Determination of absolute ion yields from a MALDI source through calibration of an image-charge detector

MALDI (matrix-assisted laser desorption/ionization) is one of the most important techniques used to produce large biomolecular ions in the gas phase. Surprisingly, the exact ionization mechanism is still not well understood and absolute values for the ion yields are scarce. This is in part due to the unknown efficiencies of typical detectors, especially for heavy biomolecular ions. As an alternative, charged particles can be non-destructively detected using an image-charge detector where the output voltage signal is proportional to the total charge within the device. In this paper, we report an absolute calibration which provides the voltage output per detected electronic charge in our experimental arrangement. A minimum of 3 x 10(3) ions were required to distinguish the signal above background noise in a single pass through the device, which could be further reduced using filtering techniques. The calibration results have been applied to raw MALDI spectra to measure absolute ion yields of both matrix and analyte ions.

Quasi-classical model of non-destructive wavepacket manipulation by intense ultrashort nonresonant laser pulses

A quasi-classical model (QCM) of nuclear wavepacket generation, modification and imaging by three intense ultrafast near-infrared laser pulses has been developed. Intensities in excess of 10(13) W cm(-2) are studied, the laser radiation is non-resonant and pulse durations are in the few-cycle regime, hence significantly removed from the conditions typical of coherent control and femtochemistry. The 1s sigma ground state of the D-2 precursor is projected onto the available electronic states in D-2(+) (1s sigma(g) ground and 2p sigma(u) dissociative) and D+ + D+ (Coulomb explosion) by tunnel ionization by an ultrashort 'pump' pulse, and relative populations are found numerically. A generalized non-adiabatic treatment allows the dependence of the initial vibrational population distribution on laser intensity to be calculated. The wavepacket is approximated as a classical ensemble of particles moving on the 1s sigma(g) potential energy surface (PES), and hence follow trajectories of different amplitudes and frequencies depending on the initial vibrational state. The 'control' pulse introduces a time-dependent polarization of the molecular orbital, causing the PES to be modified according to the dynamic Stark effect and the transition dipole. The trajectories adjust in amplitude, frequency and phase-offset as work is done on or by the resulting force; comparing the perturbed and unperturbed trajectories allows the final vibrational state populations and phases to be determined. The action of the 'probe' pulse is represented by a discrete internuclear boundary, such that elements of the ensemble at a larger internuclear separation are assumed to be photodissociated. The vibrational populations predicted by the QCM are compared to recent quantum simulations (Niederhausen and Thumm 2008 Phys. Rev. A 77 013404), and a remarkable agreement has been found. The applicability of this model to femtosecond and attosecond time-scale experiments is discussed and the relation to established femtochemistry and coherent control techniques are explored.

Increased levels of advanced glycation endproducts in the lenses and blood vessels of cigarette smokers.

BACKGROUND: Advanced glycation endproducts (AGEs) arise from the spontaneous reaction of reducing sugars with the amino groups of macromolecules. AGEs accumulate in tissue as a consequence of diabetes and aging and have been causally implicated in the pathogenesis of several of the end-organ complications of diabetes and aging, including cataract, atherosclerosis, and renal insufficiency. It has been recently proposed that components in mainstream cigarette smoke can react with plasma and extracellular matrix proteins to form covalent adducts with many of the properties of AGEs. We wished to ascertain whether AGEs or immunochemically related molecules are present at higher levels in the tissues of smokers.

MATERIALS AND METHODS: Lens and coronary artery specimens from nondiabetic smokers and nondiabetic nonsmokers were examined by immunohistochemistry, immunoelectron microscopy, and ELISA employing several distinct anti-AGE antibodies. In addition, lenticular extracts were tested for AGE-associated fluorescence by fluorescence spectroscopy.

RESULTS: Immunoreactive AGEs were present at significantly higher levels in the lenses and lenticular extracts of nondiabetic smokers (p < 0.003). Anti-AGE immunogold staining was diffusely distributed throughout lens fiber cells. AGE-associated fluorescence was significantly increased in the lenticular extracts of nondiabetic smokers (p = 0.005). AGE-immunoreactivity was significantly elevated in coronary arteries from nondiabetic smokers compared with nondiabetic nonsmokers (p = 0.015).

CONCLUSIONS: AGEs or immunochemically related molecules are present at higher levels in the tissues of smokers than in nonsmokers, irrespective of diabetes. In view of previous reports implicating AGEs in a causal association with numerous pathologies, these findings have significant ramifications for understanding the etiopathology of diseases associated with smoking, the single greatest preventable cause of morbidity and mortality in the United States.

