bluuebunny/crossref_metadata_2025_split huggingface dataset:
Crosslinked Poly(tetrahydrofuran) as a Loosely Coordinating Polymer Electrolyte
Authors: Mackanic David G. , Michaels Wesley , Lee Minah , Feng Dawei , Lopez Jeffrey , Qin Jian , Cui Yi , Bao Zhenan 
Published: July 2018

AbstractSolid polymer electrolytes (SPEs) promise to improve the safety and performance of lithium ion batteries (LIBs). However, the low ionic conductivity and transference number of conventional poly(ethylene oxide) (PEO)‐based SPEs preclude their widespread implementation. Herein, crosslinked poly(tetrahydrofuran) (xPTHF) is introduced as a promising polymer matrix for “beyond PEO” SPEs. The crosslinking procedure creates thermally stable, mechanically robust membranes for use in LIBs. Molecular dynamics and density functional theory (DFT) simulations accompanied by 7Li NMR measurements show that the lower spatial concentration of oxygen atoms in the xPTHF backbone leads to loosened O–Li+ coordination. This weakened interaction enhances ion transport; xPTHF has a high lithium transference number of 0.53 and higher lithium conductivity than a xPEO SPE of the same length at room temperature. It is demonstrated that organic additives further weaken the O–Li+ interaction, enabling room temperature ionic conductivity of 1.2 × 10−4 S cm−1 with 18 wt% N,N‐dimethylformamide in xPTHF. In a solid‐state LIB application, neat xPTHF SPEs cycle with near theoretical capacity for 100 cycles at 70 °C, with rate capability up to 1 C. The plasticized xPTHF SPEs operate at room temperature while maintaining respectable rate capability and capacity. The novel PTHF system demonstrated here represents an exciting platform for future studies involving SPEs.
Nitrogen‐Doped Wrinkled Carbon Foils Derived from MOF Nanosheets for Superior Sodium Storage
Authors: Kong Lingjun , Zhu Jian , Shuang Wei , Bu Xian‐He 
Published: July 2018

AbstractPreparation of hierarchical carbon nanomaterials from metal−organicframeworks (MOFs) offers immense potential in the improvement of energy density, tunability, and stability of functional materials for energy storage and conversion. How interconnected nitrogen (N)‐doped wrinkled carbon foils derived from MOF nanosheets can serve as high‐performance sodium storage materials due to their multiscale porous structure is shown here. The novel N‐doped carbon nanomaterials are synthesized through the pyrolysis of 2D Mn‐based MOFs, which are produced through the assistance of monodentate ligands to enable the planar growth of MOFs. Subsequent acid etching creates hierarchical pores and channels to allow rapid ion transport. The resulting materials achieve high‐rate capability (165 and 150 mA h g−1 at current densities of  8 and 10 A g−1, respectively) and high stability (capacity retention 72.8% after 1000 cycling at 1.0 A g−1), when they are used as anode in sodium‐ion capacitors.
Overcoming Space‐Charge Effect for Efficient Thick‐Film Non‐Fullerene Organic Solar Cells
Authors: Zhang Guichuan , Xia Ruoxi , Chen Zhen , Xiao Jingyang , Zhao Xuenan , Liu Shiyuan , Yip Hin‐Lap , Cao Yong 
Published: July 2018

AbstractOrganic solar cells (OSCs) containing non‐fullerene acceptors have realized high power conversion efficiency (PCE) up to 14%. However, most of these high‐performance non‐fullerene OSCs have been reported with optimal active layer thickness of about 100 nm, mainly due to the low electron mobility (≈10−4–10−5 cm2 V−1 s−1) of non‐fullerene acceptors, which are not suitable for roll‐to‐roll large‐scale processing. In this work, an efficient non‐fullerene OSC based on poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3′″‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2′″‐quaterthiophen‐5,5′′′‐diyl)] (PffBT4T‐2OD):EH‐IDTBR (consists of electron‐rich indaceno[1,2‐b:5,6‐b′]dithiophene as the central unit and an electron‐deficient 5,6‐benzo[c][1,2,5]thiadiazole unit flanked with rhodanine as the peripheral group) with thickness‐independent PCE (maintaining a PCE of 9.1% with an active layer thickness of 300 nm) is presented by optimizing device architectures to overcome the space‐charge effects. Optical modeling reveals that most of the incident light is absorbed near the transparent electrode side in thick‐film devices. The transport distance of electrons with lower mobility will therefore be shortened when using inverted device architecture, in which most of the excitons are generated close to the cathode side and therefore substantially reduces the accumulation of electrons in the device. As a result, an efficient thick‐film non‐fullerene OSC is realized. These results provide important guidelines for the development of more efficient thick‐film non‐fullerene OSCs.
Therapeutic Effects of a TANK‐Binding Kinase 1 Inhibitor in Germinal Center–Driven Collagen‐Induced Arthritis
Authors: Louis Cynthia , Ngo Devi , D'Silva Damian B. , Hansen Jacinta , Phillipson Louisa , Jousset Helene , Novello Patrizia , Segal David , Lawlor Kate E. , Burns Christopher J. , Wicks Ian P. 
Published: July 2018

