bluuebunny/crossref_metadata_2025_split huggingface dataset:
Unlocking the Electrocatalytic Activity of Antimony for CO2 Reduction by Two‐Dimensional Engineering of the Bulk Material
Authors: Li Fengwang , Xue Mianqi , Li Jiezhen , Ma Xinlei , Chen Lu , Zhang Xueji , MacFarlane Douglas R. , Zhang Jie 
Published: October 2017

AbstractTwo‐dimensional (2D) materials are known to be useful in catalysis. Engineering 3D bulk materials into the 2D form can enhance the exposure of the active edge sites, which are believed to be the origin of the high catalytic activity. Reported herein is the production of 2D “few‐layer” antimony (Sb) nanosheets by cathodic exfoliation. Application of this 2D engineering method turns Sb, an inactive material for CO2 reduction in its bulk form, into an active 2D electrocatalyst for reduction of CO2 to formate with high efficiency. The high activity is attributed to the exposure of a large number of catalytically active edge sites. Moreover, this cathodic exfoliation process can be coupled with the anodic exfoliation of graphite in a single‐compartment cell for in situ production of a few‐layer Sb nanosheets and graphene composite. The observed increased activity of this composite is attributed to the strong electronic interaction between graphene and Sb.
Small Molecules Drive Big Improvements in Immuno‐Oncology Therapies
Authors: Huck Bayard R. , Kötzner Lisa , Urbahns Klaus 
Published: October 2017

AbstractImmuno‐oncology therapies have the potential to revolutionize the armamentarium of available cancer treatments. To further improve clinical response rates, researchers are looking for novel combination regimens, with checkpoint blockade being used as a backbone of the treatment. This Review highlights the significance of small molecules in this approach, which holds promise to provide increased benefit to cancer patients.
Induction of Single‐Handed Helicity of Polyacetylenes Using Mechanically Chiral Rotaxanes as Chiral Sources
Authors: Ishiwari Fumitaka , Nakazono Kazuko , Koyama Yasuhito , Takata Toshikazu 
Published: October 2017

AbstractEffective induction of preferred‐handed helicity of polyacetylenes by pendant mechanically chiral rotaxanes is discussed. Polyacetylenes possessing optically active mechanically chiral rotaxanes in the side chains were synthesized by the polymerization of the corresponding enantiopure [2]rotaxane‐type ethynyl monomers prepared by the chiral‐phase HPLC separations. The CD Cotton effects revealed that the polyacetylenes took preferred‐handed helical conformations depending on the rotaxane chirality. The preferred‐handed helix was not disturbed by an additional chiral substituent on the rotaxane side chain. These results demonstrate the significance and utility of mechanically chiral rotaxanes for the effective construction of asymmetric fields.
Hepatocellular uptake of cyclodextrin‐complexed curcumin during liver preservation: A feasibility study
Authors: Saidi Saber Abdelkader , Meurisse Nicolas , Jochmans Ina , Heedfeld Veerle , Wylin Tine , Parkkinen Jaakko , Pirenne Jacques , Monbaliu Diethard , El Feki Abdelfattah , van Pelt Jos 
Published: October 2017

AbstractThe increasing demand for donor organs and the decreasing organ quality is prompting research toward new methods to reduce ischemia reperfusion injury (IRI). Several strategies have been proposed to protect preserved organs from this injury. Before curcumin/dextrin complex (CDC), a potent antioxidant and anti‐inflammatory agent, can be used clinically we need to better understand the intracellular uptake under hypothermic conditions on a rat model of liver donation after circulatory death (DCD) and brain death (DBD). To be able to use the fluorescence of CDC for quantification the stability of CDC in different preservation solutions at 4°C or 37°C was investigated. Livers from Wistar rats were procured after being flushed‐out through the portal vein using CDC‐enriched preservation solutions and stored at 4°C for variable periods. The CDC signal was stable in different preservation solutions over a period of 4 h and allowed the rapid and lasting uptake of curcumin into cells. After 4 h of preservation, CDC was no longer visible microscopically, and HPLC analysis showed very low to non‐detectable tissue levels of CDC, proving metabolization during preservation. However, the distribution of CDC was not affected by warm ischemia damage (p = 0.278) nor by flushing the livers before or after 4 h of cold storage and without a warm preflush. Finally, curcumin reduced oxidative stress, lowered histological injury and did not change gene expression after WI/cold storage. Therefore, the use of CDC flush solution for the initial organ flush can offer a promising approach to the enhancement of liver preservation and the maintenance of its quality.
Genomic Studies Reveal New Aspects of the Biology of DNA Damaging Agents
Authors: Gillingham Dennis , Sauter Basilius 
Published: October 2017

