bluuebunny/crossref_metadata_2025_split huggingface dataset:
A New Strategy of Constructing a Highly Fluorinated Solid‐Electrolyte Interface towards High‐Performance Lithium Anode
Authors: Li Panlong , Feng Wuliang , Dong Xiaoli , Wang Yonggang , Xia Yongyao 
Published: April 2020

AbstractLithium fluoride (LiF)‐rich solid‐electrolyte interface (SEI) layers are reported as an effective method to suppress lithium dendrites growth and capacity fading for Li‐plating/Li‐stripping. Herein, a new pre‐fluorination strategy is proposed by constructing an MgF2 thin film on pristine copper foil via the magnetron sputtering. This MgF2 film proves a lithiophilic substrate and shows highly irreversible conversion reaction to LiF in the first cycle. The resulting uniform LiF‐rich dual‐layered SEI layer helps homogenize lithium ions flux, and remaining magnesium metal particles help reduce the overpotential of lithium nucleation, which regulates the behavior of Li‐plating/Li‐stripping. As a result, the half‐cells (with a fixed plating capacity of 0.5 mAh cm−2 at 0.5 mA cm−2) with the electrode after 3 min sputtering treatment show a long cycle life and a high average Coulombic efficiencies (98.3% for 600 cycles). This pre‐fluorination strategy paves an effective and facile way for the application of lithium metal batteries.
Insights into the Storage Mechanism of Layered VS2 Cathode in Alkali Metal‐Ion Batteries
Authors: Zhang Xiao , He Qiu , Xu Xiaoming , Xiong Tengfei , Xiao Zhitong , Meng Jiashen , Wang Xuanpeng , Wu Lu , Chen Jinghui , Mai Liqiang 
Published: April 2020

AbstractVS2 is one of the attractive layered cathodes for alkali metal‐ion batteries. However, the understanding of the detailed reaction processes and energy storage mechanism is still inadequate. Herein, the Li+/Na+/K+ insertion/extraction mechanisms of VS2 cathode are elucidated on the basis of experimental analyses and theoretical simulations. It is found that the insertion/extraction behavior of Li+ is partially irreversible, while the insertion/extraction behavior of Na+/K+ is completely reversible. The detailed intermediates and final products (Li0.33VS2, LiVS2, Na0.5VS2, NaVS2, K0.6VS2, KzVS2, z > 0.6) during the discharging/charging processes are identified, indicating that VS2 undergoes different phase transitions and solid–solution reactions in different battery systems, which have a great influence on the battery performance. Moreover, the diffusion of Na+ in VS2 cathode is demonstrated to be much slower than that of Li+ and K+. Such mechanistic research provides a reference for in‐depth understanding of energy storage in layered transition metal sulfides/selenides.
Detailed modeling of the kraft pulping chemistry: carbohydrate reactions
Authors: Fearon Olesya , Nykänen Vesa , Kuitunen Susanna , Ruuttunen Kyösti , Alén Raimo , Alopaeus Ville , Vuorinen Tapani 
Published: April 2020

AbstractThe article introduces a detailed model for carbohydrate chemistry in kraft pulping. This article is continuation to the modeling work carried out for hot water extraction and chemical pulp bleaching. The model includes galactoglucomannan, xylan, and cellulose acid–base equilibria, in addition to peeling, stopping, and alkaline hydrolysis reactions of the same carbohydrates, as well as hexenuronic acid formation and degradation reactions. The Arrhenius parameters were applied from the literature or regressed against experimental data in the present study. The model is very successful in predicting the experimental data of carbohydrate reactions during kraft pulping. Many features of the pulping‐related model can be applied to specific fractionation chemistry considerations. The detailed knowledge on carbohydrates composition at any stage of pulping gives possibility for further development of biorefinery cases based on kraft pulping, such as biofuel and chemicals production.
In Situ Construction of an Ultra‐Stable Conductive Composite Interface for High‐Voltage All‐Solid‐State Lithium Metal Batteries
Authors: Shi Kai , Wan Zipei , Yang Lu , Zhang Yiwen , Huang Yanfei , Su Shiming , Xia Heyi , Jiang Keling , Shen Lu , Hu Yi , Zhang Shiqi , Yu Jing , Ren Fuzeng , He Yan‐Bing , Kang Feiyu 
Published: April 2020

