bluuebunny/crossref_metadata_2025_split huggingface dataset:
Implications of RCP emissions on future PM2.5 air quality and direct radiative forcing over China
Authors: Li Ke , Liao Hong , Zhu Jia , Moch Jonathan M. 
Published: September 2016

AbstractSevere PM2.5 air pollution in China and the First Grand National Standard (FGNS), implemented in 2016 (annual PM2.5 concentration target of less than 35 µg m−3), necessitate urgent reduction strategies. This study applied the nested‐grid version of the Goddard Earth Observing System (GEOS) chemical transport model (GEOS‐Chem) to quantify 2000–2050 changes in PM2.5 air quality and related direct radiative forcing (DRF) in China, based on future emission changes under the representative concentration pathway (RCP) scenarios of RCP2.6, RCP4.5, RCP6.0, and RCP8.5. In the near term (2000–2030), a projected maximum increase in PM2.5 concentrations of 10–15 µg m−3 is found over east China under RCP6.0 and RCP8.5 and less than 5 µg m−3 under RCP2.6 and RCP4.5. In the long term (2000–2050), PM2.5 pollution clearly improves, and the largest decrease in PM2.5 concentrations of 15–30 µg m−3 is over east China under all RCPs except RCP6.0. Focusing particularly on highly polluted regions, we find that Beijing‐Tianjin‐Hebei (BTH) wintertime PM2.5 concentrations meeting the FGNS occur after 2040 under RCP2.6, RCP4.5, and RCP8.5, and summertime PM2.5 concentrations reach this goal by 2030 under RCP2.6 and RCP4.5. In Sichuan Basin (SCB), wintertime PM2.5 concentrations below the FGNS occur only in 2050 under RCP2.6 and RCP4.5, although future summertime PM2.5 will be well controlled. The difficulty in controlling future PM2.5 concentrations relates to unmitigated high levels of nitrate, although NOx and SO2 emissions show substantial reductions during 2020–2040. The changes in aerosol concentrations lead to positive aerosol DRF over east China (20°–45°N, 100°–125°E) by 1.22, 1.88, and 0.66 W m−2 in 2050 relative to 2000 under RCP2.6, RCP4.5, and RCP8.5, respectively. When considering both health and climate effects of PM2.5 over China, for example, PM2.5 concentrations averaged over east China under RCP4.5 (RCP2.6) decrease by 54% (43%) in 2050 relative to 2000, but at the cost of warming with DRF of 1.88 (1.22) W m−2. Our results indicate that it will be possible to mitigate future PM2.5 pollution in China, but it will likely take two decades for polluted regions such as BTH and SCB to meet the FGNS, based on all RCP scenarios. At the same time, the consequent warming effects from reduced aerosols are also significant and inevitable.
Cooperative drought adaptation: Integrating infrastructure development, conservation, and water transfers into adaptive policy pathways
Authors: Zeff Harrison B. , Herman Jonathan D. , Reed Patrick M. , Characklis Gregory W. 
Published: September 2016

AbstractA considerable fraction of urban water supply capacity serves primarily as a hedge against drought. Water utilities can reduce their dependence on firm capacity and forestall the development of new supplies using short‐term drought management actions, such as conservation and transfers. Nevertheless, new supplies will often be needed, especially as demands rise due to population growth and economic development. Planning decisions regarding when and how to integrate new supply projects are fundamentally shaped by the way in which short‐term adaptive drought management strategies are employed. To date, the challenges posed by long‐term infrastructure sequencing and adaptive short‐term drought management are treated independently, neglecting important feedbacks between planning and management actions. This work contributes a risk‐based framework that uses continuously updating risk‐of‐failure (ROF) triggers to capture the feedbacks between short‐term drought management actions (e.g., conservation and water transfers) and the selection and sequencing of a set of regional supply infrastructure options over the long term. Probabilistic regional water supply pathways are discovered for four water utilities in the “Research Triangle” region of North Carolina. Furthermore, this study distinguishes the status‐quo planning path of independent action (encompassing utility‐specific conservation and new supply infrastructure only) from two cooperative formulations: “weak” cooperation, which combines utility‐specific conservation and infrastructure development with regional transfers, and “strong” cooperation, which also includes jointly developed regional infrastructure to support transfers. Results suggest that strong cooperation aids utilities in meeting their individual objectives at substantially lower costs and with less overall development. These benefits demonstrate how an adaptive, rule‐based decision framework can coordinate integrated solutions that would not be identified using more traditional optimization methods.
Enantioselective One‐Pot Reaction: Organocatalyzed Synthesis of Fully Functionalized Oxabicyclo[2.2.2]octanes with Seven Contiguous Stereocenters
Authors: Xia Ai‐Bao , Pan Gong‐Jian , Wu Chao , Liu Xue‐Li , Zhang Xiao‐Long , Li Zhao‐Bo , Du Xiao‐Hua , Xu Dan‐Qian 
Published: September 2016

