bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fixierung von NiFe‐Hydrotalkit‐Pulverkatalysatoren für die postelektrolytische strukturelle Charakterisierung von Elektrokatalysatoren für die Sauerstoffevolution
Authors: Andronescu Corina , Barwe Stefan , Ventosa Edgar , Masa Justus , Vasile Eugeniu , Konkena Bharathi , Möller Sandra , Schuhmann Wolfgang 
Published: June 2017

AbstractHochaktive Katalysatoren für die Sauerstoffevolutionsreaktion (OER) sind in den meisten Fällen Nanomaterialen. Diese erfahren substantielle Veränderungen, hervorgerufen durch die notwendigen anodischen Potentiale und hohen Stromdichten während der Sauerstoffevolution. Die Lebensdauer katalysatormodifizierter Elektroden ist unter OER‐Bedingungen aufgrund der immensen Gasentwicklung und fehlender Strategien zur stabilen Pulverfixierung auf Elektrodenoberflächen enttäuschend kurz. Aussagekräftige Studien über Katalysatoren während und vor allem nach der OER sind davon häufig beeinträchtigt. Wir schlagen hier Kompositmaterialen basierend auf Polybenzoxazinen und organophil modifizierten NiFe‐Hydrotalkitstrukturen (LDH) zur Bildung eines hochstabilen und leitfähigen Katalysatorfilms vor. Diese erlauben die Charakterisierung des Katalysators vor und nach elektrokatalytischen Untersuchungen. Die Charakterisierung des Kompositmaterials durch Röntgenbeugung (XRD) und elektronenmikroskopischen Methoden (REM, TEM) vor und nach 100 Stunden Elektrolyse bei 60 °C in 5 m KOH bei einer angelegten Stromdichte von 200 mA cm−2 zeigen bisher nicht beobachtete strukturelle Veränderungen.
Fabrication and photocatalytic behavior of a novel nanocomposite hydrogels containing Fe‐octacarboxylic acid phthalocyanine
Authors: Yuan Zhicheng , Chen Dajun 
Published: June 2017

ABSTRACTA novel poly(ethylene glycol)‐based nanocomposite hydrogels containing Fe‐octacarboxylic acid phthalocyanine (FeOCAP)/magnetic attapulgite was successfully synthesized by in situ polymerization. Fourier transform infrared spectroscopy result showed the FeOCAP/magnetic attapulgite was successfully introduced into the hydrogels matrix. Besides, the hydrogen bond interactions existed between FeOCAP/attapulgite and hydrogels, which acted as the crosslink points in the hydrogels network, and meanwhile, stabilized the nanoparticles in hydrogel without phase separation. Photocatalytic activity studies confirmed that the as‐prepared nanocomposite hydrogels had excellent photocatalytic activity for rhodamine B photodegradation, as compared to the pure hygrogels. The rhodamine B removal percentage of the hydrogels could reach nearly 100% and the kinetics of photocatalytic degradation reaction was described by the Langmuir–Hinshelwood kinetics models. The hydrogels could be reused more than five times without losing any photodegradation ability, which indicated that the hydrogels would be potentially useful in dyes wastewater treatments. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45428.
Interaction of [VIVO(acac)2] with Human Serum Transferrin and Albumin
Authors: Correia Isabel , Chorna Ielyzaveta , Cavaco Isabel , Roy Somnath , Kuznetsov Maxim L. , Ribeiro Nádia , Justino Gonçalo , Marques Fernanda , Santos‐Silva Teresa , Santos Marino F.A. , Santos Hugo M. , Capelo José L. , Doutch James , Pessoa João Costa 
Published: June 2017

Abstract[VO(acac)2] is a remarkable vanadium compound and has potential as a therapeutic drug. It is important to clarify how it is transported in blood, but the reports addressing its binding to serum proteins have been contradictory. We use several spectroscopic and mass spectrometric techniques (ESI and MALDI‐TOF), small‐angle X‐ray scattering and size exclusion chromatography (SEC) to characterize solutions containing [VO(acac)2] and either human serum apotransferrin (apoHTF) or albumin (HSA). DFT and modeling protein calculations are carried out to disclose the type of binding to apoHTF. The measured circular dichroism spectra, SEC and MALDI‐TOF data clearly prove that at least two VO–acac moieties may bind to apoHTF, most probably forming [VIVO(acac)(apoHTF)] complexes with residues of the HTF binding sites. No indication of binding of [VO(acac)2] to HSA is obtained. We conclude that VIVO–acac species may be transported in blood by transferrin. At very low complex concentrations speciation calculations suggest that [(VO)(apoHTF)] species form.
Rational engineering of p‐hydroxybenzoate hydroxylase to enable efficient gallic acid synthesis via a novel artificial biosynthetic pathway
Authors: Chen Zhenya , Shen Xiaolin , Wang Jian , Wang Jia , Yuan Qipeng , Yan Yajun 
Published: June 2017

