bluuebunny/crossref_metadata_2025_split huggingface dataset:
Benchmarking the Activity, Stability, and Inherent Electrochemistry of Amorphous Molybdenum Sulfide for Hydrogen Production
Authors: Escalera‐López Daniel , Lou Zhiheng , Rees Neil V. 
Published: January 2019

AbstractAnodically electrodeposited amorphous molybdenum sulfide (AE‐MoSx) has attracted significant attention as a non‐noble metal electrocatalyst for its high activity toward the hydrogen evolution reaction (HER). The [Mo3S13]2− polymer‐based structure confers a high density of exposed sulfur moieties, widely regarded as the HER active sites. However, their intrinsic complexity conceals full understanding of their exact role in HER catalysis, hampering their full potential for water splitting applications. In this report, a unifying approach is adopted accounting for modifications in the inherent electrochemistry (EC), HER mechanism, and surface species to maximize the AE‐MoSx electroactivity over a broad pH region (0–10). Dramatic enhancements in HER performance by selective electrochemical cycling within reductive (overpotential shift, ηHER ≈ −350 mV) and electro‐oxidative windows (ηHER ≈ −290 mV) are accompanied by highly stable performance in mildly acidic electrolytes. Joint analysis of X‐ray photoelectron spectroscopy, Raman, and EC experiments corroborate the key role of bridging and terminal S ligands as active site generators at low pH, and reveal molybdenum oxysulfides (Mo5+OxSy) to be the most active HER moiety in AE‐MoSx in mildly acidic‐to‐neutral environments. These findings will be extremely beneficial for future tailoring of MoSx materials and their implementation in commercial electrolyzer technologies.
In Vitro Reconstitution of Bacterial DMSP Biosynthesis
Authors: Liao Cangsong , Seebeck Florian P. 
Published: January 2019

AbstractDimethylsulfoniopropionate (DMSP) is one of the most abundant sulfur metabolites in marine environments. The biosynthesis of DMSP and its degradation to dimethylsulfide are important links in the planetary sulfur cycle. Herein, the first complete description of a DMSP biosynthetic pathway is provided by the in vitro reconstitution of four enzymes from Streptomyces mobaraensis. The isolation of DMSP from S. mobaraensis cells grown at high salinity confirmed that this actinobacterium is indeed is a DMSP‐producing organism. The described DMSP biosynthesis follows the same route as that previously described for angiosperm plants. Despite this chemical congruence, limited sequence similarity between plant and bacterial enzymes suggests that the two biosynthetic activities emerged by convergent evolution.
In Situ Generation of an N‐Heterocyclic Carbene Functionalized Metal–Organic Framework by Postsynthetic Ligand Exchange: Efficient and Selective Hydrosilylation of CO2
Authors: Zhang Xu , Sun Jiao , Wei Guangfeng , Liu Zhipan , Yang Huimin , Wang Kaimin , Fei Honghan 
Published: January 2019

AbstractThe reported metal–organic framework (MOF) catalyst realizes CO2 to methanol transformation under ambient conditions. The MOF is one rare example containing metal‐free N‐heterocyclic carbene (NHC) moieties, which are installed using an in situ generation strategy involving the incorporation of an imidazolium bromide based linker into the MOF by postsynthetic ligand exchange. Importantly, the resultant NHC‐functionalized MOF is the first catalyst capable of performing quantitative hydrogen transfer from silanes to CO2, thus achieving quantitative (>99 %) methanol yield. Density‐functional theory calculations indicate the high catalytic activity of the NHC sites in MOFs are attributed to the decreased reaction barrier of a reaction route involving the formation of an NHC‐silane adduct. In addition, the MOF‐immobilized NHC catalyst shows enhanced stability for up to eight cycles without base activation, as well as high selectivity towards the desired silyl methoxide product.
Economic, social, and environmental cost optimization of biomass transportation: a regional model for transportation analysis in plant location process
Authors: Ko Sangpil , Lautala Pasi , Fan Jiqing , Shonnard David R. 
Published: January 2019

