bluuebunny/crossref_metadata_2025_split huggingface dataset:
Palladium versus Platin – das Metall im Katalysezentrum eines molekularen Photokatalysators bestimmt den Mechanismus der Wasserstoffproduktion mit sichtbarem Licht
Authors: Pfeffer Michael G. , Schäfer Bernhard , Smolentsev Grigory , Uhlig Jens , Nazarenko Elena , Guthmuller Julien , Kuhnt Christian , Wächtler Maria , Dietzek Benjamin , Sundström Villy , Rau Sven 
Published: January 2015

AbstractFür die Entwicklung hocheffizienter molekularer Photokatalysatoren zur Wasserstoffproduktion mit sichtbarem Licht ist ein Verständnis der elektronischen und chemischen Prozesse im Photokatalysator von wesentlicher Bedeutung. In‐situ‐Röntgenabsorptionsspektroskopie (XAS) zeigte hierbei, dass die Art des katalytisch aktiven Metallzentrums in einer (N^N)MCl2‐Koordinationssphäre (M=Pd oder Pt) wesentlichen Einfluss auf den Mechanismus der Wasserstoffproduktion hat. Während Pd als Metallzentrum eine signifikante Veränderung der chemischen Umgebung und die Ausbildung von metallischen Kolloiden aufweist, zeigt Pt als Katalysezentrum keinerlei Veränderung der Koordinationssphäre unter katalytischen Bedingungen. Dieser Befund wird durch die Unabhängigkeit der Katalyse von Chloridionenzusatz und dem Quecksilbertest gestützt. Hieraus kann ein vollständig anderer Katalysemechanismus ohne Beteiligung von Kolloiden abgeleitet werden.
Dinuclear Copper Intermediates in Copper(I)‐Catalyzed Azide–Alkyne Cycloaddition Directly Observed by Electrospray Ionization Mass Spectrometry
Authors: Iacobucci Claudio , Reale Samantha , Gal Jean‐François , De Angelis Francesco 
Published: January 2015

AbstractThe mechanism of the CuAAC reaction has been investigated by electrospray ionization mass spectrometry (ESI‐MS) using a combination of the neutral reactant approach and the ion‐tagging strategy. Under these conditions, for the first time, putative dinuclear copper intermediates were fished out and characterized by ESI(+)‐MS/MS. New insight into the CuAAC reaction mechanisms is provided and a catalytic cycle is proposed.
Two‐Dimensional Covalent Organic Frameworks for Carbon Dioxide Capture through Channel‐Wall Functionalization
Authors: Huang Ning , Chen Xiong , Krishna Rajamani , Jiang Donglin 
Published: January 2015

AbstractOrdered open channels found in two‐dimensional covalent organic frameworks (2D COFs) could enable them to adsorb carbon dioxide. However, the frameworks’ dense layer architecture results in low porosity that has thus far restricted their potential for carbon dioxide adsorption. Here we report a strategy for converting a conventional 2D COF into an outstanding platform for carbon dioxide capture through channel‐wall functionalization. The dense layer structure enables the dense integration of functional groups on the channel walls, creating a new version of COFs with high capacity, reusability, selectivity, and separation productivity for flue gas. These results suggest that channel‐wall functional engineering could be a facile and powerful strategy to develop 2D COFs for high‐performance gas storage and separation.
Development of a predictive model for choosing cure agents for elastomer blends
Authors: Cañete Vebber Guilherme , Nunes Pereira Cláudio 
Published: January 2015

