bluuebunny/crossref_metadata_2025_split huggingface dataset:
Using First‐Principles Calculations for the Advancement of Materials for Rechargeable Batteries
Authors: Yoon Gabin , Kim Do‐Hoon , Park Inchul , Chang Donghee , Kim Byunghoon , Lee Byungju , Oh Kyungbae , Kang Kisuk 
Published: August 2017

AbstractRechargeable batteries have been regarded as leading candidates for energy storage systems to satisfy soaring energy demands and ensure efficient energy use, and intensive efforts have thus been focused on enhancing their energy densities and power capabilities. First‐principles calculations based on quantum mechanics have played an important role in obtaining a fundamental understanding of battery materials, thus providing insights for material design. In this feature article, the theoretical approaches used to determine key battery properties, such as the voltage, phase stability, and ion‐diffusion kinetics, are reviewed. Moreover, the recent contribution of first‐principles calculations to the interpretation of complicated experimental characterization measurements on battery materials, such as those obtained using X‐ray absorption spectroscopy, electron energy‐loss spectroscopy, nuclear magnetic resonance spectroscopy, and transmission electron microscopy, are introduced. Finally, perspectives are provided on the research direction of first‐principles calculations for the development of advanced batteries, including the further development of theories that can accurately describe the dissolved species, amorphous phases, and surface reactions that are integral to the operation of future battery systems beyond Li‐ion batteries.
Self‐Templated Fabrication of MoNi4/MoO3‐x Nanorod Arrays with Dual Active Components for Highly Efficient Hydrogen Evolution
Authors: Chen Yu‐Yun , Zhang Yun , Zhang Xing , Tang Tang , Luo Hao , Niu Shuai , Dai Zhi‐Hui , Wan Li‐Jun , Hu Jin‐Song 
Published: August 2017

AbstractA binder‐free efficient MoNi4/MoO3‐x nanorod array electrode with 3D open structure is developed by using Ni foam as both scaffold and Ni source to form NiMoO4 precursor, followed by subsequent annealing in a reduction atmosphere. It is discovered that the self‐templated conversion of NiMoO4 into MoNi4 nanocrystals and MoO3‐x as dual active components dramatically boosts the hydrogen evolution reaction (HER) performance. Benefiting from high intrinsic activity, high electrochemical surface area, 3D open network, and improved electron transport, the resulting MoNi4/MoO3‐x electrode exhibits a remarkable HER activity with extremely low overpotentials of 17 mV at 10 mA cm−2 and 114 mV at 500 mA cm−2, as well as a superior durability in alkaline medium. The water–alkali electrolyzer using MoNi4/MoO3‐x as cathode achieves stable overall water splitting with a small cell voltage of 1.6 V at 30 mA cm−2. These findings may inspire the exploration of cost‐effective and efficient electrodes by in situ integrating multiple highly active components on 3D platform with open conductive network for practical hydrogen production.
Polymer Microstructures through Two‐Photon Crosslinking
Authors: Schwärzle David , Hou Xiaoqang , Prucker Oswald , Rühe Jürgen 
Published: August 2017

AbstractTwo‐photon crosslinking of polymers (2PC) is proposed as a novel method for the fabrication of freestanding microstructures via two‐photon lithography. During this process in the confocal volume, two‐photon absorption leads to (formal) C,H‐insertion reactions, and consequently to a strictly localized crosslinking of the polymer. To achieve this, the polymer is coated as a solvent‐free (glassy) film onto an appropriate substrate, and the desired microstructure is written by 2PC into this glass. In all regions outside of the focal volume where no two‐photon process occurs, the polymer remains uncrosslinked and can be washed away during a developing process. Using a self‐assembled monolayer containing the same photoreactive group allows covalent attachment of the forming freestanding structures to the substrate, and thus guarantees an improved stability of these structures against shear‐induced detachment. As the two photon process is carried out in the glassy state, in a simple way, multilayer structures can be used to write structures having a varying chemical composition perpendicular to the surface. As an example, the 2PC process is used to build a structure from both protein‐repellent and protein‐adsorbing polymers so that the resulting 3D structure exhibits spatially controlled protein adsorption.
Synthesis and surface properties of a novel fluorine modified acrylate colloid
Authors: Wang Xiuming , Xu Tingting , Zhang Cuifeng , Chen Lijun 
Published: August 2017