ObjectiveThe production of class‐switched high‐affinity autoantibodies derived from organized germinal centers (GCs) is a hallmark of many autoimmune inflammatory diseases, including rheumatoid arthritis (RA). TANK‐binding kinase 1 (TBK‐1) is a serine/threonine kinase involved in the maturation of GC follicular helper T (Tfh) cells downstream of inducible costimulator signaling. We undertook this study to assess the therapeutic potential of TBK‐1 inhibition using the small‐molecule inhibitor WEHI‐112 in antibody‐dependent models of inflammatory arthritis.MethodsUsing the models of collagen‐induced arthritis (CIA), antigen‐induced arthritis (AIA), and K/BxN serum‐transfer–induced arthritis (STIA), we determined the effectiveness of WEHI‐112 at inhibiting clinical and histologic features of arthritis in C57BL/6 and DBA/1 mice. We used immunohistochemistry to characterize GC populations during CIA development, and we used enzyme‐linked immunosorbent assays to determine levels of Ig autoantibodies in WEHI‐112–treated mice compared to vehicle‐treated mice.ResultsWEHI‐112, a tool compound that is semiselective for TBK‐1 but that also has activity against IKKε and JAK2, abolished TBK‐1–dependent activation of interferon (IFN) regulatory factor 3 and inhibited type I IFN responses in vitro. In vivo, treatment with WEHI‐112 selectively abrogated clinical and histologic features of established, antibody‐dependent CIA, but had minimal effects on an antibody‐independent model of AIA or on K/BxN STIA. In keeping with these findings, WEHI‐112 reduced arthritogenic type II collagen–specific IgG1 and IgG2b antibody production. Furthermore, WEHI‐112 altered the GC Tfh cell phenotype and GC B cell function in CIA.ConclusionWe report that TBK‐1 inhibition using WEHI‐112 abrogated antibody‐dependent CIA. As WEHI‐112 failed to inhibit non–antibody‐driven joint inflammation, we conclude that the major effect of this compound was most likely the targeting of TBK‐1–mediated mechanisms in the GC reaction. This approach may have therapeutic potential in RA and in other GC‐associated autoantibody‐driven inflammatory diseases.
Synthesis of Phlorin Analogues of Dithiacorrphycene and Their Use as Specific Chemodosimetric Sensors for Fe3+ Ions
Authors: Thorat Kishor G. , Ravikanth Mangalampalli 
Published: July 2018

AbstractThe first examples of stable phlorin analogues of dithiacorrphycene were synthesized by treating appropriate tetrapyrranes with two equivalents of trifluoroacetic acid in CH2Cl2 followed by oxidation with p‐chloranil. The oxidative coupling of tetrapyrrane resulted in the formation of two unexpected phlorin analogues of dithiacorrphycenes that differed from each other at the meso‐sp3‐carbon, and the two macrocycles were easily separated and isolated by column chromatography. The novel macrocycles were confirmed by X‐ray crystallography and characterized by HRMS, 1D and 2D NMR spectroscopy, absorption spectroscopy, cyclic voltammetry, and time‐dependent DFT studies. X‐ray structure analysis revealed the highly strained and distorted nature of the macrocycles. The macrocycles showed one ill‐defined absorption band at λ≈315 nm and a broad band at λ≈530 nm. Because both macrocycles possess two thiophene and two pyrrole rings with one ionizable inner NH, the cation‐sensing properties of the phlorin analogues of dithiacorrphycenes have been investigated. The phlorin analogues of dithiacorrphycenes act as specific chemodosimetric sensors for Fe3+ ions by converting phlorin analogues of dithiacorrphycenes into dithiacorrphycene.
Circular permutation of a bacterial tyrosinase enables efficient polyphenol‐specific oxidation and quantitative preparation of orobol
Authors: Lee Pyung‐Gang , Lee Sang‐Hyuk , Hong Eun Young , Lutz Stefan , Kim Byung‐Gee 
Published: July 2018

