bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ultrahigh‐Capacity and Fire‐Resistant LiFePO4‐Based Composite Cathodes for Advanced Lithium‐Ion Batteries
Authors: Li Heng , Peng Long , Wu Dabei , Wu Jin , Zhu Ying‐Jie , Hu Xianluo 
Published: January 2019

AbstractThe growing demand for advanced energy storage devices with high energy density and high safety has continuously driven the technical upgrades of cell architectures as well as electroactive materials. Designing thick electrodes with more electroactive materials is a promising strategy to improve the energy density of lithium‐ion batteries (LIBs) without alternating the underlying chemistry. However, the progress toward thick, high areal capacity electrodes is severely limited by the sluggish electronic/ionic transport and easy deformability of conventional electrodes. A self‐supported ultrahigh‐capacity and fire‐resistant LiFePO4 (UCFR‐LFP)‐based nanocomposite cathode is demonstrated here. Benefiting from the structural and chemical uniqueness, the UCFR‐LFP electrodes demonstrate exceptional improvements in electrochemical performance and mass loading of active materials, and thermal stability. Notably, an ultrathick UCFR‐LFP electrode (1.35 mm) with remarkably high mass loading of active materials (108 mg cm−2) and areal capacity (16.4 mAh cm−2) is successfully achieved. Moreover, the 1D inorganic binder‐like ultralong hydroxyapatite nanowires (HAP NWs) enable the UCFR‐LFP electrode with excellent thermal stability (structural integrity up to 1000 °C and electrochemical activity up to 750 °C), fire‐resistance, and wide‐temperature operability. Such a unique UCFR‐LFP electrode offers a promising solution for next‐generation LIBs with high energy density, high safety, and wide operating‐temperature window.
Highly Efficient Solar‐Driven Carbon Dioxide Reduction on Molybdenum Disulfide Catalyst Using Choline Chloride‐Based Electrolyte
Authors: Asadi Mohammad , Motevaselian Mohammad Hossein , Moradzadeh Alireza , Majidi Leily , Esmaeilirad Mohammadreza , Sun Tao Victor , Liu Cong , Bose Rumki , Abbasi Pedram , Zapol Peter , Khodadoust Amid P. , Curtiss Larry A. , Aluru Narayana R. , Salehi‐Khojin Amin 
Published: January 2019

AbstractConversion of CO2 to energy‐rich chemicals using renewable energy is of much interest to close the anthropogenic carbon cycle. However, the current photoelectrochemical systems are still far from being practically feasible. Here the successful demonstration of a continuous, energy efficient, and scalable solar‐driven CO2 reduction process based on earth‐abundant molybdenum disulfide (MoS2) catalyst, which works in synergy with an inexpensive hybrid electrolyte of choline chloride (a common food additive for livestock) and potassium hydroxide (KOH) is reported. The CO2 saturated hybrid electrolyte utilized in this study also acts as a buffer solution (pH ≈ 7.6) to adjust pH during the reactions. This study reveals that this system can efficiently convert CO2 to CO with solar‐to‐fuel and catalytic conversion efficiencies of 23% and 83%, respectively. Using density functional theory calculations, a new reaction mechanism in which the water molecules near the MoS2 cathode act as proton donors to facilitate the CO2 reduction process by MoS2 catalyst is proposed. This demonstration of a continuous, cost‐effective, and energy efficient solar driven CO2 conversion process is a key step toward the industrialization of this technology.
Highly Active Cobalt‐Based Electrocatalysts with Facile Incorporation of Dopants for the Oxygen Evolution Reaction
Authors: Moon Gun‐hee , Yu Mingquan , Chan Candace K. , Tüysüz Harun 
Published: January 2019

AbstractIn situ formation of electroactive cobalt species for the oxygen evolution reaction is simply achieved by applying an anodic bias to a commercially available cobalt precursor and Nafion binder mixture coated on a glassy carbon electrode. This preparation does not require energy‐intensive materials preparation steps or noble metals, yet a low overpotential of 322 mV at 10.2 mA cm−2 and a high current density of more than 300 mA cm−2 at 1.7 VNHE were obtained in 1 m KOH. An operando electrochemical Raman spectroscopy study confirmed the formation of cobalt oxyhydroxide species and the iron stimulated the equilibrium state between Co3+ and Co4+. The iron present in the alkali electrolyte or ink solution effectively activated the cobalt species, and most of the first row transition metals could also enhance the catalytic performance. The concept presented here is one of the simplest strategies for preparing highly active electrocatalysts and is very flexible for the replacement of cobalt by other transition metals.
Enantioselective N‐Heterocyclic Carbene Catalysis that Exploits Imine Umpolung
Authors: Fernando Jared E. M. , Nakano Yuji , Zhang Changhe , Lupton David W. 
Published: January 2019