AbstractA flurry of papers has appeared recently to force a rethinking of our understanding of how chemicals, light, and metal complexes damage our genomes. Conventional wisdom was that damaging agents were indiscriminate and it was statistical bad luck, coupled with evolutionary selection, that drove mutational signatures after exposure of DNA to damaging agents. Recent data, however, suggests that primary DNA damage itself does not drive mutational signatures; instead, it is the selectivity of repair pathways on different regions of the genome that is decisive. In particular, genomic regions shielded by transcription factors or packed densely in nucleosomes are poorly repaired by nucleotide excision repair and are far more susceptible to mutation. There are plenty of approved therapies, the mode‐of‐action of which is to alkylate DNA, and although historically efforts have been focused on understanding how chemicals modify DNA, these new findings suggest that focus should be shifted to understanding genome‐wide repair specificities when different types of alkylation damage occur.
Rational design strategy for optimization of clamping pressure to minimize contact resistance between electrode and current collector while preserving porosity of electrodes in water electrolyzers
Authors: Kishor Koshal , Parashtekar Alhad , Saha Sulay , Sivakumar Sri , Ramkumar Janakaraman , Pala Raj Ganesh S. 
Published: October 2017

AbstractThe compressive clamping pressure at the interface of gas‐diffusion‐layer (GDL) and current collector decreases the contact resistance between them though it reduces the porosity and surface roughness of electrocatalysts, which would in turn decrease the efficiency of an electrolyzer. We explore these issues of trade‐off between porosity versus contact resistance and provide a design heuristic for optimum clamping pressure. The present work provides an estimate of the optimal value of clamping pressure for an alkaline water electrolyzer having membrane electrode assembly (MEA), taking account of the variation in porosity of catalyst layers and contact resistance obtained via half‐cell studies performed at different pressures. Towards this, we define the performance‐index (Φ) which is the ratio of Faradaic current density and resistances resulting from contact‐interfaces in electrolyzers and we suggest that the maxima in Φ corresponds to optimum clamping pressure.
Gold Nanoparticles on Polymer‐Wrapped Carbon Nanotubes: An Efficient and Selective Catalyst for the Electroreduction of CO2
Authors: Jhong Huei‐Ru “Molly” , Tornow Claire E. , Kim Chaerin , Verma Sumit , Oberst Justin L. , Anderson Paul S. , Gewirth Andrew A. , Fujigaya Tsuyohiko , Nakashima Naotoshi , Kenis Paul J. A. 
Published: October 2017

AbstractMultiple approaches will be needed to reduce the atmospheric CO2 levels, which have been linked to the undesirable effects of global climate change. The electroreduction of CO2 driven by renewable energy is one approach to reduce CO2 emissions while producing chemical building blocks, but current electrocatalysts exhibit low activity and selectivity. Here, we report the structural and electrochemical characterization of a promising catalyst for the electroreduction of CO2 to CO: Au nanoparticles supported on polymer‐wrapped multiwall carbon nanotubes. This catalyst exhibits high selectivity for CO over H2: 80–92 % CO, as well as high activity: partial current density for CO as high as 160 mA cm−2. The observed high activity, originating from a high electrochemically active surface area (23 m2 g−1 Au), in combination with the low loading (0.17 mg cm−2) of the highly dispersed Au nanoparticles underscores the promise of this catalyst for efficient electroreduction of CO2.
Influence of the Anion on the Oxidation of 5‐Hydroxymethylfurfural by Using Ionic‐Polymer‐Supported Platinum Nanoparticle Catalysts
Authors: Siankevich Sviatlana , Mozzettini Simone , Bobbink Felix , Ding Shipeng , Fei Zhaofu , Yan Ning , Dyson Paul J. 
Published: October 2017

