bluuebunny/crossref_metadata_2025_split huggingface dataset:
Isolated Platinum Atoms Stabilized by Amorphous Tungstenic Acid: Metal–Support Interaction for Synergistic Oxygen Activation
Authors: Zhang Qian , Qin Xi‐Xi , Duan‐Mu Fan‐Peng , Ji Hui‐Ming , Shen Zhu‐Rui , Han Xiao‐Peng , Hu Wen‐Bin 
Published: June 2018

AbstractOxygen activation plays a crucial role in many important chemical reactions such as oxidation of organic compounds and oxygen reduction. For developing highly active materials for oxygen activation, herein, we report an atomically dispersed Pt on WO3 nanoplates stabilized by in situ formed amorphous H2WO4 out‐layer and the mechanism for activating molecular oxygen. Experimental and theoretical studies demonstrate that the isolated Pt atoms coordinated with oxygen atoms from [WO6] and water of H2WO4, consequently leading to optimized surface electronic configuration and strong metal–support interaction (SMSI). In exemplified reactions of butanone oxidation sensing and oxygen reduction, the atomic Pt/WO3 hybrid exhibits superior activity than those of Pt nanoclusters/WO3 and bare WO3 as well as enhanced long‐term durability. This work will provide insight into the origin of activity and stability for atomically dispersed materials, thus promoting the development of highly efficient and durable single atom‐based catalysts.
Tunable Mechanical Response from a Crystal Undergoing Topochemical Dimerization: Instant Explosion at a Faster Rate and Chemical Storage of a Harvestable Explosion at a Slower Rate
Authors: Ravi Arthi , Sureshan Kana M. 
Published: June 2018

AbstractStrain developed in crystals in response to stimuli causes mechanical response. Methods to tune such mechanical response is important for practical applications. Crystals of a monomer having azide and alkyne units pre‐organized in a ready‐to‐react orientation, undergo thermal topochemical dimerization and show rate‐dependent mechanical response. When the reaction rate is fast, the crystals explode violently. When the reaction rate is slow, the crystals absorb water from the surroundings contemporaneously with the reaction to form the dimer‐hydrate in a single‐crystal‐to‐single‐crystal (SCSC) manner. Crystals of the dimer‐hydrate upon dehydration also undergo explosion. Thus, at slow reaction rate, the strain gets stored in crystals by hydration and the explosion can be harvested, at will, by dehydration. Use of this rate‐dependent explosion in the automatic activation of a remedial electrical circuit in case of a sudden rise in temperature has been demonstrated.
Direct Organocatalytic Enantioselective Functionalization of SiOx Surfaces
Authors: Parkin John D. , Chisholm Ross , Frost Aileen B. , Bailey Richard G. , Smith Andrew D. , Hähner Georg 
Published: June 2018

AbstractTraditional methods to prepare chiral surfaces involve either the adsorption of a chiral molecule onto an achiral surface, or adsorption of a species that forms a chiral template creating lattices with long range order. To date only limited alternative strategies to prepare chiral surfaces have been studied. In this manuscript a “bottom‐up” approach is developed that allows the preparation of chiral surfaces by direct enantioselective organocatalytic reactions on a functionalized silicon oxide supported self‐assembled monolayer (SAM). The efficient catalytic generation of enantiomerically enriched organic surfaces is achieved using a commercially available homogeneous isothiourea catalyst that promotes an enantioselective Michael‐lactonization process upon a silicon‐oxide supported SAM functionalized with a reactive trifluoroenone group. Chiral atomic force microscopy (χ‐AFM) is used to probe the enantiomeric enrichment of the organic films by measurement of the force distributions arising from interaction of d‐ or l‐cysteine‐modified AFM tips and the organic films.
Abiotic Sequence‐Coded Oligomers as Efficient In Vivo Taggants for the Identification of Implanted Materials
Authors: Karamessini Denise , Simon‐Yarza Teresa , Poyer Salomé , Konishcheva Evgeniia , Charles Laurence , Letourneur Didier , Lutz Jean‐François 
Published: June 2018