AbstractThe garnet electrolyte presents poor wettability with Li metal, resulting in an extremely large interfacial impedance and drastic growth of Li dendrites. Herein, a novel ultra‐stable conductive composite interface (CCI) consisting of LiySn alloy and Li3N is constructed in situ between Li6.4La3Zr1.4Ta0.6O12 (LLZTO) pellet and Li metal by a conversion reaction of SnNx with Li metal at 300 °C. The LiySn alloy as a continuous and robust bridge between LLZTO and Li metal can effectively reduce the LLZTO/Li interfacial resistance from 4468.0 Ω to 164.8 Ω. Meanwhile, the Li3N as a fast Li‐ion channel can efficiently transfer Li ions and give their uniform distribution at the LLZTO/Li interface. Therefore, the Li/LLZTO@CCI/Li symmetric battery stably cycles for 1200 h without short circuit, and the all‐solid‐state high‐voltage Li/LLZTO@CCI/LiNi0.5Co0.2Mn0.3O2 battery achieves a specific capacity of 161.4 mAh g−1 at 0.25 C with a capacity retention rate of 92.6 % and coulombic efficiency of 100.0 % after 200 cycles at 25 °C.
Biokatalytische Reduktionen aus der Sicht eines Chemikers
Authors: Hollmann Frank , Opperman Diederik J. , Paul Caroline E. 
Published: April 2020

AbstractReduktionsreaktionen spielen eine zentrale Rolle in der organischen Chemie zur Synthese chiraler Produkte. Insbesondere Enzyme katalysieren solche Reaktionen in hoher Stereo‐, Regio‐ und Chemoselektivität. Somit eröffnen sie kürzere Alternativrouten zur Synthese von Spezial‐ und Bulkchemikalien. Dieser Aufsatz beschreibt den aktuellen Stand, die Herausforderungen und Möglichkeiten enzymkatalysierter Reduktionen von (konjugierten) Carbonylverbindungen, Aromaten sowie der reduktiven Aminierung.
Excitonically Coupled Cyclic BF2 Arrays of Calix[8]‐ and Calix[16]phyrin as Near‐IR‐Chromophores
Authors: Kim Taeyeon , Duan Zhiming , Talukdar Sangita , Lei Chuanhu , Kim Dongho , Sessler Jonathan L. , Sarma Tridib 
Published: April 2020

AbstractTwo giant calix[n]phyrin derivatives namely calix[8]‐ (4) and calix[16]phyrin (5), involving two and four BF2 units, respectively, were prepared through the condensation of the bis‐naphthobipyrrolylmethene‐BF2 complex (3) with pentafluorobenzaldehyde. Calix[n]phyrins 4 and 5 display extremely high extinction coefficients (3.67 and 4.82×105 m−1 cm−1, respectively) in the near‐IR region, which was taken as initial evidence for strong excitonic coupling within these cyclic multi‐chromophoric systems. Detailed insights into the effect of excitonic coupling dynamics on the electronic structure and photophysical properties of the macrocycles came from fluorescence, time‐correlated single‐photon counting (TCSPC) and transient absorption (TA) measurements. Support for these experimental findings came from theoretical studies. Theory and experiment confirmed that the coupling between the excitons depends on the specifics of the calix[n]phyrin structure, not just its size.
A Highly Efficient Dimeric Manganese‐Catalyzed Selective Hydroarylation of Internal Alkynes
Authors: Pang Yubo , Liu Gengtu , Huang Congcong , Yuan Xiang‐Ai , Li Weipeng , Xie Jin 
Published: April 2020

