel Volker , Spolenak Ralph , Doebeli Max , Galinski Henning 
Published: July 2018

AbstractTo ensure safe and reliable operation of materials with high thermal loads, e.g., in turbines or thermal solar collectors, it is key to detect material degradation. Here, a sensor concept providing a direct optical feedback of thermally induced hardness and resistivity changes in transition‐metal‐nitride functional coatings is presented. The sensor concept relies on a lossy Gires–Tournois interferometer configuration using thermally induced detuning of a highly absorbing state in the optical spectrum as feedback. It is demonstrated for the specific case of TiAlN coatings that such detuning is due to a symmetry‐breaking structural phase transition, which is accompanied by the formation of saturated structural colors.
Efficient Erbium‐Sensitized Core/Shell Nanocrystals for Short Wave Infrared Bioimaging
Authors: Wang Xin , Yakovliev Artem , Ohulchanskyy Tymish Y. , Wu Lina , Zeng Songjun , Han Xiaojun , Qu Junle , Chen Guanying 
Published: July 2018

AbstractThe 1500–1700 nm spectral range in short wave infrared (SWIR) region allows for biological imaging with large imaging depth, high contrast and resolution. However, very few SWIR imaging probes exist, and rarely reported probes (e.g., rare‐earth‐based ones with excitation at 980 nm) are often associated with biological heating effect. Here, a class of erbium (Er3+)‐sensitized core–shell nanocrystals of NaErF4:Yb3+@NaLuF4, which emit efficient SWIR luminescence peaked at 1525 nm under 808 nm excitation, without producing any local heating, is described. The inert shell inhibits concentration‐dependent quenching and allows for an enriched incorporation of 100% Er3+ into the core, yielding about ≈650‐fold higher SWIR luminescence than parent core nanocrystals. Importantly, an appropriate doping of ytterbium (Yb3+) (optimized concentration, 20%) into the core is shown to further enhance SWIR luminescence (by twofold), endowing the nanocrystals with a high quantum yield of 11%. This Yb3+‐mediated enhancement is possibly due to the suppression of upconverting pathways and the formation of energy trapping centers that prevent the energy migration to intrinsic lattice defects. These bright SWIR core/shell nanocrystals allow high contrast in vitro imaging of HeLa cells and in vivo through‐skull imaging of blood vasculature in the mouse brain.
Conductivity and Pseudocapacitance Optimization of Bimetallic Antimony–Indium Sulfide Anodes for Sodium‐Ion Batteries with Favorable Kinetics
Authors: Huang Yongxin , Wang Ziheng , Jiang Ying , Li Shuaijie , Wang Min , Ye Yusheng , Wu Feng , Xie Man , Li Li , Chen Renjie 
Published: July 2018

AbstractMetal sulfides show promise for use in alkali‐ion batteries because of their high theoretical capacities. However, their poor cycling stability and rate performance hinder their further development. To avoid these issues, In2S3 into Sb2S3 is introduced to improve its electrochemical properties by optimizing its crystal structure and sodium storage mechanism. A heterostructure composed of In2S3 and Sb2S3 shows a unique morphology of formicary microspheres, which provide abundant channels for fast transfer of sodium ions, large surface area for a high pseudocapacitance effect, and enough voids to relieve volume expansion. A sodium‐ion battery containing the bimetallic sulfide anode exhibits a high reversible capacity of 400 mA h g−1 and long cycle life of about 1000 cycles. Similarly, a high capacity of ≈610 mA h g−1 is achieved for a lithium‐ion battery containing the anode. During sodiation/desodiation, the synergistic effect of In2S3 and Sb2S3 enhances electronic conductivity and supports the host structure, preventing collapse. The cycling performance and rate performance of the In2S3–Sb2S3 anode are further improved by wrapping the electrode with carbon nanotubes. Even at a high current density of 3.2 A g−1, this carbon composite structure still shows a capacity of about 355 mA h g−1.
Adaptable Fast Relaxing Boronate‐Based Hydrogels for Probing Cell–Matrix Interactions
Authors: Tang Shengchang , Ma Hao , Tu Hsiu‐Chung , Wang Huei‐Ren , Lin Po‐Chiao , Anseth Kristi S. 
Published: July 2018