Redistribution of vibrational population in a molecular ion with nonresonant strong-field laser pulses

We present an experimental demonstration of nonresonant manipulation of vibrational states in a molecule by an intense ultrashort laser pulse. A vibrational wave packet is generated in D-2(+) through tunnel ionization of D-2 by a few-cycle pump pulse. A similar control pulse is applied as the wave packet begins to dephase so that the dynamic Stark effect distorts the electronic environment of the nuclei, transferring vibrational population. The time evolution of the modified wave packet is probed via the D-2(+) photodissociation yield that results from the application of an intense probe pulse. Comparing the measured yield with a quasiclassical trajectory model allows us to determine the redistribution of vibrational population caused by the control pulse. ©

An efficient neural network approach for nanoscale FinFET modelling and circuit simulation

The present paper demonstrates the suitability of artificial neural network (ANN) for modelling of a FinFET in nano-circuit simulation. The FinFET used in this work is designed using careful engineering of source-drain extension, which simultaneously improves maximum frequency of oscillation f(max) because of lower gate to drain capacitance, and intrinsic gain A(V0) = g(m)/g(ds), due to lower output conductance g(ds). The framework for the ANN-based FinFET model is a common source equivalent circuit, where the dependence of intrinsic capacitances, resistances and dc drain current I-d on drain-source V-ds and gate-source V-gs is derived by a simple two-layered neural network architecture. All extrinsic components of the FinFET model are treated as bias independent. The model was implemented in a circuit simulator and verified by its ability to generate accurate response to excitations not used during training. The model was used to design a low-noise amplifier. At low power (J(ds) similar to 10 mu A/mu m) improvement was observed in both third-order-intercept IIP3 (similar to 10 dBm) and intrinsic gain A(V0) (similar to 20 dB), compared to a comparable bulk MOSFET with similar effective channel length. This is attributed to higher ratio of first-order to third-order derivative of I-d with respect to gate voltage and lower g(ds), in FinFET compared to bulk MOSFET. Copyright (C) 2009 John Wiley & Sons, Ltd.

Controlled redistribution of vibrational population by few-cycle strong-field laser pulses

The use of strong-field (i.e. intensities in excess of 10(13) Wcm(-2)) few-cycle ultrafast (durations of 10 femtoseconds or less) laser pulses to create, manipulate and image vibrational wavepackets is investigated. Quasi-classical modelling of the initial superposition through tunnel ionization, wavepacket modification by nonadiabatically altering the nuclear environment via the transition dipole and the Stark effect, and measuring the control outcome by fragmenting the molecule is detailed. The influence of the laser intensity on strong-field ultrafast wavepacket control is discussed in detail: by modifying the distribution of laser intensities imaged, we show that focal conditions can be created that give preference to this three-pulse technique above processes induced by the pulses alone. An experimental demonstration is presented, and the nuclear dynamics inferred by the quasi-classical model discussed. Finally, we present the results of a systematic investigation of a dual-control pulse scheme, indicating that single vibrational states should be observable with high fidelity, and the populated state defined by varying the arrival time of the two control pulses. The relevance of such strong-field coherent control methods to the manipulation of electron localization and attosecond science is discussed.

A lower mass for the exoplanet WASP-21b

We present high-precision transit observations of the exoplanet WASP-21b, obtained with the Rapid Imager to Search for Exoplanets instrument mounted on the 2.0-m Liverpool Telescope. A transit model is fitted, coupled with a Markov chain Monte Carlo routine, to derive accurate system parameters. The two new high-precision transits allow us to estimate the stellar density directly from the light curve. Our analysis suggests that WASP-21 is evolving off the main sequence which led to a previous overestimation of the stellar density. Using isochrone interpolation, we find a stellar mass of 0.86 ± 0.04 Msun, which is significantly lower than previously reported (1.01 ± 0.03 Msun). Consequently, we find a lower planetary mass of 0.27 ± 0.01 MJup. A lower inclination (87?4 ± 0?3) is also found for the system than previously reported, resulting in a slightly larger stellar (R*= 1.10 ± 0.03 Rsun) and planetary radius (Rp= 1.14 ± 0.04 RJup). The planet radius suggests a hydrogen/helium composition with no core which strengthens the correlation between planetary density and host star metallicity. A new ephemeris is determined for the system, i.e. T0= 245 5084.519 74 ± 0.000 20 (HJD) and P= 4.322 5060 ± 0.000 0031 d. We found no transit timing variations in WASP-21b.