ABSTRACTGallic acid (GA) is a naturally occurring phytochemical that has strong antioxidant and antibacterial activities. It is also used as a potential platform chemical for the synthesis of diverse high‐value compounds. Hydrolytic degradation of tannins by acids, bases or microorganisms serves as a major way for GA production, which however, might cause environmental pollution and low yield and efficiency. Here, we report a novel approach for efficient microbial production of GA. First, structure‐based rational engineering of PobA, a p‐hydroxybenzoate hydroxylase from Pseudomonas aeruginosa, generated a new mutant, Y385F/T294A PobA, which displayed much higher activity toward 3,4‐dihydroxybenzoic acid (3,4‐DHBA) than the wild‐type and any other reported mutants. Remarkably, expression of this mutant in Escherichia coli enabled generation of 1149.59 mg/L GA from 1000 mg/L 4‐hydroxybenzoic acid (4‐HBA), representing a 93% molar conversion ratio. Based on that, we designed and reconstituted a novel artificial biosynthetic pathway of GA and achieved 440.53 mg/L GA production from simple carbon sources in E. coli. Further enhancement of precursor supply through reinforcing shikimate pathway was able to improve GA de novo production to 1266.39 mg/L in shake flasks. Overall, this study not only led to the development of a highly active PobA variant for hydroxylating 3,4‐DHBA into GA via structure‐based protein engineering approach, but also demonstrated a promising pathway for bio‐based manufacturing of GA and its derived compounds. Biotechnol. Bioeng. 2017;114: 2571–2580. © 2017 Wiley Periodicals, Inc.
Transformations of Some Sesquiterpene Lactones by Filamentous Fungi and Cytotoxic Evaluations
Authors: Cano‐Flores Arturo , Delgado Guillermo 
Published: June 2017

Biotransformation is an economically and ecologically viable technology which has been used to modify the structures of many classes of biologically active products. Some fungi may be useful for the biotransformation of sesquiterpene lactones (SLs), leading to unusual structural changes that modify their biological activities, and other transformations mimic their biosynthetic pathways, generating evidences for the proposed biogenesis. Eight filamentous fungi were screened for their ability to transform different SLs (1 – 9), and microbial reactions yielded compounds 10 – 17, which in turn have been isolated as natural products, thus mimicking their biosynthesis. Their structures were identified based on NMR and MS spectroscopic analyses. The cytotoxicities of SLs 1, 4, 6, 7 and 9, and their biotransformed produts (10, 14, 15 and 17) against human cancer cell lines U251 (glia), PC3 (prostate), K562 (leukemia), HCT‐15 (colon), MCF7 (breast), and SKLU‐1 (lung), were determined, confirming that the presence of Michael acceptor is an important feature for the bioactivity.
Photoactivatable Mussel‐Based Underwater Adhesive Proteins by an Expanded Genetic Code
Authors: Hauf Matthias , Richter Florian , Schneider Tobias , Faidt Thomas , Martins Berta M. , Baumann Tobias , Durkin Patrick , Dobbek Holger , Jacobs Karin , Möglich Andreas , Budisa Nediljko 
Published: June 2017

AbstractMarine mussels exhibit potent underwater adhesion abilities under hostile conditions by employing 3,4‐dihydroxyphenylalanine (DOPA)‐rich mussel adhesive proteins (MAPs). However, their recombinant production is a major biotechnological challenge. Herein, a novel strategy based on genetic code expansion has been developed by engineering efficient aminoacyl‐transfer RNA synthetases (aaRSs) for the photocaged noncanonical amino acid ortho‐nitrobenzyl DOPA (ONB‐DOPA). The engineered ONB‐DOPARS enables in vivo production of MAP type 5 site‐specifically equipped with multiple instances of ONB‐DOPA to yield photocaged, spatiotemporally controlled underwater adhesives. Upon exposure to UV light, these proteins feature elevated wet adhesion properties. This concept offers new perspectives for the production of recombinant bioadhesives.
Asymmetric Synthesis of Pyrrolidine‐Containing Chemical Scaffolds via Tsuji–Trost Allylation of N‐tert‐Butanesulfinyl Imines
Authors: Dawood Rafid S. , Georgiou Irene , Wilkie Ross P. , Lewis William , Stockman Robert A. 
Published: June 2017

