bluuebunny/crossref_metadata_2025_split huggingface dataset:
Different pathways of the formation of highly oxidized multifunctional
organic compounds (HOMs) from the gas-phase ozonolysis of β-caryophyllene
Authors: Richters Stefanie , Herrmann Hartmut , Berndt Torsten 
Published: August 2016

Abstract. The gas-phase mechanism of the formation of highly oxidized multifunctional organic compounds (HOMs) from the ozonolysis of β-caryophyllene was investigated in a free-jet flow system at atmospheric pressure and a temperature of 295 ± 2 K. Reaction products, mainly highly oxidized RO2 radicals containing up to 14 oxygen atoms, were detected using chemical ionization – atmospheric pressure interface – time-of-flight mass spectrometry with nitrate and acetate ionization. These highly oxidized RO2 radicals react with NO, NO2, HO2 and other RO2 radicals under atmospheric conditions forming the first-generation HOM closed-shell products. Mechanistic information on the formation of the highly oxidized RO2 radicals is based on results obtained with isotopically labelled ozone (18O3) in the ozonolysis reaction and from hydrogen/deuterium (H/D) exchange experiments of acidic H atoms in the products. The experimental findings indicate that HOM formation in this reaction system is considerably influenced by the presence of a double bond in the RO2 radicals primarily formed from the β-caryophyllene ozonolysis. Three different reaction types for HOM formation can be proposed, allowing for an explanation of the detected main products: (i) the simple autoxidation, corresponding to the repetitive reaction sequence of intramolecular H-abstraction of a RO2 radical, RO2  →  QOOH, and subsequent O2 addition, next forming a peroxy radical, QOOH + O2  →  R′O2; (ii) an extended autoxidation mechanism additionally involving the internal reaction of a RO2 radical with a double bond forming most likely an endoperoxide and (iii) an extended autoxidation mechanism including CO2 elimination. The individual reaction steps of the reaction types (ii) and (iii) are uncertain at the moment. From the product analysis it can be followed that the simple autoxidation mechanism accounts only for about one-third of the formed HOMs. Time-dependent measurements showed that the HOM formation proceeds at a timescale of 3 s or less under the concentration regime applied here. The new reaction pathways represent an extension of the mechanistic understanding of HOM formation via autoxidation in the atmosphere, as recently discovered from laboratory investigations on monoterpene ozonolysis.
The Psychagogic Work of Examples in Plato'sStatesman
Authors: Moore Holly G. 
Published: August 2016

AbstractThis paper explores the role of examples (paradeigmata) as propaedeutic to philosophical inquiry, in light of a methodological digression in Plato's Statesman. Consistent with scholarship on Aristotle's view of example, scholars of Plato's work have privileged the logic of examples over their rhetorical appeal. Following a small but significant trend in recent rhetorical scholarship that emphasizes the affective nature of examples, this article assesses the psychagogic potential of paradeigmata, following the discussion of example in Plato's Statesman. I argue that by creating an expectation in the learner that he or she will find similarities, the use of examples in philosophical pedagogy engages his or her desire to discern the intelligible principles that ground experiential knowledge. Thus, examples not only serve as practice at the dialectician's method of abstraction but also cultivate a dialectical ēthos, characterized by the desire to know the logoi of all things.
Inherited dysfunctional platelet P2Y12 receptor mutations associated with bleeding disorders
Authors: Lecchi Anna , Femia Eti , Paoletta Silvia , Dupuis Arnaud , Ohlmann Philippe , Gachet Christian , Jacobson Kenneth , Podda Gian , Zieger Barbara , Cattaneo Marco , Machura Katharina 
Published: August 2016

