bluuebunny/crossref_metadata_2025_split huggingface dataset:
Surfactant‐Enhanced Adsorption of Graphene Oxide for Improved Emulsification of Oil in Water
Authors: McCoy Thomas M. , Holt Stephen A. , Rozario Ashley M. , Bell Toby D. M. , Tabor Rico F. 
Published: October 2017

AbstractGraphene oxide (GO) can be enriched at the air–water interface by the adsorption of surfactant molecules to the surfaces of the GO sheets. The synergism between the surfactant and GO is shown to be responsible for the improved interfacial performance of the composite through a subtle balance of surface charge and surface activity. The use of a photoaddressable surfactant provides a unique probe for investigating the fundamental mechanisms that control adsorption, by inducing spatiotemporal modulation of the surfactant properties by irradiation with light of certain wavelengths. Tensiometry measurements uncover the interfacial activity of the materials, whereas X‐ray reflectivity serves to independently determine the interfacial structure and composition. The ratio between the surfactant and GO appears to be the key factor controlling adsorption, with pH and salt offering additional finer control of interfacial properties. This synergism between GO sheets and a surface active small molecule surfactant is utilized to stabilize oil‐in‐water emulsions with unprecedented effectiveness.
Photothermal Surface Plasmon Resonance and Interband Transition‐Enhanced Nanocomposite Hydrogel Actuators with Hand‐Like Dynamic Manipulation
Authors: Shi Qing , Xia Hong , Li Pu , Wang Ying‐Shuai , Wang Lei , Li Shun‐Xin , Wang Gong , Lv Chao , Niu Li‐Gang , Sun Hong‐Bo 
Published: October 2017

AbstractHydrogel actuators represent a powerful tool due to their ability to capture, move, and be manipulated, which has applications in diverse fields. The development of hydrogel actuators capable of localized movement, where only a part of the whole system moves, wireless remote control, and flexible shape‐changing is critical and challenging to fulfill their potential. Here, photothermal hydrogel actuators are designed and fabricated to accomplish a precise hand‐like manipulation of encapsulating and finger‐like one‐by‐one bending by light. A thermoresponsive poly(N‐isopropylacrylamide) (PNIPAm) active layer and a non‐thermoresponsive poly(acrylamide) passive layer are combined to generate a thermal‐expansion coefficient mismatch among the interface and this energy eventually transforms into a bending motion. As an energy transformation agent, the gold nanoparticles doped in the PNIPAm hydrogel absorb the light energy and transform it into thermalenergy effectively as a result of a surface plasmon resonance electron–phonon process and intrinsic interband transitions. The resulting nanocomposite actuators exhibit flexible, reversible motions and local hand‐like finger flexion driven by either flood illumination or local irradiation. The developed programmable actuators are expected to be an attractive candidate for the next generation of “smart” soft robots.
Phosphonium Salts in Asymmetric Catalysis: A Journey in a Decade's Extensive Research Work
Authors: Golandaj Ajij , Ahmad Akil , Ramjugernath Deresh 
Published: October 2017

AbstractThe first report on a phosphonium salt as an asymmetric catalyst was published in 1997, and thereafter this area of research remained fairly dormant for almost a decade. However, the second decade (2007–2017) has recorded a significant growth in the published literature and it has now emerged as a hot topic of research. The use of phosphonium salts as a phase‐transfer catalyst has gained momentum in recent years due to their ease of availability and simple preparation technique. Most of these asymmetric phosphonium salts are derived from readily available starting materials like chiral amino acids and binaphthyl rings. With a simple modification in the basic core of these moieties, they can be used to execute a number of enantioselective organic transformations. This review presents a comprehensive overview of the historical development of catalyst design, with its necessary modification and applications in selective organic transformations.magnified image
Antimony (V) Complex Halides: Lead‐Free Perovskite‐Like Materials for Hybrid Solar Cells
Authors: Adonin Sergey A. , Frolova Lyubov A. , Sokolov Maxim N. , Shilov Gennady V. , Korchagin Denis V. , Fedin Vladimir P. , Aldoshin Sergey M. , Stevenson Keith J. , Troshin Pavel A. 
Published: October 2017