AbstractAn enantioselective one‐pot Michael/Michael/Henry/hemiacetalization reaction between α,β‐unsaturated aldehydes, α‐ketoamides, and nitroalkenes under mild conditions catalyzed by a diarylprolinol silyl ether has been developed. The sequential methodology provides a direct approach to a wide range of fully substituted chiral oxabicyclo[2.2.2]octanes with seven contiguous stereocenters in moderate to excellent yields (up to 99%), high to excellent diastereoselectivities (up to >25:1 dr), and high to excellent enantioselectivities (up to 99% ee).magnified image
Manganese(II)‐Mediated Domino Annulation Reaction of Vinyl Azides and 4‐Hydroxycoumarin: A Stereoselective Synthesis of Spirobenzofuranone‐lactams
Authors: Guo Shanshan , Chen Binhui , Zhao Donghong , Chen Wenteng , Zhang Guolin 
Published: September 2016

AbstractA manganese(II) acetate‐catalyzed domino reaction of vinyl azides and 4‐hydroxycoumarin has been developed for the synthesis of polyfunctionalized spirofuranone‐lactams. A wide range of vinyl azides are capable of providing the desired spirofuranone‐lactams in good to excellent yields. The reaction was achieved via thermal decomposition of vinyl azides to 2H‐azirines, followed by an intramolecular nucleophilic attack and stereoselective cyclization. The mild reaction conditions and easy operation make this reaction advantageous for the synthesis of spirofuranone‐lactams.magnified image
Facile Hydrogenolysis of C(sp3)–C(sp3) σ Bonds
Authors: Fillion Eric , Beaton Eric , Nguyen Yen , Wilsily Ashraf , Bondarenko Ganna , Jacq Jérôme 
Published: September 2016

AbstractThe modification of benzylic quaternary, tertiary, and secondary carbon centers through palladium‐catalyzed hydrogenolysis of C(sp3)–C(sp3) σ bonds is presented. When benzyl Meldrum's acid derivatives bearing quaternary benzylic centers are treated under mild hydrogenolysis conditions – palladium on carbon and atmospheric pressure of hydrogen – aromatics substituted with tertiary benzylic centers and Meldrum's acid are obtained with good to excellent yield. Analogously, substrates containing tertiary or secondary benzylic centers yield aromatics substituted with secondary benzylic centers or toluene derivatives, respectively. Furthermore, this strategy is used for the high yielding synthesis of diarylmethanes. The scope of the reductive dealkylation reaction is explored and the limitations with respect to steric and electronic factors are determined. A mechanistic analysis of the reaction is described that consisted of deuterium labelling experiments and hydrogenolysis of enantioenriched derivatives. The investigation shows that the C(sp3)–C(sp3) σ bond‐cleaving events occur through a hybrid SN1/SN2 mechanism, in which the palladium center displaces a carbon‐based leaving group, namely Meldrum's acid, with inversion of configuration, followed by reductive elimination of palladium to furnish a C−H bond.magnified image
Ligand‐Free Copper‐Manganese Spinel Oxide‐Catalyzed Tandem One‐Pot C–H Amidation and N‐Arylation of Benzylamines: A Facile Access to 2‐Arylquinazolin‐4(3H)‐ones
Authors: Sharma Rohit , Vishwakarma Ram A. , Bharate Sandip B. 
Published: September 2016

