Direct characterization of bitter acids in a crude hop extract by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry

The applicability of on-line coupling of reversed-phase high-performance liquid chromatography to atmospheric pressure ionization tandem mass spectrometry for the separation and characterization of hop acids mixture from the crude extract of Humulus lupulus was investigated. The solvent system consisting of acetonitrile-aqueous formic acid was used to give proper separation of the six main hop bitter acids within 30 min. Further structural information about the components was acquired by collision-induced dissociation (CID). On the basis of analyses of the fragmentation patterns of the major alpha- and beta-bitter acids respectively, identification of the minor ones was performed using selected reaction monitoring (SRM) with a group of qualitatively relevant selected precursor-product ion transitions for each bitter acid in a single high performance liquid chromatography (HPLC) run. Using this technique, six minor hop acids, including "adprelupulone" observed for the first time in natural resources, were detected along with the six major acids. This hyphenated techniques provides potency for rapid qualitative determination of analogs and homologs in mixtures. (C) 2004 American Society for Mass Spectrometry.

Distribution characteristics of (CS)-C-137 in wind-eroded soil profile and its use in estimating wind erosion modulus

Due to its inert reaction in soil system and distinctive vertical distribution in soil profile, caesium-137 (Cs-137) has been used as a tracer to assess wind erosion. In this study, 62 soil samples were collected from 4 sampling sites in Taipusi County, Inner Mongolia; Caesium-137 activities for those soil samples were measured using a gamma-ray spectrometry in Sichuan University, Chengdu. Distribution pattern of Cs-137 in vertical soil profile was different for different land use and land cover types. Caesium-137 was distributed homogeneously in plow layer of cropland, and negatively exponential in low to medium cover grassland. Distribution pattern in high covered grassland was represented by a peak at 2-4 cm soil depth followed by a negative exponential curve. Based on those findings, simplified mass balance model was chosen to estimate the rate of wind erosion for cropland, while profile distribution model was used for grassland. Estimated wind erosion rates were 7990, 4270 and 1808 Mg(.)km(-2.)a(-1) for cropland, low cover grassland and medium cover grassland, respectively. Wind erosion intensity correlated negatively with plant cover.

CE coupling with end-column electrochemiluminescence detection for chiral separation of disopyramide

CE with electrochemiluminescence, (ECL) detection technique was successfully applied for the chiral separation of a kind of class IA antiarrhythmic racemic drug. To the best of our knowledge, this is the first report of ECL detection used in chiral CE. To get better detection sensitivity and good enantioresolution at the same time, the conditions of capillary inlet and outlet buffer were systematically optimized. Unlike the traditional chiral separation method, the buffers we used in the capillary inlet and outlet differed from each other in terms of buffer pH, ionic strength, type of BGE as well as buffer composition. Under the optimum conditions, baseline enantioseparation and highly sensitive detection of the enantiomers were achieved. Wide linear relationship of each enantiomer was achieved in the range of 5 x 10(-7) to 2 x 10(-5) mol/L with relative coefficients of 0.996 and 0.997, respectively. The detection limits were estimated to be 8 x 10(-8) and 1.0 X 10(-7) mol/L (S/N = 3) for the enantiomers, respectively. In addition, a successful application of this new method to the chiral separation of the racemic drug in spiked plasma samples confirmed the validity and applicability of the chiral CE-ECL method.

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and its application for determination of amines by high performance liquid chromatography with fluorescence detection and identification with mass spectroscopy/atmospheric pressure chemical ionization