AbstractUsing bromoantimonate (V) (N‐EtPy)[SbBr6] as an example, it is demonstrated that ABX6 compounds can form perovskite‐like 3D crystalline frameworks with short interhalide contacts, enabling advanced optoelectronic characteristics of these materials. The designed compound shows an impressive performance in planar junction solar cells delivering external quantum efficiency of ≈80% and power conversion efficiency of ≈4%, thus being comparable with the conventional perovskite material MAPbBr3. The discovery of the first perovskite‐like compound ABX6 exhibiting good photovoltaic performance opens wide opportunities for rational design of novel perovskite‐like semiconductor materials for advanced electronic and photovoltaic applications.
Phase Boundary Derived Pseudocapacitance Enhanced Nickel‐Based Composites for Electrochemical Energy Storage Devices
Authors: Long Bei , Balogun Muhammad‐Sadeeq , Luo Lei , Qiu Weitao , Luo Yang , Song Shuqin , Tong Yexiang 
Published: October 2017

AbstractSeveral strategies have been employed to improve the performance of energy storage devices through the development of new electrode materials. The construction of transition metal compound composite electrodes plays an important role in promoting the performance of energy storage devices. However, understandings of and insight into how to enhance the composites properties are rarely reported. Taking nickel‐based compounds as an example, Ni3N@Ni3S2 hybrid nanosheets are reported as a high‐performance anode material for lithium‐ion batteries that delivers higher lithium storage properties than the pristine Ni3N and Ni3S2 electrodes. This demonstrates that the phase boundaries between the Ni3N and Ni3S2 may contribute additional lithium storage, which leads to a synergistic effect via the high pseudocapacitance contribution from the outstanding conductivity of Ni3N and enhanced diffusion‐controlled capacity of Ni3S2. The use of composites prepared through sulfuration of hydrothermally annealed nickel hydroxide‐based precursor provides an enhancement of the energy storage properties. These results provide an important approach for increasing the electrochemical activity of composites by the combined effect of interfacial mismatch and pseudocapacitance, as well as understandings of the mechanism of the enhancement of the composite electrode properties.
Polyion Covalency: Exotic Species from the Unexplored World of Electrostatically Shielded Molecular Ion Chemistry
Authors: Weinhold Frank 
Published: October 2017

AbstractStandard quantum chemical methods have been employed to describe a variety of kinetically stable polyionic molecular species that are trapped in appreciable potential wells by chemical bonding forces, despite powerful electrostatic opposition that challenges conventional chemical detection and characterization. The studied species are covalent or dative analogs of “anti‐electrostatic” hydrogen‐bonded (AEHB) species, all illustrating how short‐range quantum covalency can overcome the powerful “shielding” opposition of long‐range electrostatic forces to form highly charged molecular species, analogous to known neutral or singly ionic counterparts. Computational predictions of representative structural, spectroscopic, and NBO‐based electronic signatures of multiply charged analogs of common neutral species (CH3CH3, CO2, FeCO) are provided to suggest the unique material properties characteristic of this shielded domain of polyionic chemical phenomena.
Synthesis of Octaaryl Naphthalenes and Anthracenes with Different Substituents
Authors: Suzuki Shin , Itami Kenichiro , Yamaguchi Junichiro 
Published: October 2017

AbstractA synthesis of multiply arylated naphthalenes and anthracenes with eight different substituents has been accomplished. The key intermediates are tetraarylthiophene S‐oxides, which are synthesized through a method involving sequential C−H arylation and cross‐coupling from 3‐methoxythiophene, followed by oxidation of the sulfur atom. The resulting tetraarylthiophene S‐oxides can be converted into a tetraaryl benzynes or naphthalynes and then merged through [4+2] cycloaddition reaction with another tetraarylthiophene S‐oxide, thereby resulting in the programmed synthesis of octaarylnaphthalenes and octaarylanthracenes.
Discovery of a Highly Selective Cell‐Active Inhibitor of the Histone Lysine Demethylases KDM2/7
Authors: Gerken Philip A. , Wolstenhulme Jamie R. , Tumber Anthony , Hatch Stephanie B. , Zhang Yijia , Müller Susanne , Chandler Shane A. , Mair Barbara , Li Fengling , Nijman Sebastian M. B. , Konietzny Rebecca , Szommer Tamas , Yapp Clarence , Fedorov Oleg , Benesch Justin L. P. , Vedadi Masoud , Kessler Benedikt M. , Kawamura Akane , Brennan Paul E. , Smith Martin D. 
Published: October 2017

