bluuebunny/crossref_metadata_2025_split huggingface dataset:
High‐quality freestanding flexible poly(5‐(2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐5‐yl)‐1H‐indole) film: Electrosyntheses, characterization, and optical properties
Authors: Wang R. , Ye G. , Zhou W. , Jiang F. , Wu Y. , Hou J. , Li D. , Wu J. , Chang Y. , Liang A. , Xu J. , Du Y. 
Published: August 2018

ABSTRACTThe electron‐donating substituted indole is generally difficult to be polymerized into high‐quality film. The electrochemical polymerization of the electron‐donating 3,4‐ethylenedioxythiophene (EDOT)‐monosubstituted indole may be a challenge. Herein, we designed and synthesized a novel fluorescent comonomer based on the combination of indole and EDOT groups, namely, 5‐(2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐5‐yl)‐1H‐indole (EDTI), and subsequently electrodeposited into flawless freestanding flexible poly(5‐(2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐5‐yl)‐1H‐indole) (PEDTI) film with a resistance of 60 MΩ/cm in CH2Cl2 containing 0.1 M Bu4NBF4. Electrochemical results showed that the oxidation onset potential of EDTI was at 0.8 V vs Ag/AgCl, which was lower than those of indole (0.96 V vs Ag/AgCl) and EDOT (1.35 V vs Ag/AgCl). FTIR spectra indicated that the polymerization of EDTI occurred at the 5‐position on thiophene ring and 2,3‐positions on indole ring, forming the crosslinking polymer film. The colors of as‐prepared PEDTI could switch reversibly from purple to brown under applied potentials of 1.3 and −1.3 V, which were distinctly different from those of polyindole, poly(3,4‐ethylenedioxythiophene) (PEDOT), and poly(EDOT‐bis‐substituted indole) (PETI). Fluorescence spectral studies revealed that the comonomer and corresponding polymer were good blue‐green light emitters. These results implied that PEDTI had potential applications for photoelectric devices such as electrochromic devices, light‐emitting diodes, and fluorescence sensors. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47016.
Preparation and properties of porous gels from poly(l‐lactic acid) and poly(d‐lactic acid) with ionic liquids as solvents and porogens
Authors: Li Lu , Li Huaxiao , Yan Bin , Yu Shitao , Ge Xiaoping 
Published: August 2018

ABSTRACTWe prepared poly(lactic acid) (PLA) porous gel materials by combining poly(l‐lactic acid) and poly(d‐lactic acid) of three different molecular weights in different mass ratios. Moreover, we used several imidazole‐based ionic liquids with different anions as solvents and porogens at room temperature to prepare these materials. The properties of the resulting products were compared with those of materials prepared by sodium chloride as a conventional porogen and 1,4‐dioxane as a solvent. The internal morphologies of the different types of materials were observed via scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and wettability analysis. The presented results should provide guidance and reference values for the preparation of PLA materials and for the improvement of their mechanical properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47058.
Characterization of microsatellite markers forMoricandia moricandioides(Brassicaceae) and related species
Authors: Cuenot Yves , Gómez José M. , González‐Megias Adela , Pannell John R. , Torices Rubén 
Published: August 2018

Premise of the StudyPolymorphic microsatellite markers were developed to study population structure and mating patterns of the monocarpic herbMoricandia moricandioides(Brassicaceae).Methods and ResultsIllumina MiSeq sequencing was used to develop a panel of 15 polymorphic microsatellite markers that were tested across 77 individuals from three populations on the Iberian Peninsula. All markers were polymorphic in at least two studied populations, and the number of alleles ranged from one to 11 per locus. The levels of observed and expected heterozygosity ranged from 0.000 to 1.000 and from 0.153 to 0.865, respectively. Nine and 11 loci were successfully amplified in the congeneric speciesM. arvensisandM. foetida, respectively.ConclusionsThe 15 microsatellite markers will be useful for population genetic studies of the genusMoricandia. These markers will serve as a useful tool for exploring population structure and mating patterns ofM. moricandioides.
Evaluation of six regions for their potential as DNA barcodes in epiphyllous liverworts from Thailand
Authors: Yodphaka Sorrasak , Boonpragob Kansri , Lumbsch H. Thorsten , Kraichak Ekaphan 
Published: August 2018

