bluuebunny/crossref_metadata_2025 huggingface dataset:
Class I Histone Deacetylase Inhibition Modulates Metalloproteinase Expression and Blocks Cytokine‐Induced Cartilage Degradation
Authors: Culley Kirsty L. , Hui Wang , Barter Matt J. , Davidson Rose K. , Swingler Tracey E. , Destrument Auriane P. M. , Scott Jenny L. , Donell Simon T. , Fenwick Steve , Rowan Andrew D. , Young David A. , Clark Ian M.
Published: April 2013

Objective

To examine the ability of a broad‐spectrum histone deacetylase (HDAC) inhibitor to protect cartilage in vivo, and to explore the effects of class‐selective HDAC inhibitors and small interfering RNA (siRNA)–induced knockdown of HDACs on metalloproteinase expression and cartilage degradation in vitro.

Methods

A destabilization of the medial meniscus (DMM) model was used to assess the in vivo activity of the HDAC inhibitor trichostatin A (TSA). Human articular chondrocytes (HACs) and SW‐1353 chondrosarcoma cells were treated with cytokines and TSA, valproic acid, MS‐275, or siRNA, and quantitative reverse transcription–polymerase chain reaction was performed to determine the effect of treatment on metalloproteinase expression. HDAC inhibitor activity was detected by Western blotting. A bovine nasal cartilage (BNC) explant assay was performed to measure cartilage resorption in vitro.

Results

Systemically administered TSA protected cartilage in the DMM model. TSA, valproic acid, and MS‐275 repressed cytokine‐induced MMP1 and MMP13 expression in HACs. Knockdown of each class I HDAC diminished interleukin‐1–induced MMP13 expression. All of the HDAC inhibitors prevented degradation of BNC, in which TSA and MS‐275 repressed cytokine‐induced MMP expression.

Conclusion

Inhibition of class I HDACs (HDAC‐1, HDAC‐2, HDAC‐3) by MS‐275 or by specific depletion of HDACs is capable of repressing cytokine‐induced metalloproteinase expression in cartilage cells and BNC explants, resulting in inhibition of cartilage resorption. These observations indicate that specific inhibition of class I HDACs is a possible therapeutic strategy in the arthritides.
C‐Reactive Protein Inhibits Plasmacytoid Dendritic Cell Interferon Responses to Autoantibody Immune Complexes
Authors: Mold Carolyn , Clos Terry W. Du
Published: April 2013

Objective

C‐reactive protein (CRP) is a serum pattern recognition molecule that binds to apoptotic cells and nucleoprotein autoantigens and Fcγ receptors (FcγR). In systemic lupus erythematosus (SLE), immune complexes (ICs) containing nucleoprotein autoantigens activate plasmacytoid dendritic cells (PDCs) to produce type I interferon (IFN), which contributes to disease pathogenesis. Autoantibody ICs are taken up by PDCs through FcγR type IIa into endosomes, where the nucleic acid components activate Toll‐like receptor 7 (TLR‐7) or TLR‐9. The objective of this study was to investigate the effect of CRP on PDC and monocyte responses to nucleoprotein autoantigens and ICs.

Methods

Peripheral blood mononuclear cells (PBMCs), purified monocytes, and PDCs were isolated from healthy volunteers and stimulated with autoantibody ICs containing apoptotic cells, small nuclear RNPs (snRNPs), or DNA, or directly with TLR‐7 and TLR‐9 agonists. Supernatants were analyzed for IFNα and cytokine levels by enzyme‐linked immunosorbent assay and multiplex assay. Small nuclear RNPs were fluorescence‐labeled, and the effect of CRP on binding, uptake, and intracellular localization of autoantibody snRNP complexes was measured by flow cytometry and confocal microscopy.

Results

CRP bound to autoantigen did not induce IFNα in PBMCs or PDCs, whereas complexes formed with autoantibody did. Significantly, CRP inhibited the IFNα response to both anti–U1 RNP–snRNP complexes and anti‐DNA–DNA complexes, but not to other TLR‐7 and TLR‐9 agonists. CRP directly inhibited PDC IFNα release, promoted PDC differentiation, and increased late endosome localization of autoantigen in PDCs and monocytes.

Conclusion

CRP is a regulator of the type I IFN response to SLE ICs. CRP increased the intracellular processing of ICs in late endosomes, which is associated with decreased synthesis of type I IFN after intracellular TLR activation.
Cancer Incidence in Systemic Sclerosis: Meta‐Analysis of Population‐Based Cohort Studies
Authors: Onishi Akira , Sugiyama Daisuke , Kumagai Shunichi , Morinobu Akio
Published: April 2013

Objective

To examine cancer incidence in patients with systemic sclerosis (SSc) through a meta‐analysis of population‐based cohort studies.

Methods

Five different databases (Medline, Scopus, CINAHL [Cumulative Index to Nursing and Allied Health Literature], Web of Science, and Cochrane Collaboration) were searched for articles published between January 1966 and May 2012; review articles and the reference lists from the articles that resulted from the search were also evaluated. Population‐based cohort studies with data relevant to the determination of cancer risk in patients with SSc were included. All articles that met strict inclusion criteria were analyzed for data on population size, time of followup, and observed‐to‐expected cancer ratios, also known as standardized incidence ratios (SIRs).

Results

Six articles met criteria and were included in the meta‐analysis. The pooled SIR for the incidence of cancer overall was 1.41 (95% confidence interval [95% CI] 1.18–1.68), and significant heterogeneity was observed as a consequence of variability in the participants, outcome, study design, and risk of bias among the studies. Men had a significantly higher pooled SIR (1.85 [95% CI 1.49–2.31]) than women (SIR 1.33 [95% CI 1.18–1.49]) (P < 0.01), and stratification for sex eliminated heterogeneity, which indicates that variability among the studies greatly contributed to differences between the sexes. There were no differences between limited cutaneous SSc and diffuse cutaneous SSc (P = 0.77). Significant increases were observed in the risk of cancer of the lung, liver, hematologic system, and bladder, as well as of non‐Hodgkin's lymphoma and leukemia.