AbstractAn efficient ligand‐free copper‐manganese (Cu‐Mn) spinel oxide‐catalyzed direct tandem C−H oxygenation and N‐arylation of benzylamines has been developed. The method has been utilized for the synthesis of medicinally important 2‐arylquinazolin‐4(3H)‐ones. Salient features of this method include recyclable catalyst, no ligand, excellent product yields, shorter reaction times and a broad substrate scope.magnified image
Aerobic Oxidative Intramolecular Aromatic Coupling via Heterogeneous Metal Catalysts
Authors: Fujimoto Shigenobu , Matsumoto Kenji , Shindo Mitsuru 
Published: September 2016

AbstractAn aerobic, heterogeneously catalyzed oxidative intramolecular coupling reaction of aromatic compounds is reported here. Using commercially available, recyclable heterogeneous metal catalysts, the coupling reactions of o‐terphenyls and 1,ω‐biarylalkanes proceeded quickly under mild conditions, i.e., at room temperature under oxygen as a co‐oxidant almost all within 1 h, to provide the corresponding coupled products like triphenylenes and phenanthrenes in good to excellent yields. This reaction is an easily handled, practical, and atom‐economical coupling method, which is of great importance in modern organic syntheses.magnified image
Media Use and Exposure to Graphic Content in the Week Following the Boston Marathon Bombings
Authors: Jones Nickolas M. , Garfin Dana Rose , Holman E. Alison , Silver Roxane Cohen 
Published: September 2016

AbstractTraditional and new media inform and expose the public to potentially distressing graphic content following disasters, but predictors of media use have received limited attention. We examine media‐use patterns after the Boston Marathon bombings (BMB) in a representative national U.S. sample (n = 2888), with representative oversamples from metropolitan Boston (n = 845) and New York City (n = 941). Respondents completed an Internet‐based survey 2–4 weeks post‐BMB. Use of traditional media was correlated with older age, prior indirect media‐based exposure to collective traumas, and direct BMB exposure. New media use was correlated with younger age and prior direct exposure to collective traumas. Increased television and online news viewing were associated with exposure to more graphic content. The relationship between traditional and new media was stronger for young adults than all other age groups. We offer insights about the relationship between prior collective trauma exposures and media use following subsequent disasters and identify media sources likely to expose people to graphic content.
Vitamin D pathway regulatory genes encoding 1α‐hydroxylase and 24‐hydroxylase are dysregulated in sinonasal tissue during chronic rhinosinusitis
Authors: Christensen Jenna M. , Cheng Jasmine , Earls Peter , Gunton Jenny , Sewell William , Sacks Raymond , Harvey Richard J. 
Published: September 2016