AbstractSequence‐defined oligourethanes were tested as in vivo taggants for implant identification. The oligomers were prepared in an orthogonal solid‐phase iterative approach and thus contained a coded monomer sequence that can be unequivocally identified by tandem mass spectrometry (MS/MS). The oligomers were then included in small amounts (1 wt %) in square‐centimeter‐sized crosslinked poly(vinyl alcohol) (PVA) model films, which were intramuscularly and subcutaneously implanted in the abdomen of rats. After one week, one month, or three months of implantation, the PVA films were explanted. The rat tissues exposed to the implants did not exhibit any adverse reactions, which suggested that the taggants are not harmful and probably not leaching out from the films. Furthermore, the explanted films were immersed in methanol, as a solvent for oligourethanes, and the liquid extract was analyzed by mass spectrometry. In all cases, the oligourethane taggant was detected, and its sequence was identified by MS/MS.
Correlating the Surface Basicity of Metal Oxides with Photocatalytic Hydroxylation of Boronic Acids to Alcohols
Authors: Leow Wan Ru , Yu Jiancan , Li Bin , Hu Benhui , Li Wei , Chen Xiaodong 
Published: June 2018

AbstractPhotoredox catalysis provides opportunities in harnessing clean and green resources such as sunlight and O2, while the acid and base surface sites of metal oxides are critical for industrial catalysis such as oil cracking. The contribution of metal oxide surfaces towards photocatalytic aerobic reactions was elucidated, as demonstrated through the hydroxylation of boronic acids to alcohols. The strength and proximity of the surface base sites appeared to be two key factors in driving the reaction; basic and amphoteric oxides such as MgO, TiO2, ZnO, and Al2O3 enabled high alcohol yields, while acidic oxides such as SiO2 and B2O3 gave only low yields. The reaction is tunable to different irradiation sources by merely selecting photosensitizers of compatible excitation wavelengths. Such surface complexation mechanisms between reactants and earth abundant materials can be effectively utilized to achieve a wider range of photoredox reactions.
A Fluorooxosilicophosphate with an Unprecedented SiO2F4 Species
Authors: Han Guopeng , Lei Bing‐Hua , Yang Zhihua , Wang Ying , Pan Shilie 
Published: June 2018

AbstractThe large number and structural beauty of silicates are largely due to the variety of connection mode of SiO4 tetrahedra. SiO6 and SiF6 octahedra are also known and give rise for structural versatility of inorganic silicates. However, to date, the crystal structure of inorganic fluorooxosilicates with oxofluoride SiOxF4−x or SiOxF6−x species are unknown. Now, fluorine was successfully introduced into the silicophosphates, and the first fluorooxosilicophosphate K4Si3P2O7F12 with an unprecedented SiO2F4 species was synthesized. The existence of Si−F bonds was verified by comprehensively experimental and theoretical work. Using ab initio and bond valence calculations, the oxofluoride SiOxF6−x species is shown to be stable when oxygen atoms connect to other atoms with strong covalent interactions. This work will contribute to the structural diversity of silicate chemistry by the exploration of the new fluorooxosilicates.
Effects of Temperature and Heating Time on the Formation of Four Toxic α,β‐Unsaturated‐4‐Hydroxyaldehydes in Vegetable Oils
Authors: Liu Xiaoyu , Shoeman Don W. , Yuan Jieyao , Csallany A. Saari 
Published: June 2018