AbstractWe have developed a general and site‐predictable manganese‐catalyzed hydroarylation of internal alkynes in the presence of water, under an air atmosphere without the involvement of ligand. The unique catalytic feature of this reaction is highlighted by comparison with other widely used transition metal catalysts including palladium, rhodium, nickel, or copper. The simple operation, high efficiency and excellent functional group compatibility make this protocol practical for more than 90 structurally diverse internal alkynes, overcoming the influence of both electronic and steric effect of alkynes. Its exclusive regio‐ and chemoselectivity originates from the unique reactivity of the manganese‐based catalyst towards an inherent double controlled strategy of sterically hindered propargyl alcohols without the installing of external directing groups. Its synthetic robustness and practicality have been illustrated by the concise synthesis of bervastatin, a hypolipidemic drug, and late‐stage modification of complex alkynes with precise regioselectivity.
Chemical Modification of Reducing End‐Groups in Cellulose Nanocrystals
Authors: Heise Katja , Delepierre Gwendoline , King Alistair W. T. , Kostiainen Mauri A. , Zoppe Justin , Weder Christoph , Kontturi Eero 
Published: April 2020

AbstractNative plant cellulose has an intrinsic supramolecular structure. Consequently, it can be isolated as nanocellulose species, which can be utilized as building blocks for renewable nanomaterials. The structure of cellulose also permits its end‐wise modification, i.e., chemical reactions exclusively on one end of a cellulose chain or a nanocellulose particle. The premises for end‐wise modification have been known for decades. Nevertheless, different approaches for the reactions have emerged only recently, because of formidable synthetic and analytical challenges associated with the issue, including the adverse reactivity of the cellulose reducing end and the low abundance of newly introduced functionalities. This Review gives a full account of the scientific underpinnings and challenges related to end‐wise modification of cellulose nanocrystals. Furthermore, we present how the chemical modification of cellulose nanocrystal ends may be applied to directed assembly, resulting in numerous possibilities for the construction of new materials, such as responsive liquid crystal templates and composites with tailored interactions.
Electroreductive Cobalt‐Catalyzed Carboxylation: Cross‐Electrophile Electrocoupling with Atmospheric CO2
Authors: Ang Nate W. J. , Oliveira João C. A. , Ackermann Lutz 
Published: April 2020

AbstractThe chemical use of CO2 as an inexpensive, nontoxic C1 synthon is of utmost topical interest in the context of carbon capture and utilization (CCU). We present the merger of cobalt catalysis and electrochemical synthesis for mild catalytic carboxylations of allylic chlorides with CO2. Styrylacetic acid derivatives were obtained with moderate to good yields and good functional group tolerance. The thus‐obtained products are useful as versatile synthons of γ‐arylbutyrolactones. Cyclic voltammetry and in operando kinetic analysis were performed to provide mechanistic insights into the electrocatalytic carboxylation with CO2.
Epoxy loaded poly(urea‐formaldehyde) microcapsules via in situ polymerization designated for self‐healing coatings
Authors: Tzavidi Sofia , Zotiadis Christos , Porfyris Athanasios , Korres Dimitrios M. , Vouyiouka Stamatina 
Published: April 2020

AbstractSelf‐healing systems are a next‐generation technology that can offer autonomous crack repair and increase the service lifetime of a protective coating. Polymeric microcapsules containing healing agents can be used in that perspective and exhibit significant potential. In the current study, poly(urea‐formaldehyde) microcapsules containing an epoxy healing agent as core material were successfully prepared using in situ polymerization. The effect of different process parameters was studied in respect to microcapsules' characteristics, that is, morphology, particle size, encapsulation efficiency and thermal properties. Spherical microcapsules with either smooth or rough surface were obtained with a size ranging from 90 to 165 μm, controlled by the stirring rate during the emulsification stage. The encapsulation efficiency varied between 65–77% with no significant dependence on the process conditions. Finally, the stability of the microcapsules during storage was investigated at different conditions.
3′‐Methyl‐4‐thio‐1H‐tetrahydropyranspiro‐5′‐hydantoin platinum complex as a novel potent anticancer agent and xanthine oxidase inhibitor
Authors: Cherneva Emiliya , Atanasova Mariyana , Buyukliev Rossen , Tomovic Katarina , Smelcerovic Zaklina , Bakalova Adriana , Smelcerovic Andrija 
Published: April 2020

