bluuebunny/crossref_metadata_2025_split huggingface dataset:
Structure and Reactivity of an Asymmetric Synthetic Mimic of Nitrogenase Cofactor
Authors: Tanifuji Kazuki , Sickerman Nathaniel , Lee Chi Chung , Nagasawa Takayuki , Miyazaki Kosuke , Ohki Yasuhiro , Tatsumi Kazuyuki , Hu Yilin , Ribbe Markus W. 
Published: November 2016

AbstractThe Mo nitrogenase catalyzes the ambient reduction of N2 to NH3 at its M‐cluster site. A complex metallocofactor with a core composition of [MoFe7S9C], the M‐cluster, can be extracted from the protein scaffold and used to facilitate the catalytic reduction of CN−, CO, and CO2 into hydrocarbons in the isolated state. Herein, we report the synthesis, structure, and reactivity of an asymmetric M‐cluster analogue with a core composition of [MoFe5S9]. This analogue, referred to as the Mo‐cluster, is the first synthetic example of an M‐cluster mimic with Fe and Mo positioned at opposite ends of the cluster. Moreover, the ability of the Mo‐cluster to reduce C1 substrates to hydrocarbons suggests the feasibility of developing nitrogenase‐based biomimetic approaches to recycle C1 waste into fuel products.
Enhanced Hydrogen Evolution under Simulated Sunlight from Neutral Electrolytes on (ZnSe)0.85(CuIn0.7Ga0.3Se2)0.15 Photocathodes Prepared by a Bilayer Method
Authors: Kaneko Hiroyuki , Minegishi Tsutomu , Nakabayashi Mamiko , Shibata Naoya , Domen Kazunari 
Published: November 2016

AbstractA (ZnSe)0.85(CuIn0.7Ga0.3Se2)0.15 photocathode with a bilayer structure was fabricated and found to exhibit a photocurrent almost twice that of a photocathode with a monolayer structure during hydrogen evolution from water. The cathodic photocurrent reached maximum values of 12 and 4.9 mA cm−2 at 0 and 0.6 VRHE in a neutral phosphate buffer under simulated sunlight, while the half‐cell solar‐to‐hydrogen conversion efficiency was 3.0 % at 0.6 VRHE, with a maximum value of 3.6 % at 0.45 VRHE. Cross‐sectional mapping of the electron‐beam‐induced current established that the increased photocurrent can be attributed to improved uniformity at the solid–liquid junction in the bilayer sample, which results in enhanced carrier collection.
Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide
Authors: Fabini Douglas H. , Stoumpos Constantinos C. , Laurita Geneva , Kaltzoglou Andreas , Kontos Athanassios G. , Falaras Polycarpos , Kanatzidis Mercouri G. , Seshadri Ram 
Published: November 2016

AbstractThe structure of the hybrid perovskite HC(NH2)2PbI3 (formamidinium lead iodide) reflects competing interactions associated with molecular motion, hydrogen bonding tendencies, thermally activated soft octahedral rotations, and the propensity for the Pb2+ lone pair to express its stereochemistry. High‐resolution synchrotron X‐ray powder diffraction reveals a continuous transition from the cubic α‐phase (Pm
m, #221) to a tetragonal β‐phase (P4/mbm, #127) at around 285 K, followed by a first‐order transition to a tetragonal γ‐phase (retaining P4/mbm, #127) at 140 K. An unusual reentrant pseudosymmetry in the β‐to‐γ phase transition is seen that is also reflected in the photoluminescence. Around room temperature, the coefficient of volumetric thermal expansion is among the largest for any extended crystalline solid.
Quiescent crystallization of poly(lactic acid) studied by optical microscopy and light‐scattering techniques
Authors: Lohmeijer P. J. A. , Goossens J. G. P. , Peters G. W. M. 
Published: November 2016

ABSTRACTThe crystallization behavior of poly(lactic acid) (PLA) has been studied extensively, and this has resulted in different reported values for the nucleation densities (Ns) and crystal growth rates (Gs) for similar grades. These inconsistencies may be magnified when they are used in subsequent modeling studies. Therefore, the quiescent crystallization behaviors of three PLA grades were studied with polarized optical microscopy and small‐angle light‐scattering experiments. The Gs and Ns were determined at several isothermal crystallization temperatures with a device that provided near‐instantaneous cooling to the isothermal crystallization temperature. Two growth rate regimes, which were attributed to α and α′ crystallization with a transition around 120 °C, were observed. Avrami analysis revealed that the poly(l‐lactic acid) homopolymer crystal growth was three‐dimensional and was unaffected by the presence of stereocomplex PLA. The PLA copolymer crystals had a transition from an initial sheaflike conformation to three‐dimensional growth. Furthermore, the lamellar twisting of the homopolymer was observed at the isothermal crystallization temperature around 144 °C. These findings can be used for future modeling studies to predict material behavior in various industrial processes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44566.
Removal of nitrogen containing reducing agents from water coolant systems using ion exchange resin and membranes
Authors: Padmakumari T. V. , Jacob Kaleekkal Noel , Mohan D. , Velmurugan S. 
Published: November 2016