Premise of the StudyStudies on the diversity of epiphyllous bryophytes have been limited because of minute and incomplete specimens and a lack of taxonomic expertise. The recent development of the DNA barcoding approach has allowed taxon identification and species discovery of many obscure groups of organisms.MethodsWith DNA extractions from 99 samples of 16 species, we compared the efficiencies of six DNA markers (rbcL, matK, trnL‐F, psbA, ITS1, and ITS2) in their ability to amplify, using a standard set of primers, as well as their discriminatory power, using distance‐based and tree‐based approaches with nucleotide data.ResultsThe amplification success was relatively high (70–90%) with all of the markers, except for matK, which yielded no success. The barcoding gap, as calculated from the difference between inter‐ and intraspecific genetic distances, was the highest in ITS2, whereas the highest numbers of monophyletic groups were found with ITS2 and rbcL.DiscussionrbcL should be used as a main barcoding marker with the addition of ITS2 for epiphyllous species. The development of DNA barcoding as a tool for quantifying species diversity will provide a rapid and reliable identification tool for epiphyllous bryophytes.
Tetraphenylethylene–Carborane–Tetraphenylethylene Triad: Influence of Steric Bridge on Aggregation‐Induced Emission Properties
Authors: Yin Yongheng , Li Xiang , Yan Senbo , Yan Hong , Lu Changsheng 
Published: August 2018

AbstractA novel tetraphenylethylene (TPE)–bridge–tetraphenylethylene triad has been synthesized, where the o‐carboranyl moiety functions as a central bridge and two TPE units are in the lateral positions. This molecular triad has been characterized by various spectroscopic methods, and its structure has been studied by X‐ray crystallography as well as theoretical calculations. The impact of the bridging carboranyl unit on the aggregation‐induced emission (AIE) characteristics of the TPE–bridge–TPE triad has been investigated. When the central bridge is changed from one‐dimensional (1D) alkynyl to three‐dimensional (3D) carboranyl, the absolute luminescent quantum yield of the triad increased from 21.2 % to 54.7 % in the solid state, accompanied by a luminescence color change from blue to yellow (94 nm red‐shift).
Cellulases adsorb reversibly on biomass lignin
Authors: Djajadi Demi T. , Pihlajaniemi Ville , Rahikainen Jenni , Kruus Kristiina , Meyer Anne S. 
Published: August 2018

AbstractAdsorption of cellulases onto lignin is considered a major factor in retarding enzymatic cellulose degradation of lignocellulosic biomass. However, the adsorption mechanisms and kinetics are not well understood for individual types of cellulases. This study examines the binding affinity, kinetics of adsorption, and competition of four monocomponent cellulases of Trichoderma reesei during adsorption onto lignin.
TrCel7A,
TrCel6A,
TrCel7B, and
TrCel5A were radiolabeled for adsorption experiments on lignin‐rich residues (LRRs) isolated from hydrothermally pretreated spruce (L‐HPS) and wheat straw (L‐HPWS), respectively. On the basis of adsorption isotherms fitted to the Langmuir model, the ranking of binding affinities was
TrCel5A >
TrCel6A >
TrCel7B >
TrCel7A on both types of LRRs. The enzymes had a higher affinity to the L‐HPS than to the L‐HPWS. Adsorption experiments with dilution after 1 and 24 hr and kinetic modeling were performed to quantify any irreversible binding over time. Models with reversible binding parameters fitted well and can explain the results obtained. The adsorption constants obtained from the reversible models agreed with the fitted Langmuir isotherms and suggested that reversible adsorption–desorption existed at equilibrium. Competitive binding experiments showed that individual types of cellulases competed for binding sites on the lignin and the adsorption data fitted the Langmuir adsorption model. Overall, the data strongly indicate that the adsorption of cellulases onto lignin is reversible and the findings have implications for the development of more efficient cellulose degrading enzymes.
Unravelling the New Roles of Na and Mn Promoter in CO2 Hydrogenation over Fe3O4‐Based Catalysts for Enhanced Selectivity to Light α‐Olefins
Authors: Liu Bing , Geng Shunshun , Zheng Jiao , Jia Xinli , Jiang Feng , Liu Xiaohao 
Published: August 2018