BackgroundVitamin D deficiency is associated with many inflammatory respiratory disease states. However, serum vitamin D concentrations may not reflect tissue‐specific availability. In this study we sought to assess the local expression of genes essential in vitamin D regulation in chronic rhinosinusitis (CRS).MethodsA cross‐sectional study of adult patients undergoing endoscopic sinus surgery was performed. Patients were defined as having CRS with polyps (CRSwNP) or without polyps (CRSsNP), or normal sinus mucosa. Sinus mucosal biopsies were assessed using quantitative polymerase chain reaction to determine expression of genes encoding the vitamin D receptor (VDR), 25‐hydroxylase (CYP2R1), 1α‐hydroxylase (CYP27B1), and 24‐hydroxylase (CYP24A1). Expression levels correlated with serum 25(OH)D [sum 25(OH)D2 and 25(OH)D3], the 22‐item Sinonasal Outcome Test (SNOT‐22), and Nasal Symptom Score (NSS). Separate analyses were performed for patients grouped by tissue eosinophilia.ResultsThirty‐one patients were assessed (age 49.47 ± 18.14 years, 48.4% female), including 8 CRSsNP, 10 CRSwNP, and 13 controls. CRSsNP and CRSwNP mucosa exhibited decreased CYP27B1 compared with controls (0.0437 [Interquartile range (IQR) 0.0999] vs 0.3260 [IQR 2.9384] vs 0.6557 [IQR 1.1005], p = 0.039), whereas CYP24A1 was upregulated (0.8522 [IQR 1.3170] vs 1.2239 [IQR 4.4197] vs 0.1076 [IQR 0.1791], p = 0.025). CYP24A1 was upregulated in both non‐eosinophilic CRS and eosinophilic CRS (1.1337 [IQR 2.3790] vs 0.9555 [IQR 3.2811] vs 0.1076 [IQR 0.1791], p = 0.033). Significant correlations were observed between NSS and CYP2R1 (r = −0.432, p = 0.022), CYP24A1 (r = 0.420, P = 0.026), and VDR (r = 0.425, p = 0.024), although no correlations with serum 25(OH)D were observed.ConclusionsThe local regulation of vitamin D in sinonasal tissue during CRS may be independent of serum 25(OH)D levels. Vitamin D may be dysregulated at multiple levels, with decreased transcription of the metabolic gene CYP27B1 and increased transcription of the catabolic gene CYP24A1 observed.
Mikroplastik in aquatischen Ökosystemen
Authors: Ivleva Natalia P. , Wiesheu Alexandra C. , Niessner Reinhard 
Published: September 2016

AbstractDie Verunreinigung von Salz‐ und Süßwassersystemen durch Kunststoffe und insbesondere Mikroplastik (MP) stellt ein weltweites ökologisches Problem dar. Zahlreiche Studien beschäftigten sich mit dem Vorkommen von MP, der Wechselwirkung mit Schadstoffen, der Aufnahme durch aquatische Organismen und den daraus resultierenden Wirkungen. Dieser Aufsatz behandelt die wichtigsten Fragen in Bezug auf MP in aquatischen Systemen. Der Schwerpunkt liegt hierbei auf: 1) der Beschreibung der analytischen Methoden zur Probenahme, Aufbereitung, Identifikation und Quantifizierung von MP sowie deren Anwendbarkeit, Zuverlässigkeit und den benötigten Verbesserungen; 2) einer Abschätzung des MP‐Vorkommens sowie möglicher Hindernisse bei der Vergleichbarkeit unterschiedlicher Studien; 3) einer Zusammenfassung der bekannten Literatur zur Aufnahme von MP durch Organismen. Anschließend werden vorhandene Wissenslücken aufgezeigt, mögliche Strategien zur Bewertung der Umweltgefährdung vorgeschlagen und Perspektiven zur Reduzierung von MP in aquatischen Ökosystemen diskutiert.
Synthesis of cis‐1,4‐polyisoprene with Al‐Ti catalysts modified by different electron donor reagent
Authors: Wang Zhaowei , Wen Zhixia , Li Xing , Yu Junwei , Liu Xiaoxuan 
Published: September 2016

ABSTRACTThe preparation of the high cis−1,4‐polyisoprene by Ziegler‐Natta catalysis system was studied. The effect of Al‐Ti catalysts modified by ethers with different structures which are different electron donor reagent on polymerization of isoprene has been mainly investigated. By the measurement method of the monomer conversion, FTIR, and 1H NMR spectroscopy, the influence of, respectively, added diphenyl ether, anisole, dibutyl ether, or methyl tert‐butyl methyl ether as a third active component on the heterogeneous TiCl4‐Al(i‐Bu)3‐ether catalyst activity and microstructure of synthetic polyisoprene was analyzed. By the adding of diphenyl ether or dibutyl ether, the process of prefabricated heterogeneous catalyst is quickly and catalyst particle quantity is large. The polymerization conversion is high and the microstructure cis−1,4 content of the resulting polymer can reach 92%. But Al(i‐Bu)3 added anisole or methyl tert‐butyl methyl ether hard to cooperate with TiCl4. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44357.
Six‐arm star‐shaped polymer with cyclophosphazene core and poly(ε‐caprolactone) arms as modifier of epoxy thermosets
Authors: Ye Weitao , Wei Wei , Fei Xiaoma , Lu Rongjie , Liu Na , Luo Jing , Zhu Ye , Liu Xiaoya 
Published: September 2016

