bluuebunny/crossref_metadata_2025_split huggingface dataset:
Return to work after workplace injury: Injured workers, insurers and employers
Authors: Thornthwaite Louise , Markey Raymond 
Published: May 2017

AbstractReturning injured workers to work is a central object of contemporary workers’ compensation systems. Injured workers’ interactions with insurers and employers are critical to achievement of timely and sustainable return to work outcomes. This article explores the interactions of injured workers with insurers and employers through analysis of their perceptions and experiences. The focus is on experiences with the NSW Workers Compensation scheme since 2012. To frame this analysis, the article proposes a model mapping these interactions, the relationships involved, the health, social and vocational consequences, and the return to work outcomes. The research found not only that the NSW Workers’ compensation system is failing to deliver a timely and durable return to work for many injured workers, but also that, for many, problematic and often pathogenic interactions with employers and insurers are resulting in exacerbated and secondary injuries and negative social and vocational consequences.
Cofactor‐Free, Direct Photoactivation of Enoate Reductases for the Asymmetric Reduction of C=C Bonds
Authors: Lee Sahng Ha , Choi Da Som , Pesic Milja , Lee Yang Woo , Paul Caroline E. , Hollmann Frank , Park Chan Beum 
Published: May 2017

AbstractEnoate reductases from the family of old yellow enzymes (OYEs) can catalyze stereoselective trans‐hydrogenation of activated C=C bonds. Their application is limited by the necessity for a continuous supply of redox equivalents such as nicotinamide cofactors [NAD(P)H]. Visible light‐driven activation of OYEs through NAD(P)H‐free, direct transfer of photoexcited electrons from xanthene dyes to the prosthetic flavin moiety is reported. Spectroscopic and electrochemical analyses verified spontaneous association of rose bengal and its derivatives with OYEs. Illumination of a white light‐emitting‐diode triggered photoreduction of OYEs by xanthene dyes, which facilitated the enantioselective reduction of C=C bonds in the absence of NADH. The photoenzymatic conversion of 2‐methylcyclohexenone resulted in enantiopure (ee>99 %) (R)‐2‐methylcyclohexanone with conversion yields as high as 80–90 %. The turnover frequency was significantly affected by the substitution of halogen atoms in xanthene dyes.
Photoredoxkatalyse durch sensibilisierten Elektronentransfer
Authors: Ghosh Indrajit , Shaikh Rizwan S. , König Burkhard 
Published: May 2017

AbstractPhotosynthetische Organismen nutzen Antennenchromophore zur Lichtabsorption und übertragen die Anregungsenergie auf Reaktionszentren, in denen Redoxreaktionen ablaufen. Bei der chemischen Photokatalyse mit sichtbarem Licht wird dagegen nur ein einziges Molekül, der Photoredoxkatalysator, genutzt, um Licht zu absorbieren und die Redoxprozesse auszuführen. Wir berichten hier über eine Zwei‐Zentren‐Photoredoxkatalyse, bei der – in Analogie zum Energiefluss des biologischen Vorbilds – die Aufgaben der Lichtenergieabsorption und des Elektronentransfers auf zwei Moleküle verteilt werden: Ru(bpy)3Cl2 absorbiert sichtbares Licht und überträgt die Energie auf aromatische Kohlenwasserstoffe, an denen die Redoxreaktion abläuft. Dieser sensibilisierte Elektronentransfer ermöglicht die Nutzung von Aromaten, wie Anthracen oder Pyren, die selbst kein sichtbares Licht absorbieren, für die Photoredoxkatalyse. Die praktische Anwendung des Verfahrens zeigen wir anhand von Kohlenstoff‐Kohlenstoff‐ und Kohlenstoff‐Heteroatom‐Bindungsknüpfungen.
Molekulares Kästchenpapier
Authors: Lindner Marcin , Valášek Michal , Mayor Marcel , Frauhammer Timo , Wulfhekel Wulf , Gerhard Lukas 
Published: May 2017