SummaryThe platelet adenosine 5’-diphosphate (ADP) receptor P2Y12 (P2Y12R) plays a critical role in platelet aggregation. The present report illustrates an update of dysfunctional platelet P2Y12R mutations diagnosed with congenital lifelong bleeding problems. Described patients with heterozygous or homozygous substitution in the P2Y12R gene and qualitative abnormalities of the platelet P2Y12R are summarized. Recently, a further dysfunctional variant of P2Y12R has been identified in two brothers who presented with a lifelong severe bleeding disorder. During in vitro aggregation studies, the patient´s platelets show a markedly reduced and rapid reversible ADP-promoted aggregation. A homozygous c.561T>A substitution that changes the codon for His187 to Gln (p.His187Gln) in the P2Y12R gene has been identified. This mutation causes no change in receptor expression but decreases the affinity of the ligand for the receptor, even at high concentrations. Structure modelling studies indicated that the p.His187Gln mutation, located in the fifth transmembrane spanning domain (TM5), impairs conformational changes of the receptor. Structural integrity of the TM5 region is necessary for agonist and antagonist binding and for correct receptor function.
Treatment of Ingrown Toenail with a Shape Memory Alloy Device
Authors: Arik Hasan Onur , Arican Mehmet , Gunes Volkan , Kose Ozkan 
Published: August 2016

Background: We sought to report the clinical results of a new conservative treatment modality that uses a shape memory alloy device in patients with ingrown toenail.
Methods: A retrospective review was performed on 41 patients with ingrown toenail treated with the K-D device (S&C Biotech, Seoul, South Korea) between April 2013 and July 2014. Recurrence rate, cosmetic results, pain during the treatment period, and patient satisfaction were the major outcome measures.
Results: Patients were followed for at least 6 months (mean ± SD, 8.6 ± 2.1 months; range, 6–12 months). Recurrence was seen in eight patients (19.5%). Mean time to recurrence was 6.2 months (range, 3–10 months). Thirty-one patients (75.6%) were satisfied with the treatment. Thirty-five patients (85.4%) rated the application and treatment period as painless, and the remaining six (14.6%) noted pain particularly during shoe wearing. Thirty-one patients (75.6%) rated the cosmetic results as “excellent,” four (9.8%) as “acceptable,” and six (14.6%) as “poor.” Satisfaction with the treatment, the cosmetic results, and pain were significantly worse in patients with recurrence (P = .0001 for all). All of the patients returned to their work immediately after application of the device. No complications occurred.
Conclusions: The K-D device is a safe and effective treatment method for ingrown toenail. Although the recurrence rate is higher than for surgical treatment methods, the K-D device is a practical and painless method that provides immediate return to work and daily activities and excellent or acceptable cosmesis in most patients.
Twentieth century temperature trends in CMIP3, CMIP5, and CESM‐LE climate simulations: Spatial‐temporal uncertainties, differences, and their potential sources
Authors: Kumar Sanjiv , Kinter James L. , Pan Zaitao , Sheffield Justin 
Published: August 2016

AbstractThe twentieth century climate simulations from the Coupled Model Intercomparison Project Phase 3 (CMIP3) and Phase 5 (CMIP5) are compared to assess the models' ability to capture observed near‐surface air temperature trends at global, continental, and regional scales. We computed trends by using a nonparametric method and considering long‐term persistence in the time series. The role of internal variability is examined by using large ensemble climate simulations from the National Center for Atmospheric Research model Community Earth System Model (CESM). We computed temperature trends for three periods: the twentieth century, the second half of the twentieth century, and (3) the recent hiatus period to contrast the roles of external forcing and internal variability at various spatial and temporal scales. Both CMIP ensembles show statistically significant warming at global and continental scales during the twentieth century. We found a small but statistically significant difference between CMIP3 (0.57 ± 0.07 °C/century) and CMIP5 (0.47 ± 0.06 °C/century) twentieth century temperature trends, with the CMIP3 estimate being closer to the observations. The spatial structure of long‐term temperature trends, and top‐of‐the atmosphere net radiation trends, suggests that differences in model parameterizations and feedback processes that lead to a smaller net radiative forcing are likely contributing to the differences between CMIP3 and CMIP5. The estimate of internal variability based on the CESM large ensemble spans 24% of the uncertainty in CMIP5 for the twentieth century temperature trends, and 76% for the recent hiatus period, both at global scales, and 43% and almost 100% during the corresponding time periods at regional scales.
Organocatalytic Enantioselective Decarboxylative Michael Addition of β‐Keto Acids to Dicyanoolefins and Disulfonylolefins
Authors: Wei Yi , Guo Ran , Dang Yanfeng , Nie Jing , Ma Jun‐An 
Published: August 2016