ABSTRACTA six‐arm star‐shaped poly(ε‐caprolactone) (s‐PCL) based on cyclophosphazene core was obtained by presynthesis of a hydroxy‐teminated cyclophosphazene derivative and subsequent initiation of the ring‐opening polymerization of ε‐caprolactone, and its use in different proportions as toughening modifier of diglycidylether of bisphenol A/anhydride thermosets was studied. The star‐shaped polymer was characterized to have approximately 30 caprolactone units per arm. Differential scanning calorimetry revealed a nonsignificant influence on the curing process of the epoxy‐anhydride formulation by the addition of s‐PCL. The s‐PCL‐modified epoxy thermosets exhibited a great improvement in both toughness and strength compared with the neat resin, as the result of a joint effort by the internal rigid core and the external ductile polyester chains of s‐PCL. When the addition of the modifier was 3 wt %, an optimal mechanical and thermomechanical performance was achieved. The impact resistance and tensile strength of the cured epoxy resin were enhanced by 150% and 30%, respectively. The glass transition temperature was also increased slightly. Moreover, the addition of the star‐shaped modifier had little harmful effect on the thermal stability of the material. Thus s‐PCL was proved to be a superior toughening agent without sacrificing thermal and mechanical properties of the thermosets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44384.
A High Contrast Tri‐state Fluorescent Switch: Properties and Applications
Authors: Su Xing , Wang Yi , Fang Xiaofeng , Zhang Yu‐Mo , Zhang Ting , Li Minjie , Liu Yifei , Lin Tingting , Zhang Sean Xiao‐An 
Published: September 2016

AbstractA high contrast tri‐state fluorescent switch (FSPTPE) with both emission color change and on/off switching is achieved in a single molecular system by fusing the aggregation‐induced emissive tetraphenylethene (TPE) with a molecular switch of spiropyran (SP). In contrast to most of the reported solid‐state fluorescent switches, FSPTPE only exists in the amorphous phase in the ring‐closed form owing to its highly asymmetric molecular geometry and weak intermolecular interactions, which leads to its grinding‐inert stable cyan emission in the solid state. Such an amorphous phase facilitates the fast response of FSPTPE to acidic gases and induces the structural transition from the ring‐closed form to ring‐open form, accompanied with the “Off” state of the fluorescence. The structural transition leads to a planar molecular conformation and high dipole moment, which further results in strong intermolecular interactions and good crystallinity, so when the acid is added together with a solvent, both the ring‐opening reaction and re‐crystallization can be triggered to result in an orange emissive state. The reversible control between any two of the three states (cyan/orange/dark) can be achieved with acid/base or mechanical force/solvent treatment. Because of the stable initial state and high color contrast (Δλ=120 nm for cyan/orange switch, dark state ΦF<0.01 %), the fluorescent switch is very promising for applications such as displays, chemical or mechanical sensing, and anti‐counterfeiting.
Intramolecular Oxidative O‐Demethylation of an Oxoferryl Porphyrin Complexed with a Per‐O‐methylated β‐Cyclodextrin Dimer
Authors: Kitagishi Hiroaki , Kurosawa Shun , Kano Koji 
Published: September 2016

