bluuebunny/crossref_metadata_2025_split huggingface dataset:
Flexible MoS2‐Embedded Human Serum Albumin Hollow Nanocapsules with Long Circulation Times and High Targeting Ability for Efficient Tumor Ablation
Authors: Xu Chaoli , Teng Zhaogang , Zhang Yunlei , Yuwen Lihui , Zhang Qi , Su Xiaodan , Dang Meng , Tian Ying , Tao Jun , Bao Lei , Yang Bin , Lu Guangming , Zhu Jiang 
Published: September 2018

AbstractHerein, MoS2‐embedded human serum albumin hollow nanocapsules (denoted MoS2/HSA) are successfully prepared via a hard‐core‐assisted layer‐by‐layer coating approach. The hollow MoS2/HSA nanocapsules possess an uniform size (280 nm), a larger hollow cavity, a low Young's modulus (222 ± 20 MPa), excellent photothermal conversion ability, and a high drug loading capacity for doxorubicin (27 wt%). The flexible hollow MoS2/HSA nanocapsules exhibit significantly enhanced cellular uptake efficiency against breast cancer cells duo to their flexible property and targeting ability of HSA. In vivo experiments show that the flexible MoS2/HSA could reduce phagocytosis and effectively improve blood persistence and tumor accumulation. In vitro and in vivo experiments have demonstrated that the flexible MoS2/HSA based nanoplatforms effectively ablate breast cancer cells via synergistic photothermal and chemical therapy.
Highly Active Nanoperovskite Catalysts for Oxygen Evolution Reaction: Insights into Activity and Stability of Ba0.5Sr0.5Co0.8Fe0.2O2+δ and PrBaCo2O5+δ
Authors: Kim Bae‐Jung , Cheng Xi , Abbott Daniel F. , Fabbri Emiliana , Bozza Francesco , Graule Thomas , Castelli Ivano E. , Wiles Luke , Danilovic Nemanja , Ayers Katherine E. , Marzari Nicola , Schmidt Thomas J. 
Published: September 2018

AbstractIt is shown that producing PrBaCo2O5+δ and Ba0.5Sr0.5Co0.8Fe0.2O2+δ nanoparticle by a scalable synthesis method leads to high mass activities for the oxygen evolution reaction (OER) with outstanding improvements by 10× and 50×, respectively, compared to those prepared via the state‐of‐the‐art synthesis method. Here, detailed comparisons at both laboratory and industrial scales show that Ba0.5Sr0.5Co0.8Fe0.2O2+δ appears to be the most active and stable perovskite catalyst under alkaline conditions, while PrBaCo2O5+δ reveals thermodynamic instability described by the density‐functional theory based Pourbaix diagrams highlighting cation dissolution under OER conditions. Operando X‐ray absorption spectroscopy is used in parallel to monitor electronic and structural changes of the catalysts during OER. The exceptional BSCF functional stability can be correlated to its thermodynamic meta‐stability under OER conditions as highlighted by Pourbaix diagram analysis. BSCF is able to dynamically self‐reconstruct its surface, leading to formation of Co‐based oxy(hydroxide) layers while retaining its structural stability. Differently, PBCO demonstrates a high initial OER activity while it undergoes a degradation process considering its thermodynamic instability under OER conditions as anticipated by its Pourbaix diagram. Overall, this work demonstrates a synergetic approach of using both experimental and theoretical studies to understand the behavior of perovskite catalysts.
Effect of Grain Cluster Size on Back‐Contact Perovskite Solar Cells
Authors: Lin Xiongfeng , Chesman Anthony S. R. , Raga Sonia R. , Scully Andrew D. , Jiang Liangcong , Tan Boer , Lu Jianfeng , Cheng Yi‐Bing , Bach Udo 
Published: September 2018