AbstractThe novel modified acrylate colloid was synthesized by semi‐continuous seeded emulsion polymerization which was initiated with potassium persulfate (KPS), and octylphenol polyoxyethylene ether (OP‐10) and sodium dodecyl benzene sulfonate (SDBS) were used as surfactants. Butyl acrylate (BA) and methyl methacrylate (MMA) were used as the main monomers and hexafluorobutyl methacrylate (HFMA, C8H8F6O2), and benzyl methacrylate (BZMA, C11H12O2) were used as functional monomers. Factors such as the amount of initiator, mass ratio of SDBD to OP‐10 and monomers, which have an influence on particle size and morphology of the resultant colloid, are studied. Chemical composition of the modified acrylate colloid was evaluated by Fourier transform infrared spectrometry (FTIR). The thermal performances were characterized by differential scanning calorimetry (DSC) and thermogravimetry (TG). Furthermore, surface hydrophobicity of the latex film was examined by measurement of water absorption and water contact angle. Results indicate that the modified acrylate colloid has highest monomer conversion rate and lowest coagulation percentage when the mass fraction of emulsifier was 4% and mass ratio of SDBS to OP‐10 was 1:2, mass fraction of initiator was 0.3%, mass percent of HFMA was 6%, and the amount of BZMA was 2%. Benzene ring‐containing monomer is effectively participated in the reaction and has improved the thermal performance and surface properties of copolymer colloid. The resultant colloid has excellent hydrophobicity and low surface energy. Solid content of the resultant colloid was about 30% (wt %).
Improvements in mechanical strength and thermal stability of injection and compression molded components based on Poly Lactic Acids
Authors: Aversa Clizia , Barletta Massimiliano , Gisario Annamaria , Pizzi Elisa , Puopolo Michela , Vesco Silvia 
Published: August 2017

AbstractDegradable polymers are limited by their often‐insufficient mechanical and thermal properties, which limit their usage to single‐use packaging items at room temperature and in dry conditions. In this respect, the present work deals with the manufacture of custom‐built Poly Lactic Acids (PLAs), which are designed to be compostable, suitable for food contact and are characterized by a good compromise between mechanical properties and thermal stability. A commercial gradePLAwas, therefore, compounded in a twin‐screw co‐rotating extruder by the use of specific additives: maleated and glycidyl methacrylatePLAs as compatibilizers/chain extenders and microlamellar talc as mineral filler/nucleation promoter. After pelletizing, the resulting compounds were melt‐processed by injection and compression molding. Differential scanning calorimetry, flexural tests in static machine and top‐hat cylindrical flat indentations were performed to evaluate the thermal and mechanical response of the molded components. The experimental findings show that crystallization of thePLAcan be controlled by fine‐tuning the compound formulation as well as by properly setting the processing parameters. In addition, achievement of the appropriate crystallization degree in the polymer can lead to molded components, which exhibit improved mechanical strength and high thermal stability.
Contact dermatitis is an unrecognized problem in the construction industry: Comparison of four different assessment methods
Authors: Timmerman Johan G. , Heederik Dick , Spee Ton , van Rooy Frits G. , Krop Esmeralda J. M. , Rustemeyer Thomas , Smit Lidwien A. M. 
Published: August 2017

BackgroundA high contact dermatitis symptoms prevalence has been observed in Dutch construction workers.MethodsContact dermatitis was diagnosed by an expert panel using questionnaire data and photographs of 751 subjects’ hands. A subset was evaluated by two occupational physicians. Their diagnoses were compared to those of the expert panel. In addition, two self‐reported questionnaire‐based assessment methods were compared to the expert panel evaluation. Associations between contact dermatitis and determinants were assessed using log‐binomial regression analysis.ResultsContact dermatitis prevalence was high: 61.4% (expert panel's diagnosis) and 32.9% (self‐reported). Agreement between occupational physicians and the expert panel was low but increased after training. Washing hands with solvents and performing job‐related tasks at home were related to contact dermatitis.ConclusionsContact dermatitis prevalence among construction workers is high. Recognition of contact dermatitis by occupational physicians is poor but can be improved by training. Awareness of skin disorders should be raised.
Mortality in asbestos cement workers in Pavia, Italy: A cohort study
Authors: Oddone Enrico , Ferrante Daniela , Tunesi Sara , Magnani Corrado 
Published: August 2017

