bluuebunny/crossref_metadata_2025 huggingface dataset:
Amnion‐Analogous Medical Device for Fetal Membrane Healing: A Preclinical Long‐Term Study
Authors: Lee Jae Yeon , Kim Hyeonji , Ha Dong‐Heon , Shin Jong Chul , Kim Ahyoung , Ko Hyun Sun , Cho Dong‐Woo
Published: August 2018

Although recent invasive fetal surgeries have improved fetal outcomes, fetal membrane rupture remains a major complication, leading to premature delivery, thus undermining the complete benefits of such procedures. A biocompatible amnion‐analogous medical device (AMED) consisting of polycaprolactone framework and decellularized amniotic membrane (dAM)–derived hydrogel for restoration of amniotic membrane defect is developed using 3D printing technology. Its efficacy on healing iatrogenic fetal membrane defects in vitro is evaluated, showing that the dAM gel contains migratory and proliferative properties. The fetoscope feasibility of the developed AMED is assessed using a pregnant swine model. All animals had successfully recovered from anesthesia and the fetoscopic procedure and maintained a healthy condition until the end of the pregnancy. AMED exhibits superior surgical handling characteristics and is easy to manufacture, nonimmunogenic, biocompatible, and suitable for storage and transport for off‐the‐shelf use; hence, it can be used in successfully sealing defect sites, thus improving the preservation of the amniotic fluid, which in turn improves fetal survival and development.
Multifunctionality and Mechanical Actuation of 2D Materials for Skin‐Mimicking Capabilities
Authors: Chang Ting‐Hsiang , Li Kerui , Yang Haitao , Chen Po‐Yen
Published: August 2018

Human skin serves as a multifunctional organ with remarkable properties, such as sensation, protection, regulation, and mechanical stretchability. The mimicry of skin's multifunctionalities via various nanomaterials has become an emerging topic. 2D materials have attracted much interest in the field of skin mimicry due to unique physiochemical properties. Herein, recent developments of using various 2D materials to mimic skin's sensing, protecting, and regulating capabilities are summarized. Next, to endow high stretchability to 2D materials, the approaches for fabrication of stretchable bilayer structures by integrating higher dimensional 2D materials onto soft elastomeric substrates are introduced. Accordion‐like 2D material structures can elongate with elastomers and undergo programmed folding/unfolding processes to mimic skin's stretchability. That stretchable 2D material devices can achieve effective tactile sensing and protecting capabilities under large deformation is then highlighted. Finally, multiple key directions and existing challenges for future development are discussed.
Engineering 2D Architectures toward High‐Performance Micro‐Supercapacitors
Authors: Da Yumin , Liu Jinxin , Zhou Lu , Zhu Xiaohui , Chen Xiaodong , Fu Lei
Published: August 2018

The rise of micro‐supercapacitors is satisfying the demand for power storage in portable devices and wireless gadgets. But the miniaturization of the energy‐storage components is significantly limited by their energy density. Electrode materials with adequate electrochemical active surfaces are therefore required for improving performance. 2D materials with ultralarge specific surface areas offer a broad portfolio of the development of high‐performance micro‐supercapacitors in spite of their several critical drawbacks. An architecture engineering strategy is therefore developed to break these natural limits and maximize the significant advantages of these materials. Based on the approaches of phase transformation, intercalation, surface modification, material hybridization, and hierarchical structuration, 2D architectures with improved conductivity, enlarged specific surface, enhanced redox activity, as well as the unique synergetic effect exhibit great promise in the application of miniaturized supercapacitors with highly enhanced performance. Herein, the architecture engineering of emerging 2D materials beyond graphene toward optimizing the performance of micro‐supercapacitors is discussed, in order to promote the application of 2D architectures in miniaturized energy‐storage devices.
Structural Design and Electronic Modulation of Transition‐Metal‐Carbide Electrocatalysts toward Efficient Hydrogen Evolution
Authors: Gao Qingsheng , Zhang Wenbiao , Shi Zhangping , Yang Lichun , Tang Yi
Published: August 2018