Conclusion

SSc is associated with an increased risk of cancer, particularly lung, liver, hematologic, and bladder cancers, although absolute risk is relatively low. Men with SSc have a higher risk of developing cancer than women.
Effects of awareness on coordination in collaborative information seeking
Authors: Shah Chirag
Published: April 2013

Communication and coordination are considered essential components of successful collaborations, and provision of awareness is a highly valuable feature of a collaborative information seeking (CIS) system. In this article, we investigate how providing different kinds of awareness support affects people's coordination behavior in a CIS task, as reflected by the communication that took place between them. We describe a laboratory study with 84 participants in 42 pairs with an experimental CIS system. These participants were brought to the laboratory for two separate sessions and given two exploratory search tasks. They were randomly assigned to one of the three systems, defined by the kind of awareness support provided. We analyzed the messages exchanged between the participants of each team by coding them for their coordination attributes. With this coding, we show how the participants employed different kinds of coordination during the study. Using qualitative and quantitative analyses, we demonstrate that the teams with no awareness, or with only personal awareness support, needed to spend more time and effort doing coordination than those with proper group awareness support. We argue that appropriate and adequate awareness support is essential for a CIS system for reducing coordination costs and keeping the collaborators well coordinated for a productive collaboration. The findings have implications for system designers as well as cognitive scientists and CIS researchers in general.
Economic ‘revelations’ and the metaphors of the meltdown: an educational deconstruction
Authors: Stronach Ian , Clarke John , Frankham Jo
Published: April 2013

This article subjects contemporary informed discourse on the Credit Crunch/Great Recession/Long Recession to educational analysis and deconstruction. Such pro‐capitalist but not uncritical discourse is well represented by the UK Financial Times, whose columns between 2008 and 2012 comprise most of our data. We argue that the metaphors of the ‘meltdown’ are significant and performative, allowing variously moralised narratives to emerge as implicit diagnoses and remedies. In particular we identify a ‘domestic’ register of metaphors whose contained and homely tropes of austerity, prudence, book‐balancing and so on stand in dramatic contrast to a more melodramatic register, centring on various disaster scenarios. What is of most interest is that financial journalists and commentators switch between these registers, and allow ‘crossovers’ between them which are powerful in their discursive effects and political persuasiveness. These metaphorical discursive resources are intimately connected to the sorts of educational registers that characterise the ‘knowledge economy’. We conclude that our cultural ability to tell these sorts of stories rests as much on an underlying moral and theological storying as it does on any ‘scientific’ economic account (if such there can be, which we doubt). In this way we seek to educate economic discourses that are, as it were, ‘economical with the truth’.
Managing legitimacy in the educational quasi‐market: a study of ethnically diverse, inclusive schools in Flanders
Authors: Mampaey Jelle , Zanoni Patrizia
Published: April 2013

In this paper, we examine how ethnically diverse, inclusive schools manage their legitimacy in an educational quasi‐market. These schools are often threatened with a loss of legitimacy as ethnic majority parents perceive an ethnically diverse student population and radical pedagogical practices as signs of lower quality education. However, precisely legitimacy in the eyes of ethnic majority parents is crucial to acquire resources, motivate staff members and maintain their ability to offer quality education, necessary to minimize the majority–minority educational attainment gap in the long run. Drawing on a theoretical approach combining neo‐institutional and impression management theories, we empirically investigate how four ethnically diverse, inclusive secondary schools embedded in the highly exclusive Flemish educational quasi‐market manage their legitimacy. Comparing their legitimacy management strategies, we find that maintaining legitimacy is related to (1) formally conforming to dominant norms, decoupling their radical practices by relegating them to the informal sphere; and (2) proactively manipulating perceptions of the school's ethnic diversity and radical pedagogical practices. However, our findings suggest that an ambiguous version of these strategies might be sufficient to achieve this aim.
Mikroben unter Strom
Authors: Agler‐Rosenbaum Miriam , Schröder Uwe , Harnisch Falk
Published: April 2013

Stromleitende Mikroben – das klingt nach Science Fiction oder zumindest nach einem exotischen natürlichen Phänomen. Intensive Grundlagenforschung in diesem Bereich zeigt jedoch, dass dieser Prozess in der anaeroben mikrobiellen Ökologie weit verbreitet scheint. Mikroben “verdrahten” sich mit ihrer belebten und unbelebten Umwelt, um energetische Netzwerke aufzubauen. In mikrobiellen bioelektrochemischen Systemen wird versucht, diese Erkenntnisse für umwelt‐ und biotechnologischen Anwendungen nutzbar zu machen. Während frühe Vorhaben fast ausschließlich darauf abzielten, mit Hilfe dieser Netzwerke Energie als elektrischen Strom in mikrobiellen Brennstoffzellen zu gewinnen, entsteht mittlerweile eine wachsende Vielfalt weiterführender Anwendungen. Dabei ermöglicht uns unser wachsendes Verständnis des mikrobiellen extrazellulären Elektronentransfers, diese Prozesse kontrolliert für uns nutzbar zu machen.
Maikäfer flieg: Im Frühling erobern Käfer den Garten
Authors: Petrischak Hannes
Published: April 2013