AbstractThe formation of four α,β‐unsaturated hydroxyaldehydes, 4‐hydroxy‐2‐trans‐hexenal (HHE), 4‐hydroxy‐2‐trans‐octenal (HOE), 4‐hydroxy‐2‐trans‐nonenal (HNE), and 4‐hydroxy‐2‐trans‐decenal (HDE), was detected in commercial corn, soybean, peanut, and canola oils heated for 1, 3, and 5 hours at 145, 165, and 185 °C. These four toxic aldehydes were investigated using high‐performance liquid chromatography (HPLC). These oils were selected based upon different degrees of unsaturations, especially their linoleic and linolenic acid concentrations. To select the appropriate conditions of temperatures and heating times, preliminary experiments were conducted using the thiobarbituric acid assay, which detects the formation of secondary‐oxidation products such as aldehydes and related carbonyl compounds. After various heat treatments, the formation of HHE, HOE, HNE, and HDE was detected as 2,4‐dinitrophenyl hydrazine derivatives using HPLC. In general, HHE, HOE, HNE, and HDE formation increased in all four oils with higher temperatures, longer heating times, and higher concentrations of linoleic and linolenic acids in the oils. The formation of HNE in the oils was mostly much higher than the other three 4‐hydroxyaldehyde isomers under the same conditions.
Brief Report: Interleukin‐17 Blockade With Secukinumab in Peripheral Spondyloarthritis Impacts Synovial Immunopathology Without Compromising Systemic Immune Responses
Authors: van Mens Leonieke J. J. , van de Sande Marleen G. H. , Menegatti Silvia , Chen Sijia , Blijdorp Iris C. J. , de Jong Henriette M. , Fluri Inka A. , Latuhihin Talia E. , van Kuijk Arno W. R. , Rogge Lars , Yeremenko Nataliya G. , Baeten Dominique L. P. 
Published: June 2018

ObjectiveSecukinumab (anti–interleukin‐17A [anti–IL‐17A]) is an effective therapy for ankylosing spondylitis and psoriatic arthritis, the prototypical forms of spondyloarthritis (SpA). We undertook this study to determine whether secukinumab modulates the immunopathology of target lesions without blunting systemic immune responses, using peripheral SpA as a model.MethodsTwenty patients with active peripheral SpA were included in a 12‐week open‐label trial with secukinumab (300 mg once weekly from baseline to week 4 and then every 4 weeks thereafter). Outcomes included clinical response, cytokine production by peripheral blood cells using TruCulture technology, and histologic and real‐time quantitative polymerase chain reaction analysis of synovial biopsy samples before and after treatment.ResultsAll patients completed the 12‐week study without severe adverse events (AEs) or severe treatment‐related AEs. The efficacy end point, the number of patients meeting the American College of Rheumatology 20% improvement criteria (achieving an ACR20 response) at 12 weeks, was achieved by 13 of the 20 patients, of whom 8 achieved an ACR50 response and 5 achieved an ACR70 response, with rapid and significant improvements in all clinical disease activity measures. Clinical improvement in joint counts was associated with a histologic decrease in synovial sublining macrophages (P = 0.028) and neutrophils (P = 0.004), both of which are sensitive synovial biomarkers of inflammatory response in peripheral SpA, as well as with decreased synovial expression of IL‐17A messenger RNA (mRNA) (P = 0.010) but not of tumor necrosis factor mRNA. Systemically, secukinumab treatment decreased the C‐reactive protein level and the erythrocyte sedimentation rate (both P < 0.01), and also decreased matrix metalloproteinase 3 production in the TruCulture system (P < 0.05). However, with the exception of IL‐17A itself, the capacity of peripheral blood cells to produce a broad panel of cytokines and chemokines upon stimulation with microbial antigens was not affected.ConclusionThis mechanism‐of‐action study in peripheral SpA indicates that clinical improvement with secukinumab treatment is paralleled by immunomodulation of inflamed target tissues without compromising systemic immune responses.
Pharmacokinetics and Pharmacodynamics of Curcumin in regulating anti‐inflammatory and epigenetic gene expression
Authors: Boyanapalli Sarandeep S.S. , Huang Ying , Su Zhengyuan , Cheng David , Zhang Chengyue , Guo Yue , Rao Rohit , Androulakis Ioannis P. , Kong Ah‐Ng 
Published: June 2018