AbstractHistone lysine demethylases (KDMs) are of critical importance in the epigenetic regulation of gene expression, yet there are few selective, cell‐permeable inhibitors or suitable tool compounds for these enzymes. We describe the discovery of a new class of inhibitor that is highly potent towards the histone lysine demethylases KDM2A/7A. A modular synthetic approach was used to explore the chemical space and accelerate the investigation of key structure–activity relationships, leading to the development of a small molecule with around 75‐fold selectivity towards KDM2A/7A versus other KDMs, as well as cellular activity at low micromolar concentrations.
Colloidal Quantum Nanostructures: Emerging Materials for Display Applications
Authors: Panfil Yossef E. , Oded Meirav , Banin Uri 
Published: October 2017

AbstractColloidal semiconductor nanocrystals (SCNCs) or, more broadly, colloidal quantum nanostructures constitute outstanding model systems for investigating size and dimensionality effects. Their nanoscale dimensions lead to quantum confinement effects that enable tuning of their optical and electronic properties. Thus, emission color control with narrow photoluminescence spectra, wide absorbance spectra, and outstanding photostability, combined with their chemical processability through control of their surface chemistry leads to the emergence of SCNCs as outstanding materials for present and next‐generation displays. In this Review, we present the fundamental chemical and physical properties of SCNCs, followed by a description of the advantages of different colloidal quantum nanostructures for display applications. The open challenges with respect to their optical activity are addressed. Both photoluminescent and electroluminescent display scenarios utilizing SCNCs are described.
Simultaneous LC–MS/MS analysis of eicosanoids and related metabolites in human serum, sputum and BALF
Authors: Thakare Rhishikesh , Chhonker Yashpal S. , Gautam Nagsen , Nelson Amy , Casaburi Richard , Criner Gerard , Dransfield Mark T. , Make Barry , Schmid Kendra K. , Rennard Stephen I. , Alnouti Yazen 
Published: October 2017

AbstractThe differences among individual eicosanoids in eliciting different physiological and pathological responses are largely unknown because of the lack of valid and simple analytical methods for the quantification of individual eicosanoids and their metabolites in serum, sputum and bronchial alveolar lavage fluid (BALF). Therefore, a simple and sensitive LC–MS/MS method for the simultaneous quantification of 34 eicosanoids in human serum, sputum and BALF was developed and validated. This method is valid and sensitive with a limit of quantification ranging from 0.2 to 3 ng/mL for the various analytes, and has a large dynamic range (500 ng/mL) and a short run time (25 min). The intra‐ and inter‐day accuracy and precision values met the acceptance criteria according to US Food and Drug Administration guidelines. Using this method, detailed eicosanoid profiles were quantified in serum, sputum and BALF from a pilot human study. In summary, a reliable and simple LC–MS/MS method to quantify major eicosanoids and their metabolites was developed and applied to quantify eicosanoids in human various fluids, demonstrating its suitability to assess eicosanoid biomarkers in human clinical trials.
Erythropoietin regulates immune/inflammatory reaction and improves neurological function outcomes in traumatic brain injury
Authors: Zhou Zi‐wei , Li Fei , Zheng Zhi‐tong , Li Ya‐dan , Chen Tong‐heng , Gao Wei‐wei , Chen Jie‐li , Zhang Jian‐ning 
Published: October 2017

AbstractIntroductionTraumatic brain injury (TBI) remains a leading cause of disability and death among young people in China. Unfortunately, no specific pharmacological agents to block the progression of secondary brain injury have been approved for clinical treatment. Recently, neuroprotective effects of erythropoietin (EPO) have been demonstrated in addition to its principal function in erythropoiesis, and hence it is viewed as a potential drug for TBI. In this study, we have investigated the neuroprotective effects of EPO associated with immune/inflammatory modulation in a mouse experimental TBI model.MethodsEPO (5000 U/kg body weight, i.p.) was injected at 1 hr, 1, 2, and 3 days after TBI, and its effect on cognitive function, brain edema, immune/inflammatory cells including regulatory T cells (Tregs), neutrophils, CD3+ T cells, and microglia, cytokines including interleukin‐10 (IL‐10), transforming growth factor‐β (TGF‐β), interleukin‐1β (IL‐1β), and tumor necrosis factor‐α (TNF‐α) were evaluated at different time points after treatment.ResultsEPO treatment significantly decreased brain edema and improved cognitive function when compared to Saline‐treated mice (p < .05). EPO treatment also significantly increased Tregs level in spleen and injured brain tissue as well as significantly reduced the infiltration and activation of immune/inflammatory cells (neutrophils, CD3+T cells, and microglia) in the injured hemisphere compared to Saline‐treated control animals (p < .05). In addition, ELISA analysis demonstrated that EPO treatment increased the expression of anti‐inflammatory cytokine IL‐10, but decreased the expression of proinflammatory cytokine IL‐1β and TNF‐α in the injured brain tissue (p < .05).ConclusionsThese findings suggest that EPO could improve neurological and cognitive functional outcomes as well as regulate immune/inflammatory reaction in TBI.
Practitioners’ experiences of learning and implementing Counselling for Depression (CfD) in routine practice settings
Authors: Drewitt Leah , Pybis Joanne , Murphy David , Barkham Michael 
Published: October 2017