Nur versierte Spezialisten können die gesamte Käfer‐Vielfalt überschauen, die sich auf Blüten und Blättern, unter Steinen und Totholz im Garten zeigen kann. Es ist ein besonderes Naturerlebnis, wenn an warmen Frühlingsabenden große Käfer in schwerfälligem Flug ums Haus schwärmen. Durch metallischen Glanz und leuchtende Farben, interessante Lebenszyklen oder auch lästigen Fraß an Zier‐ und Nutzpflanzen machen viele Arten auf sich aufmerksam.
Das Erfolgsrezept der Blattschneiderameisen
Authors: Hille‐Rehfeld Annette
Published: April 2013

Die Anlage von Pilzgärten als protein‐ und vitaminreiche Nahrungsquelle ist bei Ameisen weit verbreitet. Die bei dieser Symbiose kultivierten Pilze stammen von frei lebenden Saprophyten ab, die frische Pflanzen wegen ihres hohen Gehalts an Abwehrstoffen schlecht verwerten können. Blattschneiderameisen gelang es dennoch, diese Nahrungsquelle für ihre Pilze zu erschließen: Sie verbessern die Bekömmlichkeit der eingetragenen Blätter durch Vorbehandlung mit einem besonders stabilen, mit dem Kot übertragenen Entgiftungsenzym des Pilzes, einer Laccase. Solche Phenoloxidasen mit breiter Substratspezifität gehören neuerdings zum Repertoire der umweltfreundlichen grünen Chemie im Biotechnologiesektor.
Ethisches Bewerten im Unterricht
Authors: Hößle Corinna
Published: April 2013

Die rasante Entwicklung der Naturwissenschaften und der Technik eröffnet viele neue Urteils‐ und Handlungsmöglichkeiten. Sie sind teilweise mit erheblichen ethischen Schwierigkeiten und Konflikten verknüpft, die durch die bestehenden traditionellen Normen nicht immer eindeutig geregelt werden. Viele neue ethische Fragestellungen beziehen sich auf Handlungsbereiche, die den Menschen erst seit wenigen Jahren oder Jahrzehnten offen stehen, beispielsweise der Anbau von gentechnisch veränderten Pflanzen oder die Pränataldiagnostik.
Erste Hilfe für historische Wandtafeln
Authors: Abramowicz Julia , Markert Michael , Hoßfeld Uwe
Published: April 2013

Wandtafeln erfahren an Schulen und Hochschulen aufgrund ihrer besonderen didaktischen Merkmale teilweise noch heute eine ausgiebige Nutzung, wobei auf den Erhaltungszustand der teilweise kostbaren und seltenen Stücke nicht unbedingt viel Rücksicht genommen wird. Eine fachgerechte Restaurierung ist für Schulen und Institute oft nicht finanzierbar – die hier vorgestellte Notsicherung gewährleistet zumindest den Erhalt der Tafeln.
Ausfällung durch Ammoniumsulfat
Authors: Hauk Andrea
Published: April 2013

Das Ausfällen von Proteinen steht oft am Anfang der Reinigungsprozedur einer Proteinlösung und dient der Entfernung grober Verunreinigungen wie Lipiden, Kohlenhydraten, Nukleinsäuren und Proteinen mit anderem Lösungsverhalten. Die einsetzbaren Techniken variieren und reichen von der Änderung des pH‐Wertes über Fällung durch Hitze bis hin zum Einsatz organischer Lösungsmittel oder hoher Salzkonzentrationen, wobei das Aussalzen hier die am häufigsten benutzte Methode darstellt. Als eine der bekanntesten Methoden gilt die Ammoniumsulfatfällung.
Alkaloids from Cephalotaxus lanceolata and Their Cytotoxicities
Authors: He Yi‐Ren , Shen Yun‐Heng , Li Bo , Li Bo , Lu Lu , Tian Jun‐Mian , Zhang Wei‐Dong
Published: April 2013

A phytochemical investigation of the branches and leaves of Cephalotaxus lanceolata resulted in the isolation of three new cephalotaxus alkaloids, cephalancetines A, B, and D (1, 2, and 4, resp.), together with ten known alkaloids, 3 and 5–13. The structures of the alkaloids were elucidated on the basis of spectroscopic analyses, including 1D‐ and 2D‐NMR, and HR‐ESI‐MS, and single‐crystal X‐ray diffraction. All isolated compounds were tested for their cytotoxicities against four human tumor cell lines, A549, HCT116, SK‐BR‐3, and HepG2. Compounds 12 and 13 showed remarkable activities against A549, HCT116, and HepG2 cell lines.
Synthesis and Antifungal Activities of Trichodermin Derivatives as Fungicides on Rice
Authors: Xu Xiaojun , Cheng Jingli , Zhou Yong , Zhang Chulong , Ou Xiaoming , Su Weike , Zhao Jinhao , Zhu Guonian
Published: April 2013

Twenty new trichodermin derivatives, 2a–5, containing alkoxy, acyloxy, and Br groups in 4‐, 8‐, 9‐, 10‐ and 16‐positions were synthesized and characterized. The antifungal activities of the new compounds against rice false smut (Ustilaginoidea virens), rice sheath blight (Rhizoctonia solani), and rice blast (Magnaporthe grisea) were evaluated. The results of bioassays indicated that the antifungal activities were particularly susceptible to changes at 4‐, 8‐, and 16‐positions, but low to changes at 9‐ and 10‐positions. Most of these target compounds exhibited good antifungal activities at the concentration of 50 mg l−1. Compound 4 (9‐formyltrichodermin; EC50 0.80 mg l−1) with an CHO group at 9‐position displayed nearly the same level of antifungal activity against Ustilaginoidea virens as the commercial fungicide prochloraz (EC50 0.82 mg l−1), while compound 3f ((8R)‐8‐{[(E)‐3‐phenylprop‐2‐enoyl]oxy}trichodermin; EC50 3.58 and 0.74 mg l−1) with a cinnamyloxy group at C(8) exhibited much higher antifungal activities against Rhizoctonia solani and Magnaporthe grisea than the commercial fungicides prochloraz (EC50 0.96 mg l−1) and propiconazole (EC50 5.92 mg l−1), respectively. These data reveal that compounds 3f and 4 possess high antifungal activities and may serve as lead compounds for the development of fungicides in the future.
Essential Oil of Indian Propolis: Chemical Composition and Repellency against the Honeybee Apis florea
Authors: Naik Dattatraya G. , Vaidya Harshada S. , Namjoshi Tejas P.
Published: April 2013