ABSTRACTOxidizing environment prevailing in water coolant systems aggravates the corrosion of structural materials. Reducing agents are added to the reactor coolant systems to control the oxidants and mitigate material corrosion. Maintenance of required concentration of the reducing agents in the system and their removal after completing the processes can be done using ion exchange resins as well as ion exchange membranes. In this article, a comparative study on the efficacy in removing the reducing agents from aqueous solutions by the cation exchange resin and membranes such as sulfonated polysulfone and nafion is evaluated. Some of the membranes were synthesized in the laboratory and characterized by SEM, FTIR and pure water flux studies. Nitrogen containing reducing agents such as hydrazine, hydroxylamine, and ammonium hydroxide have been chosen for the study. Results indicate that strong acid cation exchange (SAC) resin taken in a column and sulfonated polysulfone (SPSf) membrane as a stack are found to be equally efficient in purification of coolant system from the added reducing agents. Uptake of metal ions was observed to be higher on SAC resin column in presence of reducing agent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44588.
Thermomechanical and cyclic behavior of biocomposites based on renewable thermoplastics from dimer fatty acids
Authors: Reulier M. , Matadi Boumbimba R. , Walsh Korb Z. , Vaudemont R. , Avérous L. 
Published: November 2016

ABSTRACTMicrobiocomposites based on renewable thermoplastic matrices such as thermoplastic polyurethane (TPU) and polyamide (DAPA), synthesized from dimer fatty acids, and high aspect ratio talc were prepared. TPU/DAPA blends and their corresponding biocomposites exhibited mechanical behavior, which is linked to those of the matrices and their relative contents, i.e., going from a typical semicrystalline behavior (DAPA) to an elastomeric one (TPU). The understanding of the thermomechanical and cyclic behavior of these advanced materials, particularly for TPU/DAPA with high TPU content, is detailed. Addition of particles of high aspect ratio natural talc (HAR) improved the storage modulus over the whole temperature range (almost five times with 5 wt % HAR). Under cyclic manipulation, the biocomposites displayed a stress softening related to the Mullins' effect. An increase of the hysteresis and the residual deformation with the HAR content has been shown. The hyperelastic models of Mooney–Rivlin and Ogden–Dorfmann, used to predict the loading and unloading behavior, fitted with experimental data. The present work also reports the experimental characterization of the deformation mechanisms of these renewable biocomposites through different microscopic techniques at different scales, such as atomic force, scanning electron and transmission electron microscopies. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44610.
Progressive Decline of Lung Function in Rheumatoid Arthritis–Associated Interstitial Lung Disease
Authors: Zamora‐Legoff Jorge A. , Krause Megan L. , Crowson Cynthia S. , Ryu Jay H. , Matteson Eric L. 
Published: November 2016

ObjectiveInterstitial lung disease (ILD) is associated with substantial morbidity in rheumatoid arthritis (RA), but very little is known about its long‐term progression. This study was undertaken to investigate the progression of pulmonary disease using a large single‐center cohort of patients with RA‐associated ILD.MethodsRecords of all patients with RA‐associated ILD seen at Mayo Clinic between 1998 and 2014, with at least 4 weeks follow‐up and at least 1 pulmonary function test, were identified and manually screened for study inclusion. Progression was defined as a diffusing capacity for carbon monoxide (DLco) <40% predicted (or patients whose illness was too advanced to undergo screening) or a forced vital capacity (FVC) <50% predicted. Time to progression was analyzed using the Kaplan‐Meier method.ResultsOf the 167 patients included in the study, 81 (49%) were female, with a mean ± SD age of 67 ± 10 years at diagnosis of ILD. Median follow‐up time from diagnosis of ILD was 3.3 years (range 0.01–14.8). One‐third of the patients required supplemental oxygen, 40% developed DLco <40% predicted, and 22% developed FVC <50% predicted within 5 years after ILD diagnosis. Usual interstitial pneumonia (UIP) versus nonspecific interstitial pneumonia (NSIP) was a risk factor for DLco progression (hazard ratio 3.29 [95% confidence interval 1.28–8.41]). Lower DLco and FVC at baseline increased the risk for progression to DLco <40% predicted and FVC <50% predicted, and higher rates of change in the first 6 months also increased the risk of progression.ConclusionProgressive loss of pulmonary function is common in RA‐associated ILD and is worse in patients with UIP than in those with NSIP. Predictors of progression in patients with RA‐associated ILD may aid clinicians in identifying patients at highest risk for progression of ILD.
A rapid and high‐throughput method for the determination of serum uric acid based on microarray technology and nanomaterial
Authors: Li Xiaohua , Bai Yunfeng , Feng Feng , Zhang Zhujun 
Published: November 2016