AbstractIncorporating interdigitated back‐contact electrodes into organic–inorganic halide perovskite solar cells overcomes the optical losses and low architectural defect tolerance present in conventional “sandwich” cell configurations. However, other factors limit device performance in back‐contact architectures, such as the short charge‐carrier diffusion length within the perovskite film relative to the electrode spacing. As charge‐carrier diffusion length is crystal‐size related, in order to understand the effect of perovskite morphology on the performance of back‐contact perovskite solar cells (bc‐PSCs), perovskite films with four different grain cluster sizes, i.e., large, medium, small, and extra small, are fabricated via a solvent annealing approach. Crystallization of the perovskite is found to be closely related to the surface chemistry and topography of the substrate. The bc‐PSC photovoltaic performance correlates positively with the perovskite grain cluster size. Through a detailed analysis of transient photovoltage decay measurements, time‐resolved photoluminescence, and space charge‐limited current measurements, the effect of defect densities associated with grain cluster boundaries is elucidated.
Design of Hollow Nanostructures for Energy Storage, Conversion and Production
Authors: Wang Jiangyan , Cui Yi , Wang Dan 
Published: September 2018

AbstractHollow nanostructures have shown great promise for energy storage, conversion, and production technologies. Significant efforts have been devoted to the design and synthesis of hollow nanostructures with diverse compositional and geometric characteristics in the past decade. However, the correlation between their structure and energy‐related performance has not been reviewed thoroughly in the literature. Here, some representative examples of designing hollow nanostructure to effectively solve the problems of energy‐related technologies are highlighted, such as lithium‐ion batteries, lithium‐metal anodes, lithium–sulfur batteries, supercapacitors, dye‐sensitized solar cells, electrocatalysis, and photoelectrochemical cells. The great effect of structure engineering on the performance is discussed in depth, which will benefit the better design of hollow nanostructures to fulfill the requirements of specific applications and simultaneously enrich the diversity of the hollow nanostructure family. Finally, future directions of hollow nanostructure design to solve emerging challenges and further improve the performance of energy‐related technologies are also provided.
An Insight into the Phase Transformation of WS2 upon Fluorination
Authors: Radhakrishnan Sruthi , Das Deya , Deng Liangzi , Sudeep Parambath M. , Colas Guillaume , de los Reyes Carlos A. , Yazdi Sadegh , Chu Ching Wu , Martí Angel A. , Tiwary Chandra Sekhar , Filleter Tobin , Singh Abhishek K. , Ajayan Pulickel M. 
Published: September 2018

AbstractThe transformation from semiconducting to metallic phase, accompanied by a structural transition in 2D transition metal dichalcogenides has attracted the attention of the researchers worldwide. The unconventional structural transformation of fluorinated WS2 (FWS2) into the 1T phase is described. The energy difference between the two phases debugs this transition, as fluorination enhances the stability of 1T FWS2 and makes it energetically favorable at higher F concentration. Investigation of the electronic and optical nature of FWS2 is supplemented by possible band structures and bandgap calculations. Magnetic centers in the 1T phase appear in FWS2 possibly due to the introduction of defect sites. A direct consequence of the phase transition and associated increase in interlayer spacing is a change in friction behavior. Friction force microscopy is used to determine this effect of functionalization accompanied phase transformation.
Bioinspired Design of Vascular Artificial Muscle
Authors: He Qiguang , Wang Zhijian , Song Zhaoqiang , Cai Shengqiang 
Published: September 2018