ABSTRACTIn elastomer blends with either polarity differences or unbalanced double bond concentration, cure agents have a preferential partition to one of the phases, with a tendency of having overcure in one phase and undercure in the other. To achieve proper vulcanization and improved performance in the final product, it is essential to have a correct balance between solubility and miscibility of each of the various cure agents in the elastomer blend composite. Cure agents with varying polarities and various reactivities have different crosslinking densities in the rubber compound. A homogeneous crosslinking density leads to superior mechanical properties. The method presented in this work includes a new tool based on a genetic optimization algorithm for assessing the partitioning of cure agents in different elastomers and their blends. The quantitative data allowed for a series of analyses of the solubility of the cure agents in the elastomer mixtures of different phases and was validated by correlation with their physico–chemical and mechanical properties of the resulting blend. This is an important tool for planning a cure system in rubber blends and to avoid incorrect partitioning of cure agents and consequent uneven curing of the final compound. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41929.
Synthesis of hyperbranched polybenzoxazoles and their molecular composites with epoxy resins
Authors: Wu Jing , Wang Yan , Yu Junrong , Zhu Jing , Hu Zuming 
Published: January 2015

ABSTRACTHyperbranched aromatic polymers have attracted great attention recently because they combined the processability of hyperbranched polymers and the high‐level performance of aromatic polymers. Here, a one‐pot strategy for the synthesis of hyperbranched Polybenzoxazoles (HBPBOs) by polycondensation of 2,2‐Bis (3‐amino‐4‐hydroxyphenyl) hexafluoropropane and 1,3,5‐benzenetricarboxylic acid in Polyphosphoric acid was reported. The HBPBOs exhibited good solubility in organic solvents because of the branched structure and the flexible hexafluoropropane groups in main chains. The structure and terminal functional groups could be tailored by adjusting the molar ratio of two monomers. FT‐IR, NMR and XRD measurements confirmed the structure of HBPBOs, while thermogravimetric analysis (TGA), UV‐vis, and photoluminescence spectra, combined with the comparison with linear PBOs demonstrated the intriguing optical properties and good thermal stabilities of HBPBOs. The good solubility of HBPBOs also permitted their usage as molecular reinforcement for polymer composites as demonstrated in this study of HBPBOs/epoxy composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41942.
Tunable photoluminescence properties of Sr1‐yCayMoO4:Sm3+ phosphors (0 ≤ y < 1)
Authors: Cao Renping , Chen Kangbin , Liu Pan , Cao Chunyan , Xu Yongchun , Ao Hui , Tang Pengjie 
Published: January 2015

AbstractA series of Sr1‐x‐yCayMoO4:xSm3+ (0 ≤ x ≤ 7 mol% and 0 ≤ y < 1) phosphors was synthesized by a conventional solid‐state reaction method in air, and their structural and spectroscopic properties were investigated. The optimal doping concentration of Sm3+ in SrMoO4:Sm3+ phosphor is 5 mol%. Under excitation with 275 nm, in Sr1‐x‐yCayMoO4:xSm3+ (0 ≤ x ≤ 7 mol% and 0 ≤ y < 1) phosphors, the emission band of the host was found to overlap with the excitation bands peaking at ~500 nm of Sm3+ ion, and the energy transfer from MoO42− group to Sm3+ ion can also be observed. The International Commission on Illumination (CIE) chromaticity coordinates of Sr0.95‐yCayMoO4:0.05Sm3+ phosphors with excitation 275 nm varied systematically from an orange (0.4961, 0.3761) (y = 0) to a white color (0.33, 0.3442) (y = 0.95) with increasing calcium oxide (CaO) concentration. However, Sr0.95‐yCayMoO4:0.05Sm3+ phosphors with excitation at 404 nm only showed red emission and the energy transfer between MoO42− group to Sm3+ ion was not observed. The complex mechanisms of luminescence and energy transfer are discussed by energy level diagrams of MoO42− group and Sm3+ ion. Copyright © 2015 John Wiley & Sons, Ltd.
In vitro and in vivo identification of metabolites of magnoflorine by LC LTQ‐Orbitrap MS and its potential pharmacokinetic interaction in Coptidis Rhizoma decoction in rat
Authors: Xue Baojuan , Zhao Yuanyuan , Miao Qing , Miao Peipei , Yang Xiaoyan , Sun Guixia , Su Jin , Ye Jing , Wei Baohong , Zhang Yuanyuan , Zhang Yujie 
Published: January 2015