AbstractA convenient organocatalytic enantioselective decarboxylative Michael addition of β‐keto acids to dicyanoolefins and disulfonylolefins is realized. In the presence of saccharide‐derived chiral amino thioureas, the reaction proceeded smoothly to afford a wide range of the Michael adducts in 62–99% yield with 70–94% ee. Moreover, one of the chiral adducts obtained could be readily converted into the monofluorinated product in a total 68% yield over four steps with 85% ee.magnified image
Venous thromboembolism in patients with hematologic malignancy and thrombocytopenia
Authors: Khanal Nabin , Bociek R. Gregory , Chen Baojiang , Vose Julie M. , Armitage James O. , Bierman Philip J. , Maness Lori J. , Lunning Matthew A. , Gundabolu Krishna , Bhatt Vijaya R. 
Published: August 2016

The optimal management of hematologic malignancy‐associated venous thromboembolism (VTE) in patients with moderate‐to‐severe thrombocytopenia is unclear. This is a retrospective study of 128 adult patients with hematologic malignancies who were diagnosed with VTE. The outcome of patients with significant thrombocytopenia (≤50,000/µL) was compared with those without. Forty‐seven patients (36.7%) had a platelet count ≤50,000/µL during a period of time of perceived need for new or continued anticoagulation. The median nadir platelet count in those with significant thrombocytopenia was 10,000/µL (range 2,000–45,000/µL) versus 165,000/µL (50,000–429,000/µL) in those without (P < 0.001). The median duration of significant thrombocytopenia in the first group was 10 days (1–35 days). Therapy during the period of significant thrombocytopenia included prophylactic‐dose low‐molecular‐weight heparin (LMWH) (47%), therapeutic‐dose LMWH or heparin (30%), warfarin (2%), inferior vena cava filter (2%), and observation (17%). Patients without thrombocytopenia were managed with the standard of care therapy. At a median follow‐up of more than 2 years, the risk of clinically significant bleeding (11% vs 6%, P = 0.22) including major bleeding (6% vs 2%) and clot progression or recurrence (21% vs 22%, P = 1.00) were similar in patients with or without significant thrombocytopenia. In a multivariate analysis, the risk of recurrence/progression (hazard ratio, HR 0.59, 95% CI 0.21–1.66, P = 0.31) and hemorrhage rate (HR 0.29, 95% CI 0.05–1.56, P = 0.15) did not differ based on the presence of significant thrombocytopenia. Within the limits of this retrospective study, cautious use of prophylactic‐dose LMWH may be safe in thrombocytopenic patients with hematologic malignancy‐associated VTE. Am. J. Hematol. 91:E468–E472, 2016. © 2016 Wiley Periodicals, Inc.
Genomic validation of the differential preservation of population history in modern human cranial anatomy
Authors: Reyes‐Centeno Hugo , Ghirotto Silvia , Harvati Katerina 
Published: August 2016