AbstractPlatinum nanoparticles stabilized by an imidazolium‐based cross‐linked polymer (with chloride as the counteranion) efficiently catalyzed the oxidation of 5‐hydroxymethylfurfural to form 2,5‐furandicarboxylic acid in water under mild conditions with oxygen as the oxidant. This catalyst system is explored herein by varying the counteranion, that is, replacing chloride by BF4−, PF6−, bis(trifluoromethylsulfonyl)imide, hexanoate, or laurate anions, in the cationic polymer. The counteranion influences the structure of the obtained platinum nanoparticles, the surface electronic properties, and their catalytic activity. The highest reaction rates were obtained with the weakly nucleophilic bis(trifluoromethylsulfonyl)imide anion, which also favored platinum in the zero oxidation state, leading to complete conversion of the substrate and a high yield of 2,5‐furandicarboxylic acid under mild conditions.
Designing CdS Mesoporous Networks on Co‐C@Co9S8 Double‐Shelled Nanocages as Redox‐Mediator‐Free Z‐Scheme Photocatalyst
Authors: Reddy D. Amaranatha , Park Hanbit , Gopannagari Madhusudana , Kim Eun Hwa , Lee Seunghee , Kumar D. Praveen , Kim Tae Kyu 
Published: October 2017

AbstractDesigning porous nanostructures with unprecedented functionalities and an effective ability to harvest the maximum energy region of the solar spectrum and suppress the charge‐carrier recombination rate offers promising potential for sustainable energy production. Although several functional porous nanostructures have been developed, high‐efficiency materials are still needed. Herein, we report a new, highly active, noble‐metal‐free, and redox‐mediator‐free Z‐scheme photocatalyst, CdS/Co‐C@Co9S8, for H2 production through water splitting under solar irradiation. The designed photocatalytic system contains open 3 D CdS mesopores as a light absorber for wider solar‐light harvesting. Metal–organicframework‐derived cobalt nanocrystal‐embedded few‐layered carbon@Co9S8 double‐shelled nanocages were used as a co‐semiconductor to hamper the photo charge‐carrier recombination by accelerating the photogenerated electrons and holes from the other semiconductor. The optimized catalyst shows a H2 evolution rate of 26.69 mmol g−1 h−1 under simulated solar irradiation, which is 46 times higher than that of the as‐synthesized CdS mesoporous nanostructures. The apparent quantum yield reached 7.82 % at λ=425 nm in 5 h. The outstanding photocatalytic activity of CdS/Co‐C@Co9S8 reflects the favorable suppression of the charge‐carrier recombination rate, as determined by photoluminescence, photocurrent, and impedance analyses. We believe that the findings reported here may inspire the design of new noble‐metal‐free porous nanohybrids for sustainable H2 production.
Flower‐Like Nickel Phosphide Microballs Assembled by Nanoplates with Exposed High‐Energy (0 0 1) Facets: Efficient Electrocatalyst for the Hydrogen Evolution Reaction
Authors: Wang Honglei , Xie Ying , Cao Hongshuai , Li Yanchao , Li Lin , Xu Zhikun , Wang Xiuwen , Xiong Ni , Pan Kai 
Published: October 2017

AbstractThe fabrication of low‐cost and earth‐abundant electrocatalysts for the hydrogen evolution reaction (HER) over a broad pH range is attractive. In this work, a facile precursor route is developed to synthesize flower‐like nickel phosphide microballs with a diameter of approximately 12 μm. With a controlled phosphorization temperature, flower‐like nickel phosphide microballs with different crystalline structures (Ni5P4 and Ni2P) were obtained easily. Flower‐like Ni5P4 microballs possessed two advantageous features for enhanced HER: fast vectorial electron transfer path along the building block nanoplates and enhanced inherent catalytic activity of each active site for high‐energy (0 0 1) facets. The flower‐like Ni5P4 microballs electrocatalyst thus displayed excellent activity for the HER with a low overpotential (η) of 35.4 mV to reach current densities of 10 mA cm−2 and a small Tafel slope of 48 mV dec−1 in acid solution. In addition, it showed excellent activity in 1 m KOH with η=47 mV at 10 mA cm−2. DFT studies indicated that the free energy of hydrogen adsorbed on the Ni site of Ni5P4 was 0.152 eV, which is smaller than that of the Ni site of Ni2P (0.182 eV). Therefore, flower‐like Ni5P4 microballs exhibited better HER activity than Ni2P, which is consistent with our HER data. This hierarchical structure with exposed high‐energy (0 0 1) facets paves the way to design and synthesize low‐cost, high‐performance catalysts for the HER.
Peripheral Blood Mononuclear Cell Immunophenotyping in Fibrodysplasia Ossificans Progressiva Patients: Evidence for Monocyte DNAM1 Up‐regulation
Authors: Del Zotto Genny , Antonini Francesca , Azzari Irma , Ortolani Claudio , Tripodi Gino , Giacopelli Francesca , Cappato Serena , Moretta Lorenzo , Ravazzolo Roberto , Bocciardi Renata 
Published: October 2017