Hitherto unknown biological properties and the chemical composition of the essential oil isolated from propolis of Indian origin were established. GC/MS Analysis of the essential oil revealed the presence of 32 constituents, of which ten were major compounds, nine had intermediate contents, and 13 were minor compounds. With the exception of six minor constituents, that could not be identified, their identification was based on the comparison of their mass spectra and Kovats retention indices with those listed in the NIST and Wiley mass spectral libraries. Their structural assignment was confirmed by GC/MS co‐injection of the essential oil with authentic compounds. Quantification of the components was done by GC‐FID analyses. Moreover, the essential oil was shown to possess repellent activity against the honeybee Apis florea. The activity was found to be dose dependent. The average repellency (ΔR) increased with increasing essential‐oil concentration up to 24 μg/ml and remained constant for the formulation with the higher concentration. These findings established the chemical constitution of the essential oil and might be useful to beekeepers for the improvement of the bee management.
Essential Oils from the Roots of Echinops bannaticusRochel ex Schrad. and Echinops sphaerocephalus L. (Asteraceae): Chemotaxonomic and Biosynthetic Aspects
Authors: Radulović Niko S. , Denić Marija S.
Published: April 2013

Herein, we report, for the first time, the results of detailed chemical and statistical analyses of the essential oils from the roots of two Echinops species (Asteraceae), E. bannaticus Rochel ex Schrad., and E. sphaerocephalus L., from the weed flora of Serbia. Among 106 and 81 constituents, respectively, S‐containing polyacetylene compounds and triquinane sesquiterpenoids made up ca. 80% of the oils. Several of these compounds are reported here as new metabolites for the two species or even for the genus Echinops. A multivariate statistical comparison of the essential‐oil composition data for these two and additional six taxa of this genus available from the literature permitted an examination of the mutual relationships of the taxa within this morphologically highly uniform genus. Principal component analysis (PCA) and agglomerative hierarchical clustering revealed a grouping of E. bannaticus and E. sphaerocephalus (both belonging to the section Echinops), and their close relationship with E. grijsii, suggesting a circumscription of this Chinese taxon to the section Echinops. PCA Correlation matrix offered valuable insight into the biosynthetic links between essential‐oil constituents, and these agreed excellently with the currently proposed ones for the polyacetylene S‐containing compounds, triquinanes, and monoterpenes.
Endovascular treatment of type B dissection in patients with marfan syndrome: Mid‐term outcomes and aortic remodeling
Authors: Eid‐Lidt Guering , Gaspar Jorge , Meléndez‐Ramírez Gabriela , Cervantes S. Jorge , González‐Pacheco Hector , Dámas de Los Santos Félix , Meave‐González Aloha , Ramírez Marroquín Samuel
Published: April 2013

Objectives

To evaluate the mid‐term outcomes, and the aortic remodeling in Marfan syndrome (MFS) patients with type B dissection that were treated with endovascular repair.

Background

MFS is a relative contraindication to thoracic endovascular aortic repair (TEVAR). Mid‐term aortic outcomes data in MFS after TEVAR are limited, and the occurrence of late events remains unclear.

Methods

Of 89 patients that underwent TEVAR between September 2002 and February 2011, 10 patients with mid‐term follow‐up fulfilled the Ghent criteria for MFS and complicated type B dissection. High risk for open surgery was documented in 90%.

Results

The mean age was 35.1 ± 9.4 years and all patients presented with acute aortic syndrome complicating a chronic type B dissection (DeBakey type IIIb). Five patients underwent a Bentall surgical procedure previous to endovascular repair, and in four patients initial TEVAR was followed by surgery of the ascending aorta. Treatment was limited to endovascular repair in only one patient. In‐hospital mortality was 10%. At a mean follow‐up of 59.6 ± 38.9 months, the cumulated mortality was of 20% and late mortality 11.1%. The rate of secondary endoleak was 44.4%, and late reintervention of 33.3%. Survival freedom from cardiovascular death at 8 years was 80.0%, and positive remodeling was documented in 37.5% of patients.

Conclusions

Our results suggest that TEVAR is feasible, safe, and associated with a high reintervention rate and reduced rate of positive aortic remodeling in patients with Marfan syndrome. Survival at 8 years was comparable to contemporary series of open repair. © 2012 Wiley Periodicals, Inc.
Encapsulation of an Olefin Metathesis Catalyst in the Nanocages of SBA‐1: Facile Preparation, High Encapsulation Efficiency, and High Activity
Authors: Yang Hengquan , Ma Zhancheng , Zhou Ting , Zhang Wenjuan , Chao Jianbin , Qin Yong
Published: April 2013