AbstractTyrosinase is a type 3 copper oxygenase that catalyzes a phenol moiety into ortho‐diphenol, and subsequently to ortho‐quinone. Diverse tyrosinases have been observed across the kingdom including Animalia, Bacteria, Plantae, and Fungi. Among the tyrosinases, bacterial, and mushroom tyrosinases have been extensively exploited to prepare melanin, ortho‐hydroxy‐polyphenols, or novel plant secondary metabolites during the past decade. And their use as a biocatalyst to prepare various functional biocompounds have drawn great attention worldwide. Herein, we tailored a bacterial tyrosinase from Bacillus megaterium (BmTy) using circular permutation (CP) engineering technique which is a novel enzyme engineering technique to covalently link original N and C termini and create new termini on the middle of its polypeptide. To construct a smart rationally‐designed CP library, we introduced 18 new termini at the edge of each nine loops that link α‐helical secondary structure in BmTy. Among the small library, seven functional CP variants were successfully identified and they represented dramatic change in their enzyme characteristics including kinetic properties and substrate specificity. Especially, cp48, 102, and 245 showed dramatically decreased tyrosine hydroxylase activity, behaving like a catechol oxidase. Exploiting the dramatic increased polyphenol oxidation activity of cp48, orobol (3′‐hydroxy‐genistein) was quantitatively synthesized with 1.48 g/L, which was a 6‐fold higher yield of truncated wild‐type. We examined their kinetic characters through structural speculation, and suggest a strategy to solubilize the insoluble artificial variants effectively.
An Insight on the Electrocatalytic Mechanistic Study of Pristine Ni MOF (BTC) in Alkaline Medium for Enhanced OER and UOR
Authors: Maruthapandian Viruthasalam , Kumaraguru Shanmugasundaram , Mohan Subramanian , Saraswathy Velu , Muralidharan Srinivasan 
Published: July 2018

AbstractHydrogen production plays a major role in technologies for renewable energy storage. Water and urea electrolysis (WE, UE) are promising processes in this regard. The oxygen evolution reaction (OER) and urea oxidation reaction (UOR), respectively, are limiting the efficiency of the overall process. As catalysts for these reactions, metal‐organic frameworks (MOF) have gained increasing attention due to their combinations and co‐existence of metal and organic moiety properties. Here, we investigated the catalytic behavior of Ni MOF (1,3,5‐Benzenetricarboxylic acid (BTC)) towards OER and UOR in alkaline medium on carbon paper (CP) as a support. The Ni MOF exhibits 346 mV overpotential (η) at a current density of 10 mA cm−2, 79.03 A g−1 specific‐mass activity at 400 mV of η than compared to wet chemically prepared (WCP) NiO and RuO2 for OER in 1 M KOH. Meanwhile, ≈230 mV of η at 10 mA cm−2 current density with appreciable stability for 12 hours for Ni MOF in 30 % KOH was also observed. For UOR in UE, Ni MOF shows an onset potential of 1.34 V vs. RHE and 63.15 mA cm−2 current density at 1.5 V vs RHE in 1 M KOH in the presence of 1 M urea. The observed results of OER and UOR catalytic behavior are better than wet chemically prepared (WCP) NiO and noble benchmark RuO2 catalyst under identical conditions. The results suggested that the MOF plays a major role in enhancing the catalytic activity by the facile formation of Ni(OH)2/NiOOH, stability and electronic properties due to their porous and interconnected structure.
Production Options for Psilocybin: Making of the Magic
Authors: Fricke Janis , Lenz Claudius , Wick Jonas , Blei Felix , Hoffmeister Dirk 
Published: July 2018

AbstractThe fungal genus Psilocybe and other genera comprise numerous mushroom species that biosynthesize psilocybin (4‐phosphoryloxy‐N,N‐dimethyltryptamine). It represents the prodrug to its dephosphorylated psychotropic analogue, psilocin. The colloquial term “magic mushrooms” for these fungi alludes to their hallucinogenic effects and to their use as recreational drugs. However, clinical trials have recognized psilocybin as a valuable candidate to be developed into a medication against depression and anxiety. We here highlight its recently elucidated biosynthesis, the concurrently developed concept of enzymatic in vitro and heterologous in vivo production, along with previous synthetic routes. The prospect of psilocybin as a promising therapeutic may entail an increased demand, which can be met by biotechnological production. Therefore, we also briefly touch on psilocybin's therapeutic relevance and pharmacology.
From Indium‐Doped Ag2S to AgInS2 Nanocrystals: Low‐Temperature In Situ Conversion of Colloidal Ag2S Nanoparticles and Their NIR Fluorescence
Authors: Shang Huishan , Di Qiumei , Ji Muwei , Bai Bing , Liu Jiajia , Chen Wenxing , Xu Meng , Rong Hongpan , Liu Jia , Zhang Jiatao 
Published: July 2018