BackgroundThe aim of this study was to describe the mortality of a cohort of asbestos‐cement workers in the largest plant in the most industrialized Italian region (Lombardy).MethodsA cohort study was carried out on 1818 subjects, corresponding to 47 536.1 person‐years of observation. Standardized mortality ratios (SMRs) were computed for the major causes of death.ResultsIncreased SMRs were observed for pleural, peritoneal and lung cancers, and for asbestosis (SMR 26.73, 95% Confidence Interval (CI) 20.99‐33.55; 9.15, 95%CI 5.00‐15.34; 1.48, 95%CI 1.27‐1.72; and 368.05, 95%CI 214.40‐589.29, respectively). No excess in mortality for laryngeal cancer was observed (SMR 0.70, 95%CI 0.30‐1.39). An increased mortality for ovarian cancer (SMR 3.64, 95%CI 0.99‐9.33) was observed, although it was not statistically significant. Among men, mortality for pleural malignant mesothelioma was observed to be related to the duration of exposure, though not to latency.ConclusionsThe results of this study are generally consistent with present knowledge. Conversely, our results do not support the hypothesis that pleural malignant mesothelioma risk indefinitely increases after exposure, suggesting instead that the alternative hypothesis of a risk plateau or decrease after a time since first exposure of more than 40 years is more consistent with the observed data.
The work‐related stressors and coping strategies of group‐employed rural health care practitioners: A qualitative study
Authors: Hasbrouck Melinda A. , Waddimba Anthony C. 
Published: August 2017

BackgroundEscalating demands on practitioners, stagnating/dwindling resources, and diminishing autonomy have heightened patient‐care work‐related stress. Using qualitative content/thematic analysis of responses to open‐ended survey questions, plus spontaneous comments, we sought to identify rural clinicians’ subjective perceptions of their workplace stressors and typical adaptive/coping strategies.MethodsWithin a hybrid inductive‐deductive approach, we framed empirical themes (derived by consensus, corroborated with text segments, and extant literature) into theory‐based coding templates by which we analyzed the data.ResultsOf 308 (65.1% of) recipients completing questionnaires, 290 (94%) answered open‐ended questions and/or provided comments. Categorizing stressors by socio‐ecology, they cited four themes: Organizational, practitioner/staff‐related, patient‐related, and third party‐induced stressors. Organizational stressors were referenced most conspicuously. How respondents described their coping fitted the Stress, Appraisal and Coping. [Lazarus and Folkman (1984): New York, NY: Springer Publishing Company, Inc] model. Emotion‐focused were referenced more than problem‐focused approaches. Themes scarcely differed by demographics, except for marital status.ConclusionsFindings highlight needs for resilience coaching, rekindling work meaningfulness, mentorship in work‐home balance/limit‐setting, supportive peer networks, and deeper teamwork.
Work organization, health, and obesity in urban transit operators: A qualitative study
Authors: Dobson Marnie , Choi BongKyoo , Schnall Peter L. 
Published: August 2017

BackgroundUrban transit operators have high rates of obesity, hypertension, and other cardiovascular risk‐factors compared to other occupations. There have been few qualitative studies exploring the interrelationships between the organization of transit work, stress, and health including obesity, from the perspective of operators.MethodsFive focus groups were conducted at five Divisions in a transit authority in Southern California and included 65 bus and rail operators.ResultsOperators reported a great deal of stress related to their work, including 1) time pressures and lack of recovery time; 2) long work shifts and overtime; 3) feeling unsafe when dealing with the public; 4) lack of respect from supervisors and management. Operators believed stressful working conditions negatively impacted their health and weight.ConclusionThis qualitative study yielded new as well as confirmatory data about stress and transit work organization, health, and weight in operators. This study will add to future survey research and interventions in this population.
RuII‐Catalyzed ortho‐Sulfonamidation of α‐Tetralones with Sulfonyl Azides and Synthesis of Sivelestat by Aromatic C−H Activation
Authors: Krishna Rao Medikonda V. , Reddy Keesari Nagarjuna , Sridhar Balasubramaniam , Subba Reddy Basi V. 
Published: August 2017

AbstractA method has been developed for the sulfonamidation of tetralones and 1,4‐naphthoquinones by using sulfonyl azides in the presence of a RuII/AgI catalytic system. In case of tetralones, C−H bond functionalization occurred exclusively at the ortho position, whereas 1,4‐addition was the main transformation for 1,4‐naphthoquinones. This method is highly regioselective and was successfully utilized for the synthesis of sivelestat, an inhibitor of human neutrophil elastase.
Axonal components of nerves innervating the human arm
Authors: Gesslbauer Bernhard , Hruby Laura A. , Roche Aidan D. , Farina Dario , Blumer Roland , Aszmann Oskar C. 
Published: August 2017

