bluuebunny/crossref_metadata_2025_split huggingface dataset:
Boosting Dual‐Directional Polysulfide Electrocatalysis via Bimetallic Alloying for Printable Li–S Batteries
Authors: Shi Zixiong , Sun Zhongti , Cai Jingsheng , Fan Zhaodi , Jin Jia , Wang Menglei , Sun Jingyu 
Published: October 2020

AbstractThe rational design of electrocatalyst has readily stimulated a burgeoning interest in expediting polysulfide conversion and hence essentially restricting the “shuttle effect” in Li–S systems. Nevertheless, seldom efforts have been devoted to probing the dual‐directional polysulfide electrocatalysis to date. Herein, a CoFe alloy decorated mesoporous carbon sphere (CoFe‐MCS) serving as a promising mediator for Li–S batteries is reported. Such bimetallic alloying boosts dual‐directional electrocatalytic activity toward effective polysulfide conversion throughout detailed electroanalytic characterization, theoretical calculation, and operando instrumental probing. Accordingly, the S@CoFe‐MCS cathode harvests a stable cycling with a low capacity decay rate of 0.062% per cycle over 500 cycles at 2.0 C. More encouragingly, benefiting from the optimized redox kinetics and delicate grid architecture, printable S@CoFe‐MCS cathode achieves an excellent rate performance at a sulfur loading of 4.0 mg cm−2 and advanced areal capacity of 6.0 mAh cm−2 at 7.7 mg cm−2. This work explores non‐precious metal alloy electrocatalysts in printable cathodes toward dual‐directional polysulfide conversion, holding great potential in the pursuit of Li–S commercialization.
Dye‐Loaded Nanoemulsions: Biomimetic Fluorescent Nanocarriers for Bioimaging and Nanomedicine
Authors: Klymchenko Andrey S. , Liu Fei , Collot Mayeul , Anton Nicolas 
Published: October 2020

AbstractLipid nanoemulsions (NEs), owing to their controllable size (20 to 500 nm), stability and biocompatibility, are now frequently used in various fields, such as food, cosmetics, pharmaceuticals, drug delivery, and even as nanoreactors for chemical synthesis. Moreover, being composed of components generally recognized as safe (GRAS), they can be considered as “green” nanoparticles that mimic closely lipoproteins and intracellular lipid droplets. Therefore, they attracted attention as carriers of drugs and fluorescent dyes for both bioimaging and studying the fate of nanoemulsions in cells and small animals. In this review, the composition of dye‐loaded NEs, methods for their preparation, and emerging biological applications are described. The design of bright fluorescent NEs with high dye loading and minimal aggregation‐caused quenching (ACQ) is focused on. Common issues including dye leakage and NEs stability are discussed, highlighting advanced techniques for their characterization, such as Förster resonance energy transfer (FRET) and fluorescence correlation spectroscopy (FCS). Attempts to functionalize NEs surface are also discussed. Thereafter, biological applications for bioimaging and single‐particle tracking in cells and small animals as well as biomedical applications for photodynamic therapy are described. Finally, challenges and future perspectives of fluorescent NEs are discussed.
Shedding Light on the Role of Misfit Strain in Controlling Core–Shell Nanocrystals
Authors: Zhao Jianxiong , Chen Bing , Wang Feng 
Published: October 2020

AbstractHeteroepitaxial modification of nanomaterials has become a powerful means to create novel functionalities for various applications. One of the most elementary factors in heteroepitaxial nanostructures is the misfit strain arising from mismatched lattices of the constituent parts. Misfit strain not only dictates epitaxy kinetics for diversifying nanocrystal morphologies but also provides rational control over materials properties. In recent years, advances in chemical synthesis along with the rapid development of electron microscopy and X‐ray diffraction techniques have enabled a substantial understanding of strain‐related processes, which offers theoretical foundation and experimental guidance for researchers to refine heteroepitaxial nanostructures and their properties. Herein, recent investigations on heterogeneous core–shell nanocrystals containing misfit strains are summarized, with a focus on the mechanistic understanding of strain and strain‐induced effects such as tuning the epitaxial habit, modulating the optical emission, and enhancing the catalytic activity and magnetic coercivity.
Atomic Layer Deposition of Indium‐Tin‐Oxide as Multifunctional Coatings on V2O5 Thin‐Film Model Electrode for Lithium‐Ion Batteries
Authors: Zhao Bo , Nisula Mikko , Dhara Arpan , Henderick Lowie , Mattelaer Felix , Dendooven Jolien , Detavernier Christophe 
Published: October 2020