AbstractHydrogels with tunable viscoelasticity hold promise as materials that can recapitulate many dynamic mechanical properties found in native tissues. Here, covalent adaptable boronate bonds are exploited to prepare hydrogels that exhibit fast relaxation, with relaxation time constants on the order of seconds or less, but are stable for long‐term cell culture and are cytocompatible for 3D cell encapsulation. Using human mesenchymal stem cells (hMSC) as a model, the fast relaxation matrix mechanics are found to promote cell–matrix interactions, leading to spreading and an increase in nuclear volume, and induce yes‐associated protein/PDZ binding domain nuclear localization at longer times. All of these effects are exclusively based on the hMSCs' ability to physically remodel their surrounding microenvironment. Given the increasingly recognized importance of viscoelasticity in controlling cell function and fate, it is expected that the synthetic strategies and material platform presented should provide a useful system to study mechanotransduction on and within viscoelastic environments and explore many questions related to matrix biology.
Long‐term outcomes following restorative proctocolectomy ileal pouch‐anal anastomosis in pediatric ulcerative colitis patients: Multicenter national study in Japan
Authors: Ikeuchi Hiroki , Uchino Motoi , Sugita Akira , Futami Kitaro , Fukushima Kouhei , Hata Keisuke , Koganei Kazutaka , Kusunoki Masato , Uchida Keiichi , Nezu Riichiro , Kimura Hideaki , Takahashi Kenichi , Itabashi Michio , Kameyama Hitoshi , Higashi Daijiro , Koyama Fumikazu , Ueda Takeshi , Mizushima Tsunekazu , Suzuki Yasuo 
Published: July 2018

AbstractBackgroundFew studies have investigated surgical outcomes following a colectomy in pediatric patients with ulcerative colitis (UC).PurposeThis study aimed to determine long‐term outcomes in a large cohort of pediatric patients who underwent proctocolectomy with ileal pouch‐anal anastomosis (IPAA) for UC.MethodsPediatric patients (<17 years old) who underwent surgery at 12 different hospitals in Japan between May 1979 and March 2015 were included in this study. Information was obtained by the use of a questionnaire survey.ResultsThere were 113 (53.3%) male and 99 (46.7%) female pediatric patients. The most common indication for elective surgery was failure of medical management, whereas emergency surgery was carried out for fulminant cases. A hand‐sewn IPAA was used with a mucosectomy in 112 (52.8%), stapled anastomosis in 93 (43.9%), and not specified in 7 (3.3%) patients. Small bowel obstruction and surgical site infection were the most frequent early postoperative complications (POC), whereas pouchitis, small bowel obstruction, and perianal fistula were frequent late POC. The most common late POC was pouchitis, found in 38 (17.9%) of the patients, whereas pouch failure was noted in 11 patients at the latest follow‐up examination. Cumulative pouch survival rate after 10 years was 91.7%. There were no significant differences regarding gender or anastomotic procedure in relation to cumulative pouch survival rate.ConclusionTo avoid pouch failure following an IPAA procedure, it is important to recognize that pouchitis or an anal fistula may lead to this condition in pediatric UC patients.
Heterogeneous Bimetallic Catalysts for Upgrading Biomass‐Derived Furans
Authors: Singh Sanjay Kumar 
Published: July 2018

AbstractTransformation of furans derived from biomass is a sustainable methodology to produce a wide range of chemicals for various applications. In this direction, involvement of catalysts and catalytic processes for biomass transformation is of critical importance to achieve enhanced transformation, controlled product selectivity and less‐energy intensive process. This review focuses on the recent progress in the field of catalytic transformation of biomass derived furfural and 5‐hydroxymethylfurfural (HMF) to various value‐added chemicals using bimetallic catalysts. This review provides a detailed overview on various factors controlling the performance of the bimetallic catalysts for various reactions (e. g., hydrogenation, oxidation, hydrodeoxygenation) involved during the transformation of these furans. In particular, importance of intermetallic synergistic interactions of the bimetallic heterogeneous catalysts in biomass transformation is highlighted.
Reversible Fluorescence Modulation in a Dyad Comprising Phenothiazine Derivative and Spiropyran
Authors: Ramakrishna Bheerappagari , Narayanaswamy Kamatham , Singh Surya Prakash , Bangal Prakriti Ranjan 
Published: July 2018

