1,925 research outputs found
Aqueous-phase nitration of phenol by N2O5 and ClNO2
Nitrophenols are present in the atmospheric gas phase and in cloud and rainwater. Their formation via aqueous-phase reactions of phenol with the nitronium ion, NO2+, arising from N2O5 and ClNO2 partitioning into the aqueous phase, has been proposed but not verified experimentally. Here we demonstrate for the first time that gaseous N2O5 and ClNO2 partitioning into dilute aqueous solutions of phenol yields 2- and 4-nitrophenol (and 4-nitrosophenol), but no dinitrophenol isomers. The rate of nitration does not vary significantly between 5 and 20 degrees C, presumably because of opposing temperature dependences in Henryâs law partitioning and reaction rate coefficients. The rate coefficient for reaction of NO2+ with phenol could not be directly quantified but is evidently large enough for this reaction to compete effectively with the reaction between NO2+ and water and to provide a feasible route to nitrophenol production in the atmosphere
Experimentally determined Henry's Law coefficients of phenol, 2-methylphenol and 2-nitrophenol in the temperature range 281-302 K
The Henryâs Law coefficient is a key physical parameter in the partitioning, and hence environmental fate, of a chemical species between air and water. Despite the acknowledged polluting potential of phenol, 2-methylphenol (o-cresol) and 2-nitrophenol, there is extremely poor agreement in the literature of their Henryâs law coefficients and, in particular, no apparent systematic measurement of the variation with temperature. Here a temperature controlled column-stripping method was employed to determine the Henry's Law coefficients for these compounds over the temperature range 281-302 K. Coefficients were derived from regression fits to the observed rates of loss from the liquid phase as a function of column depth in order explicitly to take account of potential non-attainment of equilibrium between liquid and gas phases. Temperature dependent expressions summarising the Henry's Law coefficient of phenol, o-cresol and 2-nitrophenol over the stated temperature range are ln H (/ M atm-1) = 5850/T - 11.6, ln H (/ M atm-1) = 6680/T - 15.4 and ln H (/ M atm-1) = 6270/T - 16.6, respectively (to within 15% of all measured values in this work). A thorough comparison with previous literature-published values has been undertaken
Evaluation of the pathways of tropospheric nitrophenol formation from benzene and phenol using a multiphase model
Phenols are a major class of volatile organic compounds (VOC) whose reaction within, and partitioning between, the gas and liquid phases affects their lifetime within the atmosphere, the local oxidising capacity, and the extent of production of nitrophenols, which are toxic chemicals. In this work, a zero-dimension box model was constructed to quantify the relative importance of different nitration pathways, and partitioning into the liquid phase, of mono-aromatic compounds in order to help elucidate the formation pathways of 2- and 4-nitrophenol in the troposphere. The liquid phase contributed significantly to the production of nitrophenols for liquid water content (Lc) values exceeding 3x10-9, and for a range of assumed liquid droplet diameter, even though the resultant equilibrium partitioning to the liquid phase was much lower. For example, in a "typical" model scenario, with Lc=3x10-7, 58% of nitrophenol production occurred in the liquid phase but only 2% of nitrophenol remained there, i.e. a significant proportion of nitrophenol observed in the gas phase may actually be produced via the liquid phase. The importance of the liquid phase was enhanced at lower temperatures, by a factor ~1.5-2 at 278K c.f. 298K. The model showed that nitrophenol production was particularly sensitive to the values of the rate coefficients for the liquid phase reactions between phenol and OH or NO3 reactions, but insensitive to the rate coefficient for the reaction between benzene and OH, thus identifying where further experimental data are require
Deficiency of the paternally-expressed imprinted Peg3 gene in mice has sexually dimorphic consequences for offspring communication and social behaviour