AbstractThe need to build an efficient procurement system has been recognized as one of the main obstacles to the extension of the bioenergy industry. Transportation is a key component of that system, as it accounts for a significant portion of the delivered cost. One of the most critical factors affecting transportation cost is the interrelationship between feedstock sources and facility locations, including plant and off‐plant transfer / storage facilities. At the same time, biomass energy sustainability is sensitive to the performance of each component in the entire process. The main goal of this study is to build a mixed integer linear programming (MILP) model that uses region‐specific data to minimize sustainable transportation costs. This consists of economic, environmental, and societal factors. The upstream air emissions as a result of residues collection at the forest, transloading, and transportation by truck or multimodally (truck and rail), which include greenhouse gases (GHG), particulate matter (PM), and nitrogen oxides (NOx), are calculated and included in the analysis. The model was tested on a case study that evaluated transportation costs for nine alternative plant locations in the state of Wisconsin. The results revealed that when equally weighed, external (social and environmental) costs accounted for a considerable portion of total transportation cost (approximately 26–37%). The study also shows that total upstream GHG and air emissions increased as the plant capacity increased, due to the longer transportation distances, but per unit emissions decreased. © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd
Further evaluation of treatments for vocal stereotypy: Response interruption and redirection and response cost
Authors: McNamara Kiersty , Cividini‐Motta Catia 
Published: January 2019

The purpose of this study was to expand on research on treatments for stereotypy by evaluating the effects of response interruption and redirection (RIRD) and response cost (RC) alone and as a treatment package on vocal stereotypy. Treatment phases included RIRD, RC, and response interruption and redirection plus response cost (RIRD + RC). The efficacy of these treatments was determined by measuring duration of stereotypy in session and during treatment intervals. Vocal stereotypy decreased in all three treatment conditions; however, when data analysis included stereotypy occurring during treatment intervals, stereotypy during the RC condition occurred at similar levels as baseline for one treatment evaluation phase for Karl and both treatment evaluations phases for Jon. We discuss implications of these findings, limitations of the current study, and areas for future research.
IMSSAP: After‐school interactive mobile learning student support application
Authors: Khachan Ahmad M. , Özmen Ahmet 
Published: January 2019

AbstractTraditional methods intended for education are no longer suitable for it, since they are unable to meet the students’ learning needs. M‐learning is becoming a global interest. Various studies were conducted in many countries such as South Korea, Taiwan, UK, Malaysia, Serbia, European Union, and Saudi Arabia investigating student's readiness to adopt M‐learning. Our study aims to introduce a new mobile bite‐sized learning tool and to explore student's readiness to adopt M‐learning and to investigate the motivational and acceptance factors related to it. We introduced our learning tool (IMSSAP), after‐school interactive M‐learning student support Application, to university students from different majors in Turkey. Analysis of the questionnaire data revealed that an easy to use tool with social media collaboration and sharing capabilities appears to be the vital factors that will motivate students to adopt M‐learning. An improvement in the relation between the students, the teachers and the academic institution was obvious. Student's performance got much better added to better analytical and critical skills advancement. We have compared IMSSAP with another learning tool in the same class for clarity and reliability of the results.Highlights: A cloud‐based mobile application built with Google‐Firebase platform in the model of Backend as a Service (BaaS). Bite‐sized learning methodology used to fulfill student's needs in a social circle era. Lightweight learning tool created for knowledge sharing and a learning process monitoring facility.
Do doctors who order more routine medical tests diagnose more cancers? A population‐based study from Ontario Canada
Authors: Hall Stephen F. , Webber Colleen , Groome Patti A. , Booth Christopher M. , Nguyen Paul , DeWit Yvonne 
Published: January 2019