AbstractThe catalytic umpolung of imines remains an underdeveloped approach to reaction discovery. Herein we report an enantioselective aza‐Stetter reaction that proceeds via imine umpolung using N‐heterocyclic carbene catalysis. The reaction proceeds with high levels of enantioselectivity (all ≥96:4 er) and good generality (21 examples). Mechanistic studies are reported and are consistent with turnover‐limiting addition of the NHC to the imine.
Enhancement of Photodynamic Cancer Therapy by Physical and Chemical Factors
Authors: Yang Mingying , Yang Tao , Mao Chuanbin 
Published: January 2019

AbstractThe viable use of photodynamic therapy (PDT) in cancer therapy has never been fully realized because of its undesirable effects on healthy tissues. Herein we summarize some physicochemical factors that can make PDT a more viable and effective option to provide future oncological patients with better‐quality treatment options. These physicochemical factors include light sources, photosensitizer (PS) carriers, microwaves, electric fields, magnetic fields, and ultrasound. This Review is meant to provide current information pertaining to PDT use, including a discussion of in vitro and in vivo studies. Emphasis is placed on the physicochemical factors and their potential benefits in overcoming the difficulty in transitioning PDT into the medical field. Many advanced techniques, such as employing X‐rays as a light source, using nanoparticle‐loaded stem cells and bacteriophage bio‐nanowires as a photosensitizer carrier, as well as integration with immunotherapy, are among the future directions.
No Fear of Perfluorinated Peroxides: Syntheses and Solid‐State Structures of Surprisingly Inert Perfluoroalkyl Peroxides
Authors: Nissen Jan H. , Stüker Tony , Drews Thomas , Steinhauer Simon , Beckers Helmut , Riedel Sebastian 
Published: January 2019

AbstractWe report on the solid‐state structures of bis(nonafluoro‐tert‐butyl) peroxide [(F3C)3CO]2and bis(undecafluoro‐2‐methyl‐2‐butyl) peroxide [(C2F5)(F3C)2CO]2. These peroxides were prepared from the corresponding hypofluorites and fluorinated silver wool. The solid‐state structures obtained after in situ crystallisation show unusual COOC dihedral angles of 180°, as well as elongated O−O bonds because of the bulky perfluorinated alkyl groups. The perfluorinated alkyl peroxides are insensitive to both impact (>40 J) and friction (>360 N), and resistant towards mineral acids (HX; X=F, Cl, Br) and elemental halogens (X2). Ferrocene is oxidized by [(F3C)3CO]2to [FeIIICp2][OC(CF3)3].
Dynamic viscoelasticity and molecular orientation in uniaxially drawn PC/PET blends
Authors: Luo Fei , Liu Xianhu , Liu Chuntai , Ma Jianhui , Wang Xinli , Shen Changyu 
Published: January 2019

ABSTRACTThe dependence of dynamic viscoelasticity on molecular orientation of the hot‐drawn polycarbonate (PC)/poly(ethylene terephthalate) blends was studied experimentally. The oriented states of samples were investigated by wide‐angle X‐ray diffraction and quantified by Hermans' factor. The viscoelasticity was probed by dynamic mechanical analysis. For the fitting curves of dynamic modulus versus orientation, the PC‐rich blends with different compositions had an opposite concavity and convexity compared with the neat PC. The difference revealed the influence of molecular mobility on orientation and viscoelasticity. The assumption on the phase morphological change from sea‐island to local sandwich‐like structure in blends was proposed and used to interpret the variation of slope of fitting curves. The relationship between orientation and viscoelasticity was observed in PC‐rich blends, which can help understand the mechanism of molecular orientation and develop the constitutive relations for simulation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47514.
Nanoparticles of 4,7‐dichloro‐2‐quinolinemethylacrylate‐based copolymers and their potential cytotoxic activity on human breast carcinoma cells
Authors: Valle Hernán , Palao‐Suay Raquel , Aguilar María Rosa , Román Julio San , Becerra José , Rivas Bernabé , Mangalaraja Ramalinga Viswanathan 
Published: January 2019