AbstractA simple and efficient asymmetric synthesis of novel sp3‐rich pyrrolidine chemical scaffolds over five steps starting from simple ketones is described. Key steps involve the use of tert‐butanesulfinamide as a chiral auxiliary to perform an asymmetric Tsuji–Trost allylation, with subsequent cross‐metathesis with an acrylate ester and reduction of the sulfinimine/cyclisation of the resulting amine giving the pyrrolidine scaffolds in high yields and diastereoselectivites. By removing the chiral auxiliary and functionalising the ester group, the resulting scaffold core can be further derivatised.
Protein–Glycan Quinary Interactions in Crowding Environment Unveiled by NMR Spectroscopy
Authors: Diniz Ana , Dias Jorge S. , Jiménez‐Barbero Jesús , Marcelo Filipa , Cabrita Eurico J. 
Published: June 2017

AbstractProtein–glycan interactions as modulators for quinary structures in crowding environments were explored. The interaction between human galectin 3 (Gal‐3) and distinct macromolecular crowders, such as bovine and human serum albumin (BSA and HSA), Ficoll 70 and PEG3350, was scrutinized. The molecular recognition event of the specific ligand, lactose, by Gal‐3 in crowding conditions was evaluated. Gal‐3 interactions were monitored by NMR analysing chemical shift perturbation (CSP) and line broadening of 1H15N‐HSQC signals. The intensity of the Gal‐3 1H15N‐HSQC signals decreased in the presence of all crowders, due to the increase in the solution viscosity and to the formation of large protein complexes. When glycosylated containing samples of BSA and HSA were used, signal broadening was more severe than that observed in the presence of the more viscous solutions of PEG3350 and Ficoll 70. However, for the samples containing glycoproteins, the signal intensity of 1H15N‐HSQC recovered upon addition of lactose. We show that serum proteins interact with Gal‐3, through their α2,3‐linked sialylgalactose moieties exposed at their surfaces, competing with lactose for the same binding site. The quinary interaction between Gal‐3 and serum glycoproteins, could help to co‐localize Gal‐3 at the cell surface, and may play a role in adhesion and signalling functions of this protein.
Impact of Medicaid disenrollment in Tennessee on breast cancer stage at diagnosis and treatment
Authors: Tarazi Wafa W. , Bradley Cathy J. , Bear Harry D. , Harless David W. , Sabik Lindsay M. 
Published: June 2017

BACKGROUNDStates routinely may consider rollbacks of Medicaid expansions to address statewide economic conditions. To the authors' knowledge, little is known regarding the effects of public insurance contractions on health outcomes. The current study examined the effects of the 2005 Medicaid disenrollment in Tennessee on breast cancer stage at the time of diagnosis and delays in treatment among nonelderly women.METHODSThe authors used Tennessee Cancer Registry data from 2002 through 2008 and estimated a difference‐in‐difference model comparing women diagnosed with breast cancer who lived in low‐income zip codes (and therefore were more likely to be subject to disenrollment) with a similar group of women who lived in high‐income zip codes before and after the 2005 Medicaid disenrollment. The study outcomes were changes in stage of disease at the time of diagnosis and delays in treatment of >60 days and >90 days.RESULTSOverall, nonelderly women in Tennessee were diagnosed at later stages of disease and experienced more delays in treatment in the period after disenrollment. Disenrollment was found to be associated with a 3.3‐percentage point increase in late stage of disease at the time of diagnosis (P = .024), a 1.9‐percentage point decrease in having a delay of >60 days in surgery (P = .024), and a 1.4‐percentage point decrease in having a delay of >90 days in treatment (P = .054) for women living in low‐income zip codes compared with women residing in high‐income zip codes.CONCLUSIONSThe results of the current study indicate that Medicaid disenrollment is associated with a later stage of disease at the time of breast cancer diagnosis, thereby providing evidence of the potential negative health impacts of Medicaid contractions. Cancer 2017;123:3312‐9. © 2017 American Cancer Society.
Well‐Defined Cyanometallate Coordination‐Polymer Nanoarchitectures Realized by Wet‐Chemical Manipulation
Authors: Zhao Yanyi , Zhang Wei , Hu Ming 
Published: June 2017

