bluuebunny/crossref_metadata_2025_split huggingface dataset:
Progress in Materials, Solution Processes, and Long‐Term Stability for Large‐Area Organic Photovoltaics
Authors: Park Sungmin , Kim Taehee , Yoon Seongwon , Koh Chang Woo , Woo Han Young , Son Hae Jung 
Published: October 2020

AbstractOrganic solar cells based on bulk heterojunctions (BHJs) are attractive energy‐conversion devices that can generate electricity from absorbed sunlight by dissociating excitons and collecting charge carriers. Recent breakthroughs attained by development of nonfullerene acceptors result in significant enhancement in power conversion efficiency (PCEs) exceeding 17%. However, most of researches have focused on pursuing high efficiency of small‐area (<1 cm2) unit cells fabricated usually with spin coating. For practical application of organic photovoltaics (OPVs) from lab‐scale unit cells to industrial products, it is essential to develop efficient technologies that can extend active area of devices with minimized loss of performance and ensured operational stability. In this progress report, an overview of recent advancements in materials and processing technologies is provided for transitioning from small‐area laboratory‐scale devices to large‐area industrial scale modules. First, development of materials that satisfy requirements of high tolerability in active layer thickness and large‐area adaptability is introduced. Second, morphology control using various coating techniques in a large active area is discussed. Third, the recent research progress is also underlined for understanding mechanisms of OPV degradation and studies for improving device long‐term stability along with reliable evaluation procedures.
Incorporation of Natural Lithium‐Ion Trappers into Graphene Oxide Nanosheets
Authors: Ahmadi Hadi , Hosseini Ehsan , Cha‐Umpong Withita , Abdollahzadeh Mojtaba , Korayem Asghar Habibnejad , Razmjou Amir , Chen Vicki , Asadnia Mohsen 
Published: October 2020

AbstractLithium consumption is estimated to face a considerable rise in the next decade; thus, finding new reproducible lithium resources such as brine deposits and seawater has become a fast‐growing research topic. However, Li+ extraction from these resources is challenging due to its low concentration and presence of other monovalent cations exhibiting identical chemical properties. Here, it is discovered that tannic acid (TA) inside graphene oxide (GO) nanochannel acts as natural ion trapper, which possesses lithiophilic elements. The lithium‐rich feed is achieved by using the potential‐driven TA‐GO membrane by excluding lithium ions from other monovalent cations. The results showed that the ion trapping capability of inexpensive TA‐GO membrane is Li+ > Na+ > K+ with Li trapping energy of −593 KJ mol−1, respectively, where its trapping efficiency goes into a top rank among their expensive synthetic counterparts. Evaluating the combined effect of three key parameters, including barrier energy, hydration energy, and binding energy illustrates that required energy to transport Li‐ion through the membrane is higher than that for other monovalent. This proof‐of‐concept work opens up an avenue of research for designing a new class of ion‐selective membranes, based on the incorporation of naturally low cost available lithiophilic guest molecules into 2D membranes.
DNA‐Origami‐Templated Growth of Multilamellar Lipid Assemblies
Authors: Julin Sofia , Nonappa  , Shen Boxuan , Linko Veikko , Kostiainen Mauri A. 
Published: October 2020

AbstractLipids are important building blocks in cellular compartments, and therefore their self‐assembly into well‐defined hierarchical structures has gained increasing interest. Cationic lipids and unstructured DNA can co‐assemble into highly ordered structures (lipoplexes), but potential applications of lipoplexes are still limited. Using scaffolded DNA origami nanostructures could aid in resolving these drawbacks. Here, we have complexed DNA origami together with a cationic lipid 1,2‐dioleoly‐3‐trimethylammonium‐propane (DOTAP) and studied their self‐assembly driven by electrostatic and hydrophobic interactions. The results suggest that the DNA origami function as templates for the growth of multilamellar lipid structures and that the DNA origami are embedded in the formed lipid matrix. Furthermore, the lipid encapsulation was found to significantly shield the DNA origami against nuclease digestion. The presented complexation strategy is suitable for a wide range of DNA‐based templates and could therefore find uses in construction of cell‐membrane‐associated components.
Ligand‐Dependent Activity Engineering of Glutathione Peroxidase‐Mimicking MIL‐47(V) Metal–Organic Framework Nanozyme for Therapy
Authors: Wu Jiangjiexing , Yu Yijun , Cheng Yuan , Cheng Chaoqun , Zhang Yihong , Jiang Bo , Zhao Xiaozhi , Miao Leiying , Wei Hui 
Published: October 2020