AbstractIn this study, a Pt(IV) complex with 3′‐methyl‐4‐thio‐1H‐tetrahydropyranspiro‐5′‐hydantoin (complex 1) was synthesized. The structure was determined via elemental analyses, infrared, 1H, and 13C nuclear magnetic resonance techniques. Density functional theory calculations were applied to optimize the molecular geometry and to calculate structural parameters and vibrational frequencies. The cytotoxicity of the newly synthesized complex 1 was assessed against K‐562 and REH cells and compared with the cytotoxic effects of the ligand (L) and its Pd(IV) complex (complex 2). Complex 1 exhibited a better cytotoxic activity (IC50 = 76.9 µM against K‐562 and 15.6 µM against REH cells) than L and complex 2, which was closer to the cytotoxic effect of cisplatin (IC50 = 36.9 μM and 1.07 μM against K‐562 and REH cells, respectively), as compared with the ligand and complex 2. L and its complexes 1 and 2 were evaluated for inhibitory activity against xanthine oxidase (XO) in vitro, as compared with allopurinol (IC50 = 1.70 μM). Complex 1 was shown as a potent XO inhibitor, with an IC50 value of 19.33 μM, and the binding mode with the enzyme was predicted by molecular docking. Its inhibitory activity against XO is a potential advantage that might result in improved profile and anticancer activity.
A novel LC–MS/MS method for the determination of ziritaxestat in rat plasma and its pharmacokinetic study
Authors: Chen Jing , Guan Zhenhua , Dong Na , Li Xueliang 
Published: April 2020

AbstractZiritaxestat is a first‐in‐class autotoxin inhibitor. The purpose of this study was to develop a liquid chromatography/electrospray ionization tandem mass spectrometric (LC–MS/MS) method for the determination of ziritaxestat in rat plasma. The plasma sample was deproteinated using acetonitrile and then separated on an Acquity BEH C18 column with water containing 0.1% formic acid and acetonitrile as mobile phase, which was delivered at 0.4 ml/min. Ziritaxestat and the internal standard (crizotinib) were quantitatively monitored with precursor‐to‐product transitions of m/z 589.3 > 262.2 and m/z 450.1 > 260.2, respectively. The total running time was 2.5 min. The method showed excellent linearity over the concentration range 0.5–2000 ng/ml, with correlation coefficient >0.9987. The extraction recovery was >82.09% and the matrix effect was not significant. Inter‐ and intra‐day precisions (RSD) were <11.20% and accuracies were in the range of −8.50–7.45%. Ziritaxestat was demonstrated to be stable in rat plasma under the tested conditions. The validated LC–MS/MS method was successfully applied to study the pharmacokinetic profiles of ziritaxestat in rat plasma after intravenous and oral administration. Pharmacokinetic results demonstrated that ziritaxestat displayed a short half‐life (~3 h) and low bioavailability (20.52%).
Effect of CYP3A4 on liver injury induced by triptolide
Authors: Xiao Xuerong , Zhang Ting , Huang Jianfeng , Zhao Qi , Li Fei 
Published: April 2020