BackgroundFibrodysplasia ossificans progressiva (FOP) is a rare genetic disorder caused by sporadic heterozygous mutations inACVR1gene which progressively leads to severe heterotopic ossification. FOP is characterized by episodic flare‐ups triggered by different factors such as viral infections, tissue injuries, vaccinations, or occurring without a recognizable cause. The sporadic course of the disease, the documented presence of an important inflammatory reaction in early lesions and the partial response to corticosteroids support the idea that the immune system, and in particular the innate component, may play a role in FOP pathogenesis. However, an extensive expression profile of the peripheral blood mononuclear cells (PBMC) of FOP patients has never been done.MethodsIn this study, we carried out a wide PBMC immunophenotyping on a cohort of FOP patients and matching controls by multiparametric analysis of the expression of a panel of 37 markers associated with migration, adhesion, inhibition, activation, and cell death of circulating immune cells.ResultsWe observed a statistically significant increase of the expression of DNAM1 receptor in patients' monocytes as compared to controls, and little but significant differences in the expression profile of CXCR1 (CD181), CD62L, CXCR4 (CD184), and HLA‐DR molecules.ConclusionsDNAM1 had been previously shown to play a pivotal role in monocyte migration through the endothelial barrier and the increased expression detected in patients' monocytes might suggest a role of this surface receptor during the early phases of FOP flare‐ups in which the activation of the immune response is believed to represent a crucial event. © 2017 International Clinical Cytometry Society
LEF‐1: Diagnostic utility in distinguishing basaloid neoplasms of the salivary gland
Authors: Schmitt Alessandra C. , Griffith Christopher C. , Cohen Cynthia , Siddiqui Momin T. 
Published: October 2017

BackgroundLymphoid enhancer binding factor 1 (LEF‐1) has recently been reported as a potential immunohistochemical (IHC) marker for basal cell adenoma (BCA) and other salivary gland tumors, which may contribute to an increased accuracy in differentiating basaloid salivary gland neoplasms. We evaluated the utility of LEF‐1 in fine needle aspiration (FNA) and resection specimens to distinguish pleomorphic adenoma (PA), BCA, basal cell adenocarcinoma (BCAC), and adenoid cystic carcinoma (ACC) as well as in non‐neoplastic salivary gland (NNSG).MethodsCases including 66 PA (35 FNA, 31 resections), 12 BCA (5 FNA, 7 resections), 42 ACC (11 FNA, 31 resections), 1 BCAC FNA, and 10 NNSG (5 FNA, 5 resections) were obtained and stained for LEF‐1.ResultsOn cell block (CB), 51% of PA and 60% of BCA were LEF‐1 positive while 91% of ACC were LEF‐1 negative. Among resections, there was a higher percentage of LEF‐1 positive PA (84%) and BCA (86%), and a higher percentage of LEF‐1 negative ACC (97%). LEF‐1 staining had a low to moderate sensitivity for detecting benign basaloid neoplasms on FNA CB and resection specimens (52.5% and 84%, respectively), but a higher specificity (92% and 97% respectively), and positive predictive value (95% and 97% respectively).ConclusionWhen comparing benign (PA and BCA) and the most common malignant basaloid salivary gland tumor (ACC), positive LEF‐1 favors a benign neoplasm. Additional studies with LEF‐1, specifically including other rare basaloid salivary gland neoplasms are needed to further clarify the role of LEF‐1 in diagnosing these lesions on FNA.
Environmental proteomics reveals taxonomic and functional changes in an enriched aquatic ecosystem
Authors: Northrop Amanda C. , Brooks Rachel K. , Ellison Aaron M. , Gotelli Nicholas J. , Ballif Bryan A. 
Published: October 2017