Introduction: Imprinted genes are expressed from one parental allele as a consequence of epigenetic processes initiated in the germline. Consequently, their ability to influence phenotype depends on their parent-of-origin. Recent research suggests that the sex of the individual expressing the imprinted gene is also important. We have previously reported that genetically wildtype (WT) dams carrying and caring for pups mutant for PEG3 exhibit anxiety-like behaviours and their mutant pups show a reduction in ultrasonic vocalisation when separated from their mothers. Sex-specificity was not examined. Methods: WT female mice were mated with WT, heterozygous Peg3â/+ or homozygous Peg3â/â studs to generate all WT (control), 50:50 mixed or 100% mutant litters, respectively, followed by behavioural assessment of both dams and their pups. Results: We reproduced our original finding that WT dams carrying and caring for 100% mutant litters exhibit postpartum anxiety-like symptoms and delayed pup retrieval. Additionally, these WT dams were found to allocate less time to pup-directed care behaviours relative to controls. Male Peg3-deficient pups demonstrated significantly reduced vocalisation with a more subtle communication deficit in females. Postweaning, male mutants exhibited deficits across a number of key social behaviours as did WT males sharing their environment with mutants. Only modest variations in social behaviour were detected in experimental females. Discussion: We have experimentally demonstrated that Peg3 deficiency confined to the offspring causes anxiety in mouse mothers and atypical behaviour including deficits in communication in their male offspring. A male-specific reduction in expression PEG3 in the fetally-derived placenta has previously been associated with maternal depression in human pregnancy. Maternal mood disorders such as depression and anxiety are associated with delays in language development and neuroatypical behaviour more common in sons. Peg3 deficiency could drive the association of maternal and offspring behavioural disorders reported in humans
Using coordinated observations in polarized white light and Faraday rotation to probe the spatial position and magnetic field of an interplanetary sheath
Coronal mass ejections (CMEs) can be continuously tracked through a large portion of the inner heliosphere by direct imaging in visible and radio wavebands. White light (WL) signatures of solar wind transients, such as CMEs, result from Thomson scattering of sunlight by free electrons and therefore depend on both viewing geometry and electron density. The Faraday rotation (FR) of radio waves from extragalactic pulsars and quasars, which arises due to the presence of such solar wind features, depends on the line-of-sight magnetic field component B â„ and the electron density. To understand coordinated WL and FR observations of CMEs, we perform forward magnetohydrodynamic modeling of an Earth-directed shock and synthesize the signatures that would be remotely sensed at a number of widely distributed vantage points in the inner heliosphere. Removal of the background solar wind contribution reveals the shock-associated enhancements in WL and FR. While the efficiency of Thomson scattering depends on scattering angle, WL radiance I decreases with heliocentric distance r roughly according to the expression Ir â3. The sheath region downstream of the Earth-directed shock is well viewed from the L4 and L5 Lagrangian points, demonstrating the benefits of these points in terms of space weather forecasting. The spatial position of the main scattering site r sheath and the mass of plasma at that position M sheath can be inferred from the polarization of the shock-associated enhancement in WL radiance. From the FR measurements, the local B â„sheath at r sheath can then be estimated. Simultaneous observations in polarized WL and FR can not only be used to detect CMEs, but also to diagnose their plasma and magnetic field properties
Probing the Role of Magnetic-Field Variations in NOAA AR 8038 in Producing Solar Flare and CME on 12 May 1997
We carried out a multi-wavelength study of a CME and a medium-size 1B/C1.3
flare occurring on 12 May 1997. We present the investigation of magnetic-field
variations in the NOAA Active Region 8038 which was observed on the Sun during
7--16 May 1997. Analyses of H{\alpha} filtergrams and MDI/SOHO magnetograms
revealed continual but discrete surge activity, and emergence and cancellation
of flux in this active region. The movie of these magnetograms revealed two
important results that the major opposite polarities of pre-existing region as
well as in the emerging flux region (EFR) were approaching towards each other
and moving magnetic features (MMF) were ejecting out from the major north
polarity at a quasi-periodicity of about ten hrs during 10--13 May 1997. These
activities were probably caused by the magnetic reconnection in the lower
atmosphere driven by photospheric convergence motions, which were evident in
magnetograms. The magnetic field variations such as flux, gradient, and sunspot
rotation revealed that free energy was slowly being stored in the corona. The
slow low-layer magnetic reconnection may be responsible for this storage and
the formation of a sigmoidal core field or a flux rope leading to the eventual
eruption. The occurrence of EUV brightenings in the sigmoidal core field prior
to the rise of a flux rope suggests that the eruption was triggered by the
inner tether-cutting reconnection, but not the external breakout reconnection.