AbstractThe direct production of light α‐olefins (C2=‐C4=) from CO2 is of great importance as this process can convert the greenhouse gas into the desired chemicals. In this study, the crucial roles of Na and Mn promoter in CO2 hydrogenation to produce light α‐olefins via the Fischer‐Tropsch synthesis (FTS) over Fe3O4‐based catalysts are investigated. The results indicate that both Na and Mn promoter can enhance the reducibility of Fe3O4. In situ XPS and DFT calculations show that Na facilitates the reduction by electron donation from Na to Fe as the oxygen vacancy formation energy is reduced by Na. In contrast, Mn promotes the reduction by the presence of oxygen vacancy in MnO as the oxygen in Fe oxide can spillover to the vacancy in MnO spontaneously. For un‐promoted Fe3O4 catalysts, CO2 hydrogenation dominantly produces light n‐paraffins. The addition of Na remarkably shifts the selectivity to light α‐olefins with a sharp decline in the selectivity to light n‐paraffins, which is attributed to the electron donation from Na to Fe resulting in the promoted CO dissociation and the favorable β‐H abstraction of surface short alkyl‐metal intermediates. The addition of Mn into Na‐containing Fe3O4 catalysts can obviously further enhance the selectivity to light α‐olefins as the spatial hindrance of Mn suppresses the chain growth to increase the amount of surface short alkyl‐metal intermediates.
Selective Hydrogenation of Aldehydes Using a Well‐Defined Fe(II) PNP Pincer Complex in Biphasic Medium
Authors: Weber Stefan , Brünig Julian , Zeindlhofer Veronika , Schröder Christian , Stöger Berthold , Limbeck Andreas , Kirchner Karl , Bica Katharina 
Published: August 2018

AbstractA biphasic process for the hydrogenation of aldehydes was developed using a well‐defined iron (II) PNP pincer complex as model system to investigate the performance of various ionic liquids. A number of suitable hydrophobic ionic liquids based on the N(Tf)2− anion were identified, allowing to immobilize the iron (II) catalyst in the ionic liquid layer and to facilitate the separation of the desired alcohols. Further studies showed that targeted Brønsted basic ionic liquids can eliminate the need of an external base to activate the catalyst.
Robust and Environmentally Benign Solid Acid Intercalation Catalysts for the Aminolysis of Epoxides
Authors: Li Tengfei , Jin Lin , Zhang Wei , Miras Haralampos N. , Song Yu‐Fei 
Published: August 2018

AbstractThe catalytic aminolysis of epoxides can lead to a large number of β‐amino alcohols which are of particular interest in industrial applications. In this paper, we demonstrate for the first time the use of a polyoxometalate [CoW12O40]5− intercalated layered double hydroxides (Zn3Al‐LDH) material as an efficient solid acid catalyst for the catalytic aminolysis of various epoxides under mild and solvent‐free conditions. The as‐prepared heterogeneous catalyst Zn3Al‐CoW12 was fully characterized by FT‐IR, powder XRD, TG‐DTA, BET, XPS, SEM, HR‐TEM and NH3‐TPD. The catalytic performance of Zn3Al‐CoW12 for the aminolysis of epoxides revealed excellent yields with high regioselectivity and stereoselectivity. Moreover, the solid acid catalyst can be easily recycled and reused without detectable decrease of its catalytic efficiency.
Improving the Visible Light Photocatalytic Aerobic Oxidation of Sulfides into Sulfoxides on Dye‐Sensitized TiO2
Authors: Hao Huimin , Wang Zhan , Shi Ji‐Long , Li Xia , Lang Xianjun 
Published: August 2018

AbstractVisible light‐driven interfacial redox reactions during dye‐sensitized TiO2 are essential to meet the energy and environmental challenges in the form of dye‐sensitized solar cells and sensitized degradation of organic pollutants. Inspired by these prior successes, it is conceivable that the underlying principles of these processes can guide us to construct selective chemical transformations in which the control of selectivity is in higher demand. We attempt to improve the selectivity for sulfoxides during the visible light‐driven selective aerobic oxidation of sulfides in the merger of dye‐sensitized TiO2 photocatalysis with TEMPO [(2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl] catalysis. Thus, different factors like the TEMPO and its derivatives, initial O2 pressures, initial sulfide concentrations, solvents, light‐emitting diodes (LED) and TiO2 were examined to identify the critical factor for selectivity improvement. It was found that an easily synthesized anatase TiO2, sensitized by 0.33 mol % of alizarin red S, was significant in improving the selectivity for sulfoxides at high conversions of sulfides with the aid of 2 mol % of TEMPO as a redox mediator under blue LED irradiation. This work suggests that the engineering of the TiO2 materials can be a viable solution in improving the selectivity of visible light‐driven chemical transformations by dye‐sensitized TiO2 photocatalysis.
Direct Electrochemical Deposition of Lithium from Lithium Oxide in a Highly Stable Aluminium‐Containing Solvate Ionic Liquid
Authors: Zhang Baoguo , Yao Yu , Shi Zhongning , Xu Junli , Wang Zhaowen 
Published: August 2018