AbstractSerum uric acid (SUA) is a new therapeutic target for non‐alcoholic fatty liver disease (NAFLD). In this study, we introduced a chemiluminescence (CL) method combined with microarray technology and a simple fabrication procedure to obtain a highly sensitive SUA probe based on a mesoporous metal oxide nanomaterial. The high‐throughput method was based on the generation of H2O2 from SUA by immobilized uricase and its measurement by a CL reaction catalyzed by mesoporous metal oxide nanomaterials. The CL probe was designed for SUA The linear range of the uric acid concentration was 0.6–9 μM and the detection limit was 0.1 μM. In comparison with the other SUA detection techniques, this method has the advantages of a low detection limit, high sensitivity and simplicity. A new sensitive high‐throughput approach was obtained for the determination of SUA.
Evaluation of eco‐friendly zwitterionic detergents for enveloped virus inactivation
Authors: Conley Lynn , Tao Yinying , Henry Alexis , Koepf Edward , Cecchini Douglas , Pieracci John , Ghose Sanchayita 
Published: November 2016

ABSTRACTInclusion of a detergent in protein biotherapeutic purification processes is a simple and very robust method for inactivating enveloped viruses. The detergent Triton X‐100 has been used for many years and is part of the production process of several commercial therapeutic proteins. However, recent ecological studies have suggested that Triton X‐100 and its break‐down products can potentially behave as endocrine disrupters in aquatic organisms, raising concerns from an environmental impact perspective. As such, discharge of Triton X‐100 into the waste water treatment plants is regulated in some jurisdictions, and alternative detergents for viral inactivation are required. In this work, we report on the identification and evaluation of more eco‐friendly detergents as viable replacements for Triton X‐100. Five detergent candidates with low to moderate environmental impact were initially identified and evaluated with respect to protein stability, followed by proof‐of‐concept virus inactivation studies using a model enveloped virus. From the set of candidates lauryldimethylamine N‐oxide (LDAO) was identified as the most promising detergent due to its low ecotoxicity, robust anti‐viral activity (LRV >4 at validation set‐point conditions with X‐MuLX), and absence of any negative impact on protein function. This detergent exhibited effective and robust virus inactivation in a broad range of protein concentrations, solution conductivities, pHs, and in several different cell culture fluid matrices. The only process parameter which correlated with reduced virus inactivation potency was LDAO concentration, and then only when the concentration was reduced to below the detergent's critical micelle concentration (CMC). Additionally, this work also demonstrated that LDAO was cleared to below detectable levels after Protein A affinity chromatography, making it suitable for use in a platform process that utilizes this chromatographic mode for protein capture. All these findings suggest that LDAO may be a practical alternative to Triton X‐100 for use in protein therapeutic production processes for inactivating enveloped viruses. Biotechnol. Bioeng. 2017;114: 813–820. © 2016 Wiley Periodicals, Inc.
Clinical signs of fibrosis in small intestinal neuroendocrine tumours
Authors: Daskalakis K , Karakatsanis A , Stålberg P , Norlén O , Hellman P 
Published: November 2016

Abstract

Background
In patients with small intestinal neuroendocrine tumours (SI-NETs), serotonin and other cytokines released from tumour cells may induce fibrosis, leading to carcinoid heart disease and abdominal fibrotic reactions. The aim of this study was to assess the prevalence, clinical complications and management of this reaction in the abdomen.

Methods
This was a retrospective cohort study of patients with SI-NETs diagnosed between 1985 and 2015. Clinical data, outcomes, radiological findings, and surgical and radiological interventions were reviewed.