As the key of hydrogen economy, electrocatalytic hydrogen evolution reactions (HERs) depend on the availability of cost‐efficient electrocatalysts. Over the past years, there is a rapid rise in noble‐metal‐free electrocatalysts. Among them, transition metal carbides (TMCs) are highlighted due to their structural and electronic merits, e.g., high conductivity, metallic band states, tunable surface/bulk architectures, etc. Herein, representative efforts and progress made on TMCs are comprehensively reviewed, focusing on the noble‐metal‐like electronic configuration and the relevant structural/electronic modulation. Briefly, specific nanostructures and carbon‐based hybrids are introduced to increase active‐site abundance and to promote mass transportation, and heteroatom doping and heterointerface engineering are encouraged to optimize the chemical configurations of active sites toward intrinsically boosted HER kinetics. Finally, a perspective on the future development of TMC electrocatalysts is offered. The overall aim is to shed some light on the exploration of emerging materials in energy chemistry.
Tire Condition Monitoring and Intelligent Tires Using Nanogenerators Based on Piezoelectric, Electromagnetic, and Triboelectric Effects
Authors: Askari Hassan , Hashemi Ehsan , Khajepour Amir , Khamesee Mir Behrad , Wang Zhong Lin
Published: August 2018

The quest to utilize intelligent tires has prompted substantial multidisciplinary research including vehicle dynamics, control, estimation, energy harvesting, and even nanotechnology. This review article presents the progress in the area of tire condition monitoring systems (TCMS) and intelligent tires using devices fabricated based on piezoelectric, electromagnetic, and triboelectric effects. Three main branches of the research in this area are presented, including estimation techniques, sensing, and energy harvesting approaches. The authors delineate the importance of TCMS for vehicle active safety systems, its importance for transportation safety, and also its remarkable economic and environmental impacts on the development of intelligent transportation systems. The historical evolution and the perspective of research in the area of intelligent tires and TCMS are also reviewed. In addition, it is discussed how nanogenerators would be effective on the future of intelligent tires.
Triple Mode of Alkylation with Ethyl Bromodifluoroacetate: N, or O‐Difluoromethylation, N‐Ethylation and S‐(ethoxycarbonyl)difluoromethylation
Authors: Polley Arghya , Bairy Gurupada , Das Pritha , Jana Ranjan
Published: August 2018

In this report, we have explored a triple mode of chemical reactivity of ethyl bromodifluoroacetate. Typically, bromodifluoroacetic acid has been used as a difluorocarbene precursor for difluoromethylation of soft nucleophiles. Here we have disclosed nucleophilicity and base dependent divergent chemical reactivity of ethyl bromodifluoroacetate. It furnishes lithium hydroxide and cesium carbonate promoted difluoromethylation of tosyl‐protected aniline and electron‐deficient phenols respectively. Interestingly, switching the base from lithium hydroxide to 4‐N,N‐dimethylamino pyridine (DMAP) tosyl‐protected anilines afforded the corresponding N‐ethylation product. Whereas, highly nucleophilic thiophenols furnished the corresponding S‐carboethoxydifluoromethylation product via a rapid SN2 attack to the bromine atom prior to the ester hydrolysis. This mechanistic divergence was established through several control experiments. It was revealed that difluoromethylation reaction proceeds through a tandem in situ ester hydrolysis/decarboxylative‐debrominative difluorocarbene formation and subsequent trapping by the soft nucleophile‐NHTs or electron‐deficient phenolic −OH groups. In the presence of DMAP the hydrolysis of the ester is perturbed instead a nucleophilic attack at the ethyl moiety provides the N‐ethylation product. Hence, besides the development of a practical base‐promoted N‐difluoromethylation of amines and electron‐deficient phenols, divergent reactivity pattern of inexpensive and user‐friendly ethyl bromodifluoroacetate has been explored.

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Synthesis of Vinyl Triazenes by Palladium‐Catalyzed Addition Reactions to Alkynyl Triazenes
Authors: Suleymanov Abdusalom A. , Scopelliti Rosario , Tirani Farzaneh Fadaei , Severin Kay
Published: August 2018

Vinyl triazenes are potentially interesting compounds for synthetic organic and medicinal chemistry, but synthetic routes to make olefins with triazene groups are still scarce. In this work, we show that vinyl triazenes are accessible by Pd‐catalyzed addition reactions to alkynyl triazenes. Hydrogenation, hydroarylation, and haloallylation reactions allow preparing mono‐, di‐ and trisubstituted vinyl triazenes in high yields, and with good regio‐ and stereoselectivities.