AbstractGlutathione peroxidase (GPx) plays an important role in maintaining the reactive oxygen metabolic balance, yet limited GPx‐mimicking nanozymes are currently available for in vivo therapy. Herein, a ligand engineering strategy is developed to modulate the GPx‐mimicking activity of a metal–organic framework (MOF) nanozyme. With different substituted ligands, the GPx‐mimicking activities of MIL‐47(V)‐X (MIL stands for Materials of Institute Lavoisier; X=F, Br, NH2, CH3, OH, and H) MOFs are rationally regulated. With the best one as an example, both in vitro and in vivo experiments reveal the excellent antioxidation ability of MIL‐47(V)‐NH2, which alleviates the inflammatory response effectively for both ear injury and colitis, and is more active than MIL‐47(V). This study proves that high‐performance GPx‐mimicking nanozymes can be rationally designed by a ligand engineering strategy, and that structure–activity relationships can direct the in vivo therapy. This study enriches nanozyme research and expands the range of biomimetic MOFs.
Nickel‐Catalyzed Migratory Hydrocyanation of Internal Alkenes: Unexpected Diastereomeric‐Ligand‐Controlled Regiodivergence
Authors: Gao Jihui , Jiao Mingdong , Ni Jie , Yu Rongrong , Cheng Gui‐Juan , Fang Xianjie 
Published: October 2020

AbstractA regiodivergent nickel‐catalyzed hydrocyanation of a broad range of internal alkenes involving a chain‐walking process is reported. When appropriate diastereomeric biaryl diphosphite ligands are applied, the same starting materials can be converted to either linear or branched nitriles with good yields and high regioselectivities. DFT calculations suggested that the catalyst architecture determines the regioselectivity by modulating electronic and steric interactions. In addition, moderate enantioselectivities were observed when branched nitriles were produced.
Fragment‐Bindung an die Kinase‐Scharnier‐Region: Wenn Ladungsverteilung und lokale pKa‐Verschiebungen etablierte Bioisosterie‐Konzepte fehlleiten
Authors: Oebbeke Matthias , Siefker Christof , Wagner Björn , Heine Andreas , Klebe Gerhard 
Published: October 2020

AbstractDie medizinisch‐chemische Optimierung folgt einer Strategie, funktionelle Gruppen zu ersetzen und größere Substituenten an ein vielversprechendes Leitstrukturgerüst anzufügen. Wohl etablierte Bioisosterie‐Regeln werden berücksichtigt, dennoch ist es schwierig abzuschätzen, ob die durchgeführten Modifikationen auch wirklich den Anforderungen einer Bindestelle gerecht werden. Die Elektronendichteverteilung und die pKa‐Werte der Liganden werden moduliert und beeinflussen so Protonierungszustände und Bioverfügbarkeiten. Unter Berücksichtigung des benachbarten H‐Brücken‐Donor/Akzeptor‐Musters des Scharnierbindungsmotivs (“Hinge‐Region”) einer Kinase untersuchten wir kristallographisch eine Reihe von Fragmenten, um zu sehen, ob sie das erforderliche Interaktionsmuster erwidern können. Unerwarteterweise sind Benzoesäure und Benzamidin, mit den richtigen Substituenten dekoriert, ebenso wie ein Carboxamid oder eine phenolische OH‐Gruppe völlig bioisoster. Ein einzähniger Pyridinstickstoff übertrifft sogar zweizähnige Funktionalitäten am Liganden. Die Bedeutung der korrekten Einstellung von pKa‐Werten der angefügten funktionellen Gruppen am Liganden durch zusätzliche Substituenten am Molekülgerüst wird damit offensichtlich.
The Existence of a N→C Dative Bond in the C60–Piperidine Complex
Authors: Lamanec Maximilián , Lo Rabindranath , Nachtigallová Dana , Bakandritsos Aristides , Mohammadi Elmira , Dračínský Martin , Zbořil Radek , Hobza Pavel , Wang Weizhou 
Published: October 2020