AbstractBackgroundThe overuse of medical tests leads to higher costs, wasting of resources, and the potential for overdiagnosis of disease. This study was designed to determine whether the patients of family doctors who order more routine medical tests are diagnosed with more cancers.MethodA retrospective population‐based cross‐sectional study using administrative health care data in Ontario Canada. We investigated the ordering of 23 routine laboratories and imaging tests 2008‐20012 by 6849 Ontario family physicians on their 4.9 million rostered adult patients. We compared physicians’ test utilization and calculated case‐mix adjusted observed to expected (O:E) utilization ratios to categorize physicians as Typical, Higher or Lower testers. Age‐sex standardized rates (cases/10 000 patient years) and Rate Ratios were determined for cancers of the thyroid, prostate, breast, lymphoma, kidney, melanoma, uterus, ovary, lung, esophagus, and pancreas for each tester group.ResultsThere was wide variation in the use of the 23 tests by Ontario physicians. 26% and 24% of physicians were deemed Higher Testers for laboratory and imaging tests, while 41% and 38% were Typical Testers. The patients of higher test users were diagnosed with more cancers of thyroid (laboratory [RR 1.61, 95% CI 1.39‐1.87] and imaging [RR 2.08, 95% CI 0.88‐2.30]) and prostate (laboratory [RR 1.10, 95% CI 1.03‐1.18] and imaging [RR 1.05, 95% CI 1.00‐1.10]).ConclusionThere is a wide variation in the ordering of routine and common medical tests among Ontario family doctors. The patients of higher testers were diagnosed with more thyroid and prostate cancers.
Phytochemical Analysis and Total Antioxidant Capacity of Rhizome, Above‐Ground Vegetative Parts and Flower of Three Iris Species
Authors: Kostić Aleksandar Ž. , Gašić Uroš M. , Pešić Mirjana B. , Stanojević Sladjana P. , Barać Miroljub B. , Mačukanović‐Jocić Marina P. , Avramov Stevan N. , Tešić Živoslav Lj. 
Published: January 2019

AbstractThis study was aimed at investigating the phytochemical composition and antioxidant capacity of rhizomes, above‐ground vegetative parts and flowers of three Iris species: Iris humilis Georgi, Iris pumila L. and Iris variegata L. UHPLC‐Orbitrap MS analysis was used for determination of phytochemical profile. Total pigments, phenolics, flavonoids, soluble sugars and starch content as well as ABTS antioxidant capacity were also determined. In total, 52 phenolics compounds were identified with 9 compounds (derivatives of iriflophenone, apigenin C‐glycosides, luteolin O‐glycoside, isoflavones derivatives of iristectorigenin, dichotomitin, nigracin and irilone) never reported before in Iris spp. Differences in phenolic composition profile, pigments, soluble sugar, starch, total phenolics and flavonoids content and total antioxidant capacity were found among Iris species and different part of plants. Significant correlation between total phenolic content and antioxidant capacity was determined. The obtained results are comparable with those obtained for medical plants. These findings could be useful for fingerprinting characterization of Iris species and estimation of possible use in pharmaceutical industries.
A Fluorogenic AggTag Method Based on Halo‐ and SNAP‐Tags to Simultaneously Detect Aggregation of Two Proteins in Live Cells
Authors: Jung Kwan Ho , Kim Sojung F. , Liu Yu , Zhang Xin 
Published: January 2019

AbstractProtein aggregation involves the assembly of partially misfolded proteins into oligomeric and higher‐order structures that have been associated with several neurodegenerative diseases. However, numerous questions relating to protein aggregation remain unanswered due to the lack of available tools for visualization of these species in living cells. We recently developed a fluorogenic method named aggregation tag (AggTag), and presented the AggTag probe P1, based on a Halo‐tag ligand, to report on the aggregation of a protein of interest (POI) in live cells. However, the Halo‐tag‐based AggTag method only detects the aggregation of one specific POI at a time. In this study, we have expanded the AggTag method by using SNAP‐tag technology to enable fluorogenic and biorthogonal detection of the aggregation of two different POIs simultaneously in live cells. A new AggTag probe—P2, based on a SNAP‐tag ligand bearing a green solvatochromic fluorophore—was synthesized for this purpose. Using confocal imaging and chemical crosslinking experiments, we confirmed that P2 can also report both on soluble oligomers and on insoluble aggregates of a POI fused with SNAP‐tag in live cells. Ultimately, we showed that the orthogonal fluorescence of P1 and P2 allows for simultaneous visualization of two different pathogenic protein aggregates in the same cell.
Enhanced Bio‐Electrochemical Reduction of Carbon Dioxide by Using Neutral Red as a Redox Mediator
Authors: Seelajaroen Hathaichanok , Haberbauer Marianne , Hemmelmair Christine , Aljabour Abdalaziz , Dumitru Liviu Mihai , Hassel Achim Walter , Sariciftci Niyazi Serdar 
Published: January 2019