AbstractObjectivesIn modern humans, the significant correlation between neutral genetic loci and cranial anatomy suggests that the cranium preserves a population history signature. However, there is disagreement on whether certain parts of the cranium preserve this signature to a greater degree than other parts. It is also unclear how different quantitative measures of phenotype affect the association of genetic variation and anatomy. Here, we revisit these matters by testing the correlation of genetic distances and various phenotypic distances for ten modern human populations.Materials and MethodsGeometric morphometric shape data from the crania of adult individuals (n = 224) are used to calculate phenotypic PST, Procrustes, and Mahalanobis distances. We calculate their correlation to neutral genetic distances, FST, derived from single nucleotide polymorphisms (SNPs). We subset the cranial data into landmark configurations that include the neurocranium, the face, and the temporal bone in order to evaluate whether these cranial regions are differentially correlated to neutral genetic variation.ResultsOur results show that PST, Mahalanobis, and Procrustes distances are correlated with FST distances to varying degrees. They indicate that overall cranial shape is significantly correlated with neutral genetic variation. Of the component parts examined, PST distances for both the temporal bone and the face have a stronger association with FST distances than the neurocranium. When controlling for population divergence time, only the whole cranium and the temporal bone have a statistically significant association with FST distances.DiscussionOur results confirm that the cranium, as a whole, and the temporal bone can be used to reconstruct modern human population history.
A Non‐Exploding Alkali Metal Drop on Water: From Blue Solvated Electrons to Bursting Molten Hydroxide
Authors: Mason Philip E. , Buttersack Tillmann , Bauerecker Sigurd , Jungwirth Pavel 
Published: August 2016

AbstractAlkali metals in water are always at the brink of explosion. Herein, we show that this vigorous reaction can be kept in a non‐exploding regime, revealing a fascinating richness of hitherto unexplored chemical processes. A combination of high‐speed camera imaging and visible/near‐infrared/infrared spectroscopy allowed us to catch and characterize the system at each stage of the reaction. After gently placing a drop of a sodium/potassium alloy on water under an inert atmosphere, the production of solvated electrons became so strong that their characteristic blue color could be observed with the naked eye. The exoergic reaction leading to the formation of hydrogen and hydroxide eventually heated the alkali metal drop such that it became glowing red, and part of the metal evaporated. As a result of the reaction, a perfectly transparent drop consisting of molten hydroxide was temporarily stabilized on water through the Leidenfrost effect, bursting spectacularly after it had cooled sufficiently.
Coupled Biosynthesis of Volatiles and Salinosporamide A in Salinispora tropica
Authors: Groenhagen Ulrike , Leandrini De Oliveira Ana Ligia , Fielding Elisha , Moore Bradley S. , Schulz Stefan 
Published: August 2016

AbstractTerrestrial bacteria, especially actinomycetes, are known to be prolific producers of volatile compounds. We show here that bacteria from ocean sediments can also release complex bouquets of volatiles. The actinomycete Salinispora tropica produces cyclohexenyl compounds not previously known in nature, such as methyl cyclohex‐2‐ene‐1‐carboxylate (9), methyl 2‐(cyclohex‐2‐en‐1‐yl)acetate (10), methyl (E/Z)‐2‐(cyclohex‐2‐en‐1‐ylidene)acetate (11/12), and related alcohols 8 and 13. These compounds were identified by GC/MS and confirmed by synthesis. In addition, rare spiroacetals, aromatic compounds, short‐chain acids and esters, alcohols, and various cyclic compounds were produced by the bacteria. The biosynthesis of the cyclohexenyl compounds is closely coupled to that of cyclohexenylalanine (4), a building block of salinosporamide A, a proteasome inhibitor produced by S. tropica. Analysis of S. tropica strains that harbor knockouts of the salinosporamide biosynthetic genes salX and salD, coupled with feeding experiments, revealed that 3‐(cyclohex‐2‐en‐1‐yl)‐2‐oxopropanoic acid (60) and 3‐(cyclohex‐2‐en‐1‐ylidene)‐2‐oxopropanoic acid (isomers 61 and 62) are important intermediates in the biosynthesis of salinosporamide A, 4, and 8–13.
Air Extrusion System for Ionotropic Alginate Microgel Particle Formation: A Review
Authors: Lee Boon‐Beng , Bhandari Bhesh R. , Howes Tony 
Published: August 2016