AbstractThis work demonstrates the possible usages of indium tin oxide (ITO) thin‐films as multifunctional coatings on V2O5 model electrodes for lithium‐ion batteries (LIBs). The thin films are produced with the atomic layer deposition (ALD) method via adjusting the ratio of In2O3 and SnO2 sub‐layers to a well‐controlled In: Sn contents. The highest conductivity value (7.37 × 10−4 Ω cm) of as‐grown ITO film is obtained from the sample containing 5% SnO2 of overall ALD cycles. The ITO thin‐films are further investigated as multifunctional coatings on ALD V2O5 electrodes for LIBs: At first, dual electronic and ionic conductive protecting properties of ITO layer are explored to attenuate the fading of the battery capacity by improving the cycling stability. Second, the feasibility of ITO layer as a dual functioning current collector‐cum‐protective coating layer is demonstrated. Third, ITO layer is investigated as a current collector and display performance comparable to that of Pt as current collector of traditional thin‐film LIBs. The electronic and electrochemical properties of ITO provide the opportunity to use ITO as a multifunctional coating for (3D) thin‐film LIBs and can find potential usages in miniaturized electronic devices.
The Intricate Love Affairs between MoS2 and Metallic Substrates
Authors: Velický Matěj , Donnelly Gavin E. , Hendren William R. , DeBenedetti William J. I. , Hines Melissa A. , Novoselov Kostya S. , Abruña Héctor D. , Huang Fumin , Frank Otakar 
Published: October 2020

AbstractMechanical exfoliation yields high‐quality 2D materials but is challenging to scale up due to the small lateral size and low yield of the exfoliated crystals. Gold‐mediated exfoliation of macroscale monolayer MoS2 and related crystals addresses this problem. However, it remains unclear whether this method can be extended to other metals. Herein, mechanical exfoliation of MoS2 on a range of metallic substrates is studied. It is found that Au outperforms all the other metals in their ability to exfoliate macroscale monolayer MoS2. This is rationalized by gold's ability to resist oxidation, which is compromised on other metals and leads to a weakened binding with MoS2. An anomalously high monolayer yield found for Ag suggests that the large interfacial strain in the metal–MoS2 heterostructures measured by Raman spectroscopy also is a critical factor facilitating the exfoliation, while the relative differences in the metal–MoS2 binding play only a minor role. These results provide a new incentive for investigations of 2D material‐substrate combinations applicable where high‐quality 2D crystals of macroscopic dimensions are of importance.
Constructing Layered MXene/CNTs Composite Film with 2D–3D Sandwich Structure for High Thermoelectric Performance
Authors: Ding Wenjun , Liu Peng , Bai Zuzhi , Wang Yeye , Liu Guoqiang , Jiang Qinglin , Jiang Fengxing , Liu Peipei , Liu Congcong , Xu Jingkun 
Published: October 2020

AbstractReasonable heterostructure design can effectively improve the thermoelectric performance of composite materials. High‐conductivity and high‐stability MXenes are expected for the application of thermoelectric conversion benefiting from their diverse electronic properties. In this work, the 2D MXene and 1D SWCNTs are employed to construct layered composite films with 2D–3D sandwich structures in the vertical direction by the wet‐chemical assembly strategy. As a result, sandwich Ti3C2Tx–SWCNTs–Ti3C2Tx film shows a higher power factor than that of Ti3C2Tx/SWCNTs film with interlaced structure, further 25 times higher than that of Ti3C2Tx film, which mainly due to the considerable electrical conductivity (750.9 S cm−1) and enhanced Seebeck (−32.2 µV K−1) coefficient. This study provides a feasible and valuable reference for expanding the application field of MXenes‐based materials and reasonably improving their thermoelectric conversion performance.
Concealed Structural Colors Uncovered by Light Scattering
Authors: Akinoglu Eser Metin , Song Jingchao , Kinnear Calum , Xue Yafei , Zhang Heyou , Roberts Ann , Köhler Jürgen , Mulvaney Paul 
Published: October 2020

AbstractUnusual structural colors are demonstrated in thin‐film coatings due to a combination of optical interference and light scattering effects. These vivid colors are concealed under ambient illumination but can be observed when light is reflected from the film surface. The origin of the effect is explored computationally and it is shown that, in thin‐films of lossless dielectrics coated on near‐perfect conductors, incident electromagnetic waves form standing waves. Electric field intensities at the thin film interfaces are maximized for wavelengths that fulfil destructive interference conditions, while nanoscale roughness can enhance scattering at these boundaries. The interplay of these two factors yields vivid, thickness‐dependent colors. This approach increases the repertoire of optical effects and perceived colors in thin coatings. When combined with traditional thin‐film interference colours, dichromatic images with distinctly changing colors can be generated, which can function as a covert, optical security feature.
A Single‐Stranded DNA‐Encoded Chemical Library Based on a Stereoisomeric Scaffold Enables Ligand Discovery by Modular Assembly of Building Blocks
Authors: Bassi Gabriele , Favalli Nicholas , Vuk Miriam , Catalano Marco , Martinelli Adriano , Trenner Anika , Porro Antonio , Yang Su , Tham Chuin Lean , Moroglu Mustafa , Yue Wyatt W. , Conway Stuart J. , Vogt Peter K. , Sartori Alessandro A. , Scheuermann Jörg , Neri Dario 
Published: October 2020