AbstractCyano‐bridged coordination polymers have attracted wide interest owing to their promise in various applications such as molecular magnets, information storage, bio‐sensing, electrochromism, nanomedicine, catalysis, water treatment, and energy storage and conversion. Inspired by the great success of nanoengineering in noble metals and semiconductors, nanoarchitectonics of these cyano‐bridged coordination polymers has been actively explored for hunting new properties or functions with significant progress in understanding their crystallization habit and chemical stability. Although comprehensive information about the nanoarchitectonics of cyano‐bridged coordination polymers remains poorly elucidated, a systematic overview of recent advances in this area is strongly needed in order to make further progress on the basis of current developments. In this review, we intend to summarize the wet‐chemical manipulation strategies based on controlled crystallization and etching for nanostructuration of cyano‐bridged coordination polymers. Some examples of the relationship between the nanoarchitecture and the properties of the cyano‐bridged coordination polymers will be given.
Anionic Extraction for Efficient Recovery of Biobased 2,3‐Butanediol—A Platform for Bulk and Fine Chemicals
Authors: Drabo Peter , Tiso Till , Heyman Benedikt , Sarikaya Eda , Gaspar Paula , Förster Jochen , Büchs Jochen , Blank Lars Mathias , Delidovich Irina 
Published: June 2017

Abstract2,3‐Butanediol (BDO) presents a promising platform molecule for the synthesis of basic and fine chemicals. Biotechnological production of BDO from renewable resources with living microbes enables high concentrations in the fermentation broth. The recovery of high‐boiling BDO from an aqueous fermentation broth presents a subsequent challenge. A method is proposed for BDO isolation based on reversible complexation with phenylboronate in an anionic complex. BDO can be recovered by back‐extraction into an acidic solution. The composition of the extracted species was determined by NMR spectroscopy, MS, and GC–MS methods. The conditions of extraction and back‐extraction were optimized by using commercial BDO and finally applied to different fermentation broths. Up to 72–93 % BDO can be extracted and up to 80–90 % can be back‐extracted under the optimized conditions. Purified bio‐BDO was used in the presence of sulfuric acid for the synthesis of methyl ethyl ketone, an established organic solvent and discussed tailor‐made biofuel.
Two‐stage metabolism inferred from diel oxygen dynamics in aquatic ecosystems
Authors: Schindler Daniel E. , Jankowski KathiJo , A'mar Z. Teresa , Holtgrieve Gordon W. 
Published: June 2017

AbstractDynamics of dissolved oxygen in aquatic ecosystems reflect the biological, physical, and chemical processes that regulate ecosystem metabolism. Organic matter that supports ecosystem respiration (ER) is produced both by in situ photosynthesis and via loading from terrestrial ecosystems. Terrestrial‐derived organic matter is relatively recalcitrant and its availability is stable at diel time scales relative to substrates produced through photosynthesis, which are more labile and often show distinct diel changes in availability. Here, we explored whether the contributions of these two sources of organic matter to ecosystem metabolism could be quantified by a process model of photosynthesis and ER fit to high‐frequency observations of oxygen concentration in streams. We found that a two‐stage model of respiration provided a better fit to diel oxygen dynamics in most streams than a model assuming that the substrates supporting ER were one temporally stable pool. Two‐stage models estimated peak daytime respiration rates that were ~2.9× higher on average than nighttime rates, but this increase was variable and ranged from 1.1 to 11.6×. Estimates of gross primary production were 1.35× higher, on average, (range = 1.04–7.91×) compared to estimates generated by a single‐stage model. Streams draining watersheds with less than about 7% gradient exhibited oxygen dynamics that provided comparable statistical support for single‐stage metabolism, likely due to the higher loading of allochthonous organic matter that swamped metabolism based on autochthonous production in these streams. Ecosystem metabolism in streams draining steeper watersheds was best characterized by two‐stage metabolism, reflecting the greater importance of autochthonous contributions to labile organic carbon pools in these ecosystems.
Thermal Properties and Reliability of a Lauric Acid/Nonanoic Acid Binary Mixture as a Phase‐Change Material for Thermal Energy Storage
Authors: Wang Zhao , Sun Jinhe , Xie Shaolei , Ma Guixiang , Jia Yongzhong 
Published: June 2017