AbstractIonotropic alginate microgels are commonly used for bioencapsulation applications and the air extrusion system is one of the common methods employed to produce these microgels. Although there have been many individual studies, to date no single report has comprehensively summarized the findings and results of the usage of this system. This review gives insight into the air extrusion methods, covering the setup, type, and characteristics of the system, focusing on their innovative aspects. Characterization techniques for the resulting microgels are presented, along with the influence of process variables on the product size and the development of empirical models for size prediction.
Structural and Dynamic Characterization of the Molecular Hub Early Region 1A (E1A) from Human Adenovirus
Authors: Hošek Tomáš , Calçada Eduardo O. , Nogueira Marcela Oliveira , Salvi Michele , Pagani Talita Duarte , Felli Isabella C. , Pierattelli Roberta 
Published: August 2016

AbstractThe small‐DNA human adenovirus encodes one of the most versatile molecular hubs, the E1A protein. This protein is essential for productive viral infection in human cells and a vast amount of biologically relevant data are available on its interactions with host proteins. Up to now, however, no high‐resolution structural and dynamic information on E1A is available despite its important biological role. Among the different spliced variants of E1A, two are expressed at high level in the early stage of infection. These are 243 and 289 residues isoforms. Herein, we present their NMR characterization, showing that they are both highly disordered, but also demonstrate a certain heterogeneous behavior in terms of structural and dynamic properties. Furthermore, we present the characterization of the isolated domain of the longer variant, known as CR3. This study opens the way to understanding at the molecular level how E1A functions.
Rationally Designed CeNP@MnMoS4 Core‐Shell Nanoparticles for Modulating Multiple Facets of Alzheimer's Disease
Authors: Guan Yijia , Gao Nan , Ren Jinsong , Qu Xiaogang 
Published: August 2016

AbstractAlzheimer's disease (AD) is a complicated multifactorial syndrome. Lessons have been learned through failed clinical trials that targeting multiple key pathways of the AD pathogenesis is necessary to halt the disease progression. Here, we construct core‐shell nanoparticles (CeNP@MnMoS4) targeting multiple key pathways of the AD pathogenesis, including elimination of toxic metal ions, decrease of oxidative stress, and promotion of neurite outgrowth. The SOD activity and copper removal capacity of CeNP@MnMoS4‐n (n represents the number of layers of MnMoS4, n=1–5) was investigated in vitro. We found that CeNP@MnMoS4‐3 made an excellent balance between SOD activity and copper removal capacity. The effect of CeNP@MnMoS4‐3 on Cu2+‐induced Aβ aggregation was studied by gel electrophoresis, transmission electron microscope (TEM), and atomic force microscopy (AFM). Compared with MnMoS4 or CeNP alone, a synergistic effect was observed. Moreover, CeNP@MnMoS4‐3 promoted neurite outgrowth in a dose‐dependent manner. Taken together, the results reported in this work show the potential of new multifunctional core‐shell nanoparticles as AD therapeutics.
An Azulene‐Containing Low Bandgap Small Molecule for Organic Photovoltaics with High Open‐Circuit Voltage
Authors: Chen Yao , Zhu Youqin , Yang Daobin , Zhao Suling , Zhang Lei , Yang Lin , Wu Jianglin , Huang Yan , Xu Zheng , Lu Zhiyun 
Published: August 2016

AbstractA simple azulene‐containing squaraine dye (AzUSQ) showing bandgap of 1.38 eV and hole mobility up to 1.25×10−4 cm2 V−1 s−1 was synthesized. With its low bandgap, an organic photovoltaic (OPV) device based on it has been made that exhibits an impressive open‐circuit voltages (Voc) of 0.80 V. Hence, azulene might be a promising structural unit to construct OPV materials with simultaneous low bandgap, high hole mobility and high Voc.
Sulfoxide‐Based Enantioselective Nazarov Cyclization: Divergent Syntheses of (+)‐Isopaucifloral F, (+)‐Quadrangularin A, and (+)‐Pallidol
Authors: Tang Mei‐Lin , Peng Peng , Liu Zheng‐Yu , Zhang Jian , Yu Jian‐Ming , Sun Xun 
Published: August 2016