AbstractThe complexes formed between carbon allotropes (C20, C60 fullerenes, graphene, and single‐wall carbon nanotubes) and piperidine have been investigated by means of computational quantum chemical and experimental IR and NMR techniques. Alongside hydrogen bonds, the C⋅⋅⋅N tetrel bond, and lone‐pair⋅⋅⋅π interactions, the unexpected N→C dative/covalent bond has been detected solely in complexes of fullerenes with piperidine. Non‐planarity and five‐member rings of carbon allotropes represent the key structural prerequisites for the unique formation of a dative N→C bond. The results of thermodynamics calculations, molecular dynamics simulations, and NMR and FTIR spectroscopy explain the specific interactions between C60 and piperidine. The differences in behavior of individual carbon allotropes in terms of dative bonding formation brings a new insight into their controllable organic functionalization.
Structure Based Design of Bicyclic Peptide Inhibitors of RbAp48
Authors: Hart Peter 't , Hommen Pascal , Noisier Anaïs , Krzyzanowski Adrian , Schüler Darijan , Porfetye Arthur T. , Akbarzadeh Mohammad , Vetter Ingrid R. , Adihou Hélène , Waldmann Herbert 
Published: October 2020

AbstractThe scaffolding protein RbAp48 is part of several epigenetic regulation complexes and is overexpressed in a variety of cancers. In order to develop tool compounds for the study of RbAp48 function, we have developed peptide inhibitors targeting the protein–protein interaction interface between RbAp48 and the scaffold protein MTA1. Based on a MTA1‐derived linear peptide with low micromolar affinity and informed by crystallographic analysis, a bicyclic peptide was developed that inhibits the RbAp48/MTA1 interaction with a very low nanomolar KD value of 8.56 nM, and which showed appreciable stability against cellular proteases. Design included exchange of a polar amide cyclization strategy to hydrophobic aromatic linkers enabling mono‐ and bicyclization by means of cysteine alkylation, which improved affinity by direct interaction of the linkers with a hydrophobic residue on RbAp48. Our results demonstrate that stepwise evolution of a structure‐based design is a suitable strategy for inhibitor development targeting PPIs.
A BN‐Doped Cycloparaphenylene Debuts
Authors: Chen Min , Unikela Kiran S. , Ramalakshmi Rongala , Li Bo , Darrigan Clovis , Chrostowska Anna , Liu Shih‐Yuan 
Published: October 2020

AbstractThe first example of a BN‐doped cycloparaphenylene BN‐[10]CPP was synthesized and characterized. Its reactivity and photophysical properties were evaluated in direct comparison to its carbonaceous analogues Mes‐[10]CPP and [10]CPP. While the photophysical properties of BN‐[10]CPP remains similar to its carbonaceous analogues, the electronic structure changes associated with the introduction of a 1,2‐azaborine BN heterocycle into a CPP scaffold enables facile and selective late‐stage functionalizations that cannot be accomplished with carbonaceous CPPs. Specifically, Ir‐catalyzed hydrogenation of BN‐[10]CPP selectively reduces the BN heterocyclic ring, which upon hydrolysis produces a rare example of a macrocyclic paraphenylene 6 incorporating the versatile ketone functionality within the macrocyclic ring.
Magnetic‐Field‐Driven Extraction of Bioreceptors into Polymeric Membranes for Label‐Free Potentiometric Biosensing
Authors: Lv Enguang , Li Yanhong , Ding Jiawang , Qin Wei 
Published: October 2020

AbstractWe report here the concept of a magnetically controlled extraction of hydrophilic bioreceptors into polymeric membranes for bioassays. The potentiometric assay relies on the intrinsic charges of an antimicrobial peptide and its unique recognition abilities, which can eliminate the probe labeling and indicator addition. The target binding event could effectively prevent the extraction of the peptide into the polymeric membrane doped with an ion exchanger, thus resulting in a potential change. The potentiometric response properties of the peptide assembled on magnetic beads can be dynamically controlled and modulated by applying a magnetic field. Staphylococcus aureus, as a model of food‐borne pathogens, was measured at levels down to 10 CFU mL−1. Based on this sensing strategy, a potentiometric array was developed for the pattern recognition of bacteria. The proposed general platform can be used for potentiometric biosensing using other hydrophilic bioreceptors.
Nanoscale Anatomy of Iron‐Silica Self‐Organized Membranes: Implications for Prebiotic Chemistry
Authors: Kotopoulou Electra , Lopez‐Haro Miguel , Calvino Gamez Jose Juan , García‐Ruiz Juan Manuel 
Published: October 2020