AbstractRecently, liquid crystal elastomers (LCEs) have drawn much attention for its wide applications as artificial muscle in soft robotics, wearable devices, and biomedical engineering. One commonly adopted way to trigger deformation of LCEs is using embedded heating elements such as resistance heating wires and photothermal particles. To enable the material to recover to its unactuated state, passive and external cooling is often employed to lower the temperature, which is typically slow and environmentally sensitive. The slow and uncontrollable recovery speed of thermally driven artificial muscle often limits its applications when even moderate cyclic actuation rate is required. In this article, inspired by biology, a vascular LCE‐based artificial muscle (VLAM) is designed and fabricated with internal fluidic channel in which the hot or cool water is injected to heat up or cool down the material to achieve fast actuation as well as recovery. It is demonstrated that the actuation stress, strain, and cyclic response rate of the VLAM are comparable to mammalian skeletal muscle. Because of the internal heating and cooling mechanism, VLAM shows a very robust actuating performance within a wide range of environmental temperatures. The VLAM designed in this article may also provide a convenient way to harvest waste heat to conduct mechanical work.
Biocatalytic Desymmetrization of Prochiral 3‐Aryl and 3‐Arylmethyl Glutaramides: Different Remote Substituent Effect on Catalytic Efficiency and Enantioselectivity
Authors: Ao Yu‐Fei , Zhang Li‐Bin , Wang Qi‐Qiang , Wang De‐Xian , Wang Mei‐Xiang 
Published: September 2018

AbstractCatalyzed by an amidase‐containing Rhodococcus erythropolis AJ270 microbial whole cell catalyst in neutral phosphate buffer at 30 °C, desymmetric hydrolysis of a series of prochiral 3‐aryl and 3‐arylmethylglutaramides efficiently afforded 3‐substituted glutaric acid monoamides in up to 95% yield and >99.5% ee. Even far away from the reaction site, the substituents on the aryl still have a significant effect on the catalytic activity and enantioselectivity and different remote substituent effect was observed for the two types of substrates. The synthetic application of biocatalytic desymmetrization was demonstrated by the facile transformation of the obtained enantiopure (R)‐3‐substituted 4‐carbamoylbutanoic acid products to chiral dihydroquinolinone and δ‐lactone compounds.magnified image
PEPDROID: Development of a Generic DREIDING‐Based Force Field for the Assessment of Peptoid Secondary Structures
Authors: Hoyas Sébastien , Lemaur Vincent , Duez Quentin , Saintmont Fabrice , Halin Emilie , De Winter Julien , Gerbaux Pascal , Cornil Jérôme 
Published: September 2018

Abstractα‐Peptoids are peptido‐mimetic foldamers based on poly‐N‐substituted glycines that currently receive a growing interest due to their larger structural diversity, easier synthetic pathways, and larger thermal stability compared to peptides. An appropriate side chain appended to the nitrogen atoms is often crucial to constrain the peptoids into well‐defined and active rigid structures for applications. To shed light on the secondary structure of peptoids, accurate methods for structural characterization are mandatory and typically involve the association of circular dichroism and nuclear magnetic resonance spectroscopies. Molecular simulations can also prove highly complementary to rationalize the relationship between their primary and secondary structures, although much less studies have been reported to date compared to the knowledge accumulated on peptides. To this end, the PEPDROID force field has been developed based on the DREIDING force field, by incorporating a new set of parameters relative to (α and β) peptoids bearing different side chains. The ability of PEPDROID to assess the secondary structure of peptoids by generating Ramachandran‐like plots matching those previously obtained at a quantum‐chemical level for model systems has been demonstrated. For further sake of validation, it is demonstrated that PEPDROID can reproduce the experimental structures of either α‐ or β‐peptoids.
Photochemical Upconversion Light Emitting Diode (LED): Theory of Triplet Annihilation Enhanced by a Cavity
Authors: Frazer Laszlo 
Published: September 2018

AbstractArtificial lighting is a widespread technology which consumes large amounts of energy. Triplet–triplet annihilation photochemical upconversion is a method of converting light to a higher frequency. Here, it is shown theoretically that photochemical upconversion can be applied to Watt‐scale lighting, with performance closely approaching the 50% quantum yield upper limit. The dynamic equilibrium of an efficient device consisting of an LED, an upconverting material, and an optical cavity is described from optical and thermal perspectives.
Selected properties of polycaprolactone containing natural anti‐aging compounds
Authors: Moraczewski Krzysztof , Stepczyńska Magdalena , Malinowski Rafał , Budner Bogusław , Karasiewicz Tomasz , Jagodziński Bartłomiej 
Published: September 2018