AbstractChronic inflammation is a key driver of cancer development. Nitrite levels, which are regulated by inducible nitric oxide synthase (iNOS), play a critical role in inflammation. While the anti‐oxidant and anti‐inflammatory effects of curcumin, a natural product present in the roots of Curcuma longa have been studied widely, the acute pharmacokinetics (PK) and pharmacodynamics (PD) of curcumin in suppressing pro‐inflammatory markers and epigenetic modulators remain unclear. This study evaluated the PK and PD of curcumin‐induced suppression of lipopolysaccharide (LPS)‐mediated inflammation in rat lymphocytes. LPS was administered intravenously either alone or with curcumin to female Sprague–Dawley rats. Plasma samples were analysed for curcumin concentration and mRNA expression was quantified in lymphocytes. The relative gene expression of several inflammatory and epigenetic modulators was analysed. To investigate the relationship between curcumin concentration and iNOS, TNF‐α, and IL‐6 gene expression, PK/PD modeling using Jusko's indirect response model (IDR) integrating transit compartments (TC) describing the delayed response was conducted. The concentration–time profile of curcumin exhibited a bi‐exponential decline, which was well described by a two‐compartmental pharmacokinetic model. Importantly the results demonstrate that LPS induced gene expression of pro‐inflammatory markers in lymphocytes, with peak expression at approximately 3 h and curcumin suppressed the gene expression in animals administered with LPS. These effects were well captured using the IDR model and an IDR model with the transit compartments. In summary, the PK/PD modeling approach could potentially provide a robust quantitative framework for evaluating the acute anti‐inflammatory and epigenetic effects of curcumin in future clinical trials.
Ultrastructural Imaging of Salmonella–Host Interactions Using Super‐resolution Correlative Light‐Electron Microscopy of Bioorthogonal Pathogens
Authors: van Elsland Daphne M. , Pujals Sílvia , Bakkum Thomas , Bos Erik , Oikonomeas‐Koppasis Nikolaos , Berlin Ilana , Neefjes Jacques , Meijer Annemarie H. , Koster Abraham J. , Albertazzi Lorenzo , van Kasteren Sander I. 
Published: June 2018

AbstractThe imaging of intracellular pathogens inside host cells is complicated by the low resolution and sensitivity of fluorescence microscopy and by the lack of ultrastructural information to visualize the pathogens. Herein, we present a new method to visualize these pathogens during infection that circumvents these problems: by using a metabolic hijacking approach to bioorthogonally label the intracellular pathogen Salmonella Typhimurium and by using these bioorthogonal groups to introduce fluorophores compatible with stochastic optical reconstruction microscopy (STORM) and placing this in a correlative light electron microscopy (CLEM) workflow, the pathogen can be imaged within its host cell context Typhimurium with a resolution of 20 nm. This STORM‐CLEM approach thus presents a new approach to understand these pathogens during infection.
Blistering eruptions with tissue eosinophilia in a child with IgA vasculitis
Authors: Watanabe Toru , Tsukano Shinya 
Published: June 2018

Key Clinical MessageWe present a child with bullous IgA vasculitis. Because skin biopsy showed epidermal vesicles with neutrophil infiltration and leukocytoclastic vasculitis in all layers of the dermis, with IgA deposits and tissue eosinophilia, extensive dermal infiltration of neutrophils may have led to both blistering eruptions and tissue eosinophilia in our patient.
General Airbrush‐Spraying/Electrospinning Strategy for Ultrahigh Areal‐Capacity LiFePO4‐Based Cathodes
Authors: Huang Hui , Ju Xiaokang , Deng Pan , Li Shengyang , Qu Baihua , Wang Taihong 
Published: June 2018