AbstractLow‐temperature electrochemical extraction of active metals from their corresponding chlorides in ionic liquids has long been a scientific challenge, while extraction from oxides is even more difficult. Inspired by previous reports of the electrochemical deposition of various non‐active metals from their corresponding oxides in diverse ionic liquids, we demonstrate the successful electrodeposition of active Li on high‐purity Al‐plate substrates at relatively low temperature (353 K), as confirmed by X‐ray diffraction. Furthermore, Al−Li alloy nanosheets can also be obtained on the Al surface by solid‐state cathode alloying. The Li source was Li2O, which was dissolved in a highly stable Al‐containing solvate ionic liquid. The dissolution mechanism and electrodeposition behaviour of Li2O were investigated using multinuclear nuclear magnetic resonance spectroscopy, theoretical calculations, and electrochemical techniques. The findings are expected to provide a theoretical basis and method for low‐temperature electrochemical extraction of active metals from their oxides.
Cation‐Anion Redox Switching in an All‐Ferrocene Salt
Authors: Schrage Briana R. , Zhao Zhiling , Ziegler Christopher J. , Boika Aliaksei 
Published: August 2018

AbstractAn “all‐ferrocene” salt comprised of two ferrocene cations and one ferrocene dianion exhibits an unusual reversing of oxidation‐reduction potentials between the cationic and the anionic components. This redox switching can be controlled via the solvent, and is not greatly affected by the supporting electrolyte.
Supramolecular Assembly‐Improved Triplet–Triplet Annihilation Upconversion in Aqueous Solution
Authors: Xu Wei , Liang Wenting , Wu Wanhua , Fan Chunying , Rao Ming , Su Dan , Zhong Zhihui , Yang Cheng 
Published: August 2018

AbstractWater‐soluble 9,10‐diphenylanthracene‐modified γ‐cyclodextrin derivatives A1 and A2, in which the γ‐cyclodextrin unit serves as a molecular host for a binding sensitizer, and the 9,10‐diphenylanthracene moiety plays a role as an emitter/annihilator, were synthesized to investigate the supramolecular triplet–triplet annihilation (TTA) upconversion in aqueous solution. Both A1 and A2 readily aggregate and form nanoscale assemblies in water as a combined result of host–guest complexation and π–π stacking among the 9,10‐diphenylanthracenes. The aggregation behavior of the supramolecular emitters was fully characterized by using a diversity of methods, including dynamic light scattering (DLS), SEM, NMR, fluorescence, and circular dichroism studies. Fluorescence spectroscopic analysis reveals that the emitters have high fluorescence quantum yields in water (82 and 90 % for A1 and A2, respectively), thus demonstrating that aggregation does not quench the fluorescence. By using a coordinated ruthenium sensitizer, a high TTA upconversion quantum yield of up to 6.9 % was observed for this supramolecular TTA system, which is significantly higher than the value (<0.5 %) obtained with nonassembled emitters in organic solvent and in contrast to the fact that TTA upconversion emission in aqueous solution is usually low or negligible. We ascribe the strong TTA upconversion emission in the present supramolecular assembly system to an efficient TTA process, which is facilitated along the stacked emitters by triplet energy migration and improved triplet–triplet energy transfer through host–guest complexation.
Fully coupled numerical model of actin treadmilling in the lamellipodium of the cell
Authors: Kollepara Kiran S. , Mulye Paris D. , Saez Pablo 
Published: August 2018

AbstractCells rely on an interplay of subcellular elements for motility and migration. Certain regions of motile cells, such as the lamellipodium, are made of a complex mixture of actin monomers and filaments, which polymerize at the front of the cell, close to the cell membrane, and depolymerize at the rear. The dynamic actin turnover induces the so‐called intracellular retrograde flow, and it is a fundamental process for cell motility. Apart from some comprehensive mathematical models, the computational modelling of actin treadmilling has been based on simpler biophysical models. Here, we adopt a highly detailed theoretical model of the actin treadmilling process and develop a coupled unsteady finite element formulation. We clearly describe the structure and implementation of the coupled problem within the finite element method. Our numerical results show an excellent correlation with experimental results from literature and with previous models. We include time dependent effects and convective transport terms, which expose puzzling dynamics in the retrograde flow. We propose several biological scenarios to analyze the behavior of the actin treadmilling along space and time. We observed response times of the main density variables in the order of seconds. Compared with previous analytical solutions, which make assumptions related to convective transport, transient dynamics, and actin fluxes, the generic solution can have significant influence on the retrograde flow. All together, our results unveil a promising applicability of classical finite element methods to derive an in silico testing platform for the actin treadmilling processes in motile cells, which could allow for an extension to other biophysical effects.
Pd/PTABS: An Efficient Water‐Soluble Catalytic System for the Amination of 6‐Chloropurine Ribonucleoside and Synthesis of Alogliptin
Authors: Bhilare Shatrughn , Bandaru Siva Sankar Murthy , Kapdi Anant R. , Sanghvi Yogesh S. , Schulzke Carola 
Published: August 2018