AbstractPolyphenols are a group of chemical compounds that have very good anti‐aging properties. Natural plant substances may be an excellent source of polyphenols. The paper presents study on polycaprolactone containing from 0.5 to 10 wt% extracts of coffee, cocoa, or cinnamon. Preliminary investigations of anti‐aging properties of tested extracts were carried out. The selected thermal and mechanical properties have also been determined. The results indicate that tested extracts have good anti‐aging properties and do not adversely affect properties of polycaprolactone. The obtained materials had similar or even better properties than a reference sample containing a commercial anti‐aging compound.
Human body symmetry and immune efficacy in healthy adults
Authors: Pawlowski Boguslaw , Borkowska Barbara , Nowak Judyta , Augustyniak Daria , Drulis‐Kawa Zuzanna 
Published: September 2018

AbstractObjectivesMore symmetric organisms are perceived as more attractive. Fluctuating asymmetry (FA) i.e. small, random deviations from perfect bilateral symmetry, is supposed to inform about developmental instability. According to the good genes hypothesis, a low level of FA is a putative cue to an organism's biological quality. An important aspect of this quality is the immune system functioning. The aim of this study was to evaluate the relationship between immune system functioning and body symmetry in healthy people.Materials and MethodsThe composite body FA (cFA) was assessed on the basis of six bilateral traits (on hands and feet). The ISF was determined by many innate (total complement and lysozyme activity, neutrophils function) and adaptive immune parameters (T CD3 and B CD19 lymphocytes, total IgA and IgG and response to flu vaccine). A total of 98 men and 92 women were subjected to flu (among them 37 men and 30 women also to tetanus) vaccination. The blood samples were collected before and 4 weeks after the antigens exposure. Immunomodulatory factors: participant's age, body fat, and free testosterone level, were controlled.ResultsApart from the weak positive association between CD3 or CD19 and cFA in men, we found no association between the level of body symmetry and the rest of the analyzed immune parameters for both sexes.DiscussionOur results are the opposite of thegood genes hypothesisprediction and suggest that in western, healthy populations, human mate preferences for more symmetric bodies are not related to immune competence.
A Charge‐Separated State that Lives for Almost a Second at a Conductive Metal Oxide Interface
Authors: Sampaio Renato N. , Troian‐Gautier Ludovic , Meyer Gerald J. 
Published: September 2018

AbstractTransparent conductive oxides (TCOs) are widely used commercially available materials for opto‐electronic applications, yet they have received very little attention for dye‐sensitization applications. Now, mesoporous thin films of conductive indium‐doped tin oxide (ITO) nanocrystallites are shown to support long‐lived charge separation with first‐order recombination kinetics (k=1.5 s−1). A layer‐by‐layer technique was utilized to spatially arrange redox and/or chromophoric molecular components on ITO. Spectroelectrochemical measurements demonstrated that upon light absorption, each component provided a free‐energy gradient to direct electron transfer at the conductive oxide interface. The long‐lived nature of the photogenerated charge separated states provide favorable conditions for photocatalytic solar fuel production. Furthermore, the first‐order recombination kinetics are most ideal for the fundamental understanding of interfacial charge separation dynamics.
Redox‐Active Reagents for Photocatalytic Generation of the OCF3 Radical and (Hetero)Aryl C−H Trifluoromethoxylation
Authors: Zheng Weijia , Lee Johnny W. , Morales‐Rivera Cristian A. , Liu Peng , Ngai Ming‐Yu 
Published: September 2018