ObjectiveAxons traveling within the brachial plexus are responsible for the dexterous control of human arm and hand movements. Despite comprehensive knowledge on the topographical anatomy of nerves innervating the human upper limbs, the definite quantity of sensory and motor axons within this neural network remains elusive. Our aim was to perform a quantitative analysis of the axonal components of human upper limb nerves based on highly specific molecular features from spinal cord level to the terminal nerves at wrist level.MethodsNerve specimen harvest at predefined harvesting sites (plexus roots and cords as well as major nerves originating from the brachial plexus innervating the arm and hand) was performed in 9 human heart‐beating organ donors. Double immunofluorescence staining using antibodies against choline‐acetyltransferase and neurofilament was performed to differentiate motor and sensory axons on nerve cross sections.ResultsThree hundred fifty thousand axons emerge from the spinal cord to innervate the human upper limb, of which 10% are motor neurons. In all nerves studied, sensory axons outnumber motor axons by a ratio of at least 9:1. The sensory axon contribution increases when moving distally, whereas only 1,700 motor axons reach the hand to innervate the intrinsic musculature.InterpretationOur results suggest that upper limb motor execution, and particularly dexterous coordination of hand movement, require an unexpectedly low number of motor neurons, with a large convergence of afferent input for feedback control. Ann Neurol 2017;82:396–408
Cortical pathology in multiple sclerosis detected by the T1/T2‐weighted ratio from routine magnetic resonance imaging
Authors: Righart Ruthger , Biberacher Viola , Jonkman Laura E. , Klaver Roel , Schmidt Paul , Buck Dorothea , Berthele Achim , Kirschke Jan S. , Zimmer Claus , Hemmer Bernhard , Geurts Jeroen J. G. , Mühlau Mark 
Published: August 2017

ObjectiveIn multiple sclerosis, neuropathological studies have shown widespread changes in the cerebral cortex. In vivo imaging is critical, because the histopathological substrate of most measurements is unknown.MethodsUsing a novel magnetic resonance imaging analysis technique, based on the ratio of T1‐ and T2‐weighted signal intensities, we studied the cerebral cortex of a large cohort of patients in early stages of multiple sclerosis. A total of 168 patients with clinically isolated syndrome or relapsing–remitting multiple sclerosis (Expanded Disability Status Scale: median = 1, range = 0–3.5) and 80 age‐ and sex‐matched healthy controls were investigated. We also searched for the histopathological substrate of the T1/T2‐weighted ratio by combining postmortem imaging and histopathology in 9 multiple sclerosis brain donors.ResultsPatients showed lower T1/T2‐weighted ratio values in parietal and occipital areas. The 4 most significant clusters appeared in the medial occipital and posterior cingulate cortex (each left and right). The decrease of the T1/T2‐weighted ratio in the posterior cingulate was related to performance in attention. Analysis of the T1/T2‐weighted ratio values of postmortem imaging yielded a strong correlation with dendrite density but none of the other parameters including myelin.InterpretationThe T1/T2‐weighted ratio decreases in early stages of multiple sclerosis in a widespread manner, with a preponderance of posterior areas and with a contribution to attentional performance; it seems to reflect dendrite pathology. As the method is broadly available and applicable to available clinical scans, we believe that it is a promising candidate for studying and monitoring cortical pathology or therapeutic effects in multiple sclerosis. Ann Neurol 2017;82:519–529
Nickel‐Catalyzed Reductive Allylation of Tertiary Alkyl Halides with Allylic Carbonates
Authors: Chen Haifeng , Jia Xiao , Yu Yingying , Qian Qun , Gong Hegui 
Published: August 2017

AbstractThe construction of all C(sp3) quaternary centers has been successfully achieved under Ni‐catalyzed cross‐electrophile coupling of allylic carbonates with unactivated tertiary alkyl halides. For allylic carbonates bearing C1 or C3 substituents, the reaction affords excellent regioselectivity through the addition of alkyl groups to the unsubstituted allylic carbon terminus. The allylic alkylation method also exhibits excellent functional‐group compatibility, and delivers the products with high E selectivity.
Enhanced Photophosphorylation of a Chloroplast‐Entrapping Long‐Lived Photoacid
Authors: Xu Youqian , Fei Jinbo , Li Guangle , Yuan Tingting , Li Yue , Wang Chenlei , Li Xianbao , Li Junbai 
Published: August 2017

AbstractEnhancing solar energy conversion efficiency is very important for developing renewable energy, protecting the environment, and producing agricultural products. Efficient enhancement of photophosphorylation is demonstrated by coupling artificial photoacid generators (PAGs) with chloroplasts. The encapsulation of small molecular long‐lived PAGs in the thylakoid lumen is improved greatly by ultrasonication. Under visible‐light irradiation, a fast intramolecular photoreaction of the PAG occurs and produces many protons, remarkably enhancing the proton gradient in situ. Consequently, compared to pure chloroplasts, the assembled natural–artificial hybrid demonstrates approximately 3.9 times greater adenosine triphosphate (ATP) production. This work will provide new opportunities for constructing enhanced solar energy conversion systems.
Selective Ring‐Opening Polymerization of Non‐Strained γ‐Butyrolactone Catalyzed by A Cyclic Trimeric Phosphazene Base
Authors: Zhao Na , Ren Chuanli , Li Huaike , Li Yunxin , Liu Shaofeng , Li Zhibo 
Published: August 2017