AbstractHier wird eine selbstorganisierte molekulare Schablone vorgestellt, die aus Tetraphenylmethan‐basierten Derivaten besteht und auf einer Au(111)‐Oberfläche eine zweidimensional periodische Anordnung von Acetylgruppen aufweist, die aus dem molekularen Film hervorragen. Mithilfe der Spitze eines Rastertunnelmikroskops kann diese Acetylgruppe kontrolliert entfernt werden, ohne dass dabei die Anordnung des molekularen Films beeinflusst wird. Die chemisch modifizierten Moleküle sind leicht von den ursprünglichen Molekülen zu unterscheiden, sodass Informationen in den molekularen Film eingraviert werden können. Es konnte gezeigt werden, dass sowohl ein einzelnes modifiziertes Molekül als auch die Ordnung des Molekülfilms bei Raumtemperatur erhalten bleiben. Die Größe der Kästchen dieses molekularen Kästchenpapiers kann durch Variation der Länge des molekularen Abstandhalters vorgegeben werden, wodurch das Schreiben und das Lesen von Informationen auf der Nanoskala mit variabler Buchstabengröße möglich werden.
Cytoprotective Encapsulation of Individual Jurkat T Cells within Durable TiO2 Shells for T‐Cell Therapy
Authors: Youn Wongu , Ko Eun Hyea , Kim Mi‐Hee , Park Matthew , Hong Daewha , Seisenbaeva Gulaim A. , Kessler Vadim G. , Choi Insung S. 
Published: May 2017

AbstractLymphocytes, such as T cells and natural killer (NK) cells, have therapeutic promise in adoptive cell transfer (ACT) therapy, where the cells are activated and expanded in vitro and then infused into a patient. However, the in vitro preservation of labile lymphocytes during transfer, manipulation, and storage has been one of the bottlenecks in the development and commercialization of therapeutic lymphocytes. Herein, we suggest a cell‐in‐shell (or artificial spore) strategy to enhance the cell viability in the practical settings, while maintaining biological activities for therapeutic efficacy. A durable titanium oxide (TiO2) shell is formed on individual Jurkat T cells, and the CD3 and other antigens on cell surfaces remain accessible to the antibodies. Interleukin‐2 (IL‐2) secretion is also not hampered by the shell formation. This work suggests a chemical toolbox for effectively preserving lymphocytes in vitro and developing the lymphocyte‐based cancer immunotherapy.
Monofluoromethyl‐Substituted Sulfonium Ylides: Electrophilic Monofluoromethylating Reagents with Broad Substrate Scopes
Authors: Liu Yafei , Lu Long , Shen Qilong 
Published: May 2017

AbstractTwo electrophilic monofluoromethylating reagents, monofluoromethyl(phenyl)sulfonium bis(carbomethoxy)methylide (3 a) and monofluoromethyl(4‐nitrophenyl)sulfonium bis(carbomethoxy)methylide (3 b), and their reactions under mild conditions with a variety of nucleophiles, such as alcohols and malonate derivatives, sulfonic and carboxylic acids, phenols, amides, and N heteroarenes, are described. Mechanistic studies with deuterated reagents [D2]3 a/[D2]3 b suggest that these monofluoromethylation reactions proceed through an electrophilic substitution pathway.
Mechanism‐Based Enantiodivergence in Manganese Reduction Catalysis: A Chiral Pincer Complex for the Highly Enantioselective Hydroboration of Ketones
Authors: Vasilenko Vladislav , Blasius Clemens K. , Wadepohl Hubert , Gade Lutz H. 
Published: May 2017

AbstractA manganese alkyl complex containing a chiral bis(oxazolinyl‐methylidene)isoindoline pincer ligand is a precatalyst for a catalytic system of unprecedented activity and selectivity in the enantioselective hydroboration of ketones, thus producing preparatively useful chiral alcohols in excellent yields with up to greater than 99 % ee. It is applicable for both aryl alkyl and dialkyl ketone reduction under mild reaction conditions (TOF >450 h−1 at −40 °C). The earth‐abundant base‐metal catalyst operates at very low catalyst loadings (as low as 0.1 mol %) and with a high level of functional‐group tolerance. There is evidence for the existence of two distinct mechanistic pathways for manganese‐catalyzed hydride transfer and their role for enantiocontrol in the selectivity‐determining step is presented.
Evidence of Structure Sensitivity in the Fischer–Tropsch Reaction on Model Cobalt Nanoparticles by Time‐Resolved Chemical Transient Kinetics
Authors: Ralston Walter T. , Melaet Gérôme , Saephan Tommy , Somorjai Gabor A. 
Published: May 2017