By postreducing the window size through silylation, 2nd generation Hoveyda–Grubbs catalyst was encapsulated in the nanocages of a mesoporous material SBA‐1. The encapsulation efficiency of SBA‐1 was up to 70 %, much higher than that of other mesoporous materials such as SBA‐16, FDU‐12, and MCM‐41 (0–43 %). The successful encapsulation was confirmed by N2 sorption analysis and FTIR and diffusion reflectance UV/Vis spectroscopy. Such a SBA‐1‐encapsulated catalyst showed good activity in both olefin ring‐closing metathesis and cross metathesis. A wide range of olefins could be transformed to the desired products with conversions of 27–100 %. The encapsulated catalyst showed more sensitive temperature effects than the homogeneous counterpart, reflecting the unique properties of the encapsulated catalyst. At reaction temperatures of 40–60 °C, the activity of the encapsulated catalyst was sufficiently comparable to that of the homogeneous catalyst for the cross metathesis of styrene‐type substrates, probably because of the confinement effects of the nanocages. The solid catalyst could be recycled seven times. This study not only supplies a new solid catalyst for olefin metathesis but also demonstrates our improvement in immobilizing metal complex catalyst toward a green and effective level.
Protein‐Directed Synthesis of Mn‐Doped ZnS Quantum Dots: A Dual‐Channel Biosensor for Two Proteins
Authors: Wu Peng , Zhao Ting , Tian Yunfei , Wu Lan , Hou Xiandeng
Published: April 2013

Proteins typically have nanoscale dimensions and multiple binding sites with inorganic ions, which facilitates the templated synthesis of nanoparticles to yield nanoparticle–protein hybrids with tailored functionality, water solubility, and tunable frameworks with well‐defined structure. In this work, we report a protein‐templated synthesis of Mn‐doped ZnS quantum dots (QDs) by exploring bovine serum albumin (BSA) as the template. The obtained Mn‐doped ZnS QDs give phosphorescence emission centered at 590 nm, with a decay time of about 1.9 ms. A dual‐channel sensing system for two different proteins was developed through integration of the optical responses (phosphorescence emission and resonant light scattering (RLS)) of Mn‐doped ZnS QDs and recognition of them by surface BSA phosphorescent sensing of trypsin and RLS sensing of lysozyme. Trypsin can digest BSA and remove BSA from the surface of Mn‐doped ZnS QDs, thus quenching the phosphorescence of QDs, whereas lysozyme can assemble with BSA to lead to aggregation of QDs and enhanced RLS intensity. The detection limits for trypsin and lysozyme were 40 and 3 nM, respectively. The selectivity of the respective channel for trypsin and lysozyme was evaluated with a series of other proteins. Unlike other protein sensors based on nanobioconjugates, the proposed dual‐channel sensor employs only one type of QDs but can detect two different proteins. Further, we found the RLS of QDs can also be useful for studying the BSA–lysozyme binding stoichiometry, which has not been reported in the literature. These successful biosensor applications clearly demonstrate that BSA not only serves as a template for growth of Mn‐doped ZnS QDs, but also impacts the QDs for selective recognition of analyte proteins.
Intramolecular [2+2] Photocycloaddition of 3‐ and 4‐(But‐3‐enyl)oxyquinolones: Influence of the Alkene Substitution Pattern, Photophysical Studies, and Enantioselective Catalysis by a Chiral Sensitizer
Authors: Maturi Mark M. , Wenninger Matthias , Alonso Rafael , Bauer Andreas , Pöthig Alexander , Riedle Eberhard , Bach Thorsten
Published: April 2013

The intramolecular [2+2] photocycloaddition of four 4‐(but‐3‐enyl)oxyquinolones (substitution pattern at the terminal alkene carbon atom: CH2, Z‐CHEt, E‐CHEt, CMe2) and two 3‐(but‐3‐enyl)oxyquinolones (substitution pattern: CH2, CMe2) was studied. Upon direct irradiation at λ=300 nm, the respective cyclobutane products were formed in high yields (83–95 %) and for symmetrically substituted substrates with complete diastereoselectivity. Substrates with a Z‐ or E‐substituted terminal double bond showed a stereoconvergent reaction course leading to mixtures of regio‐ and diastereomers with almost identical composition. The mechanistic course of the photocycloaddition was elucidated by transient absorption spectroscopy. A triplet intermediate was detected for the title compounds, which–in contrast to simple alkoxyquinolones such as 3‐butyloxyquinolone and 4‐methoxyquinolone–decayed rapidly (τ≈1 ns) through cyclization to a triplet 1,4‐diradical. The diradical can evolve through two reaction channels, one leading to the photoproduct and the other leading back to the starting material. When the photocycloaddition was performed in the presence of a chiral sensitizer (10 mol %) upon irradiation at λ=366 nm in trifluorotoluene as the solvent, moderate to high enantioselectivities were achieved. The two 3‐(but‐3‐enyl)oxyquinolones gave enantiomeric excesses (ees) of 60 and 64 % at −25 °C, presumably because a significant racemic background reaction occurred. The 4‐substituted quinolones showed higher enantioselectivities (92–96 % ee at −25 °C) and, for the terminally Z‐ and E‐substituted substrates, an improved regio‐ and diastereoselectivity.
Molecular Design Rule of Phthalocyanine Dyes for Highly Efficient Near‐IR Performance in Dye‐Sensitized Solar Cells
Authors: Kimura Mutsumi , Nomoto Hirotaka , Suzuki Hiroyuki , Ikeuchi Takuro , Matsuzaki Hiroyuki , Murakami Takuro N. , Furube Akihiko , Masaki Naruhiko , Griffith Matthew J. , Mori Shogo
Published: April 2013

A series of zinc–phthalocyanine sensitizers (PcS16–18) with different adsorption sites have been designed and synthesized in order to investigate the dependence of adsorption‐site structures on the solar‐cell performances in zinc–phthalocyanine based dye‐sensitized solar cells. The change of adsorption site affected the electron injection efficiency from the photoexcited dye into the nanocrystalline TiO2 semiconductor, as monitored by picosecond time‐resolved fluorescence spectroscopy. The zinc–phthalocyanine sensitizer PcS18, possessing one carboxylic acid directly attached to the ZnPc ring and six 2,6‐diisopropylphenoxy units, showed a record power conversion efficiency value of 5.9 % when used as a light‐harvesting dye on a TiO2 electrode under one simulated solar condition.
Use and need for psychosocial support in cancer patients
Authors: Ernst Johanna Christine , Beierlein Volker , Romer Georg , Möller Birgit , Koch Uwe , Bergelt Corinna
Published: April 2013

BACKGROUND

Cancer patients and their minor children have been shown to experience psychological distress. The objectives of the current study were to 1) describe the need for and use of psychosocial support and 2) determine predictors of family‐centered support use in patients with minor children.