AbstractMagnoflorine, an important aporphine alkaloid in Coptidis Rhizoma, is increasingly attracting research attention because of its pharmacological activities. The in vivo and in vitro metabolism of magnoflorine was investigated by LC LTQ‐Orbitrap MS. In vivo samples including rat urine, feces, plasma and bile were collected separately after both oral (50 mg kg−1) and intravenous administration (10 mg kg−1) of magnoflorine, along with in vitro samples prepared by incubating magnoflorine with rat intestinal flora and liver microsome. As a result, 12 metabolites were found in biological samples. Phase I metabolites were identified in all biological samples, while phase II metabolites were mainly detected in urine, plasma and bile. In a pharmacokinetic study, rats were not only dosed with magnoflorine via oral (15, 30 and 60 mg kg−1) and intravenous administration (10 mg kg−1) but also dosed with Coptidis Rhizoma decoction (equivalent to 30 mg kg−1 of magnoflorine) by intragastric administration to investigate the interaction of magnoflorine with the rest of compounds in Coptidis Rhizoma. Studies showed that magnoflorine possessed lower bioavailability and faster absorption and elimination. However, pharmacokinetic parameters altered significantly (p < 0.05) when magnoflorine was administered in Coptidis Rhizoma decoction. Oral gavage of Coptidis Rhizoma decoction decreased the absorption and elimination rates of magnoflorine, which revealed that there existed pharmacokinetic interactions between magnoflorine and the rest of ingredients in Coptidis Rhizoma. Copyright © 2015 John Wiley & Sons, Ltd.
The rapid lipopolysaccharide‐induced release of matrix metalloproteinases 9 is suppressed by simvastatin
Authors: Li Dan‐Dong , Pang Hong‐Gang , Song Jin‐Ning , Huang Huan , Zhang Ming , Zhao Yong‐Lin , Sun Peng , Zhang Bin‐Fei , Ma Xu‐Dong 
Published: January 2015

AbstractA rapid increase in matrix metalloproteinase‐9 (MMP‐9) expression by stimulated leukocytes is common in many diseases. Recent evidence suggests that the beneficial effects of statins are mediated in part by the suppression of MMP‐9 release. In this study, we investigated the effect of statin on MMP‐9 expression and its antagonist, tissue inhibitor of metalloproteinase‐1 (TIMP‐1) in LPS‐stimulated leukocytes. Rat neutrophils and monocytes were stimulated with lipopolysaccharide (LPS) in the presence of simvastatin. MMP‐9 secretion and mRNA expression were analyzed using ELISA and RT‐PCR, respectively. Total MMP‐9 protein production was measured by Western blot analysis. Potential signal transduction pathways responsible for MMP‐9 production were investigated using luciferase reporter assays (NF‐κB), pull‐down assays (RhoA), and pharmacological inhibition. Our data show that MMP‐9 and TIMP‐1 expression are differentially induced by LPS in neutrophils and monocytes. We showed that rapid MMP‐9 release occurred mainly via secretion from intracellular stores. Moreover, we showed that statin significantly suppressed LPS‐induced MMP‐9 release and mRNA expression in a time‐ and concentration‐dependent manner. We also evaluated that simvastain postponed the rapid LPS‐induced MMP‐9 release for about 20 min. In conclusion, we demonstrated that the suppressive effect of simvastatin on LPS‐stimulated MMP‐9 release does not occur via the NF‐κB pathway and the MAPKs pathway, but via the RhoA/ROCK pathway.
Novel hemodynamic index for assessment of aortic regurgitation after transcatheter aortic valve replacement
Authors: Bugan Baris , Kapadia Samir , Svensson Lars , Krishnaswamy Amar , Tuzcu Emin Murat 
Published: January 2015