AbstractA new superbase, the cyclic trimeric phosphazene base (CTPB), was prepared with high yield and purity. In the presence of alcohol, the CTPB serves as a highly efficient organocatalyst for ring‐opening polymerization of the “non‐polymerizable” γ‐butyrolactone to offer well‐defined poly(γ‐butyrolactone) with high conversions (up to 98 %) at −60 °C. The produced polymers have high molecular weights (up to 22.9 kg mol−1) and low polydispersity distributions (1.27–1.50). NMR analysis of initiation process and the structural analysis of resulting polymers by MALDI‐TOF suggest a mechanism involving an activating initiator which leads only to linear polymers with BnO/H chain ends.
Homo‐ and Heteroleptic Phototoxic Dinuclear Metallo‐Intercalators Based on RuII(dppn) Intercalating Moieties: Synthesis, Optical, and Biological Studies
Authors: Saeed Hiwa K. , Jarman Paul J. , Archer Stuart , Sreedharan Sreejesh , Saeed Ibrahim Q. , Mckenzie Luke K. , Weinstein Julia A. , Buurma Niklaas J. , Smythe Carl G. W. , Thomas Jim A. 
Published: August 2017

AbstractUsing a new mononuclear “building block,” for the first time, a dinuclear RuII(dppn) complex and a heteroleptic system containing both RuII(dppz) and RuII(dppn) moieties are reported. The complexes, including the mixed dppz/dppn system, are 1O2 sensitizers. However, unlike the homoleptic dppn systems, the mixed dppz/dppn complex also displays a luminescence “switch on” DNA light‐switch effect. In both cisplatin sensitive and resistant human ovarian carcinoma lines the dinuclear complexes show enhanced uptake compared to their mononuclear analogue. Thanks to a favorable combination of singlet oxygen generation and cellular uptake properties all three of the new complexes are phototoxic and display potent activity against chemotherapeutically resistant cells.
Intramolekulare π‐π‐Wechselwirkungen in flexibel verbrückten, teilweise fluorierten Bisarenen in der Gasphase
Authors: Blomeyer Sebastian , Linnemannstöns Marvin , Nissen Jan Hendrick , Paulus Jannik , Neumann Beate , Stammler Hans‐Georg , Mitzel Norbert W. 
Published: August 2017

AbstractMittels Hydrosilylierungs‐ und C‐C‐Kupplungsreaktionen wurden drei mit (CH2)3‐ und (CH2)2SiMe2‐Einheiten verbrückte Verbindungen mit Phenyl‐ und Pentafluorphenylringen synthetisiert. Im Festkörper bilden sie primär dimere oder kettenartige, von intermolekularen π‐π‐Wechselwirkungen dominierte Aggregate. Die Struktur des häufigsten Konformers der freien Moleküle zeigt jeweils, bestimmt mittels Gas‐Elektronen‐Diffraktion, eine signifikante intramolekulare Stabilisierung durch π‐π‐Wechselwirkungen. Die nächstenergiereicheren Konformere für die Siliciumverbindungen zeigen σ‐π‐Wechselwirkungen zwischen Methyl‐ und (Pentafluor‐)Phenylgruppen und können im GED‐Experiment nicht vollständig ausgeschlossen werden. Im Unterschied dazu besteht C6H5(CH2)3C6F5 nur aus einem einzigen Konformer. Die Gasphasenstrukturen dienen als Referenz für die Evaluation einer Reihe (dispersionskorrigierter) quantenchemischer Methoden.
Stereospecific Electrophilic Fluorination of Alkylcarbastannatrane Reagents
Authors: Ma Xinghua , Diane Mohamed , Ralph Glenn , Chen Christine , Biscoe Mark R. 
Published: August 2017

AbstractWe report the use of isolable primary and secondary alkylcarbastannatrane nucleophiles in site‐specific fluorination reactions. These reactions occur without the need for transition metal catalysis or in situ activation of the nucleophile. In the absence of the carbastannatrane backbone, alkyltin nucleophiles exhibit no activity towards fluorination. When enantioenriched alkylcarbastannatranes are employed, fluorination occurs predominately via a stereoinvertive mechanism to generate highly enantioenriched alkyl fluoride compounds. These conditions can also be extended to stereospecific chlorination, bromination, and iodination reactions.