METHODS

A population‐based sample of 1809 patients was recruited via 2 cancer registries. The eligibility criteria were age 25 years to 55 years, an initial diagnosis received no longer than 6 years before this survey, and having at least 1 minor child. Medical characteristics and self‐report measures were used.

RESULTS

Overall, approximately 38% cases were identified as being borderline or probable anxiety cases and 16% were identified as being borderline or probable depression cases. Since diagnosis, 44% of the patients had used psychosocial support and 9% had received family‐focused and child‐focused support. These patients perceived a lower quality of life and poorer family functioning. Approximately 73% of patients with children wanted information concerning or psychosocial services to support their children or parenting. Use of family‐centered support was not found to be predicted by disease‐related factors (eg, cancer staging) but rather by subjective needs (eg, mental health and having a distressed child in the family).

CONCLUSIONS

The results of the current study emphasize the importance of child and parenting concerns in psychosocial care in oncology. Screenings for children and appropriate training programs for health care may increase awareness of this issue. Cancer 2013;119:2333–2341. © 2013 American Cancer Society.
Close margin alone does not warrant postoperative adjuvant radiotherapy in oral squamous cell carcinoma
Authors: Ch'ng Sydney , Corbett‐Burns Sophie , Stanton Norm , Gao Kan , Shannon Kerwin , Clifford Anthony , Gupta Ruta , Clark Jonathan R.
Published: April 2013

BACKGROUND

There are major variations between institutions regarding postoperative adjuvant therapy for adverse features in patients with oral squamous cell carcinoma (SCC). The authors' practice has been to not recommend any adjuvant therapy on the basis of close (<5 mm but uninvolved) margins unless there are additional adverse features. The primary objective of this study was to assess whether the local control achieved in this patient cohort was acceptable.

METHODS

In this single‐institution, retrospective analysis, local control was the primary endpoint, and disease‐specific survival (DSS) was the secondary endpoint. Differences in survival were determined using the log‐rank test, and survival curves were generated using the Kaplan‐Meier method.

RESULTS

One hundred forty‐four patients (79 men and 65 women; median age, 64.1 years; mean follow‐up, 3.3 years) underwent surgery alone for oral SCC with curative intent and were recorded as having close tumor margins on histology. The local control rate for all patients who underwent surgery alone was 91% (95% confidence interval, 81.9%‐95.2%), and the DSS rate was 84% (95% confidence interval, 74.0%‐89.9%) at 5 years. There was no pattern of worse local control or DSS rates with the ordered stratification of close margins. The 5‐year local control rates for having 0, 1, 2, and 3 additional adverse features were 100%, 96%, 83%, and 71%, respectively (P = .004; trend test).

CONCLUSIONS

Surgery alone without postoperative adjuvant therapy offered acceptable local control in patients who had close margin status as their only adverse feature and may be reasonable in the presence of 1 other adverse clinicopathologic feature. Cancer 2013;119:2427‐2437. © 2013 American Cancer Society.
Synthesis of Oxindoles through the Gold‐Catalyzed Oxidation of N‐Arylynamides
Authors: Yang Liu‐Qing , Wang Kai‐Bing , Li Chuan‐Ying
Published: April 2013

α‐Oxo gold carbenoids generated by the oxidation of N‐arylynamides can be trapped intramolecularly at the ortho position of the aryl ring to give functionalized oxindoles under mild reaction conditions. Pyridine N‐oxide works as the oxidant, ligand, and base in this transformation.
Easy peak tracking in CE‐UV and CE‐UV‐ESI‐MS by incorporating temperature‐correlated mobility scaling
Authors: Li Bin , Petersen Nickolaj J. , Andersen Line H. , Hansen Steen H.
Published: April 2013

A simple data reconstruction technique in CE‐UV‐ESI‐MS (where UV stands for ultraviolet) is presented to overcome the drift in mobilities caused by various factors compromising the reproducibility of such data, for example Joule heating effects and the variation in thermostatic control along the capillary, drift in EOF and the suction effect caused by the nebulizing gas in coaxial CE‐MS interfaces. We present here a method to transform the traditional time‐based electropherogram into the corresponding temperature‐correlated mobility scale allowing tracking of analytes independent from capillary dimensions, electric field strengths, temperature control, and distance between the detectors. The main principle of this alignment is based on including the current in the mobility calculations and relating this to the initial electrical resistance of the buffer‐filled capillary. The temperature‐correlated mobility calculation eliminates the peak shifts due to the viscosity changes, improves the precision of peak identification using the observed temperature‐correlated mobilities, and allows a direct comparison of signals from different detection combinations. The method allows peaks from normal CE‐UV separations to be correlated with the corresponding peak obtained by MS detection in CE‐MS even for differences in capillary dimensions and thermostatic control.
Treatment of pyrolysis wastewater using heterogeneous advanced oxidation processes
Authors: Mehrjouei Mohammad , Müller Siegfried , Möller Detlev
Published: April 2013