AbstractThe Fischer–Tropsch process, or the catalytic hydrogenation of carbon monoxide (CO), produces long chain hydrocarbons and offers an alternative to the use of crude oil for chemical feedstocks. The observed size dependence of cobalt (Co) catalysts for the Fischer–Tropsch reaction was studied with colloidally prepared Co nanoparticles and a chemical transient kinetics reactor capable of measurements under non‐steady‐state conditions. Co nanoparticles of 4.3 nm and 9.5 nm diameters were synthesized and tested under atmospheric pressure conditions and H2/CO=2. Large differences in carbon coverage (ΘC) were observed for the two catalysts: the 4.3 nm Co catalyst has a ΘC less than one while the 9.5 nm Co catalyst supports a ΘC greater than two. The monomer units present on the surface during reaction are identified as single carbon species for both sizes of Co nanoparticles, and the major CO dissociation site is identified as the B5‐B geometry. The difference in activity of Co nanoparticles was found to be a result of the structure sensitivity caused by the loss of these specific types of sites at smaller nanoparticle sizes.
Trapping a Silicon(I) Radical with Carbenes: A Cationic cAAC–Silicon(I) Radical and an NHC–Parent‐Silyliumylidene Cation
Authors: Li Yan , Chan Yuk‐Chi , Leong Bi‐Xiang , Li Yongxin , Richards Emma , Purushothaman Indu , De Susmita , Parameswaran Pattiyil , So Cheuk‐Wai 
Published: May 2017

AbstractThe trapping of a silicon(I) radical with N‐heterocyclic carbenes is described. The reaction of the cyclic (alkyl)(amino) carbene [cAACMe] (cAACMe=:C(CMe2)2(CH2)NAr, Ar=2,6‐iPr2C6H3) with H2SiI2 in a 3:1 molar ratio in DME afforded a mixture of the separated ion pair [(cAACMe)2Si:.]+I− (1), which features a cationic cAAC–silicon(I) radical, and [cAACMe−H]+I−. In addition, the reaction of the NHC–iodosilicon(I) dimer [IAr(I)Si:]2 (IAr=:C{N(Ar)CH}2) with 4 equiv of IMe (:C{N(Me)CMe}2), which proceeded through the formation of a silicon(I) radical intermediate, afforded [(IMe)2SiH]+I− (2) comprising the first NHC–parent‐silyliumylidene cation. Its further reaction with fluorobenzene afforded the CAr−H bond activation product [1‐F‐2‐IMe‐C6H4]+I− (3). The isolation of 2 and 3 confirmed the reaction mechanism for the formation of 1. Compounds 1–3 were analyzed by EPR and NMR spectroscopy, DFT calculations, and X‐ray crystallography.
Effect of CO conversion upon product distribution using bimetallic Co‐Ni mesoporous silica catalyst for Fischer–Tropsch synthesis: a comparative study of fixed‐bed reactor and slurry continuous stirred tank reactor
Authors: Sun Yong , Yang Gang , Sun Zhi , Zhang Lian 
Published: May 2017

AbstractFischer–Tropsch synthesis was studied on mesoporous silica supported bimetallic Co‐Ni catalyst in the fixed‐bed reactor (FBR) and slurry continuous stirred tank reactor (CSTR) under different CO conversions by fixing other process parameters, for example, reaction temperature (300°C), syngas ratio (2), and total pressure (3 MPa). The CO conversion is more sensitive in responding to the decrease of gas hour space velocity in FBR than that in CSTR. The intra‐particle diffusional limitation was much improved in the CSTR system during Fischer–Tropsch synthesis due to the smaller particle size of the catalyst. The selectivity of gasoline fraction (C5–C13) was larger in CSTR than that in FBR when it was operated at relatively higher CO conversions (65%). The FBR tends to produce higher selectivity of longer‐chain hydrocarbons than that in CSTR when the CO conversion was kept at around 22%. The increased 1‐olefin selectivity was observed in both FBR and CSTR as CO conversion decrease with the FBR being more sensitive in responding to the CO conversion variation. The CSTR is found to be more effective in increasing light olefin fraction (C2–C6) when the CO conversion varies from 22 to 65%. © 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
Thermo‐physical and kinetics parameters determination and gases emissions of self‐ignition of sieved rice husk of different sizes on a hot plate
Authors: El‐Sayed Saad A. , Khass T.M. , Mostafa Mohamed E. 
Published: May 2017