BackgroundParavalvular aortic regurgitation (AR) after transcatheter aortic valve replacement (TAVR) has been associated with increased mortality. Precise assessment of the degree of AR within the catheterization laboratory is crucial to take counter measures, but it remains challenging. The aim of this study was to determine whether any modification to AR index can improve its performance.MethodsThe study included 64 patients treated with the Sapien valve (Edwards Life Sciences, Inc., Irvine, CA). The severity of AR was evaluated using echocardiography, angiography, and invasive hemodynamic parameters. We evaluated the time‐integrated aortic regurgitation (TIAR) index as follows: (LV − Ao diastolic pressure time integral)/(LV systolic pressure time integral) × 100. We analyzed the AR index and TIAR index with the receiver operating characteristic (ROC) curve.ResultsAR was observed in 58 patients (90.7%) and graded as mild in 33 (51.6%), moderate in 20 (31.3%), or moderate to severe in 5 (7.8%) patients. No severe AR was detected. The AR index and TIAR index decreased proportionately to the increased severity of AR (P = 0.002 and P < 0.001, respectively). TIAR index < 80 was associated with a sensitivity of 86% and a specificity of 83% for ≥mild AR. The area under the curve was greater for the TIAR index compared to the AR index (0.93 vs. 0.74).ConclusionThe TIAR index provides a better hemodynamic measure for assessing severity of AR compared to the AR index. © 2015 Wiley Periodicals, Inc.
Tumoral calcinosis in a patient with hypoparathyroidism, sensorineural deafness, and renal dysplasia syndrome undergoing hemodialysis
Authors: Hiramatsu Rikako , Ubara Yoshifumi , Tajima Toshihiro , Usui Takeshi , Namba Kazutaka , Takeuchi Yasuhiro , Sawa Naoki , Hasegawa Eiko , Takaichi Kenmei 
Published: January 2015

Key Clinical MessageWe describe a hemodialysis patient with hypoparathyroidism due to HDR (hypoparathyroidism, sensorineural deafness, and renal dysplasia) syndrome caused by GATA3 mutation. She presents tumoral calcinosis which is a rare complication of end‐stage renal failure. A novel mutation of GATA3 is identified in this patient.
Big data‐based extraction of fuzzy partition rules for heart arrhythmia detection: a semi‐automated approach
Authors: Behadada Omar , Trovati Marcello , Chikh MA , Bessis Nik 
Published: January 2015

SummaryIn this paper, we introduce a novel method to define semi‐automatically fuzzy partition rules to provide a powerful and accurate insight into cardiac arrhythmia. In particular, we define a text mining approach applied to a large dataset consisting of the freely available scientific papers provided by PubMed. The information extracted is then integrated with expert knowledge, as well as experimental data, to provide a robust, scalable and accurate system, which can successfully address the challenges posed by the management and assessment of big data in the medical sector. The evaluation we carried out shows an accuracy rate of 93% and interpretability of 0.646, which clearly shows that our method provides an excellent balance between accuracy and system transparency. Furthermore, this contributes substantially to the knowledge discovery and offers a powerful tool to facilitate the decision‐making process. Copyright © 2015 John Wiley & Sons, Ltd.
Life history correlates of fecal bacterial species richness in a wild population of the blue tit Cyanistes caeruleus
Authors: Benskin Clare McW. H. , Rhodes Glenn , Pickup Roger W. , Mainwaring Mark C. , Wilson Kenneth , Hartley Ian R. 
Published: January 2015

AbstractVery little is known about the normal gastrointestinal flora of wild birds, or how it might affect or reflect the host's life‐history traits. The aim of this study was to survey the species richness of bacteria in the feces of a wild population of blue tits Cyanistes caeruleus and to explore the relationships between bacterial species richness and various life‐history traits, such as age, sex, and reproductive success. Using PCR‐TGGE, 55 operational taxonomic units (OTUs) were identified in blue tit feces. DNA sequencing revealed that the 16S rRNA gene was amplified from a diverse range of bacteria, including those that shared closest homology with Bacillus licheniformis, Campylobacter lari, Pseudomonas spp., and Salmonella spp. For adults, there was a significant negative relationship between bacterial species richness and the likelihood of being detected alive the following breeding season; bacterial richness was consistent across years but declined through the breeding season; and breeding pairs had significantly more similar bacterial richness than expected by chance alone. Reduced adult survival was correlated with the presence of an OTU most closely resembling C. lari; enhanced adult survival was associated with an OTU most similar to Arthrobacter spp. For nestlings, there was no significant change in bacterial species richness between the first and second week after hatching, and nestlings sharing the same nest had significantly more similar bacterial richness. Collectively, these results provide compelling evidence that bacterial species richness was associated with several aspects of the life history of their hosts.
Three Scandium Compounds with Unsaturated Coordinative Metal Sites – Structures and Catalysis
Authors: Zhang Liying , Wang Li , Wang PengCheng , Song Tianyou , Li Da , Chen Xiaobo , Fan Yong , Xu Jianing 
Published: January 2015