AbstractA versatile electrode fabrication strategy based on electrospinning combined with airbrush–spraying (ECAS) is developed for the preparation of composite paper electrodes. The LiFePO4 paper electrodes (ca. 13 mg cm−2) display good cycling stability with a capacity decay of only 15 % over 300 cycles at 1 C for lithium‐ion batteries. It is also demonstrated that the ECAS technique can obtain ultrahigh areal capacities of 12.3 mAh cm−2 using electrodes with an extra‐high areal loading of LiFePO4 paper (>75 mg cm−2). A full cell is constructed with ECAS LiFePO4 paper as the cathode and ECAS Li4Ti5O12 paper as the anode.
(Co, Ni)Sn0.5 Nanoparticles Supported on Hierarchical Carbon Nitride‐Graphene‐Based Electrocatalysts for the Oxygen Reduction Reaction
Authors: Negro Enrico , Nale Angeloclaudio , Vezzù Keti , Pagot Gioele , Herve Bang Yannick , Polizzi Stefano , Colombo Massimo , Prato Mirko , Crociani Laura , Bonaccorso Francesco , Di Noto Vito 
Published: June 2018

AbstractThe synthesis of new “Pt‐free” electrocatalysts (ECs) for the oxygen reduction reaction (ORR) is reported. The ECs are characterized by a hierarchical “core‐shell” morphology; the “core” is made of graphene, that is covered by a cratered, microporous carbon nitride (CN) “shell”. The latter supports nanoparticles of M1 and Sn metals (M1=Co; Ni) in “coordination nests”. The latter are holes in the CN matrix, whose walls consist of N‐ and C‐ligands. Two groups of ECs are studied: (i) “pristine” ECs; and (ii) “activated” ECs, that are obtained from the “pristine” ECs by means of a suitable activation process (A) aimed at improving the performance in the ORR. Here, the interplay existent between (i) the chemical composition, morphology, structure and A; and (ii) the ORR performance and mechanism is investigated. The resulting insights improve the fundamental understanding of this family of ECs and open the door to the devising of new preparations of “Pt‐free” ECs for the ORR, which: (i) are stabilized by a CN matrix and; (ii) exhibit an improved performance.
Enhanced oil recovery assignment using a new strategy for clustering oil reservoirs: Application of fuzzy logics
Authors: Khojastehmehr Mohsen , Naderifar Abbas , Aminshahidy Babak 
Published: June 2018

AbstractEnhanced Oil Recovery (EOR) aims at producing more oil from low productive reservoirs. EOR is a costly process due to the time and expenses required to allocate a suitable EOR method to an oil reservoir. For this purpose, this work presents a systematic approach to incorporate past experiences into a compact system to assign the EOR process to oil reservoirs. Because the number of clusters within the reservoirs data is not known, the method proposes a novel validity index to calculate optimal number of clusters copt. Then, the data are clustered to coptcompact clusters according to their similarities, dissimilarities, rock, and fluid properties using fuzzy clustering algorithm. To decide on the EOR process to be applied to a new reservoir, this reservoir is assigned to one of the copt clusters based on similarity, and then the EOR method is chosen based on that cluster. This approach is used for available reservoirs data from different oil fields, and its effectiveness and superiority over previous methods are confirmed.
Life's Biological Chemistry: A Destiny or Destination Starting from Prebiotic Chemistry?
Authors: Krishnamurthy Ramanarayanan 
Published: June 2018

AbstractResearch into understanding the origins—and evolution—of life has long been dominated by the concept of taking clues from extant biology and extrapolating its molecules and pathways backwards in time. This approach has also guided the search for solutions to the problem of how contemporary biomolecules would have arisen directly from prebiotic chemistry on early earth. However, the continuing difficulties in finding universally convincing solutions in connecting prebiotic chemistry to biological chemistry should give us pause, and prompt us to rethink this concept of treating extant life's chemical processes as the sole end goal and, therefore, focusing only, and implicitly, on the respective extant chemical building blocks. Rather, it may be worthwhile “to set aside the goal” and begin with what would have been plausible prebiotic reaction mixtures (which may have no obvious or direct connection to life's chemical building blocks and processes) and allow their chemistries and interactions, under different geochemical constraints, to guide and illuminate as to what processes and systems can emerge. Such a conceptual approach gives rise to the prospect that chemistry of life‐as‐we‐know‐it is not the only result (not a “destiny”), but one that has emerged among many potential possibilities (a “destination”). This postulate, in turn, could impact the way we think about chemical signatures and criteria used in the search for alternative and extraterrestrial “life”. As a bonus, we may discover the chemistries and pathways naturally that led to the emergence of life as we know it.
Hierarchical MoS2/Carbon Composite Microspheres as Advanced Anodes for Lithium/Sodium‐Ion Batteries
Authors: Tang Wangjia , Wang Xiuli , Zhong Yu , Xie Dong , Zhang Xuqing , Xia Xinhui , Wu Jiangbo , Gu Changdong , Tu Jiangping 
Published: June 2018