An impulsive acceleration revealed from fast separation of the H{\alpha}
ribbons of the first 150 seconds suggests the CME accelerated in the inner
corona, which is consistent with the temporal profile of the reconnection
electric field. In conclusion, we propose a qualitative model in view of
framework of a solar eruption involving, mass ejections, filament eruption,
CME, and subsequent flare.Comment: 8 figures, accepted for publication in Solar Physic
Chemotherapeutic agents subvert tumor immunity by generating agonists of platelet-activating factor
Oxidative stress suppresses host immunity by generating oxidized lipid agonists of the platelet-activating factor receptor (PAF-R). Because many classical chemotherapeutic drugs induce reactive oxygen species (ROS), we investigated whether these drugs might subvert host immunity by activating PAF-R. Here, we show that PAF-R agonists are produced in melanoma cells by chemotherapy that is administered in vitro, in vivo, or in human subjects. Structural characterization of the PAF-R agonists induced revealed multiple oxidized glycerophosphocholines that are generated nonenzymatically. In a murine model of melanoma, chemotherapeutic administration could augment tumor growth by a PAF-R-dependent process that could be blocked by treatment with antioxidants or COX-2 inhibitors or by depletion of regulatory T cells. Our findings reveal how PAF-R agonists induced by chemotherapy treatment can promote treatment failure. Furthermore, they offer new insights into how to improve the efficacy of chemotherapy by blocking its heretofore unknown impact on PAF-R activation
Recommended from our members
Tracking CMEs using data from the Solar Stormwatch project; observing deflections and other properties
With increasing technological dependence, society is becoming ever more affected by changes in the near-Earth space environment caused by space weather. The primary driver of these hazards are coronal mass ejections (CMEs). Solar Stormwatch is a citizen science project in which volunteers participated in several activities which characterised CMEs in the remote sensing images from the SECCHI instrument package on the twin STEREO spacecraft. Here, we analyse the results of the 'Track-it-back' activity, in which CMEs were tracked back through the COR2, COR1 and EUVI images. Analysis of the COR1, COR2 and EUVI data together allows CMEs to be studied consistently throughout the whole field-of-view spanned by these instruments (out to 15 solar radii). 4783 volunteers took part in this activity, creating a dataset containing 23,801 estimates of CME timing, location and size. We used this data to produce a catalogue of 41 CMEs, which is the first to consistently track CMEs through each of these instruments. We assess how the CME speeds, propagation directions and widths vary as the CMEs propagate through the fields of view of the different imagers. In particular, we compare the observed CME deflections between the COR1 and COR2 fields of view to the separation between the CME source region and the heliospheric current sheet (HCS), demonstrating that, in general, these CMEs appear to deflect towards the HCS, consistent with other modelling studies of CME propagation
Correlations in the chemical composition of rural background atmospheric aerosol in the UK determined in real time using time-of-flight mass spectrometry
An aerosol time-of-flight mass spectrometer (ATOFMS) was used to determine, in real time, the size and chemical composition of individual particles in the atmosphere at the remote inland site of Eskdalemuir, Scotland. A total of 51980 particles, in the size range 0.3â7.4 ”m, were detected between the 25th and 30th June 2001. Rapid changes in the number density, size and chemical composition of the atmospheric aerosol were observed. These changes are attributed to two distinct types of air mass; a polluted air mass that had passed over the British mainland before reaching Eskdalemuir, interposed between two cleaner air masses that had arrived directly from the sea. Such changes in the background aerosol could clearly be very important to studies of urban aerosols and attempts at source apportionment. The results of an objective method of data analysis are presented. Correlations were sought between the occurrence of: lithium, potassium, rubidium, caesium, beryllium, strontium, barium, ammonium, amines, nitrate, nitrite, boron, mercury, sulfate, phosphate, fluorine, chlorine, bromine, iodine and carbon (both elemental and organic hydrocarbon) in both fine (d 2.5 ”m) particle fractions. Several previously unreported correlations were observed, for instance between the elements lithium, beryllium and boron. The results suggest that about 2 in 3 of all fine particles (by number rather than by mass), and 1 in 2 of all coarse particles containing carbon, consisted of elemental carbon rather than organic hydrocarbon (although a bias in the sensitivity of the ATOFMS could have affected these numbers). The ratio of the number of coarse particles containing nitrate anions to the number of particles containing chloride anions exceeded unity when the air mass had travelled over the British mainland. The analysis also illustrates that an air mass of marine origin that had travelled slowly over agricultural land can accumulate amines and ammonium
- âŠ