AbstractMicrobial electrosynthetic cells containing Methylobacterium extorquens were studied for the reduction of CO2 to formate by direct electron injection and redox mediator‐assisted approaches, with CO2 as the sole carbon source. The formation of a biofilm on a carbon felt (CF) electrode was achieved while applying a constant potential of −0.75 V versus Ag/AgCl under CO2‐saturated conditions. During the biofilm growth period, continuous H2 evolution was observed. The long‐term performance for CO2 reduction of the biofilm with and without neutral red as a redox mediator was studied by an applied potential of −0.75 V versus Ag/AgCl. The neutral red was introduced into the systems in two different ways: homogeneous (dissolved in solution) and heterogeneous (electropolymerized onto the working electrode). The heterogeneous approach was investigated in the microbial system, for the first time, where the CF working electrode was coated with poly(neutral red) by the oxidative electropolymerization thereof. The formation of poly(neutral red) was characterized by spectroscopic techniques. During long‐term electrolysis up to 17 weeks, the formation of formate was observed continuously with an average Faradaic efficiency of 4 %. With the contribution of neutral red, higher formate accumulation was observed. Moreover, the microbial electrosynthetic cell was characterized by means of electrochemical impedance spectroscopy to obtain more information on the CO2 reduction mechanism.
Fe−N3/C Active Catalytic Sites for the Oxygen Reduction Reaction Prepared with Molecular‐Level Geometry Control through the Covalent Immobilization of an Iron−Terpyridine Motif onto Carbon
Authors: Fruehwald Holly M. , Ebralidze Iraklii I. , Zenkina Olena V. , Easton E. Bradley 
Published: January 2019

AbstractA model for a non‐precious metal catalyst for the oxygen reduction reaction (ORR) in aqueous media has been prepared by functionalizing a commercial Vulcan XC‐72 carbon support with a terpyridine‐based nitrogenous ligand. The terpyridine ligand geometry allows the formation of active catalytic sites by selectively embedding a N3/C structural motif into the carbon support confirmed by using thermogravimetric analysis (TGA) and X‐ray photoelectron spectroscopy (XPS) measurements. Room‐temperature metal–ligand coordination results in the desired Fe−N3/C moieties on the surface. This model system was used to demonstrate the catalytic activity of the surfaces containing mainly Fe−N3 sites for the ORR in acidic and basic media. Importantly, we demonstrate that the system could be prepared under mild reaction conditions, does not require high‐ temperature treatments, and shows catalytic activity for the ORR. Interestingly, when the system was pyrolyzed in an N2 atmosphere at 700 °C the resulting activity declined. The non‐heat‐treated Fe−N3/C surface demonstrates comparable activity in acidic electrolyte medium when compared to most literature catalysts that are typically heat treated to produce four nitrogen atoms coordinated to one iron center (Fe−N2+2/C). Interestingly, despite the fact that many systems reported so far in the literature exhibit enhanced activity after heat treatment, our system showed an increase in activity when the material was not pyrolyzed.
Solid‐Phase Synthesis and Purification of Protein–DNA Origami Nanostructures
Authors: Burgahn Teresa , Garrecht Ruben , Rabe Kersten S. , Niemeyer Christof M. 
Published: January 2019

AbstractWe present a facile method for the combined synthesis and purification of protein‐decorated DNA origami nanostructures (DONs). DONs bearing reductively cleavable biotin groups in addition to ligands for ligation of recombinant proteins are bound to magnetic beads. Protein immobilization is conducted with a large protein excess to achieve high ligation yields. Subsequent to cleavage from the solid support, pure sample solutions are obtained which are suitable for direct AFM analysis of occupation patterns. We demonstrate the method's utility using three different orthogonal ligation methods, the “halo‐based oligonucleotide binder” (HOB), a variant of Halo‐tag, the “SpyTag/SpyCatcher” (ST/SC) system, and the enzymatic “ybbR tag” coupling. We find surprisingly low efficiency for ST/SC ligation, presumably due to electrostatic repulsion and steric hindrance, whereas the ybbR method, despite its ternary nature, shows good ligation yields. Our method is particularly useful for the development of novel ligation methods and the synthesis of mechanically fragile DONs that present protein patterns for surface‐based cell assays.
Total Synthesis of Spirotryprostatins through Organomediated Intramolecular Umpolung Cyclization
Authors: Xi Yong‐Kai , Zhang Hongbin , Li Rui‐Xi , Kang Shi‐Yuan , Li Jin , Li Yan 
Published: January 2019

