bluuebunny/crossref_metadata_2025_split huggingface dataset:
The application of constitutively solvent‐tolerant P. taiwanensis VLB120ΔCΔttgV for stereospecific epoxidation of toxic styrene alleviates carrier solvent use
Authors: Volmer Jan , Schmid Andreas , Bühler Bruno 
Published: March 2017

AbstractFor whole‐cell biotransformations involving toxic organic compounds, two‐liquid phase setups are typically applied employing an apolar extractive phase. Bis(2‐ethylhexyl)phthalate (BEHP) has proven to be an ideal solvent for stereospecific styrene epoxidation with recombinant E. coli, providing excellent extractive properties and a high biocompatibility. In eco‐efficiency evaluations, BEHP, however, has been identified as a critical factor regarding costs and environmental impact. In this study, the constitutive solvent tolerance of Pseudomonas taiwanensis VLB120ΔCΔttgV is shown to enable high specific activities (up to 180 U gCDW−1) and extensive reduction of the BEHP amount in two‐liquid phase setups and thus to constitute an excellent tool to improve the environmental and economic efficiency of such processes. At a 90% reduction of carrier solvent use and accordingly increased aqueous styrene concentrations, this strain still showed reasonably high specific styrene epoxidation activities (100 U gCDW−1), while the solvent‐adaptable wildtype strain immediately was toxified. A moderate 55% reduction of BEHP enabled a specific activity of 150 U gCDW−1 and thus represents a good trade‐off between volumetric productivity maximization and environmental impact minimization. These results for the first time show a clear benefit of a solvent‐tolerant compared to solvent‐sensitive host strains and how such a benefit can be achieved.
Mapping the Interactions of Selective Biochemical Probes of Antibody Conformation by Hydrogen–Deuterium Exchange Mass Spectrometry
Authors: Leurs Ulrike , Beck Hermann , Bonnington Lea , Lindner Ingo , Pol Ewa , Rand Kasper 
Published: March 2017

AbstractProtein‐based pharmaceuticals represent the fastest growing group of drugs in development in the pharmaceutical industry. One of the major challenges in the discovery, development, and distribution of biopharmaceuticals is the assessment of changes in their higher‐order structure due to chemical modification. Here, we investigated the interactions of three different biochemical probes (Fabs) generated to detect conformational changes in a therapeutic IgG1 antibody (mAbX) by local hydrogen‐deuterium exchange mass spectrometry (HDX‐MS). We show that two of the probes target the Fc part of the antibody, whereas the third probe binds to the hinge region. Through HDX‐ETD, we could distinguish specific binding patterns of the Fc‐binding probes on mAbX at the amino‐acid level. Preliminary surface plasmon resonance (SPR) experiments showed that these domain‐selective Fab probes are sensitive to conformational changes in distinct regions of a full‐length therapeutic antibody upon oxidation.
Lewis Acid Mediated Nazarov Cyclization as a Convergent and Enantioselective Entry to C‐nor‐D‐homo‐Steroids
Authors: Krieger Johannes , Smeilus Toni , Schackow Oliver , Giannis Athanassios 
Published: March 2017

AbstractA straightforward synthesis of C‐nor‐D‐homo steroids starting from (+)‐Wieland–Miescher ketone is reported. This convergent synthetic strategy utilizes a scalable diastereoselective Nazarov cyclization of functionalized chiral aryl vinyl ketones, allowing for further functionalization. The ability to conduct this key transformation on a multi‐gram scale paves the way for the synthesis of a variety of completely new C‐nor‐D‐homo steroids, without the need of a classic steran steroid rearrangement or achiral linear reaction sequences.
Direct C−H Phosphonylation of Electron‐Rich Arenes and Heteroarenes by Visible‐Light Photoredox Catalysis
Authors: Shaikh Rizwan S. , Ghosh Indrajit , König Burkhard 
Published: March 2017

AbstractThe direct transformation of ubiquitous, but chemically inert C−H bonds into diverse functional groups is an important strategy in organic synthesis that improves the atom economy and faclitates the preparation and modification of complex molecules. In contrast to the wide applications of aryl phosphonates, their synthesis via direct C−H bond phosphonylation is a less explored area. We report here a general, mild, and broadly applicable visible‐light photoredox C−H bond phosphonylation method for electron‐rich arenes and heteroarenes. The photoredox catalytic protocol utilizes electron‐rich arenes and biologically important heteroarenes as substrates, [Ru(bpz)3][PF6]2 as photocatalyst, ammonium persulfate as oxidant, and trialkyl phosphites as the phosphorus source to provide a wide range of aryl phosphonates at ambient temperature under very mild reaction conditions.
Vinylpyridines as Building Blocks for the Photocatalyzed Synthesis of Alkylpyridines
Authors: Capaldo Luca , Fagnoni Maurizio , Ravelli Davide 
Published: March 2017