AbstractAimCounselling for Depression (CfD) is a person‐centred experiential therapy developed for implementation in the Improving Access to Psychological Therapies (IAPT) programme. Training in this model has been available across England since 2011. This study aims to investigate counselling practitioners’ experiences of learning the CfD model and implementing CfD in practice settings.MethodParticipants were recruited by an email sent to the British Association for Counselling and Psychotherapy's (BACP) CfD Practice Research Network (PRN). Of the 53 CfD practitioners belonging to BACP's CfD PRN, 18 participated in this mixed‐methods piece of research. All 18 participants completed an online questionnaire, and one hour follow‐up semi‐structured interviews were conducted with six of the participants.ResultsDescriptive analyses from the online questionnaire indicated a positive experience of CfD training, with practitioners indicating a positive impact on sense of self, practice and skill set. Although a degree of challenge was encountered when training in the CfD model, thematic analysis from the six semi‐structured interviews revealed factors contributing to the positives and challenges experienced on the course. Themes also revealed a predominately negative experience of CfD in practice and service settings, although this was service dependent.Conclusions and implications for practiceThe findings can inform future recruitment of trainees to CfD training programmes and the training programme itself. They can also be used to achieve greater congruence between training in CfD and the delivery of the model. Future research may need to focus on the service level factors influencing practitioners’ experiences, and whether this experience is specific to the CfD modality in IAPT.
Bifunctional Electrocatalytic Behavior of Sodium Cobalt Phosphates in Alkaline Solution
Authors: Gond Ritambhara , Sada Krishnakanth , Senthilkumar Baskar , Barpanda Prabeer 
Published: October 2017

AbstractNoble‐metal‐free, bifunctional catalysts are essential to develop high‐performance, cost‐effective water‐splitting systems. The current work explores the bifunctional electrocatalytic behavior of two sodium cobalt phosphate systems, namely, NaCoPO4 and Na2CoP2O7, prepared by solution combustion synthesis (SCS) for the first time. Formation of phase‐pure orthorhombic maricite NaCoPO4 (space group: Pnma) and orthorhombic Na2CoP2O7 (space group: Pna21) was confirmed by Rietveld refinement. The electrocatalytic activity of maricite NaCoPO4 and Na2CoP2O7 was investigated by using linear sweep voltammetry with a rotating disk electrode (RDE). The oxygen reduction reaction (ORR) activities of these sodium cobalt phosphates are comparable to Vulcan carbon black and Pt/C. Oxygen evolution reaction (OER) activity of Na2CoP2O7 is dominant compared to NaCoPO4 and Pt/C. The Tafel slope, electron‐transfer number, and stability of the sodium‐metal phosphates were calculated in different concentrations of Na+‐containing aqueous electrolyte. The bifunctional activity and good stability of the sodium cobalt phosphates stem from cobalt ions and stabilization of the catalytic centers by the phosphate frameworks. The present work demonstrates sodium cobalt phosphates as alternate cost‐effective, novel electrocatalysts for efficient OER/ORR activity in alkaline solution.
Ni‐Assisted Low Temperature Synthesis of MoCx with Enhanced HER Activity
Authors: Zhou Yajun , Huang Weimin , Zhang Xiaohua , Wang Min , Zhang Lingxia , Shi Jianlin 
Published: October 2017