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Recognition Behavior of a Porphyrin Heterodimer Self‐Assembled through an Amidinium‐Carboxylate Salt Bridge
Authors: Kimura Masaki , Miyashita Jyunichi , Miyagawa Shinobu , Kawasaki Tsuneomi , Takaya Hikaru , Tokunaga Yuji
Published: August 2018

In this study, we synthesized two porphyrins (P1 and P2) featuring two carboxybenzene and two 2‐aminoquinoline units at meso‐positions, respectively, and these porphyrins quantitatively self‐assembled into a heterodimer (P1⋅P2) through an amidinium‐carboxylate salt bridge formation in aprotic and non‐polar solvents. The capsule‐like dimer, possessing two cofacial porphyrin units, binds electron‐deficient aromatic compounds as guests, forming three‐layer π‐aromatic structures, and NMR and UV/Vis spectroscopies were used to determine the association constants (e. g., 1,3,5‐trinitrobenzene: Ka>104 M−1 in dichloromethane). The association constants and the rates of association and dissociation between the dimer and the guests were related to the electron deficiency of the aromatic guests.
The ligamentum teres femoris in orangutans
Authors: Muchlinski Magdalena N. , Hammond Ashley S. , Deane Andrew S. , Purcell Maureen , Hemingway Holden W. , Hantke Georg , Pastor Francisco , Garrosa Manuel , Hartstone‐Rose Adam
Published: August 2018

Objectives

It is widely viewed that orangutans lack a ligamentum teres femoris (LTF) inserting on the femoral head because orangutans lack a distinct fovea capitis. Orangutans employ acrobatic quadrumanous clambering that requires a high level of hip joint mobility, and the absence of an LTF is believed to be an adaptation to increase hip mobility. However, there are conflicting reports in the literature about whether there may be a different LTF configuration in orangutans, perhaps with a ligament inserting on the femoral neck instead. Here we perform a dissection‐based study of orangutan hip joints, assess the soft tissue and hard tissue correlates of the orangutan LTF, and histologically examination the LTF to evaluate whether it is homologous to that found in other hominoids.

Materials and methods

The hip joints from six orangutans were dissected. In the two orangutans with an LTF passing to the femoral head, the LTF was assessed histologically. Skeletonized femora (n=56) in osteological repositories were examined for evidence of a foveal pit.

Results

We observed an LTF in two of the three infant orangutans but not in the sub‐adult or adult specimens. Histological examination of the infant LTF shows a distinct artery coursing through the LTF to the head of the femur. One percent of orangutan femora present with a foveal scar, but no pit, on the femoral head.

Discussion

Despite being absent in adults, the LTF is present in at least some orangutans during infancy. We suggest that the LTF maintains a role in blood supply to the femoral head early in life. Because the LTF can limit hip mobility, this may explain why the LTF may be lost as an orangutan ages and gains locomotor independence. These findings enhance our understanding of orangutan hip morphology and underscore the need for future soft tissue investigations.
Annealing for the improvement of the capabilities of parylene C as electret
Authors: Kachroudi A. , Lagomarsini C. , Mareau V. H. , Sylvestre A.
Published: August 2018

Parylene C is a polymer elaborated by chemical vapor deposition and is particularly useful for the coating of deformed structures. New‐generation soft energy harvesting electrostatic generators can be of complex shape. These generators need electret material in order for them to function. It could thus be interesting to incorporate parylene C in this device. However, this polymer suffers from bad retention of trapped charges after corona discharge and a poor thermal stability of these charges. In this work, parylene C polymers were subjected to specific annealing before corona charging. This induces strong changes in the crystallinity of the material. Atomic force microscopy and X‐ray diffraction quantified the crystalline nature of parylene C following the annealing temperature. Surface potential decay of corona‐charged parylene C demonstrated that annealing to about 150°C is beneficial for the trapping of charges for a long time (analysis over 12 days). At the same time, thermal stability of the electret parylene C is achieved up to 100°C. Spherulites with a specific area close to the surface of the polymer could explain such performances due to their influence on the distribution of traps. Dielectric analysis does not confirm that the decay of surface charges is correlated to the dynamics of polymer chains, although the moving of chains probably influences the flowing of these charges. In sum, annealed parylene C appears to be a new interesting candidate for electret‐based electrostatic generators. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 46908.
Tensile properties, thermal stability, and the mechanism of PVC stabilized with zinc and calcium oxolinic complexes
Authors: Shi Yanqin , Wang Yating , Ma Biao , Ma Meng , Chen Si , Wang Xu
Published: August 2018