A simple, sensitive, and mild method for the determination of amino compounds based on a condensation reaction with 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC-HCI) as the dehydrant with fluorescence detection has been developed. Amines were derivatized to their acidamides with labeling reagent 2-(2-phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA). Studies on derivatization conditions indicated that the coupling reaction proceeded rapidly and smoothly in the presence of a base catalyst in acetonitrile to give the corresponding sensitively fluorescent derivatives with an excitation maximum at lambda(ex) 260nm and an emission maximum at lambda(em) 380nm. The labeled derivatives exhibited high stability and were enough to be efficiently analyzed by high-performance liquid chromatography. Identification of derivatives was carried out by online post-column mass spectrometry (LC/APCI-MS/MS) and showed an intense protonated molecular ion corresponding m/z [MH](+) under APCI in positive-ion mode. At the same time, the fluorescence properties of derivatives in various solvents or at different temperature were investigated. The method, in conjunction with a gradient elution, offered a baseline resolution of the common amine derivatives on a reversed-phase Eclipse XDB-C-8 column. LC separation for the derivatized amines showed good reproducibility with acetonitrile-water as mobile phase. Detection limits calculated from 0.78 pmol injection, at a signal-to-noise ratio of 3, were 3.1-18.2 fmol. The mean intra- and inter-assay precision for all amine levels were < 3.85% and 2.11%, respectively. Excellent linear responses were observed with coefficients of > 0.9996. The established method for the determination of aliphatic amines from real wastewater and biological samples was satisfactory. (c) 2006 Elsevier B.V. All rights reserved.

磁层-电离层耦合现象的分析研究

The magnetosphere-ionosphere coupling is mainly manifested by the trans- porting processes of energy into the ionosphere , the energy is carried by solar wind and firstly accumulate at the magnetosphere, and the coupling processes also significantly include the interaction between the magnetosphere and ionosphere for mass and energy. At the quiet condition, energy is delivered by the large-scale convection of the geomagnetic field; the huge energy from solar wind bulk will be injected into and consumed at the near magnetosphere and ionosphere by the geomagnetic storm and substorm activities. Aurorae and FACs (Field-aligned currents) are the important phenomena in the coupling processes. In the present work, firstly, we analyze the activity characteristics of auroral precipitating particle, secondly, we study the distribution characters of large-scale field aligned currents (LS FACs) at storm-time using the observations from different satellites at different altitudes. Finally, we investigate the evolution of the geomagnetic field configuration at the nightside sector on the onset of the expansion phase in a substorm event, the substorm event happened at 0430UT to 0630UT on 8th Nov. 2004. The main results as follows： At the first, the data of the estimated power input (EPI) of auroral particles from NOAA/POES (Polar orbiting environmental satellite) for some 30 years have been analyzed. The variation tendencies of the EPI generally coincide with aa, AE and Dst indices. The annual variation of EPI shows equinox peaks and an asymmetric-activity with a higher peak in the winter-hemisphere than in the summer-hemisphere. The diurnal UT variations are different from north and south hemisphere: for north hemisphere, the peak appears at 1200UT, and the relative deviation is 22% to the daily average of the north hemisphere. For south hemisphere, the maximal deviation is 22% at 2000UT. So the diurnal variation of EPI is more dominant than the annual variation which maximal deviation is 3% to 12% for different seasons. Studies on correlations of the hourly average of EPI, Pa, with AE and Dst indices show a correlation coefficient r=0.74 of Pa and AE, and r=-0.55 of Pa and Dst. The hourly EPIs for north and south polar regions, NPa and SPa, show a north-south asymmetry with a higher correlation of SPa and AE (or Dst). Time delays of EPI with respect to magnetic indices are examined, the maximum correlation coefficient of Pa with AE (r=0.78) occurs when the time delay =0, suggesting a synchronous activity of auroral electrojet and auroral precipitating particles, while =1-2h, the correlation coefficient of Pa with Dst is maximum (r=0.57), suggesting that the activity of auroral particle precipitating may influence the ring current on some extent. Sencondly, we use the high-resolution magnetic field vector data of the CHAMP satellite to investigate the distribution of large-scale FACs during the great magnetic storm on 7th to 8th Nov. 2004. The results show that, whether in the northern or southern hemisphere, the number and density of large-scale FACs during the main-phase are more and bigger than these during the recover-phase, and the number of large-scale FACs in morning sector obviously is more than that in afternoon sector. In terms of the magnetic indices, we find that large-scale FACs in morning sector significantly affected by the substorm activities, while in afternoon sector the large-scale FACs mainly indicate the fluctuations of the ring-current in storm time. Accordingly to the former studies, similarly, we find that in the morning sector, the scale of the large-scale FACs move to the high-latitude region, and in the afternoon sector, large-scale FACs distinctly expand to the low-latitude region. During the time periods that the NOAA/POES auroral precipitating particle power data temporally correspond to the large-scale FACs, the more the power of auroral particle is, the more and bigger the number and density of FACs are. At the same time, we use the magnetic field vector data of POLAR obtain a good form of region 1, region 2, and three pieces of cusp FACs during a single transit at 1930UT-2006UT on 07th. And the characteristics of simultaneous electric field and energy particles observations on Polar are coincide with the five FACs pieces. Finally, by means of the observation of Cluster 4 and Goes 10、 Goes 12, we analyze the evolution process of the change of the magnetic field configuration at night sector at the expansion phase of a substorm event which happened during 0430UT to 0630UT on 8th Nov. 2004, we find that the times of the beginning of the polarizations of magnetic field are observed from Goes 10 to Goes 12 then to Cluster 4. So, at the synchronous orbit ( 6.6 RE) to 10RE distance scale of the neutral sheet, the current disruption spread tailward. Simultaneously, the strengthen of the FACs deduced from these satellites’ magnetic field observations are almost consistent with the times of polarizations, as well as the high energy particles injection and the electric field dominant variation. The onset times determined by the magnetic field polarizations from these satellites are all ahead of the onset time that confirmed from the auroral electrojet indices. So, these characters of different observations can be used as the criterions to determine the onset time for the substorms of such type as we studied.