In this study, treatment of a real wastewater sample produced in a thermal pyrolysis plant for plastic waste disposal was performed using a practical design of multiphase falling film reactor. The reduction in the level of chemical oxygen demand (COD) as well as color removal of this type of wastewater was evaluated by means of three different heterogeneous advanced oxidation processes (TiO2/UVA/O2, TiO2/O3, and TiO2/UVA/O3). In addition, the effect of acidification of this type of wastewater as well as the influence of the content of phosphate anions existing in the wastewater for biological treatment purposes on several treatment aspects were investigated and discussed in detail. The COD level of pyrolysis wastewater was decreased by about 32 and 38% after 1 h of treatment using the catalytic ozonation and photocatalytic ozonation approaches, respectively, while the decrease in the COD of this wastewater was negligible during the photocatalytic oxidation. The wastewater color was completely removed after 40 min of treatment using both ozone‐based oxidation systems, while the photocatalytic oxidation led to a slight decrease in color extinction by about 10% after 1 h of treatment. © 2013 American Institute of Chemical Engineers Environ Prog, 33: 178–183, 2014
Sea‐cliff retreat and shore platform widening: steady‐state equilibrium?
Authors: Dickson Mark E. , Ogawa Hiroki , Kench Paul S. , Hutchinson Andrew
Published: April 2013

We challenge the notion of steady‐state equilibrium in the context of progressive cliff retreat on micro‐tidal coasts. Ocean waves break at or close to the abrupt seaward edge of near‐horizontal shore platforms and then rapidly lose height due to turbulence and friction. Conceptual models assume that wave height decays exponentially with distance from the platform edge, and that the platform edge does not erode under stable sea‐level. These assumptions combine to a steady‐state view of Holocene cliff retreat. We argue that this model is not generally applicable. Recent data show that: (1) exponential decay in wave height is not the most appropriate conceptual model of wave decay; (2) by solely considering wave energy at gravity wave frequencies the steady‐state model neglects a possible formative role for infragravity waves. Here we draw attention to possible mechanisms through which infragravity waves may drive cliff retreat over much greater distances (and longer timescales) than imaginable under the established conceptual model. Copyright © 2013 John Wiley & Sons, Ltd.
A developmental and energetic basis linking larval oyster shell formation to acidification sensitivity
Authors: Waldbusser George G. , Brunner Elizabeth L. , Haley Brian A. , Hales Burke , Langdon Christopher J. , Prahl Frederick G.
Published: April 2013

Acidified waters are impacting commercial oyster production in the U.S. Pacific Northwest, and favorable carbonate chemistry conditions are predicted to become less frequent. Within 48 h of fertilization, unshelled Pacific oyster (Crassostrea gigas) larvae precipitate roughly 90% of their body weight as calcium carbonate. We measured stable carbon isotopes in larval shell and tissue and in algal food and seawater dissolved inorganic carbon in a longitudinal study of larval development and growth. Using these data and measured biochemical composition of larvae, we show that sensitivity of initial shell formation to ocean acidification results from diminished ability to isolate calcifying fluid from surrounding seawater, a limited energy budget and a strong kinetic demand for calcium carbonate precipitation. Our results highlight an important link between organism physiology and mineral kinetics in larval bivalves and suggest the consideration of mineral kinetics may improve understanding winners and losers in a high CO2 world.
‘BEHOLD, A VIRGIN IS WITH HIV!’ MISREPORTING SEXUAL BEHAVIOR AMONG INFECTED ADOLESCENTS
Authors: Tennekoon Vidhura , Rosenman Robert
Published: April 2013

In four Southern African countries where the HIV prevalence rate is among the highest in the world, 46.4% of a sample of female adolescents infected with HIV report having never engaged in sex. This would indicate either the dominance of non‐sexual modes of HIV transmission or rampant misreporting of sexual behavior in the sample. We propose a method to estimate the extent of misreporting and calculate that the true percentages of virgins among the sample of HIV‐infected adolescent women is 32.1%. After accounting for misreporting, the contribution of sexual modes of HIV transmission is projected as 50.4%, compared with an estimate of 35.5% if we assume no misreporting. Copyright © 2013 John Wiley & Sons, Ltd.
Determination Limit of Fluorescence Turn‐On Probes for the Acetate Anion
Authors: Shang Xuefang , Yuan Jianmei , Du Zhimin , Wang Yingling , Jia Shenyu , Han Jie , Li Yue , Zhang Jinlian , Xu Xiufang
Published: April 2013

Three fluorescent turn‐on probes containing 3,6‐dichloro‐9H‐carbazole as carbazyl part have been designed and synthesized. Among studied anions F−, AcO−, H2PO$\rm{{_{4}^{-}}}$, Cl−, Br− and I−, AcO− showed the strongest binding ability with all probes. The strong basic anions, such as AcO−, H2PO$\rm{{_{4}^{-}}}$, and F−, induced a significant red‐shift in absorption and a concomitant increase in fluorescent emission of the probes caused by photoinduced electron transfer (PET). The determination limit of probe 3 (Scheme 1) toward AcO− is 3.0×10−7 M. 1H‐NMR Titration experiments shed light on the nature of the interaction between the probes and the anions. Theoretical investigation further illustrated the possible binding mode in these hostguest interactions and the roles of molecular frontier orbitals in molecular interplay.
Synthesis and Characterization of Carbonyl Group‐6‐Metal Derivatives with LigandN,N‐Bis(diphenylphosphino)naphthalen‐1‐amine (=N‐(Diphenylphosphino)‐N‐naphthalen‐1‐yl‐P,P‐diphenylphosphinous Amide). Molecular Structure ofcis‐Tetracarbonyl[N‐(diphenylphosphino‐κP)‐N‐naphthalen‐1‐yl‐P,P‐diphenylphosphinous amide‐κP]molybdenum (cis‐[Mo(CO)4{C10H7‐1‐N(PPh2)2}])
Authors: Al‐Masri Harbi Tomah , Mohamed Beshir M. , Moussa Ziad , Alkordi Mohamed H.
Published: April 2013