AbstractThe trifluoromethoxy (OCF3) radical is of great importance in organic chemistry. Yet, the catalytic and selective generation of this radical at room temperature and pressure remains a longstanding challenge. Herein, the design and development of a redox‐active cationic reagent (1) that enables the formation of the OCF3 radical in a controllable, selective, and catalytic fashion under visible‐light photocatalytic conditions is reported. More importantly, the reagent allows catalytic, intermolecular C−H trifluoromethoxylation of a broad array of (hetero)arenes and biorelevant compounds. Experimental and computational studies suggest single electron transfer (SET) from excited photoredox catalysts to 1 resulting in exclusive liberation of the OCF3 radical. Addition of this radical to (hetero)arenes gives trifluoromethoxylated cyclohexadienyl radicals that are oxidized and deprotonated to afford the products of trifluoromethoxylation.
Mechanically Responsive Crystalline Coordination Polymers with Controllable Elasticity
Authors: Đaković Marijana , Borovina Mladen , Pisačić Mateja , Aakeröy Christer B. , Soldin Željka , Kukovec Boris‐Marko , Kodrin Ivan 
Published: September 2018

AbstractCrystalline coordination polymers tend to be brittle and inelastic, however, we now describe a family of such compounds that are capable of displaying mechanical elasticity in response to external pressure. The design approach successfully targets structural features that are critical for producing the desired mechanical output. The elastic crystals all comprise 1D cadmium(II) halide polymeric chains with adjacent metal centres bridged by two halide ions resulting in the required stacking interactions and short “4 Å” crystallographic axes. These polymeric chains (structural “spines”) are further organized via hydrogen bonds and halogen bonds perpendicular to the direction of the chains. By carefully altering the strength and the geometry of these non‐covalent interactions, we have demonstrated that it is possible to control the extent of elastic bending in crystalline coordination compounds.
Observation of Carbodicarbene Ligand Redox Noninnocence in Highly Oxidized Iron Complexes
Authors: Chan Siu‐Chung , Gupta Puneet , Engelmann Xenia , Ang Zhi Zhong , Ganguly Rakesh , Bill Eckhard , Ray Kallol , Ye Shengfa , England Jason 
Published: September 2018

AbstractTo probe the possibility that carbodicarbenes (CDCs) are redox active ligands, all four members of the redox series [Fe(1)2]n+ (n=2–5) were synthesized, where 1 is a neutral tridentate CDC. Through a combination of spectroscopy and DFT calculations, the electronic structure of the pentacation is shown to be [FeIII(1.+)2]5+ (S=
). That of [Fe(1)2]4+ is more ambiguous, but it has significant contributions from the open‐shell singlet [FeIII(1)(1.+)]4+ (S=0). The observed spin states derive from antiferromagnetic coupling of their constituent low‐spin iron(III) centres and cation radical ligands. This marks the first time redox activity has been observed for carbones and expands the diverse chemical behaviour known for these ligands.
Cyclodextrin‐Based [3]Rotaxane‐Crosslinked Fluorescent Polymer: Synthesis and De‐Crosslinking Using Size Complementarity
Authors: Akae Yosuke , Sogawa Hiromitsu , Takata Toshikazu 
Published: September 2018

AbstractVinyl‐group‐substituted, α‐cyclodextrin‐based, size‐complementary [3]rotaxanes were synthesized as crosslinkers for rotaxane‐crosslinked poly(methyl methacrylate) (RCP) by radical polymerization. The size complementarity of the crosslinkers made it possible to de‐crosslink the RCP by heating, and the degree of decoupling was monitored by fluorescence intensity, depending on the state of the axle component of the rotaxane crosslink moiety.
Einfacher Zugang zum ersten stabilen {BH2}− Dihydroborylanion
Authors: Arrowsmith Merle , Mattock James D. , Hagspiel Stephan , Krummenacher Ivo , Vargas Alfredo , Braunschweig Holger 
Published: September 2018