Distance limits to intermediate- and high-velocity clouds

We present optical spectra of 403 stars and quasi-stellar objects in order to obtain distance limits towards intermediate- and high-velocity clouds (IHVCs), including new Fibre-fed Extended Range Optical Spectrograph (FEROS) observations plus archival ELODIE, FEROS, High Resolution Echelle Spectrometer (HIRES) and Ultraviolet and Visual Echelle Spectrograph (UVES) data. The non-detection of Ca II K interstellar (IS) absorption at a velocity of −130 to −60 km s−1 towards HDE 248894 (d ∼ 3 kpc) and HDE 256725 (d ∼ 8 kpc) in data at signal-to-noise ratio (S/N) > 450 provides a new firm lower distance limit of 8 kpc for the anti-centre shell HVC. Similarly, the non-detection of Ca II K IS absorption towards HD 86248 at S/N ∼ 500 places a lower distance limit of 7.6 kpc for Complex EP, unsurprising since this feature is probably related to the Magellanic System. The lack of detection of Na I D at S/N = 35 towards Mrk 595 puts an improved upper limit for the Na I column density of log (NNaD <) 10.95 cm−2 towards this part of the Cohen Stream where Ca II was detected by Wakker et al. Absorption at ∼ −40 km s−1 is detected in Na I D towards the Galactic star PG 0039+049 at S/N = 75, placing a firm upper distance limit of 1 kpc for the intermediate-velocity cloud south (IVS), where a tentative detection had previously been obtained by Centurion et al. Ca ´ II K and Na I D absorption is detected at −53 km s−1 towards HD 93521, which confirms the upper distance limit of 2.4 kpc for part of the IV arch complex obtained using the International Ultraviolet Explorer (IUE) data by Danly. Towards HD 216411 in Complex H a non-detection in Na D towards gas with log(NH I) = 20.69 cm−2 puts a lower distance limit of 6.6 kpc towards this HVC complex. Additionally, Na I D absorption is detected at −43.7 km s−1 in the star HD 218915 at a distance of 5.0 kpc in gas in the same region of the sky as Complex H. Finally, the Na I/Ca II and Ca II/H I ratios of the current sample are found to lie in the range observed for previous studies of IHVCs.

Early-type stars observed in the ESO UVES Paranal Observatory Project - III. Sub-parsec and AU-scale structure in the interstellar medium

UVES interstellar observations from the Paranal Observatory Project are presented for early-type stars located in the line of sight to the nearby open clusters IC 2391 (Omni Vel) and NGC 6475 (M7), with spectroscopic resolution R similar to 80 000 and signal-to-noise ratios in the Ti II (3383 angstrom), Ca II K, CH+ (4232 angstrom), Na I D and K I (7698 angstrom) lines of several hundred. The sightlines are a mixture of cluster and non-cluster objects. A total of 22 early-type stars (A and B type) are present in our sample towards IC 2391, with 21 towards NGC 6475/M7, and enable us to probe for differences in column density on scales from similar to 0.07 to 7.3 and similar to 0.05 to 4.9 pc in the respective clusters. Additionally, towards Praesepe the Na I D interstellar variation only is probed towards 13 sightlines and transverse scales of similar to 0.16-10.7 pc at R = 70 000. Towards IC 2391 variations are found in Ti II, Ca II K and Na I D column density in different sightlines of up to 0.7, 1.0 and 1.8 dex (excluding one star), respectively. This kind of variability correlates well with the Hipparcos parallax of the objects, and probes structure within the Local Bubble. For cluster-only objects the variations are 0.3, 0.3 and 0.5 dex, respectively. For the field of view towards NGC6475 the corresponding maximum variations are somewhat smaller, being 0.5, 0.3, 0.8 and 1.0 dex for Ti II, Ca II K, Na I and K I, respectively, for all objects and 0.4, 0.2, 0.6 and 0.7 dex for the cluster-only objects. These are uncorrelated with parallax, and again demonstrate that Ca II K tends to be more smoothly distributed than Na I D. A few likely cluster sightlines show evidence for CH+ and variations in this molecular species of a factor of 10 in equivalent width over sub-pc scales. Towards Praesepe variation in interstellar Na I D is small, being a maximum of only similar to 0.4 dex (including measurement errors), but with fewer sightlines studied. Overall, the scatter in the data is similar for the singly ionized species Ti II and Ca II, lending more support to the hypothesis that these two species sample similar parts of the interstellar medium (ISM). This also appears to be the case for the neutral species Na I D and K I in the one cluster studied. Finally, multiple-epoch observations from a variety of archive sources are used to search for astronomical unit (au) scale structure in the ISM towards 46 sightlines. There are tentative indications of structure on scales of tens to thousands of au for three sightlines. Future observations will confirm the veracity or otherwise of the time-variable components and others presented.