The reaction ofN,N‐bis(diphenylphosphino)naphthalen‐1‐amine (1) with [M(CO)6] (M=Cr, Mo, W; 1 : 1 molar ratio) affordedcis‐[M(CO)4(1)]2(M=Cr),3(M=Mo), and4(M=W). Compounds2–4were identified and characterized by elemental analysis and multinuclear NMR (1H‐,13C‐, and31P‐NMR) and IR spectroscopy. A crystal‐structure determination of complex3was carried out.
ROUNDING, FOCAL POINT ANSWERS AND NONRESPONSE TO SUBJECTIVE PROBABILITY QUESTIONS
Authors: Kleinjans Kristin J. , Soest Arthur Van
Published: April 2013

We develop a panel data model explaining answers to subjective probabilities about binary events and estimate it using data from the Health and Retirement Study on six such probabilities. The model explicitly accounts for several forms of ‘reporting behavior’: rounding, focal point ‘50%’ answers and item nonresponse. We find observed and unobserved heterogeneity in the tendencies to report rounded values or a focal answer, explaining persistency in 50% answers over time. Focal 50% answers matter for some of the probabilities. Incorporating reporting behavior does not have a large effect on the estimated distribution of the genuine subjective probabilities. Copyright © 2013 John Wiley & Sons, Ltd.
THE ROLE OF INVENTORIES AND SPECULATIVE TRADING IN THE GLOBAL MARKET FOR CRUDE OIL
Authors: Kilian Lutz , Murphy Daniel P.
Published: April 2013

We develop a structural model of the global market for crude oil that for the first time explicitly allows for shocks to the speculative demand for oil as well as shocks to flow demand and flow supply. The speculative component of the real price of oil is identified with the help of data on oil inventories. Our estimates rule out explanations of the 2003–2008 oil price surge based on unexpectedly diminishing oil supplies and based on speculative trading. Instead, this surge was caused by unexpected increases in world oil consumption driven by the global business cycle. There is evidence, however, that speculative demand shifts played an important role during earlier oil price shock episodes including 1979, 1986 and 1990. Our analysis implies that additional regulation of oil markets would not have prevented the 2003–2008 oil price surge. We also show that, even after accounting for the role of inventories in smoothing oil consumption, our estimate of the short‐run price elasticity of oil demand is much higher than traditional estimates from dynamic models that do not account for for the endogeneity of the price of oil. Copyright © 2013 John Wiley & Sons, Ltd.
The biological treatment of high salinity synthetic oilfield produced water in a submerged membrane bioreactor using a halophilic bacterial consortium
Authors: Sharghi Elham Abdollahzadeh , Bonakdarpour Babak , Roustazade Pegah , Amoozegar Mohammad A. , Rabbani Ahamad R.
Published: April 2013

Background

Produced water (PW) is the most important wastewater of the oil industry and if disposed of without adequate treatment can cause serious environmental pollution. Biological treatment is one option explored in recent years for treatment of PW but traditional biological processes potentially fail when the salinity level of the PW is high. In the present study, a halophilic bacterial consortium was employed for treatment of high salinity synthetic PW in a membrane bioreactor (MBR).

Results

During the 112 days operation of the MBR at hydraulic retention time (HRT) and sludge retention time (SRT) of 48 h and 80 days respectively, there was a consistently low turbidity in the MBR effluent. Oil and grease (O&G) content of the effluent was also consistently below international limits for discharge to the sea or re‐injection to oil wells. With increase in organic loading rate from 0.3 to 0.9 kg COD m−3 d−1, O&G removal efficiency increased from 89.2% to 95.5% whereas chemical oxygen demand (COD) removal efficiency (c. 83%) did not change. Also, the transmembrane pressure during operation of the MBR remained in the range 1–2 kPa.

Conclusion

The results of the present study indicate the very good potential of the MBR, both in terms of removal performance and membrane fouling, for treatment of high salinity PW. © 2013 Society of Chemical Industry
Novel Synthetic Approach Toward C‐Substituted Piperazine Derivatives via C‐N Bonds Formation of α‐Bromoarylethanones and Ethanolamine
Authors: Cao Gao , Hu Ai‐Xi , Xie Yan‐Li , Zhou Zhen
Published: April 2013

A new method for the synthesis of novel C‐substituted piperazine derivatives bearing aryl substituents on 2,6‐C positions has been developed by one‐pot three‐component sequential reaction of α‐bromoarylethanones with ethanolamine in the presence of formic acid. The structure of the novel compounds was established by nuclear magnetic resonance (NMR), mass spectrometry (MS), and elemental analysis. In addition, the crystal structure of 4e was determined by single X‐ray crystallography and a possible reaction mechanism was proposed.
Influence of neighborhood household income on early death or urgent hospital readmission
Authors: van Walraven Carl , Wong Jenna , Forster Alan J.
Published: April 2013

BACKGROUND

The relationship of socioeconomic status (SES) with hospital readmissions is unclear.

METHODS

We used population‐based administrative datasets to randomly select 40,827 adult Ontarians discharged from hospital to the community. Patient postal codes were linked to average neighborhood household‐income quintiles. The association of this SES measure with 30‐day death or urgent readmission was measured after controlling for outcome risk using a validated index, LACE+: length of stay (L), acuity of the admission (A), comorbidity of the patient (measured with the Charlson Comorbidity Index score (C), and emergency‐department use (E).

RESULTS

Within 1 month of discharge, 2638 (6.5%) people died or were urgently readmitted. Lower neighborhood income was significantly associated with both an increased outcome risk (P < 0.0001) and LACE+ score. After adjusting for LACE+ score, neighborhood income was no longer associated with 30‐day death or urgent readmission (P = 0.21).

CONCLUSIONS

After accounting for known risk factors, early death or readmission is not more common in people from lower‐income neighborhoods. Further study is required to determine if SES is associated with adverse postdischarge outcomes in settings without publicly funded healthcare. Journal of Hospital Medicine 2013;8:261–266. © 2013 Society of Hospital Medicine