Two novel thermal stabilizers, zinc and calcium oxolinic complexes (Zn(Oxo)2 and Ca(Oxo)2), with superior tensile properties and notable thermal stability effect for polyvinyl chloride (PVC) are reported here. The complexes are synthesized without any organic solvents, and the structures are confirmed as Zn(C13H10NO5)2·H2O and Ca(C13H10NO5)2·3H2O by Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray fluorescence spectrometry, and elemental analysis. The PVC samples stabilized with the complexes show superior tensile strength and elongation at break compared with zinc and calcium stearates by tensile test. The results of Congo red test, dehydrochlorination test, and discoloration test show that: (1) Zn(Oxo)2 is better than zinc stearate as thermal stabilizer for PVC; (2) Zn(Oxo)2 and Ca(Oxo)2 show notable synergistic effect with calcium stearate and zinc norfloxacin respectively. The mechanism of the superior tensile properties and notable thermal stability effect is due to the ability of the complexes to absorbing HCl and reacting with PVC chains, which result in the special chain extension of PVC and the delay of autocatalytic effect and zipper‐like dehydrochlorination. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47004.
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

The 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

We 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 Study

Polymorphic microsatellite markers were developed to study population structure and mating patterns of the monocarpic herbMoricandia moricandioides(Brassicaceae).

Methods and Results

Illumina 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.

Conclusions

The 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 Study

Studies 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.

Methods

With 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.

Results

The 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.

Discussion

rbcL 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

A 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

Adsorption 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.
Volunteers in higher education emergency management: Use them wisely
Authors: Zacarese Lawrence M.
Published: August 2018

When disasters strike, regardless of the location, there is usually no shortage of people willing to lend a hand to support those in need. Sometimes the help comes in the form of monetary assistance or fundraising to support the relief, and sometimes people simply want to raise awareness about the incident. Often, however, people just want to be involved and feel like they are making a difference. If people want to help, we should let them, right? The answer is yes, with a few caveats and suggestions.
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

The 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

A 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

The 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

Visible 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

Low‐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

An “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

Water‐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

Cells 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

The 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

Non‐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.
Process and outcomes of a court‐administered civil mediation program
Authors: Vidal Sarah , Kaasa Suzanne , Harmon Michele
Published: August 2018

This paper extends the current literature on court‐connected civil mediation programs and provides implications for future research and court administration policy and practice. Using administrative court data, we describe the mediation case processing, explore the factors associated with case participation in mediation, and examine how mediation processes and case characteristics relate to different case outcomes. Our findings indicate that 77.5% of cases assigned to a mediation track resulted in settlement, 17% reached resolution through a judicial ruling, and only 5.5% had trial‐related outcomes. More than two thirds of cases that went through mediation settled after mediation and prior to trial.
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

A 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.
Förster Resonance Energy Transfer‐Activated Processes in Smart Nanotheranostics Fabricated in a Sustainable Manner
Authors: Wawrzyńczyk Dominika , Bazylińska Urszula , Lamch Łukasz , Kulbacka Julita , Szewczyk Anna , Bednarkiewicz Artur , Wilk Kazimiera A. , Samoć Marek
Published: August 2018

Multilayer nanocarriers loaded with optically activated payloads are gaining increasing attention due to their anticipated crucial role for providing new mechanisms of energy transfers in the health‐oriented applications, as well as for energy storage and environmental protection. The combination of careful selection of optical components for efficient Förster resonance energy transfer, and surface engineering of the nanocarriers, allowed us to synthesize and characterize novel theranostic nanosystems for diagnosis and therapy of deep‐seated tumors. The cargo, constrained within the oil core of the nanocapsules, composed of NaYF4:Tm+3, Yb+3 up‐converting nanoparticles together with a second‐generation porphyrin‐based photosensitizing agent—Verteporfin, assured requisite diagnostic and therapeutic functions under near‐IR laser excitation. The outer polyaminoacid shell of the nanocapsules was functionalized with a ligand—poly(l‐glutamic acid) functionalized by PEG‐ylated folic acid—to ensure both a “stealth” effect and active targeting towards human breast cancer cells. The preparation criteria of all nanocarrier building blocks meet the requirements for sustainable and green chemistry practices. The multifunctionality of the proposed nanocarriers is a consequence of both the surface‐functionalized organic exterior part, which was accessible for selective accumulation in cancer cells, and the hydrophobic optically active interior, which shows phototoxicity upon irradiation within the first biological window.
Tuning Expanded Pores in Metal–Organic Frameworks for Selective Capture and Catalytic Conversion of Carbon Dioxide
Authors: Meng Wei , Zeng Yongfei , Liang Zibin , Guo Wenhan , Zhi Chenxu , Wu Yingxiao , Zhong Ruiqin , Qu Chong , Zou Ruqiang
Published: August 2018