ABSTRACTIn this article, an improved synthesis strategy of the potent anticancer compound 4,7‐dichloro‐2‐quinolinemethanol (QM) and its acrylate ester 4,7‐dichloro‐2‐quinolinemethylacrylate (AQM) are described. AQM is copolymerized using free‐radical polymerization with N‐vinyl‐2‐pyrrolidone (VP) and the copolymers obtained from different molar ratios of monomers are subjected to nanoprecipitation to produce suspensions of nanoparticles (NPs) in phosphate buffered saline (PBS). The smallest and stable NPs are prepared with the AQM‐VP copolymers 45:55 and 40:60 (118.9 and 128.7 nm in diameter, respectively) at 1 mg mL−1, and along with AQM and QM, are evaluated for their cytotoxic activity on MDA‐MB‐453 breast carcinoma cells using MTT bioassay. AQM and QM are highly cytotoxic (IC50: 19 and 41 μM, respectively); however, the NPs are not cytotoxic in the range of the assayed concentrations. These results contribute to the search for new polymeric NPs with potential application as QM delivery systems for the treatment of cancer or other diseases treatable with QM. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47545.
Genesis through Lacan: A shift in God's discourse toward therapeutic management
Authors: Schreiber Ephraim , Schreiber Gabriel , Avissar Sofia , Halperin Demian 
Published: January 2019

AbstractWe propose a reading of Genesis through Jacques Lacan: Acquiring language skills is seen as the passage from preverbal Real Order to Symbolic Order, interpreted in Genesis as the passage from Heaven to Knowledge of Death. Lacan's schemata of the four discourses enables the understanding of four key social phenomena: educating (University Discourse), governing (Master Discourse), protesting (Hysteric Discourse), and revolutionizing (Treatment Discourse). God monolog‐type discourse in Chapter 1 is similar to the University Discourse, representing a Mechanistic–Instrumental management mode, governed by the principle man = machine, a working tool, taken as an input for output production. God changes his mode of administrating in Chapters 2 and 3 to dialog‐type Treatment Discourse (Human Relations mode), enabling man to become a master of its own. We propose this reading of Genesis as an encouragement to use the Treatment Discourse as main management mode. We shall call it “therapeutic management.”
Cognitive and behavioral differences in toddlers with autism spectrum disorder from multiplex and simplex families
Authors: Dissanayake Cheryl , Searles James , Barbaro Josephine , Sadka Nancy , Lawson Lauren P. 
Published: January 2019

Prospective, longitudinal designs utilizing “high‐risk” infant siblings of children diagnosed with Autism Spectrum Disorder (ASD‐sibs) have provided unique and valuable insights regarding the early ASD phenotype. However, it remains unclear whether these cases are representative of all children with ASD. The objective in the present study was to investigate whether the early development of toddlers with ASD from multiplex (MPX) families, who have an affected older sibling, is similar or different to toddlers with ASD from simplex (SPX) families, where there is no affected sibling. A further aim was to examine patterns of association between autism symptom severity and cognitive functioning within each group to inform possible mechanisms for group similarities/differences. Behavioral and cognitive assessment data from a sample of toddlers with ASD was utilized, comprising 45 MPX, 127 first‐born SPX, and 72 later‐born SPX toddlers. Participants in the MPX group had significantly higher developmental quotients on the Mullen Scales of Early Learning compared to those in the SPX groups, who did not differ from each other. However, all three groups were similar on their autism severity scores (measured using the Autism Diagnostic Observation Schedule and the Autism Diagnostic Interview), and the pattern of relationships between cognitive ability and autism symptom severity. The results suggest that caution be exercised in generalizing findings from ASD‐sib samples to other samples of children with ASD. The higher cognitive abilities in the MPX group, in addition to biological differences, may also be an outcome of family environmental factors, which deserves further investigation. Autism Research 2019, 12: 682–693. © 2019 International Society for Autism Research, Wiley Periodicals, Inc.Lay SummaryWe sought to establish whether toddlers with autism from families where there is more than one affected child, called multiplex families, are different to children from simplex families, where there is only one affected child, and no other members within the immediate family with an autism diagnosis. We found that while toddlers from multiplex families were similar to those from simplex families in their autism symptoms, they were more developmentally advanced than children in the latter group.
A simple FRET system using two‐color CdTe quantum dots assisted by cetyltrimethylammonium bromide and its application to Hg(II) detection
Authors: Wang Jing , Song Fengjuan , Ai Yongling , Hu Shanwen , Huang Zhizhou , Zhong Wenying 
Published: January 2019