AbstractTriptolide (TP), one of the main bioactive diterpenes of the herbal medicine Tripterygium wilfordii Hook F, is used for the treatment of autoimmune diseases in the clinic and is accompanied by severe hepatotoxicity. CYP3A4 has been reported to be responsible for TP metabolism, but the mechanism remains unclear. The present study applied a UPLC–QTOF–MS‐based metabolomics analysis to characterize the effect of CYP3A4 on TP‐induced hepatotoxicity. The metabolites carnitines, lysophosphatidylcholines (LPCs) and a serious of amino acids were found to be closely related to liver damage indexes in TP‐treated female mice. Metabolomics analysis further revealed that the CYP3A4 inducer dexamethasone improved the level of LPCs and amino acids, and defended against oxidative stress. On the contrary, pretreatment with the CYP3A4 inhibitor ketoconazole increased liver damage with most metabolites being markedly altered, especially carnitines. Among these metabolites, except for LPC18:2, LPC20:1 and arginine, dexamethasone and ketoconazole both affected oxidative stress induced by TP. The current study provides new mechanistic insights into the metabolic alterations, leading to understanding of the role of CYP3A4 in hepatotoxicity induced by TP.
Porous‐Organic‐Polymer‐Triggered Advancement of Sustainable Magnetic Efficient Catalyst for Chemoselective Hydrogenation of Cinnamaldehyde
Authors: Paul Ratul , Sarkar Chitra , Yan Yong , Trinh Quang Thang , Rao Bolla Srinivasa , Pao Chih‐Wen , Lee Jyh‐Fu , Liu Wen , Mondal John 
Published: April 2020

AbstractIn this study, we adopted a cost‐effective, facile and metal & template‐free strategy for the successful synthesis of hydroxyl enriched POP (denoted as TPT). An integrated catalyst, Pd−Fe3O4@TPT, has been developed for the liquid phase selective hydrogenation cinnamaldehyde (CAL). Pd−Fe3O4@TPT exhibited excellent catalytic performance, providing 100 % selectivity towards hydrocinnamaldehyde (HCAL) under mild reaction conditions (with relatively low hydrogen pressure and very short reaction time), whereas Fe2O3@TPT appeared inert. Compared with the conventional catalytic systems, our newly designed catalyst was superior in many aspects, owing to the rigid nature of TPT‐POP, which prevents aggregation and leaching of the metal nanoparticles.
Renewable RGO@CuI Nanocomposites for Redox Triggered Single Electron Transfer (SET) Reaction Under Aerobic and Anaerobic Conditions
Authors: Gulati Upasana , Chinna Rajesh U. , Rawat Diwan S. 
Published: April 2020

AbstractRenewable mineral derived nanocatalysts are of special interest to accomplish green and sustainable goals with unique advantages over homogeneous catalysts such as recyclability, robustness, superior activity and minimum waste generation. Here, we synthesized reduced graphene oxide supported copper iodide (RGO@CuI) nanocomposites from renewable malachite mineral derived RGO@CuO precursor by treatment with NH2OH and KI in water. The characterization results reveal the role of RGO sheets as capping agent and supporting material for CuO seeds which control the diffusion of iodide, NH2OH reagents and stabilizes the generated CuI prism morphologies. The RGO@CuI‐20 nanocatalyst is robust to produce wide range of N‐heterocycles such as 5‐diarylamino benzimidazole and spiropyrroline via aerobic and anaerobic single electron transfer (SET) reactions, respectively. The nanocatalysis study delineates two distinct mechanistic pathways for aerobic and anaerobic SET reactions. The present method offers the advantages of utilizing a renewable copper precursor for catalyst preparation, catalyst recyclability over five times, excellent product yields and green reaction conditions with minimum waste (Low E‐factor).
Dense Sandwich‐like Na2Ti3O7@rGO Composite with Superior Performance for Sodium Storage
Authors: Li Zehua , Huang Yongxing , Jiang Ying , Wang Ziheng , Lu Baoping , Zhou Jiahui , Xie Man 
Published: April 2020