Results
A total of 824 patients were diagnosed with SI-NETs in the study interval. Clinically significant abdominal signs and symptoms of fibrosis occurred in 36 patients. Of these, 20 had critically symptomatic central mesenteric fibrosis causing obstruction of mesenteric vessels, and 16 had retroperitoneal fibrosis causing obstructive uropathy with hydronephrosis. Extensive fibrosis causing mesenteric vessel obstruction and/or obstructive uropathy was more often associated with symptomatic and advanced disease encompassing lymph node metastases in the mesenteric root, para-aortic lymph node metastases, as well as liver metastases and peritoneal carcinomatosis. Palliative intervention in terms of superior mesenteric vein stenting or resection of central mesenteric metastases and/or percutaneous nephrostomy and J stent treatment was beneficial in the majority of the patients.

Conclusion
Extensive abdominal fibrosis associated with clinically significant symptoms of intestinal ischaemia and/or obstructive uropathy was linked to advanced disease in patients with SI-NETs. Prompt recognition and minimally invasive intervention was effective in disease palliation.
Long non‐coding RNA MALAT1 functions as a mediator in cardioprotective effects of fentanyl in myocardial ischemia‐reperfusion injury
Authors: Zhao Zhi‐hui , Hao Wei , Meng Qing‐tao , Du Xiao‐bing , Lei Shao‐qing , Xia Zhong‐yuan 
Published: November 2016

AbstractLong non‐coding (lncRNA) MALAT1 can be increased by hypoxia or ischemic limbs. Also, downregulation of MALAT1 contributes to reduction of cardiomyocyte apoptosis. However, the functional involvement of MALAT1 in myocardial ischemia‐reperfusion (I/R) injury has not been defined. This study investigated the functional involvement of lncRNA‐MALAT1 in cardioprotective effects of fentanyl. HL‐1, a cardiac muscle cell line from the AT‐1 mouse atrial cardiomyocyte tumor lineage was pre‐treated with fentanyl and generated cell model of hypoxia‐reoxygenation (H/R). Relative expression of MALAT1, miR‐145, and Bnip3 mRNA in cells was determined by quantitative real‐time PCR. Cardiomyocyte H/R injury was indicated by lactate dehydrogenase (LDH) release and cell apoptosis. The results showed that fentanyl abrogates expression of responsive gene for H/R and induces downregulation of MALAT1 and Bnip3 and upregulation of miR‐145. We found that miR‐145/Bnip3 pathway was negatively regulated by MALAT1 in H/R‐HL‐1 cell with or without fentanyl treatment. Moreover, both MALAT1 overexpression and miR‐145 knockdown reverse cardioprotective effects of fentanyl, as indicated by increase in LDH release and cell apoptosis. The reversal effect of MALAT1 for fentanyl is confirmed in cardiac ischemia/reperfusion (I/R) mice. In summary, lncRNA‐MALAT1 is sensitive to H/R injury and abrogates cardioprotective effects of Fentanyl by negatively regulating miR‐145/Bnip3 pathway.
Nuclear subcompartments: an overview
Authors: Nunes Vinícius Santana , Moretti Nilmar Silvio 
Published: November 2016

AbstractThe advance in biochemical and microscopy techniques has revealed the complexity and intricate nucleoplasm structure. Several subcompartments were identified in nucleus and the importance of these subcompartments in processes crucial for normal nuclear activity has been demonstrated. In this mini‐review, we will give an overview about the composition, function, and importance of the major nuclear subcompartments. Also, we will show the impact that perturbing these structures can cause in normal nuclear activity, and how these can contribute to the development of some human diseases.
Mechanistic Studies of Ullmann‐Type C–N Coupling Reactions: Carbonate‐Ligated Copper(III) Intermediates
Authors: Gurjar Kamlesh K. , Sharma Rajendra K. 
Published: November 2016

AbstractIn Ullmann‐type C−N coupling reactions, the involvement of CuIII species has been proposed many times on the basis of the oxidative addition–reductive elimination (OA‐RE) path for these reactions, but actual species could not be traced in experimental studies. In the C−N coupling reactions, carbonate and phosphate were considered widely as bases. In the present study, Cu‐mediated C−N coupling reactions of aryl halides and NuNH (amide and imide) were investigated extensively, and we provide direct spectroscopic evidence of actual CuIII species. For the first time, we reveal that carbonate and phosphate ions act as bidentate ligands as well as a base in the catalytic cycle, and thus the actual intermediate species is a carbonate‐ or phosphate‐ligated, distorted octahedral CuIII complex. Our experimental and computational studies have strengthened the hypothesis that these reactions follow an OA‐RE path.
One‐Pot Facile Fabrication of Multiple Nickel Nanoparticles Confined in Microporous Silica Giving a Multiple‐Cores@Shell Structure as a Highly Efficient Catalyst for Methane Dry Reforming
Authors: Peng Honggen , Zhang Xianhua , Zhang Li , Rao Cheng , Lian Jie , Liu Wenming , Ying Jiawei , Zhang Guohua , Wang Zheng , Zhang Ning , Wang Xiang 
Published: November 2016