AbstractThe photocatalyzed addition of several hydrogen donors (ethers, aldehydes, alkanes, amides) onto vinylpyridines was achieved. This approach provided access to alkylpyridines, which are important building blocks for the preparation of compounds with biological activity. The strategy was very simple and straightforward because it required only a small amount of a cheap decatungstate salt as photocatalyst. As an added advantage, the reaction could be performed under sunlight irradiation as well as under flow conditions.
Highly Chemoselective Reduction of Nitroarenes Using a Titania‐Supported Platinum‐Nanoparticle Catalyst under a CO Atmosphere
Authors: Li Shushuang , Wang Fuzerong , Liu Yongmei , Cao Yong 
Published: March 2017

AbstractThe discovery that supported gold catalysts can promote CO/H2O‐mediated reduction at ambient temperatures is important to chemoselective synthesis and has gained significant attention in recent years. Whether the alternative Pt group metal (PGM) catalysts can exhibit such exceptional performance is thus an interesting research issue. So far, no PGM catalyst shows activity for CO/H2O‐mediated reduction at ambient temperatures. Here, we demonstrate that it is possible to transform nonactive into highly active and selective catalysts for CO/H2O‐mediated reduction by modulating the interfacial structure and electronic properties at the metal‐support interfaces. Thus, highly active and chemoselective hydrogenation Pt, Ir, Rh and Pd catalysts can be prepared by decorating the exposed metal faces with partially reduced support species by means of a simple catalyst activation procedure. In this way, it has been possible to dramatically facilitate the previously unappreciated PGM‐catalyzed activation of CO molecules under mild conditions, which can make a significant contribution not only to reveal the intrinsic catalytic potential of supported PGMs but also to establish a more sustainable and industrially‐relevant process.
Agreement between cytotechnologists and cytopathologists as a new measure of cytopathologist performance in gynecologic cytology
Authors: Quinn Andrew M. , Minhajuddin Abu T. , Hynan Linda S. , Reisch Joan S. , Cibas Edmund S. 
Published: March 2017

BACKGROUNDAlthough objective measures of cytotechnologist (CT) and cytopathologist (CP) performance exist, challenges remain. Two assumptions deserve examination: CPs' interpretations are correct, and CTs and CPs render interpretations independently of each other. This study presents a CT‐CP interpretation comparison and provides insight into these assumptions.METHODSEvery gynecologic cytology specimen examined by both a CT and a CP from December 2004 to March 2015 was extracted from the laboratory information system; glandular interpretations were excluded. Excel and SAS were used for CT‐CP pair analysis. CT‐CP pairs with fewer than 32 specimens (the lowest quartile) were excluded. For the remaining CT‐CP pairs, 30 specimens or 10% of the specimens (whichever was higher) were randomly selected for comparison by a weighted κ statistic. κ values greater than 0.6 represented good agreement within CT‐CP pairs.RESULTSThis study evaluated 7116 of 53,241 gynecologic cytology specimens (13.4%) that received CT and CP interpretations. This resulted in 155 pair‐specific κ values from 15 CTs and 16 CPs. In aggregate, the κ values had a mean of 0.64, a standard deviation of 0.14, a median of 0.65, and a range of 0.27 to 0.91. Nine CTs exhibited good agreement in the majority of their pair‐specific κ values with CPs (high‐concordance CTs; 88 pair‐specific κ values). This allowed us to identify outlier CPs who did not demonstrate good agreement with high‐concordance CTs (16 of 88 pair‐specific κ values [18.2%]).CONCLUSIONSLaboratories can use this κ to determine when CP levels of agreement with CTs depart from those of their peers. Adding this to established metrics can give a more nuanced impression of CP performance. Cancer Cytopathol 2017;125:576–80. © 2017 American Cancer Society.
Fine‐Tunable Electronic Energy Levels of Mixed‐Metal Prussian‐Blue Alloy Nanoparticles
Authors: Ishizaki Manabu , Ono Kenta , Suzuki Kento , Naito Wataru , Kanaizuka Katsuhiko , Kawamoto Tohru , Tanaka Hisashi , Kurihara Masato 
Published: March 2017