AbstractSodium titanate (Na2Ti3O7) has been considered as a promising anode in sodium‐ion batteries (SIBs) because of its low working voltage, high energy density and low cost. However, low electronic and ionic conductivity become the major obstacles to affect the improvement of its electrochemical performance. Here, based on the high specific surface area and high conductivity of reduced graphene oxides (rGO), a dense sandwich‐like structure was built through a facile hydrothermal route. The Na2Ti3O7@rGO (NTO@rGO) composites have a stable two‐dimensional conductive network framework and the Na2Ti3O7 particles grow in situ on the surface of the rGO nanosheets, greatly improving the utilization of rGO by reducing the introduction of rGO. Moreover, when the NTO@rGO was used as an anode for SIBs, it showed an excellent cycle stability and rate performance with 137 mAh g−1 at 100 mA g−1 after 500 cycles and 92 mA g−1 at 2 A g−1, respectively.
Synthesis, Photophysical and Electronic Properties of Mono‐, Di‐, and Tri‐Amino‐Substituted Ortho‐Perylenes, and Comparison to the Tetra‐Substituted Derivative
Authors: Merz Julia , Dietrich Lena , Nitsch Jörn , Krummenacher Ivo , Braunschweig Holger , Moos Michael , Mims David , Lambert Christoph , Marder Todd B. 
Published: April 2020

AbstractWe synthesized a series of new mono‐, di‐, tri‐ and tetra‐substituted perylene derivatives with strong bis(para‐methoxyphenyl)amine (DPA) donors at the uncommon 2,5,8,11‐positions. The properties of our new donor‐substituted perylenes were studied in detail to establish a structure‐property relationship. Interesting trends and unusual properties are observed for this series of new perylene derivatives, such as a decreasing charge transfer (CT) character with increasing number of DPA moieties and individual reversible oxidations for each DPA moiety. Thus, (DPA)‐Per possesses one reversible oxidation while (DPA)4‐Per has four. The mono‐ and di‐substituted derivatives display unusually large Stokes shifts not previously reported for perylenes. Furthermore, transient absorption measurements of the new derivatives reveal an excited state with lifetimes of several hundred microseconds, which sensitizes singlet oxygen with quantum yields of up to 0.83.
Clinical determinants of the PR interval duration in Swiss middle‐aged adults: The CoLaus/PsyCoLaus study
Authors: Bay Marylène , Vollenweider Peter , Marques‐Vidal Pedro , Bocchi Federica , Pruvot Etienne , Schläpfer Jürg 
Published: April 2020

AbstractBackgroundProlonged PR interval (PRi) is associated with adverse outcomes. However, PRi determinants are poorly known. We aimed to identify the clinical determinants of the PRi duration in the general population.HypothesisSome clinical data are associated with prolonged PRi.MethodsCross‐sectional study conducted between 2014 and 2017. Electrocardiogram‐derived PRi duration was categorized into normal or prolonged (>200 ms). Determinants were identified using stepwise logistic regression, and results were expressed as multivariable‐adjusted odds ratio (OR) (95% confidence interval). A further analysis was performed adjusting for antiarrhythmic drugs, P‐wave contribution to PRi duration, electrolytes (kalemia, calcemia, and magnesemia), and history of cardiovascular disease.ResultsOverall, 3655 participants with measurable PRi duration were included (55.6% females; mean age 62 ± 10 years), and 330 (9.0%) had prolonged PRi. Stepwise logistic regression identified male sex (OR 1.41 [1.02‐1.97]); aging (65‐74 years: OR 2.29 [1.61‐3.24], and ≥ 75 years: OR 4.21 [2.81‐6.31]); increased height (per 5 cm, OR 1.15 [1.06‐1.25]); hypertension (OR 1.37 [1.06‐1.77]); and hs troponin T (OR 1.67 [1.15‐2.43]) as significantly and positively associated, and high resting heart rate (≥70 beats/min, OR 0.43 [0.29‐0.62]) as negatively associated with prolonged PRi. After further adjustment, male sex, aging and increased height remained positively, and high resting heart rate negatively associated with prolonged PRi. Hypertension and hs troponin T were no longer associated.ConclusionIn a sample of the Swiss middle‐aged population, male sex, aging and increased height significantly increased the likelihood of a prolonged PRi duration, whereas a high resting heart rate decreased it.