AbstractWith the objective of developing fluorescent switch molecule, we have designed, synthesized and photophysically characterized a novel fluorophore‐photochrome dyad molecule comprising Phenothiazine derivative (PTCN, 4) and photochromic spiropyran (SP, 6). We successfully demonstrate that the photochromic behaviours of spiropyran unit regulate the fluorescence behaviours of phenothiazine derivative in terms of change in fluorescence intensity in PTCN‐SP(8) dyad in the solution as well as in the solid state by employing steady state spectroscopic techniques. The as prepared PTCN‐SP(8) is strongly fluorescent with fluorescent quantum yield more than 10% and regards as fluorescent “on” state. The spiropyran ring of photochrome (SP) opens up forming isomeric conformer, known as marocyanin (MC), upon UV irradiation in the dyad. This photogenerated isomer (MC) acts as an energy acceptor for PTCN fluorophore and energy transfer occurs from PTCN to MC via Förster resonance energy transfer (FRET) mechanism which leads to quench the fluorescence of PTCN and it is assigned to fluorescent “off” state. Subsequent visible light irradiation or thermal stimulation to the dyad is accompanied by ring close isomer SP along with complete reversal of the characteristic fluorescence of the PTCN(4), fluorescent “on” state. As a result, the photoinduced reversible transformations of the photochromic component within the dyad effectively bring “on” and “off” states of the PTCN fluorescence emission. Indeed, the fluorescence of this photoswitchable dyad is modulated for several cycles with excellent fatigue resistance under optical control for both in solution and solid phases. Thus, the choice of PTCN(4) as fluorescent probe in the dyad can ultimately lead to the development of valuable photoswitchable fluorescent probe for device applications.
Automated Electrochemical Assembly of the β‐(1,3)‐β‐(1,6)‐Glucan Hexasaccharide Using Thioglucoside Building Blocks
Authors: Manmode Sujit , Kato Moeko , Ichiyanagi Tsuyoshi , Nokami Toshiki , Itoh Toshiyuki 
Published: July 2018

AbstractThis study deals with the design, synthesis, and rational optimization of carbohydrate building blocks of glucosides for automated electrochemical assembly of β‐glucans. Oxidation potentials of building blocks with various types of protecting groups of hydroxyl groups were measured to estimate their reactivity under anodic oxidation conditions. Building blocks for both β‐1,3‐ and β‐1,6‐glycosidic linkages were optimized by an automated electrochemical assembly of disaccharides and trisaccharides. Several synthetic attempts were also made for the synthesis of the hexasaccharide repeating unit in a macrocyclic β‐glucan tridecasaccharide.
Katalytische, aerobe Oxidation von C(sp3)‐H‐Bindungen
Authors: Sterckx Hans , Morel Bénédicte , Maes Bert U. W. 
Published: July 2018

AbstractOxidationsreaktionen sind eine Schlüsseltechnologie in der Umwandlung von Rohstoffen aus Erdöl zu Substanzen höherer Oxidationsstufen, von denen ausgehend weitere Umsetzungen möglich sind. Diese Oxidationsprozesse nutzen meist molekularen Sauerstoff im letzten Schritt, da dieser im Großmaßstab typischerweise das einzige wirtschaftliche Oxidationsmittel darstellt. Die so hergestellten Basischemikalien weisen üblicherweise kaum funktionelle Gruppen auf und sind zudem meist hoch symmetrisch, weshalb die Frage nach der Selektivität oft keine Rolle spielt. Dagegen werden bei der Herstellung von Feinchemikalien noch immer klassische Oxidationsmittel bevorzugt. Für die Entwicklung nachhaltigerer Produktionsprozesse ist der Einsatz von Sauerstoff eine logische Wahl. Wegen der zahlreichen funktionellen Gruppen und der Komplexität von Feinchemikalien ist das Erreichen von Regio‐ und Chemoselektivität hier besonders anspruchsvoll. Dieser Aufsatz präsentiert die wichtigsten derzeitigen katalytischen Systeme zur aeroben Oxidation sowie die aktuellen Erkenntnisse über die jeweiligen Reaktionsmechansimen.
Aryldiazonium Salts as Nitrogen‐Based Lewis Acids: Facile Synthesis of Tuneable Azophosphonium Salts
Authors: Habraken Evi R. M. , van Leest Nicolaas P. , Hooijschuur Pim , de Bruin Bas , Ehlers Andreas W. , Lutz Martin , Slootweg J. Chris 
Published: July 2018