AbstractIn this study, we developed a novel simple fluorescence resonance‐energy transfer (FRET) system between two‐color CdTe quantum dots (QDs) assisted by cetyltrimethylammonium bromide (CTAB). Mercaptopropionic (MPA)‐capped CdTe QDs serving as both donors and acceptors were successfully synthesized by changing the refluxing time in aqueous solution. CTAB micelles formed in water and minimized the distance between the donors and acceptors significantly by electrostatic interactions, improving FRET efficiency. Several factors that affected the fluorescence spectra of the FRET system were investigated. The prepared FRET system was feasible as an effective fluorescent probe to detect Hg(II) in aqueous solution. At pH 7.0, a linear relationship between the quenched fluorescence intensity of orange‐emitting acceptors (QDs(A)) and Hg(II) concentration was acquired in the range 5–250 nmol/L with a detection limit of 1.95 nmol/L. The developed method showed excellent analytical performance for Hg(II) with high sensitivity and acceptable selectivity, reproducibility and stability. This finding indicated that the method has a promising potential application for environmental monitoring. This study demonstrated the great promise of QDs for expedient, low‐cost and high‐sensitivity detection of Hg(II).
Systematic review to assess the possibility of return of cerebral and cardiac activity after normothermic regional perfusion for donors after circulatory death
Authors: Shapey I M , Summers A , Augustine T , van Dellen D 
Published: January 2019

AbstractBackgroundNormothermic regional perfusion (NRP) is a novel technique that aids organ recovery from donors after circulatory death (DCDs). However, ethical concerns exist regarding the potential return of spontaneous cerebral and cardiac activity (ROSCCA). This study aimed to determine the likelihood of ROSCCA in NRP-DCDs of abdominal organs.MethodsExtracorporeal cardiopulmonary resuscitation (ECPR) for refractory out-of-hospital cardiac arrest (OOHCA) was identified as a comparator for NRP-DCDs and as a validation cohort. A systematic search identified all articles relating to NRP-DCDs and ECPR-OOHCA. Rates of ROSCCA and survival outcomes (ECPR-OOHCA only) were recorded and analysed according to the duration of no perfusion.ResultsIn NRP-DCDs, 12 of 410 articles identified by database searching were eligible for inclusion. There were no instances of ROSCCA recorded among 493 donors. In ECPR-OOHCA, eight of 947 screened articles were eligible for inclusion (254 patients). Where the absence of perfusion exceeded 5 min in ECPR-OOHCA, there were no survivors with a favourable neurological outcome.ConclusionROSCCA is unlikely following commencement of NRP and has not occurred to date. Strict observance of the 5-min interval following asystole provides satisfactory assurance that ROSCCA will not occur following NRP.
Caryophyllene Sesquiterpenes from Pulicaria vulgarisGaertn.: Isolation, Structure Determination, Bioactivity and Structure−Activity Relationship
Authors: Zardi‐Bergaoui Afifa , Znati Mansour , Harzallah‐Skhiri Fethia , Jannet Hichem Ben 
Published: January 2019

AbstractA new caryophyllene, named pulicaryenne A (1), along with four other known caryophyllene derivatives (2, 3, 4 and 5) were isolated from the ethyl acetate extract of aerial parts of Pulicaria vulgaris Gaertn. (Asteraceae). All compounds were isolated for the first time from this species. Compound 2 was identified as a new epimer of a known caryophyllene derivative isolated previously from P. dysenterica. Their structures were established by spectroscopic means including NMR analysis (1D‐ and 2D‐NMR) and ESI‐TOF‐MS. All compounds were evaluated for their anticholinesterase, antityrosinase and cytotoxic activities against two human cell lines (A549 and HeLa). Results showed that compound 5 exhibited the highest cytotoxic effect against A549 and anticholinesterase activity with IC50 values of 8.50±0.75 and 6.45±0.09 μg/mL, respectively. Furthermore, compound 5 showed also an interesting antityrosinase activity with percent inhibition value of 79.0±2.5 % at 50 μg/mL. The bioactivity and drug likeness scores of the isolated compounds 1–5 were calculated using Molinspiration software and discussed. These results may suggest that the five caryophyllene derivatives endowed with good biological properties, which could be used as bioactive alternatives in pharmaceutical preparations.
Synthesis‐Gas Absorption under Real Process Conditions: Thermodynamic Aspects
Authors: Stepacheva Antonina A. , Markova Mariia E. , Gavrilenko Alexandra V. , Sidorov Alexander I. , Matveeva Valentina G. , Sulman Mikhail G. , Sulman Esther M. 
Published: January 2019