AbstractThe synthesis of enantiomerically pure 3‐aryl substituted indanones is developed using an enantioselective sulfoxide‐based Knoevenagel condensation/Nazarov cyclization procedure. After the reductive desulfonation of the methyl para‐tolyl sulfoxide‐containing chiral auxiliary under mild conditions, selected enantiomerically pure indanone is used for the divergent total syntheses of three resveratrol natural products (+)‐isopaucifloral F, (+)‐quadrangularin A, and (+)‐pallidol.
ChemInform Abstract: Single Crystal Growth and Characterization of NaxLn1‐xMoO4, Ln: La, Ce, Pr, Nd, Sm, and Eu (x: 0.397—0.499).
Authors: Cortese Anthony J. , Abeysinghe Dileka , Smith Mark D. , zur Loye Hans‐Conrad 
Published: August 2016

AbstractSingle crystals of the reduced lanthanoid‐containing compounds La0.516Na0.484MoO4, Ce0.512Na0.488MoO4, Pr0.502Na0.498MoO4, Nd0.501Na0.499MoO4, Sm0.509Na0.491MoO4, and Eu0.603Na0.397MoO4 are grown from a NaCl/CsCl eutectic flux by in‐situ reduction using 2:1:0.5 molar mixtures of MoO3, Ln2O3, and Mo, the latter acting as reducing agent (evacuated silica tubes, 825 °C, 24 h; cooling to 450 °C at a rate of 6 °C/h).
ChemInform Abstract: Asymmetric Three‐Component Coupling Reaction of Alkyne, Enone, and Aldehyde Catalyzed by Chiral Phebox Ruthenium Catalysts.
Authors: Ubukata Shino , Ito Jun‐ichi , Oguri Ryota , Nishiyama Hisao 
Published: August 2016

AbstractThe one‐pot reaction consisting of an alkynylation and successive aldol reaction provides various novel α‐propargyl group containing β‐hydroxyketone derivatives in high yields.
ChemInform Abstract: ′On Water′ Direct Vinylogous Henry (Nitroaldol) Reactions of 3,5‐Dimethyl‐4‐nitroisoxazole with Aldehydes and Trifluoromethyl Ketones.
Authors: Zhang Yong , Wei Biao‐Wen , Zou Li‐Na , Kang Mei‐Lian , Luo Hai‐Qing , Fan Xiao‐Lin 
Published: August 2016

AbstractThe scalable protocol is applicable to the diastereoselective transformation of 3,5‐diethyl‐4‐nitroisoxazole.
ChemInform Abstract: One‐Pot Synthesis and Evaluation of Antileishmanial Activities of Functionalized S‐Alkyl/Aryl Benzothiazole‐2‐carbothioate Scaffold.
Authors: Dar Ajaz A. , Shadab M. , Khan Suman , Ali Nahid , Khan Abu T. 
Published: August 2016

AbstractThe three component condensation of 2‐aminothiopenols, oxalyl chloride and aryl or alkyl thiols efficiently provides various benzothiazole‐2‐carbothioates some of which are shown to exhibit interesting antileishmanial activity.
ChemInform Abstract: Use of Mesoporous Molecular Sieves in the Production of Fine Chemicals: Preparation of Dihydroquinolinones of Pharmaceutical Interest from 2′‐Aminochalcones.
Authors: Climent Maria J. , Corma Avelino , Iborra Sara , Marti Laura 
Published: August 2016

AbstractSolid catalysts are investigated in detail for the title reaction.
ChemInform Abstract: A Pseudo Six‐Component Process for the Synthesis of Tetrahydrodipyrazolo Pyridines Using an Ionic Liquid Immobilized on a FeNi3 Nanocatalyst.
Authors: Safaei‐Ghomi Javad , Sadeghzadeh Reyhaneh , Shahbazi‐Alavi Hossein 
Published: August 2016

AbstractThe title pyridines are prepared under mild reaction conditions by multi‐component reaction of ethyl acetoacetate, benzaldehydes, hydrazine, and ammonium acetate.