Transition region, coronal heating and the fast solar wind

Li, Xing, 'Transition region, coronal heating and the fast solar wind', Astronomy and Astrophysics (2003) 406 pp.345-356 RAE2008

Heat and mass transfer in two-phase porous materials under intensive microwave heating

Computational results for the intensive microwave heating of porous materials are presented in this work. A multi-phase porous media model has been developed to predict the heating mechanism. Combined finite difference time-domain and finite volume methods were used to solve equations that describe the electromagnetic field and heat and mass transfer in porous media. The coupling between the two schemes is through a change in dielectric properties which were assumed to be dependent both on temperature and moisture content. The model was able to reflect the evolution of both temperature and moisture fields as well as energy penetration as the moisture in the porous medium evaporates. Moisture movement results from internal pressure gradients produced by the internal heating and phase change.

Measurements of OVOC fluxes by eddy covariance using a proton-transfer-reaction mass spectrometer – method development at a coastal site

We present here vertical fluxes of oxygenated volatile organic compounds (OVOCs) measured with eddy covariance (EC) during the period of March to July 2012 near the southwest coast of the United Kingdom. The performance of the proton-transfer-reaction mass spectrometer (PTR-MS) for flux measurement is characterized, with additional considerations given to the homogeneity and stationarity assumptions required by EC. Observed mixing ratios and fluxes of OVOCs (specifically methanol, acetaldehyde, and acetone) vary significantly with time of day and wind direction. Higher mixing ratios and fluxes of acetaldehyde and acetone are found in the daytime and from the direction of a forested park, most likely due to light-driven emissions from terrestrial plants. Methanol mixing ratio and flux do not demonstrate consistent diel variability, suggesting sources in addition to plants. We estimate air-sea exchange and photochemical rates of these compounds, which are compared to measured vertical fluxes. For acetaldehyde, the mean (1 sigma) mixing ratio of 0.13 (0.02) ppb at night may be maintained by oceanic emission, while photochemical destruction out-paces production during the day. Air-sea exchange and photochemistry are probably net sinks of methanol and acetone in this region. Their nighttime mixing ratios of 0.46 (0.20) and 0.39 (0.08) ppb appear to be affected more by terrestrial emissions and long-distance transport, respectively.

Towards Surface Plasmon Resonance biosensing combined with bioaffinity-assisted nano HILIC Liquid Chromatography Time-of-flight Mass Spectrometry identification of Paralytic Shellfish Poisons

The potential for coupling technologies to deliver new, improved forms of bioanalysis is still in its infancy. We review a number of examples in which coupling has been successful, with special emphasis on combining surface-plasmon-resonance biosensors with mass spectrometry. We give an overview of current progress towards combining biosensor-based bioanalysis with chemical analysis for confirmation of paralytic shellfish poisons that are marine toxins. This comprehensive approach could be an alternative to the official methods currently used (e.g., animal testing and high-performance liquid chromatography with fluorescence detection) and could serve as a model for many more such applications. (C) 2009 Elsevier Ltd. All rights reserved.