AbstractA versatile and Lipinski‐compliant DNA‐encoded library (DEL), comprising 366 600 glutamic acid derivatives coupled to oligonucleotides serving as amplifiable identification barcodes is designed, constructed, and characterized. The GB‐DEL library, constructed in single‐stranded DNA format, allows de novo identification of specific binders against several pharmaceutically relevant proteins. Moreover, hybridization of the single‐stranded DEL with a set of known protein ligands of low to medium affinity coupled to a complementary DNA strand results in self‐assembled selectable chemical structures, leading to the identification of affinity‐matured compounds.
Role of Li‐Ion Depletion on Electrode Surface: Underlying Mechanism for Electrodeposition Behavior of Lithium Metal Anode
Authors: Xu Xieyu , Liu Yangyang , Hwang Jang‐Yeon , Kapitanova Olesya O. , Song Zhongxiao , Sun Yang‐Kook , Matic Aleksandar , Xiong Shizhao 
Published: October 2020

AbstractThe application of lithium metal as an anode material for next generation high energy‐density batteries has to overcome the major bottleneck that is the seemingly unavoidable growth of Li dendrites caused by non‐uniform electrodeposition on the electrode surface. This problem must be addressed by clarifying the detailed mechanism. In this work the mass‐transfer of Li‐ions is investigated, a key process controlling the electrochemical reaction. By a phase field modeling approach, the Li‐ion concentration and the electric fields are visualized to reveal the role of three key experimental parameters, operating temperature, Li‐salt concentration in electrolyte, and applied current density, on the microstructure of deposited Li. It is shown that a rapid depletion of Li‐ions on electrode surface, induced by, e.g., low operating temperature, diluted electrolyte and a high applied current density, is the underlying driving force for non‐uniform electrodeposition of Li. Thus, a viable route to realize a dendrite‐free Li plating process would be to mitigate the depletion of Li‐ions on the electrode surface. The methodology and results in this work may boost the practical applicability of Li anodes in Li metal batteries and other battery systems using metal anodes.
Do SNAP Households Pay Different Prices throughout the Benefit Month?
Authors: Valizadeh Pourya , Smith Travis A. , Ver Ploeg Michele 
Published: October 2020

AbstractFor households participating in the Supplemental Nutrition Assistance Program (SNAP), food expenditures spike upon benefit arrival. We show the price component of expenditure is sensitive to benefit arrival: by the beginning of the fourth week of the benefit month, households pay 20% less on food items. This decline is not induced by changes in shopping behaviors (usage of SNAP, bulk purchases, on‐sale, branded, and discount stores) but rather concentrated among a subset of households with financial constraints and/or a preference for higher‐quality foods. Increased benefit adequacy and/or financial stability for participants could help households smooth their purchasing power.
Chronic subdural hematoma: A previously unreported life‐threatening complication in adult with Sotos syndrome
Authors: Carli Diana , Gazzin Andrea , Bongioanni Maria Roberta , Bergui Mauro , Mussa Alessandro , Ferrero Giovanni Battista 
Published: October 2020

AbstractMacrocephaly, defined as head circumference ≥ 2 SDs, is a cardinal feature of Sotos syndrome (SS) and generally persists in adulthood. Subdural fluid collection, typically associated with macrocephaly, is described in children due to anatomical conformation, and in adulthood due to brain atrophy and ex‐vacuo hydrocephalus. On the other hand, a true, symptomatic, chronic subdural hematoma (CSH) is a previously unreported complication of SS in adulthood. Here we describe the first SS patient presenting symptomatic CSH, leading to frequent hospitalizations for surgical evacuations that consistently recurred. Middle meningeal artery (MMA) embolization and epidural blood patch (EBP) allowed to resolve the CSH with complete resolution of clinical signs and symptoms. We hypothesize that appearance and recurrences of CSH may be related to pathological biomechanics of brain, cerebro‐spinal fluid and skull, secondary to anatomical features of SS. In this context, surgical evacuation may be less efficient than usual to cure CSH. Alternative treatment to avoid blood extravasation, as MMA embolization, or to cure concurrent causes of the pathology, as EBP, may be considered.
Die größenbeschleunigte kinetische Racematspaltung sekundärer Alkohole
Authors: Pölloth Benjamin , Sibi Mukund P. , Zipse Hendrik 
Published: October 2020