THE VLT-FLAMES TARANTULA SURVEY: THE FASTEST ROTATING O-TYPE STAR AND SHORTEST PERIOD LMC PULSAR-REMNANTS OF A SUPERNOVA DISRUPTED BINARY?

We present a spectroscopic analysis of an extremely rapidly rotating late O-type star, VFTS102, observed during a spectroscopic survey of 30 Doradus. VFTS102 has a projected rotational velocity larger than 500 km s(-1) and probably as large as 600 km s-1; as such it would appear to be the most rapidly rotating massive star currently identified. Its radial velocity differs by 40 kms(-1) from the mean for 30 Doradus, suggesting that it is a runaway. VFTS102 lies 12 pc from the X-ray pulsar PSR J0537-6910 in the tail of its X-ray diffuse emission. We suggest that these objects originated from a binary system with the rotational and radial velocities of VFTS102 resulting from mass transfer from the progenitor of PSR J0537-691 and the supernova explosion, respectively.

Simultaneous optical and X-ray observations of flares and rotational modulation on the RS CVn binary HR 1099 (V711 Tau) from the MUSICOS 1998 campaign

We present simultaneous and continuous observations of the Halpha, Hbeta, He I D-3, Na I D-1,D-2 doublet and the Ca II H&K lines for the RS CVn system HR 1099. The spectroscopic observations were obtained during the MUSICOS 1998 campaign involving several observatories and instruments, both echelle and long-slit spectrographs. During this campaign, HR 1099 was observed almost continuously for more than 8 orbits of 2.(d)8. Two large optical flares were observed, both showing an increase in the emission of Halpha, Ca II H K, Hbeta and He I D-3 and a strong filling-in of the Na I D-1, D-2 doublet. Contemporary photometric observations were carried out with the robotic telescopes APT-80 of Catania and Phoenix-25 of Fairborn Observatories. Maps of the distribution of the spotted regions on the photosphere of the binary components were derived using the Maximum Entropy and Tikhonov photometric regularization criteria. Rotational modulation was observed in Halpha and He I D-3 in anti-correlation with the photometric light curves. Both flares occurred at the same binary phase (0.85), suggesting that these events took place in the same active region. Simultaneous X-ray observations, performed by ASM on board RXTE, show several flare-like events, some of which correlate well with the observed optical flares. Rotational modulation in the X-ray light curve has been detected with minimum flux when the less active G5 V star was in front. A possible periodicity in the X-ray flare-like events was also found.

LS 4825: A blue supergiant on the far side of the galaxy

We present high-resolution spectroscopic observations of LS 4825, a V = 12 B-type star in the Galactic center direction. On the basis of its stellar and interstellar spectra, we infer that it is likely to be a young supergiant at a distance of 21 +/- 5 kpc, and hence lying on the far side of the 'Galaxy. Adopting this hypothesis, a differential abundance analysis shows LS 4825 to have a chemical composition that is consistent with local B-type supergiants. These observations therefore represent the first detailed investigation of a star on the far side of the Galactic center. We trace multiple interstellar components in Ca II K and Na I D spectra, with velocities -206 less than or equal to v(lst) less than or equal to +93 km s(-1). We consider the likely origin of this gas and find that some components appear to trace matter lying close to the Galactic center. We discuss the possible use of such sight lines in furthering our understanding both of the nature of gas around the Galactic center and of the abundance gradient of the Galaxy.

Femtosecond lasers for mass spectrometry: Proposed application to catalytic hydrogenation of butadiene

Mass spectra from the interaction of intense, femtosecond laser pulses with 1,3-butadiene, 1-butene, and n-butane have been obtained. The proportion of the fragment ions produced as a function of intensity, pulse length, and wavelength was investigated. Potential mass spectrometry applications, for example in the analysis of catalytic reaction products, are discussed.

Dexamethasone reduces pain, vomiting and overall complications following tonsillectomy in adults: a systematic review and meta-analysis of randomised controlled trials

Background: Tonsillectomy is one of the most common surgical procedures, but there is debate whether systemic steroids should be used to reduce pain and post-operative complications.