AbstractIron‐silica self‐organized membranes, so‐called chemical gardens, behave as fuel cells and catalyze the formation of amino/carboxylic acids and RNA nucleobases from organics that were available on early Earth. Despite their relevance for prebiotic chemistry, little is known about their structure and mineralogy at the nanoscale. Studied here are focused ion beam milled sections of iron‐silica membranes, grown from synthetic and natural, alkaline, serpentinization‐derived fluids thought to be widespread on early Earth. Electron microscopy shows they comprise amorphous silica and iron nanoparticles of large surface areas and inter/intraparticle porosities. Their construction resembles that of a heterogeneous catalyst, but they can also exhibit a bilayer structure. Surface‐area measurements suggest that membranes grown from natural waters have even higher catalytic potential. Considering their geochemically plausible precipitation in the early hydrothermal systems where abiotic organics were produced, iron‐silica membranes might have assisted the generation and organization of the first biologically relevant organics.
A Radical Approach to Making Unnatural Amino Acids: Conversion of C−S Bonds in Cysteine Derivatives into C−C Bonds
Authors: Wang Yingwei , Deng Li‐Fan , Zhang Xia , Mou Ze‐Dong , Niu Dawen 
Published: October 2020

AbstractHere we report a general approach to make unnatural amino acids from readily available cysteine derivatives. This method capitalizes on an intramolecular radical substitution process that generates alkyl radicals through C−S cleavage. The resulting alkyl radicals partook in diverse C−C bond forming events. These reactions proceed under mild, photocatalytic conditions at room temperature, and can be performed open to air. The utility of these transformations is further demonstrated in the straightforward synthesis of various unnatural amino acids and peptides that are difficult to access previously.
gem‐Difluoromethylene Alkyne‐Enabled Diverse C−H Functionalization and Application to the on‐DNA Synthesis of Difluorinated Isocoumarins
Authors: Gao Hui , Lin Shuang , Zhang Shuning , Chen Weijie , Liu Xiawen , Yang Guang , Lerner Richard A. , Xu Hongtao , Zhou Zhi , Yi Wei 
Published: October 2020

AbstractUsing gem‐difluoromethylene alkynes as effectors, unprecedented diverse C−H activation/[4+2] annulations of simple benzoic acids are reported. The chemodivergent reaction outcomes are well‐tuned by Rh/Ir‐catalyzed system; in the RhIII catalysis, 3‐alkenyl‐1H‐isochromen‐1‐one and 3,4‐dialkylideneisochroman‐1‐one skeletons are afforded in a solvent‐dependent manner whereas difluoromethylene‐substituted 1H‐isochromen‐1‐ones are generated under the IrIII‐catalyzed system. Mechanistic studies revealed that unusually double β‐F eliminations and fluorine effect‐induced regioselective reductive elimination are independently involved to enable distinct reaction modes for divergent product formations. Besides, synthetic application in both the derivatization of obtained diene products and the on‐DNA synthesis of DNA‐tagged difluorinated isocoumarin have been demonstrated, which manifested great potential for synthetic utility of the developed protocols.
Imaging Sodium Dendrite Growth in All‐Solid‐State Sodium Batteries Using 23Na T2‐Weighted Magnetic Resonance Imaging
Authors: Rees Gregory J. , Spencer Jolly Dominic , Ning Ziyang , Marrow T. James , Pavlovskaya Galina E. , Bruce Peter G. 
Published: October 2020

AbstractTwo‐dimensional, Knight‐shifted, T2‐contrasted 23Na magnetic resonance imaging (MRI) of an all‐solid‐state cell with a Na electrode and a ceramic electrolyte is employed to directly observe Na microstructural growth. A spalling dendritic morphology is observed and confirmed by more conventional post‐mortem analysis; X‐ray tomography and scanning electron microscopy. A significantly larger 23Na T2 for the dendritic growth, compared with the bulk metal electrode, is attributed to increased sodium ion mobility in the dendrite. 23Na T2‐contrast MRI of metallic sodium offers a clear, routine method for observing and isolating microstructural growths and can supplement the current suite of techniques utilised to analyse dendritic growth in all‐solid‐state cells.
Comparative neuroanatomical study of the amygdala and fear conditioning in Nigerian breeds of Artiodactyla: Sheep (Uda) and goats (Red Sokoto)
Authors: George Itoro , Alawa Judith , Akpulu Peter , Alawa Clement 
Published: October 2020