AbstractThe solubility of synthesis gas was measured in the temperature range of 100–300 °C and pressure range of 1.0–5.0 MPa in polar (2‐propanol) and nonpolar (n‐dodecane) solvents. Thermodynamic parameters of the absorption, such as the Henry constant, absorption enthalpy, and apparent activation energy of absorption, were calculated on the basis of the obtained results. The phase equilibrium was calculated by using the Soave‐Redlich‐Kwong cubic equation of state, which could be used to predict the optimal process conditions for liquid‐phase Fischer‐Tropsch reactions in different solvents.
Selenium as Extra Binding Site for Sulfur Species in Sulfurized Polyacrylonitrile Cathodes for High Capacity Lithium‐Sulfur Batteries
Authors: Jiang Mao , Wang Kangli , Gao Shu , Wang Ruxing , Han Jing , Yan Jie , Cheng Shijie , Jiang Kai 
Published: January 2019

AbstractDue to their high theoretical energy density, lithium sulfur (Li−S) batteries are promising candidates for next generation energy storage systems. Unfortunately, polysulfide dissolution in ether‐based electrolytes is still a major problem of Li−S batteries. Sulfurized polyacrylonitrile (SPAN) can be used as electrode material in carbonate‐based electrolytes to avoid large‐scale dissolution of polysulfides. But SPAN composites usually suffer from low sulfur content (<50 wt %) and low capacity, limiting their practical application. Here, we synthesize a novel Se doped SPAN (SeSPAN) composite by one‐step thermal treatment. Se atoms are uniformly distributed in the SeSPAN composite and serve as binding sites for S species, increasing the sulfur content up to about 60 wt %, higher than previously reported results. In addition, the Se doping itself is contributing to an increased capacity. The discharge/charge mechanism of the SeSPAN composite is investigate by Raman and X‐ray photoelectron spectroscopy, indicating the existence of Se−S bonds and good electrochemical reversibility. Thus, the SeSPAN cathode delivers an excellent initial specific capacity of 1044 mA h g−1 (calculated for the mass of the whole composite) and a high coulombic efficiency of almost 100 %. Compared with conventional SPAN composites, our SeSPAN material shows a great improvement on the capacity and cycle life and provides a new way to build high capacity SPAN composites.
Electrochemical Synthesis of Aryl Methoxymethyl Ethers
Authors: de Kruijff Goswinus H. M. , Waldvogel Siegfried R. 
Published: January 2019

AbstractMethoxymethyl protected phenols are accessible by our safe, reagent‐ and reagent waste‐free anodic decarboxylation protocol. High current efficiencies and good functional group tolerance makes this methodology a useful tool for the preparation of these valuable and protected phenol building blocks.
Biocatalytic Strategies towards [4+2] Cycloadditions
Authors: Lichman Benjamin R. , O'Connor Sarah E. , Kries Hajo 
Published: January 2019

AbstractLong sought after [4+2] cyclases have sprouted up in numerous biosynthetic pathways in recent years, raising hopes for biocatalytic solutions to cycloaddition catalysis, an important problem in chemical synthesis. In a few cases, detailed pictures of the inner workings of these catalysts have emerged, but intense efforts to gain deeper understanding are underway by means of crystallography and computational modelling. This Minireview aims to shed light on the catalytic strategies that this highly diverse family of enzymes employs to accelerate and direct the course of [4+2] cycloadditions with reference to small‐molecule catalysts and designer enzymes. These catalytic strategies include oxidative or reductive triggers and lid‐like movements of enzyme domains. A precise understanding of natural cycloaddition catalysts will be instrumental for customizing them for various synthetic applications.
Collective Synthesis of Schilancidilactones A, B and Schilancitrilactones A, B, C, 20‐epi‐Schilancitrilactone A
Authors: Wang Hengtao , Wang Liang , Li Yihang , Zhang Xiunan , Tang Pingping 
Published: January 2019

Summary of main observation and conclusionSchisandraceae triterpenoids are novel natural products that contain highly fused ring systems bearing multiple chiral centers surrounding. Some of them exhibit promising bioactivities, such as antitumor, anti‐HIV, etc. In this article, we describe our efforts to the collective total synthesis of schilancidilactones A, B, schilancitrilactones A, B, C, and 20‐epi‐schilancitrilactone A from common precursors. An intramolecular radical cyclization, late‐stage halogenation and AIBN‐mediated or Ni‐catalyzed intermolecular radical cross coupling reaction were employed as the key steps.