AbstractCyclodipeptide 2,5‐diketopiperazines (DKP) are privileged structural units present in drugs and natural alkaloids. This work reports a new method for the synthesis of biologically important DKP scaffolds based on an intramolecular nucleophilic α‐addition of general amides towards an alkynamide system. The utility of this umpolung cyclization mediated by trimethyl phosphine and l‐glutamic acid is highlighted by its application to the concise total syntheses of 6‐methoxyspirotryprostatin B (the first total synthesis), spirotryprostatin A, and spirotryprostatin B.
Atomically Precise Bimetallic Nanoclusters as Photosensitizers in Photoelectrochemical Cells
Authors: Wang Yu , Liu Xiao‐He , Kovalenko Sergey A. , Chen Qing‐Yun , Pinna Nicola 
Published: January 2019

AbstractThe atomically precise bimetallic nanocluster (NC), Au24Ag20(PhCC)20(SPy)4Cl2 (1) (Py=pyridine), was employed for the first time as a stable photosensitizer for photoelectrochemical applications. The sensitization of TiO2 nanotube arrays (TNA) with 1 greatly enhances the light‐harvesting ability of the composite because 1 shows a high molar extinction coefficient (ϵ) in the UV/Vis region. Compared to a more standard Au25(SG)18‐TNA (2‐TNA; SG=glutathione) composite, 1‐TNA shows a much better stability under illumination in both neutral and basic conditions. The precise composition of the photosensitizers enables a direct comparison of the sensitization ability between 1 and 2. With the same cluster loading, the photocurrent produced by 1‐TNA is 15 times larger than that of 2‐TNA. The superior performance of 1‐TNA over 2‐TNA is attributed not only to the higher light absorption ability of 1 but also to the higher charge‐separation efficiency. Besides, a ligand effect on the stability of the photoelectrode and charge‐transfer between the NCs and the semiconductor is revealed. This work paves the way to study the role of metal nanoclusters as photosensitizers at the atomic level, which is essential for the design of better material for light energy conversion.
Evaluation of the enantioselectivity of capillary electrokinetic chromatography using ethanediamine‐bonded poly (glycidyl methacrylate) microspheres as the pseudostationary phases
Authors: Sun Xiaodong , Yu Tao , Xu Guangfu , Du Yingxiang , Chen Jiaquan , Li Xiaoqi 
Published: January 2019

AbstractIn this work, a new capillary electrokinetic chromatography (EKC) approach using ethanediamine‐bonded poly (glycidyl methacrylate) (Ami‐PGMA) microspheres as pseudostationary phases (PSPs) for enantioseparation with a polysaccharide, chondroitin sulfate E (CSE), as the chiral selector. The CSE@Ami‐PGMA EKC system was applied to enantioseparate basic drugs, and distinct improved separations of tested enantiomers were obtained while comparing with the single CSE system (the resolution increased from 0.41 to 1.26 for nefopam, from 1.24 to 2.15 for laudanosine, and from 0.92 to 2.36 for amlodipine). The Ami‐PGMA microspheres were fully characterized by scanning electron microscopy (SEM) and Fourier Transform Infrared (FT‐IR) spectroscopy, and the results showed Ami‐PGMA microspheres were uniform and spherical in size (1 μm). Several principal parameters were systematically investigated, and the optimal chiral separations were obtained with Tris/H3PO4 (20 mM, pH 2.4, and 3.4 for NEF) containing 2.5% (w/v) CSE and 20‐μg Ami‐PGMA microspheres in 20°C. Subsequently, the concentrations of Ami‐PGMA microspheres and CSE were proved to be the dominant factors for the separation in the CSE@Ami‐PGMA EKC system by Statistical Product and Service Solutions (SPSS).
An approach to chance constrained problems using weighted empirical distribution and differential evolution with application to flood control planning
Authors: Tagawa Kiyoharu , Miyanaga Shun 
Published: January 2019

AbstractThis paper proposes a new approach to solve chance constrained problems (CCPs) efficiently. Specifically, the probabilistic constraint in CCP can be evaluated directly if the cumulative distribution function (CDF) of uncertain function value is known. Therefore, the CDF is approximated by using weighted empirical CDF (W ECDF). Then a powerful evolutionary algorithm, namely differential evolution, combined with W ECDF is used to solve CCP. In order to demonstrate the performance of the proposed method, it is applied to flood control planning problems.