AbstractThe aim of this study was to evaluate fear condition responses in sheep and goat and to relate this to the neuroarchitecture of their amygdala. Forty adult sheep (Uda breed) and 40 adult goats (Red Sokoto breed) were fear‐conditioned by associating the sound of a car horn (neutral stimuli) with water spray (aversive stimuli) and the fear response was determined by direct observation of the behavior of the sheep and goats and measuring their flight distances and escape time. Eight groups were studied, each comprising of 10 animals (five sheep and five goats). Goats and sheep were tested alternately in the morning of every day of the week for three consecutive weeks, in which 4 days was used for habituation and 3 days for testing. Histologically, neurons in the central and basolateral complex of the amygdala were studied and analyzed using Nissl and golgi staines. Behaviorally, goats elicited an active avoidance response expressed as flight with concomitant intense flight distances (p < .001) compared to sheep. Although, sheep had larger brain parameters, it showed attenuated basolateral amygdala cytoarchitecture consistent with reduced fear perception and response. Goats had significantly more densely distributed pyramidal and spiny stellate neurons in the basolateral amygdala while sheep showed more non‐pyramidal and aspiny neurons. These results provide interesting practical perspectives on how adaptions in the amygdala coincides with alterations in fear conditioning in domestic animals and may be the basis for the higher incidence of the sheep in automobile accidents than goats in developing countries especially Africa.
Mechanosensitive Control of Articular Cartilage and Subchondral Bone Homeostasis in Mice Requires Osteocytic Transforming Growth Factor β Signaling
Authors: Bailey Karsyn N. , Nguyen Jeffrey , Yee Cristal S. , Dole Neha S. , Dang Alexis , Alliston Tamara 
Published: October 2020

ObjectiveTransforming growth factor β (TGFβ) signaling plays a complex tissue‐specific and nonlinear role in osteoarthritis (OA). This study was conducted to determine the osteocytic contributions of TGFβ signaling to OA.MethodsTo identify the role of osteocytic TGFβ signaling in joint homeostasis, we used 16‐week‐old male mice (n = 9–11 per group) and female mice (n = 7–11 per group) with an osteocyte‐intrinsic ablation of TGFβ receptor type II (TβRIIocy−/− mice) and assessed defects in cartilage degeneration, subchondral bone plate (SBP) thickness, and SBP sclerostin expression. To further investigate these mechanisms in 16‐week‐old male mice, we perturbed joint homeostasis by subjecting 8‐week‐old mice to medial meniscal/ligamentous injury (MLI), which preferentially disrupts the mechanical environment of the medial joint to induce OA.ResultsIn all contexts, independent of sex, genotype, or medial or lateral joint compartment, increased SBP thickness and SBP sclerostin expression were spatially associated with cartilage degeneration. Male TβRIIocy−/− mice, but not female TβRIIocy−/− mice, had increased cartilage degeneration, increased SBP thickness, and higher levels of SBP sclerostin compared with control mice (all P < 0.05), demonstrating that the role of osteocytic TGFβ signaling on joint homeostasis is sexually dimorphic. With changes in joint mechanics following injury, control mice had increased SBP thickness, subchondral bone volume, and SBP sclerostin expression (all P < 0.05). TβRIIocy−/− mice, however, were insensitive to subchondral bone changes with injury, suggesting that mechanosensation at the SBP requires osteocytic TGFβ signaling.ConclusionOur results provide new evidence that osteocytic TGFβ signaling is required for a mechanosensitive response to injury, and that osteocytes control SBP homeostasis to maintain cartilage health, identifying osteocytic TGFβ signaling as a novel therapeutic target for OA.
Tuning the Electronic Structure of Monoclinic Tungsten Oxide Nanoblocks by Indium Doping for Boosted Photoelectrochemical Performance
Authors: Kumar Mohanta Manoj , Kanta Sahu Tushar , Alam Suhaib , Qureshi Mohammad 
Published: October 2020

AbstractPhotoelectrochemical (PEC) water oxidation, a desirable strategy to meet future energy demands, has several bottle‐necks to resolve. One of the prominent issues is the availability of charge carriers at the surface reaction site to promote water oxidation. Of the several approaches, metal dopants to enhance the carrier density of the semiconductors, is an important one. In this work, we have studied the effect of In‐doping on monoclinic WO3 nanoblocks, growing vertically over fluorine‐doped tin oxide (FTO) without the aid of any seed layer. X‐ray photoelectron spectroscopy (XPS) data reveals that In3+ ions are partially occupying the W6+ ions in In‐doped WO3 photoanode. In3+ ions are offering better performance by adding additional charge carriers for amplifying the expression of the number of carriers. The maximum current density value of 2.18 mA/cm2 has been provided by the optimized In‐doped WO3 photoanode with 3 wt% indium doping at 1.23 V vs. RHE, which is ∼3 times higher than that of undoped monoclinic WO3 photoanode. Mott‐Schottky (MS) analysis reveals charge carrier density (ND) for In‐doped WO3 photoanode has been enhanced by a factor of 3. An average Faradic yield of ∼90 percent has been achieved which can serve as a model system using In3+ as a dopant for an inexpensive and attractive method for enhanced WO3 based PEC water oxidation.