AbstractHot plate self‐ignition standard tests at constant temperature have been performed on a paddle rice husk of size 75 to 1500 μm and a sieved rice husk of sizes 75 : 106, 106 : 120, and 120 : 150 μm. Modified tests using insulated metal ring have been investigated and compared with the standard test. Gases emissions showed that CO is the main component, and its maximum percentage occurs at the maximum temperature and depends on the dust layer thickness. It was found that as the thickness of dust layer increases, the maximum temperature and its corresponding time increase. Ring with insulation showed lower maximum and ignition temperature and ignition time compared with that without insulation. The flue gases temperature and CO% and CO2% emissions were higher in case of insulated ring. Thermal and physical properties as density, thermal conductivity, heat transfer coefficient, and kinetic parameters as activation energy and frequency factor have been determined. The activation energy of the sieved husk (75 : 106, 106 : 120, 120 : 150 μm) and paddle husk was 174.76, 183.37, 189.1, and 206.1 kJ/mol, respectively. Also, (QA0) factors were 2.696 × 1014, 6.211 × 1016, 6.105 × 1019 and 3.0461 × 1016 (J/kg s), respectively. It has been noted that as the dust particle size increases, the (E) and (QA0) values increase. © 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
Syntheses and properties of the PET‐co‐PEA copolyester
Authors: Wang Lipeng , Wang Yu , Zhang Fuchen , Bai Yongping , Ding Liping 
Published: May 2017

ABSTRACTAn aliphatic‐aromatic random‐block copolyester of poly(ethylene terephthalate) (PET), and poly(enthylene adipate) (PEA), PET‐co‐PEA, was synthesized via melt polycondensation. The chemical structure of the products were characterized by two kinds of spectroscopic techniques (Fourier transform infrared and 1H‐NMR). The thermal properties of the copolyester were characterized by thermogravimetry analysis, differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscopy. It was found that the crystallization ability, melting point, glass transition temperature of the random‐block coplyester decreased apparently. Meanwhile, the tensile strength and hydrolysis performance were measured as well. The result showed that the random‐block copolyesters PET‐co‐PEA displayed excellent properties in elasticity and strength. In addition, the potential degradability was found in hydrolysis measurement. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44967.
Antioxidant and hydrophilic poly(lactic acid) fibers obtained through their modification with amines and ferulic acid
Authors: Wojciechowska Dorota , Herczyńska Lucyna , Simon Frank , Puchalski Michał , Stawski Dawid 
Published: May 2017

ABSTRACTThe ferulic acid (FA) is a natural antioxidant, abundantly present in plants, which acts as the plant's immune system. In order to take advantage of its properties, a method has been developed, which combines antioxidant FA with bio‐based biodegradable poly(lactic acid) fibers and biocompatible hydrophilic polyallylamine, enabling the production of versatile base material that could be used for active anti‐inflammatory wound dressings. The fibers are first subjected to aminolysis in order to obtain amino moieties on the surface, able to react with the molecules of FA. Next, the FA was attached to the aminolyzed fibers surface with use of 1‐ethyl‐3–(3‐dimethylaminopropyl) carbodiimide and N‐hydroxysuccinimide. The anti‐inflammatory properties of the modified fibers were assessed using 2,2‐diphenyl‐1‐picrylhydrazyl radical scavenging assay. Presence of FA on the fibers’ surface was investigated through X‐ray photoelectron spectroscopy analysis and Folin–Ciocalteu (total phenolic content) test. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45112.
Graphene nanosheets‐filled epoxy composites prepared by a fast dispersion method
Authors: Li An , Zhang Cong , Zhang Yang‐Fei 
Published: May 2017

ABSTRACTGraphene nanosheets‐filled epoxy composites (GNS/Epoxy) were prepared at different filler loading levels from 0.25 to 3.00 wt %. A fast dispersion method as short as 5 min is employed to disperse GNS in epoxy matrix, which was enough for the homogeneous dispersion of GNS with the help of high ultrasonic frequency of 100 kHz and power of 200 W and high heat treatment temperature of 70 °C. The maximum electrical conductivity and thermal conductivity of the composites achieved 0.058 S m−1 and 0.57 W m−1 K−1, respectively, with a low electrical percolation threshold of 1.50 wt %. The electrical conductivities were further predicted by percolation theory and found to agree well with the experimental results, which indicated that the graphene nanosheets dispersed very well in the matrix even at very short processing time. The results showed that the microstructures, thermal, electrical, and mechanical properties of epoxy polymer were significantly improved by adding a low amount of graphene nanosheets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45152.
Morphology and properties of electrically and rheologically percolated PLA/PCL/CNT nanocomposites
Authors: Urquijo J. , Dagréou S. , Guerrica‐Echevarría G. , Eguiazábal J. I. 
Published: May 2017