AbstractThe synthesis and catalytic applications of the highly water‐soluble ligand 7‐phospha‐1,3,5‐triaza‐admantane butane sultonate (PTABS) has been described. The synthesized PTABS ligand along with palladium acetate exhibits excellent reactivity towards the amination reaction of 6‐chloro‐9‐(β‐D‐ribofuranosyl)‐9H‐purine at ambient temperature. This protocol offers an advantage over the previously published procedures for the amination of 6‐chloropurine nucleoside furnishing 6‐N‐substituted adenosine analogues. The validation of the present strategy has been demonstrated via synthesis of a uracil‐based, anti‐diabetic drug alogliptin. © 2018 by John Wiley & Sons, Inc.
Solar Water Oxidation by a Visible‐Light‐Responsive Tantalum/Nitrogen‐Codoped Rutile Titania Anode for Photoelectrochemical Water Splitting and Carbon Dioxide Fixation
Authors: Nakada Akinobu , Uchiyama Tomoki , Kawakami Nozomi , Sahara Go , Nishioka Shunta , Kamata Ryutaro , Kumagai Hiromu , Ishitani Osamu , Uchimoto Yoshiharu , Maeda Kazuhiko 
Published: August 2018

AbstractNon‐oxide materials such as oxynitrides are good candidates as photoanodes for visible‐light‐driven water oxidation, but most of them suffer from oxidative degradation by photogenerated holes, resulting in low stability. Herein we developed a photoanode using a visible‐light‐responsive TiO2 powder doped with tantalum and nitrogen (TiO2:Ta/N) for water oxidation. The Ta/N codoping enabled a stable anodic photocurrent response attributable to water oxidation under visible‐light irradiation. Surface modification of the TiO2:Ta/N anode with RuOx species further facilitated water oxidation catalysis, achieving stable O2 evolution over 5 h of operation with no sign of deactivation. Operando XAFS measurements revealed an important function of the RuOx species as a collector of photogenerated holes in TiO2:Ta/N, facilitating the photoelectrochemical water oxidation. Visible‐light‐driven H2 evolution and solar‐driven CO2 reduction into CO were both achieved by using water as an electron donor in photoelectrochemical cells with the TiO2:Ta/N photoanode coupled to a Pt cathode and a Ru(II)–Re(I) binuclear complex photocathode, respectively.
Ion Dynamics in Ionic‐Liquid‐Based Li‐Ion Electrolytes Investigated by Neutron Scattering and Dielectric Spectroscopy
Authors: Jafta Charl J. , Bridges Craig , Haupt Leon , Do Changwoo , Sippel Pit , Cochran Malcolm J. , Krohns Stephan , Ohl Michael , Loidl Alois , Mamontov Eugene , Lunkenheimer Peter , Dai Sheng , Sun Xiao‐Guang 
Published: August 2018

AbstractA detailed understanding of the diffusion mechanisms of ions in pure and doped ionic liquids remains an important aspect in the design of new ionic‐liquid electrolytes for energy storage. To gain more insight into the widely used imidazolium‐based ionic liquids, the relationship between viscosity, ionic conductivity, diffusion coefficients, and reorientational dynamics in the ionic liquid 3‐methyl‐1‐methylimidazolium bis(trifluoromethanesulfonyl)imide (DMIM‐TFSI) with and without lithium bis(trifluoromethanesulfonyl)imide (Li‐TFSI) was examined. The diffusion coefficients for the DMIM+ cation and the role of ion aggregates were investigated by using the quasielastic neutron scattering (QENS) and neutron spin echo techniques. Two diffusion mechanisms are observed for the DMIM+ cation with and without Li‐TFSI, that is, translational and local. The data additionally suggest that Li+ ion transport along with ion aggregates, known as the vehicle mechanism, may play a significant role in the ion diffusion process. These dielectric‐spectroscopy investigations in a broad temperature and frequency range reveal a typical α–β‐relaxation scenario. The α relaxation mirrors the glassy freezing of the dipolar ions, and the β relaxation exhibits the signatures of a Johari–Goldstein relaxation. In contrast to the translational mode detected by neutron scattering, arising from the decoupled faster motion of the DMIM+ ions, the α relaxation is well coupled to the dc charge transport, that is, the average translational motion of all three ion species in the material. The local diffusion process detected by QENS is only weakly dependent on temperature and viscosity and can be ascribed to the typical fast dynamics of glass‐forming liquids.