AbstractA specific electronic interaction among metal ions emerges in solution‐processed films of coordination polymer (CP) nanoparticles (NPs). The most classic CP, Prussian blue (PB), is alloyed with Ni to form FexNi3−x[Fe(CN)6]2 showing an identical X‐ray crystallographic phase in all composition ratios of 0≤x≤3. By surface modification using [Fe(CN)6]4−, the PB alloy NPs are dispersed into water, and spin‐coated films of the NPs adhere to indium‐tin‐oxide substrates via a low‐temperature heating process at 100 °C. It is revealed that systematic fine tuning of the electronic energy levels is optically and electrochemically possible in the films by controlling the composition ratios. This is possible due to the d(t2g)–π*(C≡N−) electronic conjugation among three redox‐active iron species, FeII−C≡N, FeIII−C≡N, and FeIII−N≡C, which coexist by alloying with Ni. The heating process conducts the restoration of discontinued d–π* bonding networks among the NPs.
Predation environment affects boldness temperament of neotropical livebearers
Authors: Rasmussen Josh E. , Belk Mark C. 
Published: March 2017

AbstractBehavioral traits of individuals are important phenotypes that potentially interact with many other traits, an understanding of which may illuminate the evolutionary forces affecting populations and species. Among the five axes of temperament is the propensity to behave boldly in the presence of a perceived risk. To determine the effect of different predatorial regimes on boldness and fearfulness, we assessed the behavior of individuals in a novel portable swim chamber (i.e., forced open‐field test) by Brachyrhaphis rhabdophora (n = 633). We used an information theoretic framework to compare generalized (logistic) linear fixed‐effects models of predatorial regime (predator‐free [n = 6] and predator [n = 4] sites), sex, and standard length (SL). Fish from predator sites were much more fearful in the novel arena than fish from nonpredator sites. This varied by length, but not by sex. At 48 mm SL, fish from nonpredator sites were 4.9 times more likely to express bold behavior (ambulation) in the novel swim chamber as fish from predator sites. Probabilities of “ambulating” within the swim chamber increased with size for nonpredator sites and decreased with size for predator sites.
Outcome of subsequent pregnancies in patients with a history of peripartum cardiomyopathy
Authors: Hilfiker‐Kleiner Denise , Haghikia Arash , Masuko David , Nonhoff Justus , Held Dominik , Libhaber Elena , Petrie Mark C. , Walker Niki L. , Podewski Edith , Berliner Dominik , Bauersachs Johann , Sliwa Karen 
Published: March 2017

AbstractAimsSubsequent pregnancies (SSPs) in patients with peripartum cardiomyopathy (PPCM) have a high risk of heart failure relapse. We report on outcome of SSPs in PPCM patients in Germany, Scotland, and South Africa.Methods and resultsAmong 34 PPCM patients with a SSP, pregnancy ended prematurely in four patients while it was full‐term in 30. Overall relapse rate [left ventricular ejection fraction, (LVEF) <50% or death after at least 6‐month follow‐up] was 56% with 12% (4/34) mortality. Relapse of PPCM after SSP was not associated with differences in parity, twin pregnancy, gestational hypertension, or smoking. Persistently reduced LVEF (<50%) before entering SSP was present in 47% of patients while full recovery (LVEF ≥50%) was present in 53%. The majority of patients entering SSP with persistently reduced LVEF were of African ethnicity (75%). Persistently reduced LVEF before SSP was associated with higher mortality (25% vs. 0%) and lower rate of full recovery at follow‐up. Patients obtaining standard therapy for heart failure and bromocriptine immediately after delivery displayed significantly better LVEF at follow‐up and a higher rate of full recovery with no patient dying compared with patients obtaining standard therapy for heart failure alone. This was independent of African or Caucasian race.ConclusionFull recovery of LVEF before SSP was associated with lower mortality and better cardiac function at follow‐up. Addition of bromocriptine to standard therapy for heart failure immediately after delivery was safe and seemed to be associated with a better outcome of SSP in African and Caucasian patients.
Adsorption of phosphorus based on Hangjin clay granular ceramic from aqueous solution and sewage: Fixed‐bed column study
Authors: Yu Yang , Chen Nan , Wang Di , Tian Caixing , Li Miao , Feng Chuanping 
Published: March 2017