AbstractDie Ursachen für die kinetische Racematspaltung von Alkoholen durch chirale Pyridinderivate wurden untersucht. Dafür wurden relative Reaktionsgeschwindigkeiten für eine Reihe von Substraten mit systematisch wachsenden aromatischen Resten durch eine lineare Regressionsanalyse von Konkurrenzexperimenten bestimmt. Durch das Vergrößern der Seitenketten von Phenyl zu Pyrenyl wurde die Umsetzung des bevorzugt reagierenden Enantiomers mehr als 40‐fach beschleunigt. Basierend auf diesen Beobachtungen wurde ein neuer Katalysator mit vergrößertem sterischem Anspruch synthetisiert, mit dem Selektivitätswerte von bis zu s=250 erreicht wurden. Eine ausgiebige Konformationsanalyse für die entsprechenden Übergangszustände legt nahe, dass ein Angriff des Alkohols an der sterisch stärker gehinderten Seite des Acyl‐Katalysator‐Intermediats durch stabilisierende CH‐π‐Wechselwirkungen begünstigt wird. Experimentelle und theoretische Ergebnisse weisen darauf hin, dass die Zunahme der Enantioselektivität auf eine Reaktionsbeschleunigung des bevorzugten Enantiomers durch nicht‐kovalente Wechselwirkungen (NKW) zurückzuführen ist und nicht auf eine Verlangsamung des langsamer reagierenden Enantiomers durch repulsive sterische Kräfte.
Cobalt‐Catalyzed Diastereo‐ and Enantioselective Hydroalkylation of Cyclopropenes with Cobalt Homoenolates
Authors: Huang Wei , Meng Fanke 
Published: October 2020

AbstractCatalylic diastereo‐ and enantioselective hydroalkylation of 3,3‐disubstituted cyclopropenes with Co‐homoenolate generated in situ from ring‐opening of easily accessible cyclopropanols promoted by a chiral phosphine–cobalt complex is presented. Such a process represents the unprecedented and direct introduction of a wide range of functionalized alkyl groups without the need of pre‐formation of stoichiometric amounts of organometallic reagents onto the cyclopropane motif, affording multi‐substituted cyclopropanes in up to 99 % yield with >95:5 dr and 98:2 er. Functionalization of the products delivered enantioenriched cyclopropanes that are otherwise difficult to access.
The “Hidden” Reductive [2+2+1]‐Cycloaddition Chemistry of 2‐Phosphaethynolate Revealed by Reduction of a Th‐OCP Linkage
Authors: Du Jingzhen , Balázs Gábor , Wooles Ashley J. , Scheer Manfred , Liddle Stephen T. 
Published: October 2020

AbstractThe reduction chemistry of the newly emerging 2‐phosphaethynolate (OCP)− is not well explored, and many unanswered questions remain about this ligand in this context. We report that reduction of [Th(TrenTIPS)(OCP)] (2, TrenTIPS=[N(CH2CH2NSiPri3)]3−), with RbC8 via [2+2+1] cycloaddition, produces an unprecedented hexathorium complex [{Th(TrenTIPS)}6(μ‐OC2P3)2(μ‐OC2P3H)2Rb4] (5) featuring four five‐membered [C2P3] phosphorus heterocycles, which can be converted to a rare oxo complex [{Th(TrenTIPS)(μ‐ORb)}2] (6) and the known cyclometallated complex [Th{N(CH2CH2NSiPri3)2(CH2CH2SiPri2CHMeCH2)}] (4) by thermolysis; thereby, providing an unprecedented example of reductive cycloaddition reactivity in the chemistry of 2‐phosphaethynolate. This has permitted us to isolate intermediates that might normally remain unseen. We have debunked an erroneous assumption of a concerted fragmentation process for (OCP)−, rather than cycloaddition products that then decompose with [Th(TrenTIPS)O]− essentially acting as a protecting then leaving group. In contrast, when KC8 or CsC8 were used the phosphinidiide C−H bond activation product [{Th(TrenTIPS)}Th{N(CH2CH2NSiPri3)2[CH2CH2SiPri2CH(Me)CH2C(O)μ‐P]}] (3) and the oxo complex [{Th(TrenTIPS)(μ‐OCs)}2] (7) were isolated.
Visible‐Light‐Promoted Metal‐Free Synthesis of (Hetero)Aromatic Nitriles from C(sp3)−H Bonds**
Authors: Murugesan Kathiravan , Donabauer Karsten , König Burkhard 
Published: October 2020