The empirical metallicity dependence of the mass-loss rate of O- and early B-type stars

We present a comprehensive study of the observational dependence of the mass-loss rate in stationary stellar winds of hot massive stars on the metal content of their atmospheres. The metal content of stars in the Magellanic Clouds is discussed, and a critical assessment is given of state-of-the-art mass-loss determinations of OB stars in these two satellite systems and the Milky-Way. Assuming a power-law dependence of mass loss on metal content,. M. Z(m), and adopting a theoretical relation between the terminal flow velocity and metal content, v(infinity). Z(0.13) (Leitherer et al. 1992, ApJ, 401, 596), we find m = 0.83 +/- 0.16 for non-clumped outflows from an analysis of the wind momentum luminosity relation (WLR) for stars more luminous than 105.2 L circle dot. Within the errors, this result is in agreement with the prediction m = 0.69 +/- 0.10 by Vink et al. (2001, A& A, 369, 574). Absolute empirical values for the mass loss, based on Ha and ultraviolet (UV) wind lines, are found to be a factor of two higher than predictions in this high luminosity regime. If this difference is attributed to inhomogeneities in the wind, and this clumping does not impact the predictions, this would imply that luminous O and early-B stars have clumping factors in their Ha and UV line forming regions of about a factor of four. For lower luminosity stars, the winds are so weak that their strengths can generally no longer be derived from optical spectral lines (essentially Ha) and one must currently rely on the analysis of UV lines. We confirm that in this low-luminosity domain the observed Galactic WLR is found to be much steeper than expected from theory (although the specific sample is rather small), leading to a discrepancy between UV mass-loss rates and the predictions by a factor 100 at luminosities of L similar to 10(4.75) L circle dot, the origin of which is unknown. We emphasize that even if the current mass-loss rates of hot luminous stars would turn out to be overestimated as a result of wind clumping, but the degree of clumping would be rather independent of metallicity, the scalings derived in this study are expected to remain correct.

The VLT-FLAMES survey of massive stars: wind properties and evolution of hot massive stars in the Large Magellanic Cloud

We have studied the optical spectra of a sample of 28 O- and early B-type stars in the Large Magellanic Cloud, 22 of which are associated with the young star forming region N11. Our observations sample the central associations of LH9 and LH10, and the surrounding regions. Stellar parameters are determined using an automated fitting method ( Mokiem et al. 2005), which combines the stellar atmosphere code fastwind ( Puls et al. 2005) with the genetic algorithm based optimisation routine PIKAIA ( Charbonneau 1995). We derive an age of 7.0 +/- 1.0 and 3.0 +/- 1.0 Myr for LH9 and LH10, respectively. The age difference and relative distance of the associations are consistent with a sequential star formation scenario in which stellar activity in LH9 triggered the formation of LH10. Our sample contains four stars of spectral type O2. From helium and hydrogen line fitting we find the hottest three of these stars to be similar to 49- 54 kK ( compared to similar to 45- 46 kK for O3 stars). Detailed determination of the helium mass fraction reveals that the masses of helium enriched dwarfs and giants derived in our spectroscopic analysis are systematically lower than those implied by non-rotating evolutionary tracks. We interpret this as evidence for efficient rotationally enhanced mixing leading to the surfacing of primary helium and to an increase of the stellar luminosity. This result is consistent with findings for SMC stars by Mokiem et al. ( 2006). For bright giants and supergiants no such mass discrepancy is found; these stars therefore appear to follow tracks of modestly or non-rotating objects. The set of programme stars was sufficiently large to establish the mass loss rates of OB stars in this Z similar to 1/2 Z(circle dot) environment sufficiently accurate to allow for a quantitative comparison with similar objects in the Galaxy and the SMC. The mass loss properties are found to be intermediate to massive stars in the Galaxy and SMC. Comparing the derived modified wind momenta D-mom as a function of luminosity with predictions for LMC metallicities by Vink et al. ( 2001) yields good agreement in the entire luminosity range that was investigated, i.e. 5.0