The aim of this study was to evaluate the potential use of the Hangjin clay ceramic adsorbent for phosphorus removal from aqueous solution and municipal sewage in column systems. The effect of several factors, including bed depth, initial phosphorus concentration, and flow rate was investigated at room temperature. As a result, the breakthrough time increased with increasing in the bed depth, whereas inverse relationship was observed with the initial phosphorus concentration and flow rate. Moreover, municipal sewage treatment results proved the effectiveness of the adsorbent in practical application and further demonstrated some co‐existing ions in sewage had little effect on the continuous adsorption process. Adsorption models, which are the basis for the process design at a real scale, were used to estimate the characteristic parameters of columns. The dynamic adsorption kinetic data well agreed with the Adams‐Bohart and Clark models. The Yoon‐Nelson and BDST models could be successfully used to predict the breakthrough time. The observed maximum dynamic adsorption capacity of the ceramic adsorbent for phosphorus removal was 19.28 mg g−1. The Hangjin clay granular ceramic could be used as a high‐efficiency phosphorus adsorbent in the aspect of the municipal sewage treatment. © 2017 American Institute of Chemical Engineers Environ Prog, 36: 1323–1332, 2017
Mincer–Zarnowitz quantile and expectile regressions for forecast evaluations under aysmmetric loss functions
Authors: Guler Kemal , Ng Pin T. , Xiao Zhijie 
Published: March 2017

AbstractForecasts are pervasive in all areas of applications in business and daily life. Hence evaluating the accuracy of a forecast is important for both the generators and consumers of forecasts. There are two aspects in forecast evaluation: (a) measuring the accuracy of past forecasts using some summary statistics, and (b) testing the optimality properties of the forecasts through some diagnostic tests. On measuring the accuracy of a past forecast, this paper illustrates that the summary statistics used should match the loss function that was used to generate the forecast. If there is strong evidence that an asymmetric loss function has been used in the generation of a forecast, then a summary statistic that corresponds to that asymmetric loss function should be used in assessing the accuracy of the forecast instead of the popular root mean square error or mean absolute error. On testing the optimality of the forecasts, it is demonstrated how the quantile regressions set in the prediction–realization framework of Mincer and Zarnowitz (in J. Mincer (Ed.), Economic Forecasts and Expectations: Analysis of Forecasting Behavior and Performance (pp. 14–20), 1969) can be used to recover the unknown parameter that controls the potentially asymmetric loss function used in generating the past forecasts. Finally, the prediction–realization framework is applied to the Federal Reserve's economic growth forecast and forecast sharing in a PC manufacturing supply chain. It is found that the Federal Reserve values overprediction approximately 1.5 times more costly than underprediction. It is also found that the PC manufacturer weighs positive forecast errors (under forecasts) about four times as costly as negative forecast errors (over forecasts).
Synthetic β‐nitrostyrene derivative CYT‐Rx20 as inhibitor of oral cancer cell proliferation and tumor growth through glutathione suppression and reactive oxygen species induction
Authors: Wang Yen‐Yun , Chen Yuk‐Kwan , Hsu Ya‐Ling , Chiu Wen‐Chin , Tsai Chun‐Hao , Hu Stephen Chu‐Sung , Hsieh Pei‐Wen , Yuan Shyng‐Shiou F. 
Published: March 2017

ABSTRACTBackgroundThe β‐nitrostyrene family possesses anticancer properties. In this study, β‐nitrostyrene derivative CYT‐Rx20 (3′‐hydroxy‐4′‐methoxy‐β‐methyl‐β‐nitrostyrene) was synthesized and investigated its anticancer activity in oral cancer.MethodsAnticancer activity of CYT‐Rx20 and the underlying mechanisms were analyzed using cell viability assay, reactive oxygen species (ROS) generation assay, fluorescence‐activated cell sorter analysis, annexin V staining, comet assay, glutathione (GSH)/glutathione disulfide (GSSG) ratio, immunoblotting, soft agar assay, nude mice xenograft study, and immunohistochemistry.ResultsCYT‐Rx20‐induced cell apoptosis via ROS generation and mitochondrial membrane potential reduction, associated with release of mitochondrial cytochrome C to cytosol and activation of downstream caspases and poly ADP‐ribose polymerase (PARP). Furthermore, CYT‐Rx20 induced mitochondrial ROS accumulation and mitochondrial dysfunction, followed by GSH downregulation. CYT‐Rx20‐induced cell apoptosis, ROS generation, and DNA damage were reversed by thiol antioxidants. In nude mice, CYT‐Rx20 inhibited oral tumor growth accompanied by increased expression of γH2AX, GSH reductase, and cleaved‐caspase‐3.ConclusionCYT‐Rx20 has the potential to be further developed into an antioral cancer drug clinically. © 2017 Wiley Periodicals, Inc. Head Neck 39: 1055–1064, 2017
HydRun: A MATLAB toolbox for rainfall–runoff analysis
Authors: Tang Weigang , Carey Sean K. 
Published: March 2017