AbstractMethane dry reforming (MDR) is a very important reaction, which can efficiently use two kinds of greenhouse gases (CO2 and CH4) to prepare synthesis gas or produce green hydrogen energy. What inhibits the industrialization of MDR is the sintering of active Ni nanoparticles and severe carbon deposition for Ni‐based catalysts. To resolve these problems, a novel structured catalyst with multiple ultra‐small Ni nanoparticles (4.3 nm) as the core and microporous silica as the shell was rationally fabricated by a facial one‐pot reverse micelle method and applied for MDR. The multiple‐cores@shell (M‐Ni@SiO2) catalyst displays superior carbon resistance and long‐term durability with the methane and carbon dioxide conversion close to thermodynamic equilibrium and a H2 to CO molar ratio near 1, whereas the commercial catalyst, Ni/Al2O3, and Ni directly supported on silica spheres (Ni/SiO2) show low stability and notable carbon deposition. The ultra‐small Ni particle size and confinement effect of the porous silica shell are believed to be the determining factors for the outstanding performance of the multiple‐cores@shell catalyst. The novel multiple‐cores@shell structure catalyst could be potentially used for industrial applications of MDR.
Deciphering the Platinized Surface Reactivity to Improve the Detection of Hydrogen Peroxide in Bioanalyses
Authors: Badets Vasilica , Pandard Justine , Sojic Neso , Arbault Stéphane 
Published: November 2016

AbstractThe reactivity of platinized electrode surface (Pt‐black) towards the oxidation of hydrogen peroxide is analyzed in the most common physiological buffer, namely phosphate buffer saline, used in the development of biosensors. It is shown here that the oxidation of hydrogen peroxide by Pt‐black involves first the adsorption of phosphate anions, which facilitates the oxidation of hydrogen peroxide at lower potentials when compared to classic polycrystalline platinum. This gives insight in the excellent analytical features of platinized electrodes for the detection of H2O2, even at nanomolar concentrations. The reactivity of platinized electrodes can be further improved by an oxygen plasma treatment. We demonstrate herein that such treatment creates an outermost layer of PtO2 oxides on the deposit, which improves the oxidation of hydrogen peroxide thermodynamically and kinetically, as well as of hydroquinone and superoxide radical anion.
Converting a Semiconducting Polymer from Ambipolar into n‐Type Dominant by Amine End‐Capping
Authors: Quinn Jesse , Patel Haritosh , Haider Fezza , Khan Daid A. , Li Yuning 
Published: November 2016

AbstractA donor‐acceptor polymer of (3E,7E)‐3,7‐bis(2‐oxoindolin‐3‐ylidene)benzo[1,2‐b : 4,5‐b′]difuran‐2,6(3H,7H)‐dione (IBDF) and bithiophene (BT) exhibits typical ambipolar charge transport behaviour in organic thin film transistors. Using the electron rich triphenylamine as an end capping group, a notable suppression of hole transport is observed. This interesting phenomenon is accounted for by the hole trapping effect of the triphenylamine end‐capper. Thus, this study provides a novel and facile approach to tuning the charge carrier polarity of a polymer semiconductor from ambipolar to n‐type dominant.
Influence of Metal, Ligand and Solvent on Supramolecular Polymerizations with Transition‐Metal Compounds: A Theoretical Study
Authors: Caturello Naidel A. M. S. , Csók Zsolt , Fernández Gustavo , Albuquerque Rodrigo Q. 
Published: November 2016

AbstractThe nature of intermolecular interactions governing supramolecular polymerizations is very important for controlling their cooperativity. In order to address this problem, supramolecular columns made of PtII and PdII complexes of oligo(phenylene ethynylene)‐based pyridine (OPE) and tetrazolylpyridine ligands (TEP) were investigated through the dispersion‐corrected PM6 method. Aromatic, CH–π, M–Cl and metallophilic interactions helped stabilize the supramolecules studied, and their geometries and associated cooperativities were in excellent agreement with experimental data. The OPE ligand and/or the presence of PtII led to stronger metallophilic interactions and also to cooperative supramolecular polymerizations, which clearly suggests that metallophilic interactions are a key factor for controlling cooperativity. The results indicate that sequential monomer addition is in general less spontaneous than the combination of two larger preformed stacks. The present theoretical investigations contribute to the further understanding of the relation between the thermodynamics of supramolecular polymerizations and the nature of different synthons.