Physical Models of Wind Instruments : A Generalized Excitation Coupled with a Modular Tube Simulation Platform

To develop real-time simulations of wind instruments, digital waveguides filters can be used as an efficient representation of the air column. Many aerophones are shaped as horns which can be approximated using conical sections. Therefore the derivation of conical waveguide filters is of special interest. When these filters are used in combination with a generalized reed excitation, several classes of wind instruments can be simulated. In this paper we present the methods for transforming a continuous description of conical tube segments to a discrete filter representation. The coupling of the reed model with the conical waveguide and a simplified model of the termination at the open end are described in the same way. It turns out that the complete lossless conical waveguide requires only one type of filter.Furthermore, we developed a digital reed excitation model, which is purely based on numerical integration methods, i.e., without the use of a look-up table.

The geometry and ionization structure of the wind in the eclipsing nova-like variables RW Tri and UX UMa

The UV spectra of nova-like variables are dominated by emission from the accretion disk, modified by scattering in a wind emanating from the disk. Here, we model the spectra of RW Tri and UX UMa, the only two eclipsing nova-like variables which have been observed with the Hubble Space Telescope in the far-ultraviolet, in an attempt to constrain the geometry and the ionization structure of their winds. Using our Monte Carlo radiative transfer code, we computed spectra for simply parameterized axisymmetric biconical outflow models and were able to find plausible models for both systems. These reproduce the primary UV resonance lines-N v, Si iv, and C iv-in the observed spectra in and out of eclipse. The distribution of these ions in the wind models is similar in both cases as is the extent of the primary scattering regions in which these lines are formed. The inferred mass-loss rates are 6%-8% of the mass accretion rates for the systems. We discuss the implication of our point models for our understanding of accretion disk winds in cataclysmic variables. © 2010. The American Astronomical Society. All rights reserved.

Mass-loss rates for hot luminous stars:The influence of line branching

The effect of photon frequency redistribution by line branching on mass-loss rates for hot luminous stars is investigated. Monte Carlo simulations are carried out for a range of OB star models which show that previous mass-loss calculations which neglect non-resonance line scattering overestimate mass-loss rates for luminous O stars by ~20 per cent. For luminous B stars the effect is somewhat larger, typically ~50 per cent. A Wolf-Rayet star model is used to investigate line branching in the strong wind limit. In this case the effect of line branching is much greater, giving mass-loss rates that are smaller by a factor ~3 from computations which neglect branching.

A simple disc wind model for broad absorption line quasars

Approximately 20 per cent of quasi-stellar objects (QSOs) exhibit broad, blue-shifted absorption lines in their ultraviolet spectra. Such features provide clear evidence for significant outflows from these systems, most likely in the form of accretion disc winds. These winds may represent the ‘quasar’ mode of feedback that is often invoked in galaxy formation/evolution models, and they are also key to unification scenarios for active galactic nuclei (AGN) and QSOs. To test these ideas, we construct a simple benchmark model of an equatorial, biconical accretion disc wind in a QSO and use a Monte Carlo ionization/radiative transfer code to calculate the ultraviolet spectra as a function of viewing angle. We find that for plausible outflow parameters, sightlines looking directly into the wind cone do produce broad, blue-shifted absorption features in the transitions typically seen in broad absorption line (BAL) QSOs. However, our benchmark model is intrinsically X-ray weak in order to prevent overionization of the outflow, and the wind does not yet produce collisionally excited line emission at the level observed in non-BAL QSOs. As a first step towards addressing these shortcomings, we discuss the sensitivity of our results to changes in the assumed X-ray luminosity and mass-loss rate, Ṁwind. In the context of our adopted geometry, Ṁwind ∼ Ṁacc is required in order to produce significant BAL features. The kinetic luminosity and momentum carried by such outflows would be sufficient to provide significant feedback.