AbstractThe intramolecular oxidation of ROCH3 to ROCH2OH, where the latter compound spontaneously decomposed to ROH and HCHO, was observed during the reaction of the supramolecular complex (met‐hemoCD3) with cumene hydroperoxide in aqueous solution. Met‐hemoCD3 is composed of meso‐tetrakis(4‐sulfonatophenyl)porphinatoiron(III) (FeIIITPPS) and a per‐O‐methylated β‐cyclodextrin dimer having an ‐OCH2PyCH2O‐ linker (Py=pyridine‐3,5‐diyl). The O=FeIVTPPS complex was formed by the reaction of met‐hemoCD3 with cumene hydroperoxide, and isolated by gel‐filtration chromatography. Although the isolated O=FeIVTPPS complex in the cyclodextrin cage was stable in aqueous solution at 25 °C, it was gradually converted to FeIITPPS (t1/2=7.6 h). This conversion was accompanied by oxidative O‐demethylation of an OCH3 group in the cyclodextrin dimer. The results indicated that hydrogen abstraction by O=FeIVTPPS from ROCH3 yields HO‐FeIIITPPS and ROCH2.. This was followed by radical coupling to afford FeIITPPS and ROCH2OH. The hemiacetal (ROCH2OH) immediately decomposed to ROH and HCHO. This study revealed the ability of oxoferryl porphyrin to induce two‐electron oxidation.
Dynamic changes of substrate reactivity and enzyme adsorption on partially hydrolyzed cellulose
Authors: Shi Jian , Wu Dong , Zhang Libing , Simmons Blake A. , Singh Seema , Yang Bin , Wyman Charles E. 
Published: September 2016

ABSTRACTThe enzymatic hydrolysis of cellulose is a thermodynamically challenging catalytic process that is influenced by both substrate‐related and enzyme‐related factors. In this study, a proteolysis approach was applied to recover and clean the partially converted cellulose at the different stages of enzymatic hydrolysis to monitor the hydrolysis rate as a function of substrate reactivity/accessibility and investigate surface characteristics of the partially converted cellulose. Enzyme‐substrate interactions between individual key cellulase components from wild‐type Trichoderma reesei and partially converted cellulose were followed and correlated to the enzyme adsorption capacity and dynamic sugar release. Results suggest that cellobiohydrolase CBH1 (Cel7A) and endoglucanases EG2 (Cel5A) adsorption capacities decreased as cellulose was progressively hydrolyzed, likely due to the “depletion” of binding sites. Furthermore, the degree of synergism between CBH1 and EG2 varied depending on the enzyme loading and the substrates. The results provide a better understanding of the relationship between dynamic change of substrate features and the functionality of various cellulase components during enzymatic hydrolysis. Biotechnol. Bioeng. 2017;114: 503–515. © 2016 Wiley Periodicals, Inc.
Fam60A plays a role for production stabilities of recombinant CHO cell lines
Authors: Ritter Anett , Nuciforo Sandro , Schulze Axel , Oertli Mevion , Rauschert Tatjana , Voedisch Bernd , Geisse Sabine , Jostock Thomas , Laux Holger 
Published: September 2016

ABSTRACTRecombinant CHO (Chinese hamster ovary) cell lines producing therapeutic proteins often lose their production capability during long‐term cultivation. To ensure that CHO production cell lines can be up‐scaled to high‐volume bioreactors, labor intensive stability studies of several months have to be performed to deselect clones that are losing productivity over time. The ability to predict whether clones will produce recombinant proteins at constant high levels, for example, through determination of biomarkers such as expression of specific genes, plasmid integration sites, or epigenetic patterns, or even to improve CHO host cell lines to increase the probability of the generation of stable clones would be highly beneficial. Previously, we reported that the lack of a telomeric region of chromosome 8 correlates with increased productivities and higher production stabilities of monoclonal antibody expressing CHO cell lines (Ritter A, Voedisch B, Wienberg J, Wilms B, Geisse S, Jostock T, Laux H. 2016a. Biotechnol Bioeng 113(5):1084–1093). Herein, we describe that the knock‐out of the gene Fam60A, which is one of the genes located within the telomeric region of chromosome 8, in CHO‐K1a cells leads to the isolation of significantly more clones with higher protein production stabilities of monoclonal antibodies during long‐term cultivation. Biotechnol. Bioeng. 2017;114: 701–704. © 2016 Wiley Periodicals, Inc.