AbstractFocusing on ternary I‐III‐VI2 colloidal nanocrystals (NCs) synthesized with precise control of the composition (from doping to ternary composition) and NIR fluorescence performance, monodisperse binary In3+‐doped Ag2S NCs and ternary AgInS2 NCs have been achieved successfully by facile low‐temperature in situ conversion of colloidal Ag2S nanoparticles. In3+ ions were inserted into the crystal lattice of Ag2S NCs at a relatively low temperature as dopant and ternary AgInS2 NCs were obtained at a higher temperature following a phase transition. These doped Ag2S and AgInS2 NCs based on different indium precursor concentrations were explored with respect to the position and intensity of the near‐infrared photoluminescent emission at different doping levels and crystal phase evolution.
When Kinases Meet PROTACs
Authors: Tan Li , Gray Nathanael S. 
Published: July 2018

AbstractSmall molecule drugs targeting kinases have revolutionized treatment options for millions of patients worldwide, especially in oncology. These targeted treatments have less side effects because they inhibit a specific dysfunctional kinase usually with relatively narrow selectivity. However, kinase inhibitors do have well‐established liabilities, most prominently the emergence of drug resistance. Moreover, the majority of kinases are multidomain and multifunctional proteins that in addition to their enzymatic activity have scaffolding and other roles, and inhibitors seldom address these alternative functions. Recently, small molecule mediated targeted protein degradation emerged as a new pharmacological strategy. The majority of small molecule degraders are bispecific molecules called proteolysis targeting chimeras (PROTACs), and their mechanism of action is based on simultaneous recruitment of the target of interest and an E3 ligase, resulting in target polyubiquitination and eventual destruction by the proteasome. Over the last couple of years, PROTAC strategy has been developed and validated for a range of targets, including kinases. Here, we introduce the targeted protein degradation strategy, provide an overview of representative kinase PROTACs, and describe design rationales, efficacy and specificity. We also discuss their potential advantages, as well as comment on some of the limitations of this emerging pharmacological modality.
Progress in the Development of Platelet‐Activating Factor Receptor (PAFr) Antagonists and Applications in the Treatment of Inflammatory Diseases
Authors: Hyland Isabel K. , O'Toole Ronan F. , Smith Jason A. , Bissember Alex C. 
Published: July 2018

AbstractPlatelet‐activating factor (PAF) and its receptor (PAFr) have been implicated in a wide range of diseases and disorders that originate from the activation of inflammatory pathways. Although the exact structure of the binding site on the PAFr remains unknown, the PAFr is a well‐established therapeutic target, and an array of structurally diverse PAFr antagonists have been identified. These include compounds that are structurally similar to the natural PAF ligand, synthetic heterocycles, complex polycyclic natural products, and various metal complexes. This review provides an update on more than 20 years of progress in this area. The development and synthesis of new PAFr antagonists, structure–activity relationship studies, the biological activity of these molecules, and their therapeutic potential are discussed.
Production of Human β‐Actin Using a Bacterial Expression System with a Cold Shock Vector
Authors: Tamura Minoru 
Published: July 2018

AbstractActin is one of the most abundant proteins in the cytoplasm of eukaryotic cells and plays important roles in a variety of cellular functions. However, it has been difficult to produce actin in substantial amounts using bacterial expression systems. In this article, a new method is described for the production of recombinant actin in bacterial cells. Human β‐actin (His‐tagged) can be expressed using a cold shock vector, pCold, in a bacterial expression system and then separated with a Ni‐chelating resin, followed by a polymerization/depolymerization cycle or column chromatography with the Ni‐chelating resin. The purified recombinant β‐actin shows normal polymerization ability compared with commercially available β‐actin purified from human platelets. This article also describes the preparation of mutant actin(G168R). This purified mutant exhibits impaired polymerization ability. The system and procedures described here will provide a useful method for the production of actin isoforms and their mutants. © 2018 by John Wiley & Sons, Inc.
Using Fluorescence Anisotropy for Ligand Binding Kinetics of Membrane Proteins
Authors: Swonger Kirsten N. , Robinson Anne S. 
Published: July 2018