ABSTRACTPoly(lactic acid)/poly(ɛ‐caprolactone)/carbon nanotube (PLA/PCL/CNT) nanocomposites (NCs) were melt‐processed in a conventional industrial‐like twin‐screw extruder maintaining a constant PLA/PCL 80/20 wt. ratio. CNTs located in the thermodynamically favored PCL phase and, as a result, the “sea–island” morphology of the unfilled blend was replaced by a more continuous PCL dispersed phase in the ternary NCs. Rheological and electrical percolation took place at the same CNT contents (over 1.2 wt %) that TEM images suggest continuity of the PCL phase. The electrical and the low‐strain mechanical behaviors upon CNT addition were similar in the reference binary PLA/CNT and ternary PLA/PCL/CNT NCs. In the percolated NCs, the conductivity became 106–107 times higher than in the insulating compositions, while the Young modulus increased linearly upon the addition of CNT (12% increase at 4.9 wt % loading). Moreover, all the PLA/PCL/CNT NCs showed a ductile behavior (elongation at break >130%) similar to that of the unfilled PLA/PCL blend (140%), in contrast to the brittle behavior of binary PLA/CNT NCs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45265.
Bipartite Linear χ‐Consensus of Double‐Integrator Multi‐Agent Systems With Measurement Noise
Authors: Ma Cuiqin , Zhao Weiwei , Zhao Yun‐Bo 
Published: May 2017

AbstractThe bipartite consensus problem is investigated for double‐integrator multi‐agent systems in the presence of measurement noise. A distributed protocol with time‐varying consensus gain is proposed. By using tools of state transition matrix and algebraic graph theory, necessary and sufficient conditions for the designed protocol to be a mean square bipartite linear χ‐consensus protocol are given. It is shown that the signed digraph being structurally balanced and having a spanning tree are not only sufficient, but also necessary for bipartite consensus. Furthermore, the protocol is proved to be a mean square bipartite average consensus protocol if the signed graph is weight balanced.
Taking control over microbial populations: Current approaches for exploiting biological noise in bioprocesses
Authors: Delvigne Frank , Baert Jonathan , Sassi Hosni , Fickers Patrick , Grünberger Alexander , Dusny Christian 
Published: May 2017

AbstractPhenotypic plasticity of microbial cells has attracted much attention and several research efforts have been dedicated to the description of methods aiming at characterizing phenotypic heterogeneity and its impact on microbial populations. However, different approaches have also been suggested in order to take benefit from noise in a bioprocess perspective, e.g. by increasing the robustness or productivity of a microbial population. This review is dedicated to outline these controlling methods. A common issue, that has still to be addressed, is the experimental identification and the mathematical expression of noise. Indeed, the effective interfacing of microbial physiology with external parameters that can be used for controlling physiology depends on the acquisition of reliable signals. Latest technologies, like single cell microfluidics and advanced flow cytometric approaches, enable linking physiology, noise, heterogeneity in productive microbes with environmental cues and hence allow correctly mapping and predicting biological behavior via mathematical representations. However, like in the field of electronics, signals are perpetually subjected to noise. If appropriately interpreted, this noise can give an additional insight into the behavior of the individual cells within a microbial population of interest. This review focuses on recent progress made at describing, treating and exploiting biological noise in the context of microbial populations used in various bioprocess applications.
Fabrication of viable and functional pre‐vascularized modular bone tissues by coculturing MSCs and HUVECs on microcarriers in spinner flasks
Authors: Zhang Songjie , Zhou Min , Ye Zhaoyang , Zhou Yan , Tan Wen‐Song 
Published: May 2017

AbstractSlow vascularization often impedes the viability and function of engineered bone replacements. Prevascularization is a promising way to solve this problem. In this study, a new process was developed by integrating microcarrier culture and coculture to fabricate pre‐vascularized bone microtissues with mesenchymal stem cells (MSCs) and human umbilical vein endothelial cells (HUVECs). Initially, coculture medium and cell ratio between MSCs and HUVECs were optimized in tissue culture plates concerning cell proliferation, osteogenesis and angiogenesis. Subsequently, cells were seeded onto CultiSpher S microcarriers in spinner flasks and subjected to a two‐stage (proliferative‐osteogenic) culture process for four weeks. Both cells proliferated and functioned well in chosen medium and a 1 : 1 ratio between MSCs and HUVECs was chosen for better angiogenesis. After four weeks of culture in spinner flasks, the microtissues were formed with high cellularity, evenly distributed cells and tube formation ability. While coculture with HUVECs exerted an inhibitory effect on osteogenic differentiation of MSCs, with downregulated alkaline phosphatase activity, mineralization and gene expression of COLI, RUNX2 and OCN, this could be attenuated by employing a delayed seeding strategy of HUVECs against MSCs during the microtissue fabrication process. Conclusion: Collectively, this work established an effective method to fabricate pre‐vascularized bone microtissues, which would lay a solid foundation for subsequent development of vascularized tissue grafts for bone regeneration.