AbstractThe metal‐free activation of C(sp3)−H bonds to value‐added products is of paramount importance in organic synthesis. We report the use of the commercially available organic dye 2,4,6‐triphenylpyrylium tetrafluoroborate (TPP) for the conversion of methylarenes to the corresponding aryl nitriles via a photocatalytic process. Applying this methodology, a variety of cyanobenzenes have been synthesized in good to excellent yield under metal‐ and cyanide‐free conditions. We demonstrate the scope of the method with over 50 examples including late‐stage functionalization of drug molecules (celecoxib) and complex structures such as l‐menthol, amino acids, and cholesterol derivatives. Furthermore, the presented synthetic protocol is applicable for gram‐scale reactions. In addition to methylarenes, selected examples for the cyanation of aldehydes, alcohols and oximes are demonstrated as well. Detailed mechanistic investigations have been carried out using time‐resolved luminescence quenching studies, control experiments, and NMR spectroscopy as well as kinetic studies, all supporting the proposed catalytic cycle.
Cocoa Butter Alternatives from Enzymatic Interesterification of Palm Kernel Stearin, Coconut Oil, and Fully Hydrogenated Palm Stearin Blends
Authors: Ornla‐ied Pimwalan , Tan Chin Ping , Wang Yong , Sonwai Sopark 
Published: October 2020

AbstractStructured lipids (SL) were produced from enzymatic interesterification (EIE) of palm kernel stearin (PKS), coconut oil (CNO), and fully hydrogenated palm stearin (FHPS) blends in various mass ratios. The EIE reactions were performed at 60 °C for 6 hours using immobilized Lipozyme RM IM with a mixing speed of 300 rpm. The physicochemical properties, crystallization and melting behavior, solid fat content (SFC), crystal morphology and polymorphism of the physical blends (PB), and the SL were characterized and compared with commercial cocoa butter and cocoa butter alternatives (CBA). EIE significantly modified the triacylglycerol compositions of the fat blends, resulting in changes in the physical properties and the crystallization and melting behavior. SFC and slip melting point of all SL decreased from those of their counterpart PB. In particular, SL obtained from EIE of blends 60:10:30 and 70:10:20 (PKS:CNO:FHPS) exhibited a high potential to be used astrans‐free CBA as they showed similar melting ranges, melting peak temperatures, and SFC curves to the commercial CBA with fine needle‐like crystals and desirable β' polymorph.
Flavors' Decreasing Contribution to p‐Anisidine Value over Shelf Life May Invalidate the Current Recommended Protocol for Flavored Fish Oils
Authors: Ye Liyun , Harris Emily , Budge Suzanne M. , Sullivan Ritter Jenna 
Published: October 2020

AbstractThe American Oil Chemists' Society (AOCS) Official Method Cd 18–90 for p‐Anisidine Value (pAV) is commonly used to evaluate secondary oxidation in fish oils. Flavoring agents in fish oil products may interfere with pAV and lead to inaccurate results. The Global Organization for EPA and DHA (GOED) recommends a protocol for calculating pAV of flavored fish oils based on the assumption that flavors' contribution to the pAV does not change over the course of oxidation. The objective of this study was to test this assumption. All 14 flavors evaluated increased the pAV when added to fresh fish oil; chocolate‐vanilla and lemon flavors generated the largest increase. Under accelerated oxidation conditions, both chocolate‐vanilla and lemon flavors had a similar effect; oxidized flavored fish oils had lower pAV than oxidized fish oils with newly added flavors. This was due to either an antioxidant effect of the flavor or loss of the flavor during oxidation. Following the GOED recommendation, we would have underestimated the oxidation in the flavored oils. For this reason, the pAV of flavored fish oils should be considered with caution and used in combination with other secondary oxidation markers when possible.
How accurate are the Doing Business indicators? A Pacific Island case study
Authors: Holden Paul , Pekmezovic Alma 
Published: October 2020

AbstractWhile there have been several attempts to measure the investment climate, by far the most widely recognised measure is the World Bank's Doing Business indicators (DBIs), ranking some 200 countries on their ease of doing business. Methodological criticisms have failed to dent their stature. This article is based on case studies of Pacific Island countries that demonstrate that identical reforms in different countries are assigned rankings so widely divergent that they call into question the validity of the DBIs. The findings cast doubt on targeting improved DBI rankings as a policy goal. Our case studies are the first to provide detailed country evidence supporting the criticisms levelled against the DBIs on conceptual grounds.