AbstractTwo scandium coordination polymers, a 2D supermolecule structure {[Sc(OH)(L1)2(H2O)]}n (1) (HL1 = isonicotinic acid), a 1D infinite chain structure {[Sc3(L2)4(H2O)4]·NO3·H2O}n (2) (H2L2 = 4,5‐imidazole dicarboxylic acid), as well as a scandium complex {[Sc2(OH)2(L3)2(H2O)4]}n (3) (H2L3 = 1,2,3‐triazole‐4,5‐dicarboxylic acid), were synthesized and characterized by X‐ray crystallography. Compounds 1–3 are active heterogeneous catalysts for high‐yield cyanosilylation of aromatic aldehydes in acetonitrile, particularly for p‐nitrobenzaldehyde. Moreover, these three catalysts can be reused three times without significant loss in activity or mass.
The Orthoperiodates of Calcium, Strontium, and Barium
Authors: Hummel Thorsten , Salk Florian , Ströbele Markus , Enseling David , Jüstel Thomas , Meyer H.‐Jürgen 
Published: January 2015

AbstractOrthoperiodates of calcium, strontium, and barium were prepared by solid‐state reactions of metal iodides or metal iodates with oxygen in air. M(IO3)2 (M = Ca) or MI2 (M = Sr, Ba) were heated in an open corundum crucible to yield M5(IO6)2 as a product with beige to light brown body color. Reactions were investigated by thermal analyses, using differential thermal analysis (DTA) and thermogravimetric analysis (TGA). Two distinct crystal structures were assigned for M5(IO6)2 with the space group R$\bar {3}$c for M = Ca, Sr (isotypic with Ca, Sr perrhenates) and Pnma for M = Ba based on recorded powder X‐ray diffraction data. Luminescence properties of europium‐doped samples are reported.
Metal–Organic Frameworks Based on Alkaline Earth Metals – Hydrothermal Synthesis, X‐ray Structures, Gas Adsorption, and Heterogeneously Catalyzed Hydrogenation Reactions
Authors: Saha Debraj , Maity Tanmoy , Koner Subratanath 
Published: January 2015

AbstractNew carboxylate systems with alkaline earth metals, namely, [Ca2Na2(L)2(H2O)6]n·nH2O (1, H3L = chelidamic acid) and [Sr3(L)2(H2O)9]n·2nH2O (2), have been prepared by hydrothermal reactions and characterized. The compounds featured different three‐dimensional (3D) structural motifs and new topologies. The amount of void space for the dehydrated materials of 1 and 2 was calculated to be ca. 19 and 35 %, respectively. The dehydrated materials are thermally stable to more than 450 °C. The dehydrated species of 1 and 2 displayed excellent N2, H2, and CO2 sorption capacity at 1 atm pressure. Furthermore, both compounds efficiently catalyze the hydrogenation of alkenes under mild heterogeneous conditions (60 °C, 1 atm H2). The porous catalysts demonstrate size selectivity towards substrates owing to presence of active sites inside the pores of the MOF.
Amperometric Detection and Quantification of Nitrate Ions Using a Highly Sensitive Nanostructured Membrane Electrocodeposited Biosensor Array
Authors: Gokhale Ankush A. , Lu Jue , Weerasiri Rankothge R. , Yu Jing , Lee Ilsoon 
Published: January 2015