Three Co‐based isostructural MOF‐74‐III materials with expanded pores are synthesized, with varied extent of fused benzene rings onto sidechain of same‐length ligands to finely tune the pore sizes to 2.6, 2.4, and 2.2 nm. Gas sorption results for these highly mesoporous materials show that alternately arranged fused benzene rings on one side of the ligand could serve as extra anchoring sites for CO2 molecules with π–π interactions, conspicuously enhancing CO2 uptake and CO2/CH4 and CO2/N2 selectivity; while more steric hindrance effect towards open CoII sites were imposed by ligands flanked with fused benzene rings on both sides, compromising such extra‐sites enhancement. In the catalytic conversion of CO2 with propylene oxide to form propylene carbonate, the as‐synthesized MOF‐74‐III(Co) with desired properties of highly exposed and accessible open CoII centers, large mesopore apertures and multi‐interactive sites, demonstrated higher catalytic activity compared with other two MOFs, with benzene rings fused to ligands hampering the functionality of CoII centers as Lewis acid sites. Our results highlight the viability of finely tuning the expanded pores of MOF‐74 isostructure and the effect of fused benzene rings as functional groups onto selective CO2 capture and conversion.
Plan career steps, be strategic about first year in position
Authors: Hope Joan
Published: August 2018

Before Jennifer Cowley accepted the position of provost and vice president for academic affairs at the University of North Texas, she researched the options to choose an institution that would be a good fit. After spending 17 years at Ohio State University, starting as a faculty member and ending as vice provost, she gave a lot of thought to her next career step.
Investigating the appearance of new psychoactive substances in South Australia using wastewater and forensic data
Authors: Bade Richard , Stockham Peter , Painter Ben , Celma Alberto , Bijlsma Lubertus , Hernandez Felix , White Jason M. , Gerber Cobus
Published: August 2018

New psychoactive substances (NPS) have increased in use and popularity worldwide. Wastewater analysis has been successfully applied to evaluate illicit drugs use within a population. However, for NPS, such an approach may be limited due to low doses of NPS combined with their ever‐changing composition and usage. The dynamic nature of the NPS market means use may be opportunistic, infrequent, and with few users. Hence, the use of complementary information sources is recommended to improve the knowledge on NPS consumption. The aim of this study was to investigate the changing landscape of NPS use on a community scale by combining wastewater analysis and forensic toxicology. Forensic analysis provided specific information on NPS prevalence in post‐mortem blood samples in Adelaide, South Australia over five years, while wastewater analysis showed community use over the same period. A qualitative liquid chromatography–‐high resolution mass spectrometry method was initially used to screen the wastewater samples. A total of 24 NPS were found: 6 in wastewater only, 13 in forensic post‐mortem toxicology samples only, and 5 in both. As these results showed the presence of NPS, a targeted method was subsequently employed to quantify levels of these NPS in wastewater. Temporal trends were found in wastewater with distinct tendencies for synthetic cathinones visible over the period studied.
Ectomesoderm and epithelial–mesenchymal transition‐related genes in spiralian development
Authors: Osborne C. Cornelia , Perry Kimberly J. , Shankland Marty , Henry Jonathan Q.
Published: August 2018

Background: Spiralians (e.g., annelids, molluscs, and flatworms) possess two sources of mesoderm. One is from endodermal precursors (endomesoderm), which is considered to be the ancestral source in metazoans. The second is from ectoderm (ectomesoderm) and may represent a novel cell type in the Spiralia. In the mollusc Crepidula fornicata, ectomesoderm is derived from micromere daughters within the A and B cell quadrants. Their progeny lie along the anterolateral edges of the blastopore. There they undergo epithelial–mesenchymal transition (EMT), become rounded and undergo delamination/ingression. Subsequently, they assume the mesenchymal phenotype, and migrate beneath the surface ectoderm to differentiate various cell types, including muscles and pigment cells. Results: We examined expression of several genes whose homologs are known to regulate Type 1 EMT in other metazoans. Most of these genes were expressed within spiralian ectomesoderm during EMT. Conclusions: We propose that spiralian ectomesoderm, which exhibits analogous cellular behaviors to other populations of mesenchymal cells, may be controlled by the same genes that drive EMT in other metazoans. Perhaps these genes comprise a conserved metazoan EMT gene regulatory network (GRN). This study represents the first step in elucidating the GRN controlling the development of a novel spiralian cell type (ectomesoderm). Developmental Dynamics 247:1097‐1120, 2018. © 2018 Wiley Periodicals, Inc.