AbstractAquatic ecosystem enrichment can lead to distinct and irreversible changes to undesirable states. Understanding changes in active microbial community function and composition following organic matter loading in enriched ecosystems can help identify biomarkers of such state changes. In a field experiment, we enriched replicate aquatic ecosystems in the pitchers of the northern pitcher plant, Sarracenia purpurea. Shotgun metaproteomics using a custom metagenomic database identified proteins, molecular pathways, and contributing microbial taxa that differentiated control ecosystems from those that were enriched. The number of microbial taxa contributing to protein expression was comparable between treatments; however, taxonomic evenness was higher in controls. Functionally active bacterial composition differed significantly among treatments and was more divergent in control pitchers than in enriched pitchers. Aerobic and facultative anaerobic bacteria contributed most to identified proteins in control and enriched ecosystems, respectively. The molecular pathways and contributing taxa in enriched pitcher ecosystems were similar to those found in larger enriched aquatic ecosystems and are consistent with microbial processes occurring at the base of detrital food webs. Detectable differences between protein profiles of enriched and control ecosystems suggest that a time series of environmental proteomics data may identify protein biomarkers of impending state changes to enriched states.
Characterization of a novel capsaicin/heat ongoing pain model
Authors: Price R.C. , Gandhi W. , Nadeau C. , Tarnavskiy R. , Qu A. , Fahey E. , Stone L. , Schweinhardt P. 
Published: October 2017

AbstractBackgroundHuman experimental pain models provide an important translational link between pre‐clinical models and clinical pain. Using topical capsaicin and continuous heat application, the novel capsaicin/heat ongoing pain (CHOP) model induces long‐lasting experimental pain of which the perceived intensity can be individually adjusted.MethodsIn the CHOP model, capsaicin or control cream is applied to a 10 × 10 cm skin area and a heating pad is applied over the area after cream removal. Two experiments in healthy participants were performed for model characterization. In Experiment 1, a constant temperature was applied for 60 min; in Experiment 2, temperature was adjusted to maintain a constant perceived intensity for 60 min.ResultsExperiment 1: across participants, constant temperature induced initial habituation followed by an increase in sensation back to baseline. Cluster analysis revealed that half the participants sensitized to the constant temperature, while the other half did not. The degree of sensitization was related to the baseline pain unpleasantness, relative to pain intensity. Experiment 2: constant perceived intensity was achieved in the painful and a non‐painful control condition. The two conditions did not differ regarding possibly confounding variables, including blood pressure, heart rate, inflammation or physiological stress as measured by surrogate markers. Secondary allodynia and hyperalgesia were reported more following painful compared to control stimulation. Sensitizers as determined in Experiment 1 were also more pain sensitive in Experiment 2.ConclusionThe CHOP model reproduces some aspects of clinical pain, such as longer duration, sensitization, secondary allodynia and hyperalgesia.SignificanceHere we demonstrate a novel pain model that can be applied for up to an hour without tissue damage. The CHOP model allows for investigation of primary and secondary hyperalgesia as well as top‐down influences on sensitization, thereby providing an experimental model that can be used to assess clinically‐oriented questions.
Copper‐based Metal‐organic Framework Applied in the Development of an Electrochemical Biomimetic Sensor for Catechol Determination
Authors: Brondani Daniela , Zapp Eduardo , da Silva Heying Renata , de Souza Bernardo , Cruz Vieira Iolanda 
Published: October 2017

AbstractIn this study, the synthesis and characterization of a Cu‐based metal‐organic framework (MOF) [Cu3(BTC)2(H2O)3]n (where BTC=benzene‐1,3,5‐tricarboxylate), known as HKUST‐1, were performed. The Cu‐MOF was applied in the modification of a carbon paste to obtain a biomimetic sensor for the electrochemical determination of catechol. Kinetic assays confirmed that the Cu‐MOF acts as a catalyst for the oxidation of catechol and it can be considered as a catechol oxidase mimetic. Under optimized conditions, the calibration curve for catechol presented a linear range of 8.0×10−7 to 3.2×10−5 mol L−1, with detection limit of=1.0×10−7 mol L−1. The sensor demonstrated good intra‐day repeatability and inter‐electrode reproducibility (relative standard deviations of 3.8 % (n=10) and 4.3 % (n=6), respectively). In the selectivity study, an adequate peak‐to‐peak separation was observed for hydroquinone and uric acid in relation to catechol, demonstrating that this sensor has the potential for use in the simultaneous determination of these compounds. This sensor was successfully applied in the determination of catechol in water samples.