AbstractDetermining ligand binding kinetics provides an indirect route to probe the functional capabilities of the binding pocket of a membrane protein receptor. Presented in this unit are four ligand‐binding protocols that provide data useful for characterizing membrane proteins, including equilibrium binding, thermostability, competitive ligand binding, and kinetic ligand binding. These techniques use fluorescence anisotropy, which is safer, less costly, and simpler to execute than radioactive ligand binding. Each protocol may be used on its own or in combination with others to quantify a number of ligand binding constants. © 2018 by John Wiley & Sons, Inc.
An open outdoor algal growth system of improved productivity for biofuel production
Authors: Kannan Dheeban Chakravarthi , Venkat Devi 
Published: July 2018

AbstractBACKGROUNDMicroalgae are among the most promising options for renewable fuel production in the future. Translating high laboratory yields to outdoor productivity has been a major challenge. Outdoor sunlight intensity is much greater than the saturation light intensities of algae. An open outdoor growth system design has been developed based on systematic distribution of sunlight to improve the productivity.RESULTSThe first stage of the light‐distribution design (1800 L) yielded 1.5–2.0 times better productivity than a standard open system, and the next stage (630 L) yielded 2–3 times better productivity. Productivities up to 36–42 g m−2 day−1 were obtained in a region where the climatic conditions are mostly adverse for algal growth. Comparison with other similar climatic conditions validated the performance improvement of the growth system over a wide range. Light distribution profiles illustrated the distribution patterns and gave cues for further improvement. Cost comparison of light distribution against the additional land and infrastructure indicates promising reductions.CONCLUSIONThe performance improvement shown by the designed growth system is significant and shows good potential for advancement of outdoor algal production for biofuels and related products. © 2018 Society of Chemical Industry
Co‐immobilization of P450 BM3 and glucose dehydrogenase on different supports for application as a self‐sufficient oxidative biocatalyst
Authors: Solé Jordi , Caminal Gloria , Schürmann Martin , Álvaro Gregorio , Guillén Marina 
Published: July 2018

AbstractBACKGROUNDThe oxy‐functionalization of non‐activated carbon bonds by the bacterial cytochrome P450 BM3 from Bacillus megaterium, presents a promising field in biosynthesis and it has gained much interest in recent decades. Nevertheless, the need for the expensive cofactor NADPH, together with low operational stability of the enzyme have made the implementation of this biocatalyst unfeasible in most cases for industry.RESULTSP450 BM3 and glucose dehydrogenase (GDH), as a cofactor regeneration enzyme, were successfully co‐immobilized obtaining a bi‐functional self‐sufficient oxidative biocatalyst. First, a broad screening of 13 different supports was carried out. Five selected agaroses with three different functionalities (epoxy, amine and aldehyde) were studied and their immobilization processes optimized. Finally, P450 BM3 and GDH were co‐immobilized on those supports showing the best performance for P450 BM3 immobilization: epoxy‐agarose (epoxy‐agarose‐UAB) presenting 83% and 20% retained activities respectively; AMINO‐agarose presenting 28% and 25%, and Lentikats® with which both enzymes retained 100% of the initial activity. Furthermore, the re‐utilization of the self‐sufficient immobilized derivatives was tested in five repeated cycles.CONCLUSIONSP450 BM3 and GDH have been successfully immobilized on three supports and their re‐usability has been tested in a model reaction. It represents a step forward for future P450 BM3 industrial implementations. © 2018 Society of Chemical Industry
Highly concentrated omega‐3 fatty acid ethyl esters by urea complexation and molecular distillation
Authors: Magallanes Leisa M , Tarditto Lorena V , Grosso Nelson R , Pramparo María C , Gayol María F 
Published: July 2018

AbstractBACKGROUNDRaya liver deodorized oil contains high concentrations of eicosapentaenoic acid (EPA), docosapentaenoic acid (DPA) and docosahexaenoic acid (DHA). The present study investigated the processes of urea complexation (UC) and molecular distillation (MD) to determine the most adequate operation conditions for each process, separately and together, aiming to obtain highly concentrated EPA, DPA and DHA ethyl esters with chemical indicator values permitted by the current legislation for edible oils.RESULTSIn the second stage of MD, a concentration of 820.27 g kg−1 in the distillate and 951.06 g kg−1 of omega‐3 fatty acid ethyl esters in the residue was obtained. The distillate showed values of free fatty acids, peroxide and p‐anisidine lower than the maximum allowed for edible oils in accordance with the current legislation.CONCLUSIONThe use of UC and MD together has revealed a significant improvement in the total concentration of omega‐3 fatty acid ethyl esters in the final product and good application prospects. © 2018 Society of Chemical Industry