AbstractUnderstanding the nature of streamflow response to precipitation inputs is at the core of hydrological applications and water resource management. Indices such as the base flow index, recession constant, and response lag of a watershed retain an important place in hydrology as metrics to compare watersheds and understand the impact of human activity, geology, geomorphology, soils, and climate on precipitation–runoff relations. Extracting characteristics of the hyetograph–hydrograph relationship is often done manually, which is time consuming and may result in subjective and potentially inconsistent outcomes. Here, we present a MATLAB‐based toolbox, called HydRun, for rapid and flexible rainfall–runoff analysis. HydRun uses a series of flexible routines to extract base flow from the hydrograph and then computes commonly used time instants of the rainfall–runoff relationship. HydRun provides users the flexibility to decide thresholds and limits of analysis, but objectively computes hydrometric indices. The toolkit includes a graphical user interface and example files. In this paper, we apply HydRun to 4 watersheds, 3 in Scotland and 1 in Canada, to demonstrate the software functions and highlight important decisions the user must make in its application.
Fabrication of a mechanically anisotropic poly(glycerol sebacate) membrane for tissue engineering
Authors: Hsu Chi‐Nung , Lee Pei‐Yuan , Tuan‐Mu Ho‐Yi , Li Chen‐Yu , Hu Jin‐Jia 
Published: March 2017

AbstractPoly(glycerol sebacate) (PGS) has been used successfully as a scaffolding material for soft tissue engineering. PGS scaffolds, however, are usually mechanically isotropic, which may restrict their use in tissue repairs as many soft tissues in the body have anisotropic mechanical behaviors. Although various methods have been used to fabricate anisotropic scaffolds, it remains challenging to make anisotropic scaffolds from thermoset PGS. Here a new, simple method to fabricate an anisotropic PGS membrane which can then be used to construct thicker three‐dimensional anisotropic scaffolds was developed. First, an aligned sacrificial poly(vinyl alcohol) fibrous membrane was prepared by electrospinning. The fibrous membrane was then partially immersed in PGS prepolymer solution, resulting in a composite membrane upon drying. After curing, the sacrificial fibers within the membrane were removed by water, supposedly leaving aligned cylindrical pores in the membrane. Both SEM and AFM illustrated aligned grooves on the surface of the resultant PGS membrane, indicating the successful removal of sacrificial fibers. The PGS membrane was validated to be mechanically anisotropic using uniaxial tensile testing along and perpendicular to the predominant pore direction. The in vitro cytocompatibility of the PGS membrane was confirmed. As a demonstration of its potential application in vascular tissue engineering, a tubular scaffold was constructed by wrapping a stack of two axisymmetric pieces of the anisotropic PGS membranes on a mandrel. The compliance of the scaffold was found to depend on the pitch angle of its double helical structure, imitating the anisotropic mechanical behavior of the arterial media. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 760–770, 2018.
Exploring the influence of MPA‐capped CdTe quantum dots on the structure and function of lysozyme probing by spectroscopic and calorimetric methods
Authors: Zhao Lining , Sun Tao , Zhang Xun , Song Wei , Liu Rutao 
Published: March 2017

AbstractThe effect of 3‐mercaptopropionic acid (MPA)‐capped CdTe quantum dots (QDs) on lysozyme was systematically investigated by spectroscopic methods, enzyme activity assay, and calorimetry techniques. Results show that the MPA‐capped CdTe QDs binded to lysozyme through van der Walls forces and hydrogen bondings, causing the decrement of α‐helical content (∼7%) and increment of β‐sheet content (∼11%) of lysozyme. The binding caused static quenching of the fluorescence, while the microenvironment of aromatic amino acid residues did not show any significant alteration. The lysozyme activity was affected by the increasing exposure of QDs, it was inhibited to 53.77% under a 6 × 10−7 M exposure compared with the control group. This work will provide direct evidence about enzyme toxicity of QDs to lysozyme in vitro.