AbstractThe thermal properties of a binary system composed of lauric acid (LA) and nonanoic acid (NA) and its binary phase diagram were studied. To put this binary system into practice, the mixture containing 96 wt % of LA was selected, which has a phase‐change temperature of 41 °C and a latent heat of 163 J g−1, which is suitable for a domestic water heating application. Additionally, its thermal and chemical structure stability, thermal conductivity, degree of supercooling, and thermal reliability were investigated by using thermogravimetric analysis, FTIR spectroscopy, thermal conductivity analysis, the T‐history method, and an accelerated thermal cycle test for 1000 melt/freeze cycles, respectively. The results of these tests indicated that the mixture has a remarkable thermal stability, a good chemical structure stability, no supercooling, and an excellent thermal reliability. Therefore, the mixture can be a potential phase‐change material for thermal energy storage.
Geochronology, geochemistry, and tectonic implications of Jishou Cretaceous diabase, western Xuefengshan tectonic zone in South China
Authors: Su Jinbao , Dong Shuwen , Zhang Yueqiao , Ma Licheng , Chen Xuanhua 
Published: June 2017

From the east of the Xuefengshan tectonic zone (XTZ) to the Pacific coast of the South China Block, there exist widespread Mesozoic magmatic rocks, which attract a great deal of attention for their forming mechanism and evolutional history. Among them, the Mesozoic Jishou diabase located at the west of the XTZ is reported in this study. Based on our geochronologic analysis, the diabase has a U–Pb age of 134 ± 2.3 Ma. The diabase belongs to calc‐alkaline series in a SiO2‐K2O diagram and illustrates significant enrichment in light rare earth elements and flat heavy rare earth elements without obvious Eu anomalies. Meanwhile, the diabase has negative εHf(t) and εNd(t) values and higher radiogenic 87Sr/86Sr(t) ratios, suggestive of EM2‐like Sr‐Nd isotopic compositions. The diabase shows high variations in 207Pb/204Pb(t; 15.609–15.671), 206Pb/204Pb(t; 17.943–18.742), and 208Pb/204Pb(t; 38.268–39.302). It is suggested that the Jishou diabase may be generated from the lithospheric mantle in response to the decompression melting accompanied by lithospheric extension during Pacific subduction process. During the Early Cretaceous (145–120 Ma), the upwelling and melting of the mantle occurred under the XTZ, causing intraplate Jishou diabase magma. Subsequently, the significantly descending of the subducted Paleo‐Pacific slab led progressively eastward generation and migration of subduction‐related magmas, resulting in a widespread distribution of igneous rocks in the Cathaysia Block.
The effect of adhesives on inflammatory immune‐markers during renal injury healing
Authors: Lloris‐Carsí José Miguel , Barrios Carlos , Prieto‐Moure Beatriz , Lloris‐Cejalvo José Miguel , Cejalvo‐Lapeña Dolores 
Published: June 2017

AbstractRenal injury is common in abdominal trauma. Adhesives and sealants can be used to repair and preserve damaged organs. We describe the effect of three biomaterial treatments (TachoSil, GelitaSpon, and Adhflex) on injured renal tissue. Renal traumatic injuries were experimentally induced in male Wistar rats (n = 90) using a punch. Animals were divided into five groups: (1) sham noninjured (n = 3) and punch injury groups; (2) nontreated (n = 6); (3) TachoSil (n = 27); (4) GelitaSpon (n = 27); and (5) Adhflex (n = 27). Wound healing was evaluated 2, 6, and 18 days postinjury by inflammatory cytokines response, histopathological evolution of lesions, inflammatory reaction markers (CD68), and vascular neoformation (CD31). The TachoSil group showed the least inflammatory reaction among the three treated groups, which showed similarly low inflammatory reaction 18 days postinjury. Ciliary neurotrophic factor, soluble intercellular adhesion molecule‐1, L‐selectin, thymus chemokine, and TIMP metallopeptidase inhibitor 1 expression peaked between 2 and 6 days postinjury. TachoSil promoted the highest cytokine expression. The Adhflex group had the highest CD31 inflammatory immune‐marker levels at 2 and 6 days postinjury, but there was a similar decrease in CD31 levels in all three groups at 18 days postinjury. The results show that all three sealant treatments induced a normal healing process with the typical pattern of proinflammatory cytokine and immune‐marker expression. Each tested sealant substance could be suitable treatment for renal lacerations. The findings of this study indicate that Adhflex® elastic cyanoacrylate does not induce an adverse inflammatory reaction, and therefore, could be considered as one of the first‐line treatments for renal injuries. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1444–1455, 2018.