AbstractWährend die Ein‐Elektronen‐Reduktion von (CAACMe)BH2Br (CAACMe=1‐(2,6‐Diisopropylphenyl)‐3,3,5,5‐tetramethylpyrrolidin‐2‐yliden) das Hydridumlagerungsisomer des entsprechenden Tetrahydrodiborans erzeugt, führt eine weitere, reversible Reduktion zur ersten stabilen Borylanion‐Stammverbindung, [(CAACMe)BH2]−, die als besonders starkes Bornukleophil reagiert.
Palladium Phosphide as a Stable and Efficient Electrocatalyst for Overall Water Splitting
Authors: Luo Fang , Zhang Quan , Yu Xinxin , Xiao Shenglin , Ling Ying , Hu Hao , Guo Long , Yang Zehui , Huang Liang , Cai Weiwei , Cheng Hansong 
Published: September 2018

AbstractA palladium phosphide electrocatalyst supported on carbon black (PdP2@CB) shows efficient water splitting in both alkaline and neutral electrolytes. Significantly lower overpotentials are required for PdP2@CB (27.5 mV in 0.5 m H2SO4; 35.4 mV in 1 m KOH; 84.6 mV in 1 m PBS) to achieve a HER electrocatalytic current density of 10 mA cm−2 compared to commercial Pt/CB (30.1 mV in 0.5 m H2SO4; 46.6 mV in 1 m KOH; 122.7 mV in 1 m PBS). Moreover, no loss in HER activity is detectable after 5000 potential sweeps. Only 270 mV and 277 mV overpotentials are required to reach a current density of 10 mA cm−2 for PdP2@CB to catalyze OER in 1 m KOH and 1 m PBS electrolytes, which is better OER activity than the benchmark IrO2 electrocatalyst (301 mV and 313 mV to drive a current density of 10 mA cm−2). 1.59 V and 1.72 V are needed for PdP2@CB to achieve stable water splitting catalytic current density of 10 mA cm−2 in 1 m PBS and 50 mA cm−2 in 1 m KOH for 10 h, respectively.
Aerobic Solid State Red Phosphorescence from Benzobismole Monomers and Patternable Self‐Assembled Block Copolymers
Authors: Parke Sarah M. , Hupf Emanuel , Matharu Gunwant K. , de Aguiar Inara , Xu Letian , Yu Haoyang , Boone Michael P. , de Souza Gabriel L. C. , McDonald Robert , Ferguson Michael J. , He Gang , Brown Alex , Rivard Eric 
Published: September 2018

AbstractThe synthesis of the first bismuth‐containing macromolecules that exhibit phosphorescence in the solid state and in the presence of oxygen is reported. These red emissive high molecular weight polymers (>300 kDa) feature benzobismoles appended to a hydrocarbon scaffold, and were built via an efficient ring‐opening metathesis (ROMP) protocol. Moreover, our general procedure readily allows for the formation of cross‐linked networks and block copolymers. Attaining stable red phosphorescence with non‐toxic elements remains a challenge and, thus, our new class of soluble (processable) polymeric phosphor is of great interest. Furthermore, the formation of bismuth‐rich cores within organic–inorganic block copolymer spherical micelles is possible, leading to patterned arrays of bismuth in the film state.
Stable Face‐to‐Face Singlet Diradicaloids: Triply Linked Corrole Dimer Gallium(III) Complexes with Two μ‐Hydroxo‐Bridges
Authors: Ooi Shota , Shimizu Daiki , Furukawa Ko , Tanaka Takayuki , Osuka Atsuhiro 
Published: September 2018

AbstractIn known singlet diradicaloid molecules, two inherent radicals are interacted antiferromagnetically as a result of delicate energetic balances between closed‐shell and open‐shell states. Reported herein is that gallium(III) metalations of triply linked corrole dimers provide face‐to‐face dimers, with two μ‐hydroxo‐bridges, and they display curved π‐planes nearing each other at about 3.24 Å. Based on ESR and SQUID measurements, and theoretical calculations, the dimers have been assigned as singlet diradicaloids that consist of two monoradicals each delocalized on the triply linked corrole dimer planes. Therefore, it is concluded that the dimers have unusual open‐shell states stabilized by large through‐space spin‐exchange interactions.