AbstractIt is crucial to design advanced electrodes with large Li/Na‐ion storage capacities for the development of next‐generation battery systems. Herein, hierarchical MoS2/C composite microspheres were constructed by facile template‐free self‐assembly sulfurization plus post‐carbonization. Cross‐linked MoS2 nanosheets and outer carbon layer are organically combined together to form composite microspheres with diameters of 400–500 nm. Due to enhanced electrical conductivity and good structural stability, the MoS2/C composite microspheres exhibit substantially improved Li/Na‐ion storage performance. Compared to unmodified MoS2, MoS2/C composite microspheres deliver higher Li/Na‐ion storage capacity (Li+: 1017 mA h g−1 at 100 mA g−1 and Na+: 531 mA h g−1 at 100 mA g−1), as well as better rate capability (Li+: 434 mA h g−1 at 1 Ag−1 and Na+: 102 mA h g−1 at 1 Ag−1) and capacity retention (Li+: 902 mA h g−1 after 200 cycles and Na+: 342 mA h g−1 over 100 cycles). The superior Li/Na‐ion storage performance is mainly attributed to the unique porous microsphere architecture with increased electrode/electrolyte interfaces and more diffusion paths for Li/Na ion insertion. Additionally, the carbon coating can not only improve the electronic conductivity, but also suppress the shuttle effect of polysulfides.
High prevalence of occult heart disease in normotensive patients with rheumatoid arthritis
Authors: Cioffi Giovanni , Ognibeni Federica , Dalbeni Andrea , Giollo Alessandro , Orsolini Giovanni , Gatti Davide , Rossini Maurizio , Viapiana Ombretta 
Published: June 2018

BackgroundDue to chronic inflammatory status, rheumatoid arthritis (RA) patients are exposed to changes in left ventricular (LV) geometry and function. We assessed prevalence, factors associated with, and prognostic role of concentric LV geometry and systolic dysfunction (LVSD) detected by echocardiography in a large cohort of patients with RA and normal blood pressure.HypothesisChanges in LV geometry and function are widely detectable in normotensive patients with RA analyzed in primary prevention.MethodsWe prospectively analyzed 194 normotensive RA patients without overt cardiac disease recruited between March 2014 and May 2016, compared with 194 non‐RA matched controls. Relative wall thickness >0.43 defined concentric LV geometry. LVSD was defined as impaired global longitudinal strain (GLS). The prespecified study endpoints were all‐cause hospitalization and hospitalization for cardiovascular cause.ResultsThe 194 normotensive subjects (mean age, 54 years; 63% female; RA duration 13 years) had a prevalence of LV concentric geometry 5‐fold higher and LVSD 5‐fold higher than non‐RA matched controls. Body mass index, LVSD, and diastolic dysfunction were associated with concentric LV geometry, while worsening renal function and older age were associated with LVSD. LVSD was independently related to the study endpoints (HR 2.37 [1.24‐4.53], p = 0.009, for all‐causes hospitalization and HR 6.60 [1.47‐29.72], p = 0.01 for cardiovascular hospitalization).ConclusionsDespite normotensive status, a consistent proportion of RA patients analyzed in primary prevention have cardiac abnormalities detectable by echocardiography. LVSD is a strong prognosticator of adverse outcome at midterm period in these patients.