AbstractInspired by the commercially available azoimidazolium dyes (e.g., Basic Red 51) that can be obtained from aryldiazonium salts and N‐heterocyclic carbenes, we developed the synthesis of a unique set of arylazophosphonium salts. A range of colours were obtained by applying readily tuneable phosphine donor ligands and para‐substituted aryldiazonium salts as nitrogen‐based Lewis acids. With cyclic voltammetry, a general procedure was designed to establish whether the reaction between a Lewis acid and a Lewis base occurs by single‐electron transfer or electron‐pair transfer.
Catalytic Aerobic Oxidation of C(sp3)−H Bonds
Authors: Sterckx Hans , Morel Bénédicte , Maes Bert U. W. 
Published: July 2018

AbstractOxidation reactions are a key technology to transform hydrocarbons from petroleum feedstock into chemicals of a higher oxidation state, allowing further chemical transformations. These bulk‐scale oxidation processes usually employ molecular oxygen as the terminal oxidant as at this scale it is typically the only economically viable oxidant. The produced commodity chemicals possess limited functionality and usually show a high degree of symmetry thereby avoiding selectivity issues. In sharp contrast, in the production of fine chemicals preference is still given to classical oxidants. Considering the strive for greener production processes, the use of O2, the most abundant and greenest oxidant, is a logical choice. Given the rich functionality and complexity of fine chemicals, achieving regio/chemoselectivity is a major challenge. This review presents an overview of the most important catalytic systems recently described for aerobic oxidation, and the current insight in their reaction mechanism.
Synthesis, DNA binding mode, singlet oxygen photogeneration and DNA photocleavage activity of ruthenium compounds with porphyrin–imidazo[4,5‐f]phenanthroline conjugated ligand
Authors: Jiang Jun , Liu Dan , Zhao Yimei , Wu Fengshou , Yang Ke , Wang Kai 
Published: July 2018

Using 1,10‐phenanothroline‐5,6‐dione and 10,20‐bis(4‐methylphenyl)porphyrin copper as starting materials, a conjugated porphyrin–imidazo[4,5‐f]‐1,10‐phenanothroline ligand (Por1) was prepared. Subsequently, the copper complex of Por1was reacted with Ru(1,10‐phenanothroline)2Cl2to yield ruthenium compound Por2. After removal of copper metal under acid condition, the free base porphyrin of Por2(Por3) was prepared. The structure of these compounds was confirmed using UV–visible,1H NMR, mass and infrared spectroscopies and elemental analysis. Through UV–visible, fluorescence and circular dichroism analyses, the interaction modes between Por1–3and calf thymus DNA were investigated. Por1interacted with DNA via outside groove face, but Por2and Por3showed intercalative interaction with DNA. Binding constants between Por1–3and DNA were 7.79 × 105, 1.29 × 106and 1.32 × 106 M−1, respectively. With 5,10,15,20‐tetraphenylporphyrin (H2TPP) as a control, the singlet oxygen (1O2) generation of Por1–3was measured using the 1,3‐diphenylisobenzofuran method. The1O2generation rate of Por1–3followed the order: Por3>Por1>H2TPPP >Por2. Por1and Por3showed better1O2quantum yields than Por2, which were almost threefold higher than that of H2TPP. The DNA cleavage ability of Por1–3was analyzed using gel electrophoresis. Por3showed higher DNA photocleavage activity, with more than 50% photocleavage rate at 20 μM. These results suggest that amphipathic (hydrophilic/lipophilic) Por3with conjugated Por1ligand is a potential photosensitizer in cancer therapy.