AbstractHere we report a novel one‐pot approach to synthesize MoCx catalysts at much lowered temperature for hydrogen evolution reaction (HER) in acidic solution. A room‐temperature co‐precipitation reaction among Ni2+, MoO42− and 2‐methylimidazole in an aqueous solution produced a Mo−Ni−imidazole complex, which was used as the precursor to fabricate MoCx. The morphological and chemical properties of the obtained MoCx affected by calcination and other additive metal sources (like Fe, Co, Cu) were investigated in detail. We demonstrated that Ni−Mo alloying took place prior to MoCx formation during heating, which catalyzed the crystallization of MoCx at relatively low temperature. The MoCx/Ni‐650 catalyst exhibited a quite low overpotential of 172 mV at 20 mA cm−2. The high performance originates from the synergistic effect between MoCx and Ni−Mo alloy, high ratio of Mo3+/Mo2+, as well as high electrochemically active surface area and low charge‐transfer resistance. This work would open a new way to the design and fabrication of other transition‐metal carbide catalysts.
K‐Region‐Extended [c]‐Heteroannulated Pyrenes
Authors: Baumgärtner Kevin , Kirschbaum Tobias , Krutzek Fabian , Dreuw Andreas , Rominger Frank , Mastalerz Michael 
Published: October 2017

AbstractExtended fused aromatic compounds are promising materials for organic electronics. Among them, structures with five‐membered annulated rings differ from those consisting only of six‐membered carbocyclic rings. To date, fusion of five‐membered rings has been realized mainly via the [b]‐edge, and systems fused via the [c]‐edge are of low stability. Whereas linearly double [b]‐fused systems are stable, analogous [c]‐fused systems have not been described to date. Comparable to the stabilization of longer acenes by peri‐fusion, herein the synthesis of doubly [c]‐annulated systems stabilized by double peri‐fusion is described. The compounds were analyzed by X‐ray crystallography, photophysical methods, and DFT calculations to gain deeper insight into the nature of conjugation in these new systems.
Improving the Catalytic Power of the DszD Enzyme for the Biodesulfurization of Crude Oil and Derivatives
Authors: Ferreira Pedro , Sousa Sérgio F. , Fernandes Pedro A. , Ramos Maria João 
Published: October 2017

AbstractThe enhancement of the catalytic power of enzymes is a subject of enormous interest both for science and for industry. The latter, in particular, due to the vast applications enzymes can have in industrial processes, for instance in the desulfurization of crude oil, which is mandatory by law in many developed countries and is currently performed using costly chemical processes. In this work we sought to enhance the turnover rate of DszD from Rhodococcus erythropolis, a NADH‐FMN oxidoreductase responsible for supplying FMNH2 to DszA and DszC in the biodesulfurization process of crude oil, the 4S pathway. For this purpose, we replaced the wild type spectator residue of the rate limiting step of the reduction of FMN to FMNH2, a process catalysed by DszD and known to play an important role in the reaction energy profile. As replacements, we used all the naturally occurring amino acids, one at a time, using computational methodologies, and repeated the above‐mentioned reaction with each mutant. To calculate the different free energy profiles, one for each mutated model, we applied quantum mechanics/molecular mechanics (QM/MM) methods within an ONIOM scheme. The free energy barriers obtained varied between 15.1 and 29.9 kcal mol−1. Multiple factors contributed to the different ΔG values. The most relevant were electrostatic interactions and the induction of a favourable alignment between substrate and cofactor. These results confirm the great potential that chirurgic mutations have for increasing the catalytic power of DszD in relation to the wild type (wt) enzyme.
Generation of α‐Iminyl Radicals from α‐Bromo Cyclic N‐Sulfonylimines and Application to Coupling with Various Radical Acceptors Using a Photoredox Catalyst
Authors: Esumi Naoto , Suzuki Kensuke , Nishimoto Yoshihiro , Yasuda Makoto 
Published: October 2017

AbstractVisible‐light‐induced generation of α‐iminyl radicals was accomplished using α‐bromo cyclic N‐sulfonylimines and photoredox catalysts such as erythrosine B or Ru(bpy)3(PF6)2. The generated α‐iminyl radical was utilized for various radical reactions with allylation reagents, silyl enol ethers and allenyl stannane to give the corresponding coupling products. Furthermore, atom transfer radical addition (ATRA) to olefin proceeded to provide the ATRA product. This process provided a mild and efficient method for the synthesis of cyclic N‐sulfonylimine‐containing molecules that act as bioactive compounds and become the precursors in sultam synthesis.