AbstractIn the past few decades, there has been a steady rise in the release of nitrate (NO3−), a prominent water soluble contaminant associated with the increasing use of nitrate based fertilizers. In this study, we suggest the use of a highly sensitive, enzymatic biosensor capable of quantifying minute concentrations of nitrate. The disposable nitrate biosensor consists of a sensing element in the form of nitrate reductase which is immobilized within a conductive polymer matrix to generate a quantifiable amperometric response. In this work, nanoarrays of co‐immobilized nitrate reductase and poly(3,4‐ethylenedioxythiophene) (PEDOT), were grown using a template assisted electropolymerization route. The performance of the biosensor is a strong function of electropolymerization conditions and the morphology of the PEDOT nanostructures. The electropolymerized biosensor displays excellent specificity w.r.t other interfering ions as evidenced from the initial rate kinetics. With a response time of a few seconds, limit of detection (LOD) as low as 0.16 ppm and sensitivity of about 92 µA/mM , the one‐step electropolymerized nanostructured nitrate biosensor developed in this study shows improved performance compared to similar electrochemical sensors reported in literature. The PEDOT/nitrate reductase nanowire sensor developed in this work shows superior attributes compared to a flat 2D nitrate reductase‐co‐immobilized PEDOT film grown using similar electropolymerization conditions. This combined with easy and fast fabrication technique opens up exciting opportunities for developing high accuracy PEDOT based nanobiosensors for field testing of nitrate contaminants in the future.
QTc prolongation in schizophrenia patients in Asia: clinical correlates and trends between 2004 and 2008/2009
Authors: Xiang Yu‐Tao , Chiu Helen F. K. , Ungvari Gabor S. , Correll Christoph U. , Lai Kelly Y. C. , Wang Chuan‐Yue , Si Tian‐Mei , Lee Edwin H. M. , He Yan‐Ling , Yang Shu‐Yu , Chong Mian‐Yoon , Kua Ee‐Heok , Fujii Senta , Sim Kang , Yong Michael K. H. , Trivedi Jitendra K. , Chung Eun‐Kee , Udomratn Pichet , Chee Kok‐Yoon , Sartorius Norman , Tan Chay‐Hoon , Shinfuku Naotaka 
Published: January 2015

ObjectiveLittle is known about the pattern of QT interval (QTc) prolongation in Asian patients with schizophrenia. This study examined trends of QTc prolongation in schizophrenia inpatients in six Asian countries and territories between 2004 and 2008/2009 and its independent demographic and clinical correlates.MethodData on 3482 hospitalized schizophrenia patients (2004 = 1826 and 2008/2009 = 1656) in six Asian countries and territories were collected by either chart review or interviews during a 1‐month period. Patients' sociodemographic and clinical characteristics, prescriptions of psychotropic drugs, and QTc interval were recorded using a standardized protocol and data collection procedure.ResultsThe frequency of QTc prolongation (>456 ms) was 2.4% in the whole sample, decreasing from 3.1% in 2004 to 1.6% in 2008/2009 (p = 0.004) with wide intercountry variations. However, this decreased trend was driven by decreased QTc prolongation detected in China and Hong Kong (both p‐values < 0.05). Multiple logistic regression analysis of the whole sample revealed that patients having more likely to have an illness lasting longer than 5 years and received antipsychotics classified as list‐1 drugs according to the Arizona Centre for Education and Research on Therapeutics. Compared with 2004, patients in 2008/2009 were less likely to have QTc prolongation. Thioridazine caused QTc prolongation most frequently (odds ratio (OR) 4.4; 95% confidence interval (CI) 1.2–15.2), followed by sulpiride (OR 2.4; 95% CI 1.3–4.5), clozapine (OR 2.4; 95% CI 1.4–4.2), and chlorpromazine (OR 1.9; 95% CI 1.07–3.5).ConclusionsFrequency of QTc prolongation was low in Asian patients with schizophrenia. QTc prolongation in schizophrenia decreased in China and Hong Kong between 2004 and 2008/2009 but increased in Taiwan over the same period, remaining low in the other countries. Copyright © 2015 John Wiley & Sons, Ltd.