Direct observation by time-resolved infrared spectroscopy of the bright and the dark excited states of the [Ru(phen)2(dppz)]2+ light-switch compound in solution and when bound to DNA

The [Ru(phen)2(dppz)]2+ complex (1) is non-emissive in water but is highly luminescent in organic solvents or when bound to DNA, making it a useful probe for DNA binding. To date, a complete mechanistic explanation for this “light-switch” effect is still lacking. With this in mind we have undertaken an ultrafast time resolved infrared (TRIR) study of 1 and directly observe marker bands between 1280–1450 cm-1, which characterise both the emissive “bright” and the non-emissive “dark” excited states of the complex, in CD3CN and D2O respectively. These characteristic spectral features are present in the [Ru(dppz)3]2+ solvent light-switch complex but absent in [Ru(phen)3]2+, which is luminescent in both solvents. DFT calculations show that the vibrational modes responsible for these characteristic bands are predominantly localised on the dppz ligand. Moreover, they reveal that certain vibrational modes of the “dark” excited state couple with vibrational modes of two coordinating water molecules, and through these to the bulk solvent, thus providing a new insight into the mechanism of the light-switch effect. We also demonstrate that the marker bands for the “bright” state are observed for both L- and D enantiomers of 1 when bound to DNA and that photo-excitation of the complex induces perturbation of the guanine and cytosine carbonyl bands. This perturbation is shown to be stronger for the L enantiomer, demonstrating the different binding site properties of the two enantiomers and the ability of this technique to determine the identity and nature of the binding site of such intercalators.

Daily thin-ice thickness maps from modis thermal infrared imagery

Accurate knowledge of ice-production rates within the marginal ice zones of the Arctic Ocean requires monitoring of the thin-ice distribution within polynyas. The thickness of the ice layer controls the heat loss and hence the new-ice formation. An established thinice algorithm using high-resolution MODIS data allows deriving the ice-thickness distribution within polynyas. The average uncertainty is ±4.7 cm for ice thicknesses below 0.2 m. In this study, the ice-thickness distributions within the Laptev Sea polynya for the two winter seasons 2007/08 and 2008/09 are calculated. Then, a new method is applied to determine a daily MODIS thin-ice product.

Evaluation of a polynya flux model by means of thermal infrared satellite estimates

We test the ability of a two-dimensional flux model to simulate polynya events with narrow open-water zones by comparing model results to ice-thickness and ice-production estimates derived from thermal infrared Moderate Resolution Imaging Spectroradiometer (MODIS) observations in conjunction with an atmospheric dataset. Given a polynya boundary and an atmospheric dataset, the model correctly reproduces the shape of an 11 day long event, using only a few simple conservation laws. Ice production is slightly overestimated by the model, owing to an underestimated ice thickness. We achieved best model results with the consolidation thickness parameterization developed by Biggs and others (2000). Observed regional discrepancies between model and satellite estimates might be a consequence of the missing representation of the dynamic of the thin-ice thickening (e.g. rafting). We conclude that this simplified polynya model is a valuable tool for studying polynya dynamics and estimating associated fluxes of single polynya events.

Long-lived excited-state dynamics of i-motif structures probed by time-resolved infrared spectroscopy

UV-generated excited states of cytosine (C) nucleobases are precursors to mutagenic photoproduct formation. The i-motif formed from C-rich sequences is known to exhibit high yields of long-lived excited states following UV absorption. Here the excited states of several i-motif structures have been characterized following 267 nm laser excitation using time-resolved infrared spectroscopy (TRIR). All structures possess a long-lived excited state of ~300 ps and notably in some cases decays greater than 1 ns are observed. These unusually long-lived lifetimes are attributed to the interdigitated DNA structure which prevents direct base stacking overlap.

The water vapour continuum in near-infrared windows – current understanding and prospects for its inclusion in spectroscopic databases

Spectroscopic catalogues, such as GEISA and HITRAN, do not yet include information on the water vapour continuum that pervades visible, infrared and microwave spectral regions. This is partly because, in some spectral regions, there are rather few laboratory measurements in conditions close to those in the Earth’s atmosphere; hence understanding of the characteristics of the continuum absorption is still emerging. This is particularly so in the near-infrared and visible, where there has been renewed interest and activity in recent years. In this paper we present a critical review focusing on recent laboratory measurements in two near-infrared window regions (centred on 4700 and 6300 cm−1) and include reference to the window centred on 2600 cm−1 where more measurements have been reported. The rather few available measurements, have used Fourier transform spectroscopy (FTS), cavity ring down spectroscopy, optical-feedback – cavity enhanced laser spectroscopy and, in very narrow regions, calorimetric interferometry. These systems have different advantages and disadvantages. Fourier Transform Spectroscopy can measure the continuum across both these and neighbouring windows; by contrast, the cavity laser techniques are limited to fewer wavenumbers, but have a much higher inherent sensitivity. The available results present a diverse view of the characteristics of continuum absorption, with differences in continuum strength exceeding a factor of 10 in the cores of these windows. In individual windows, the temperature dependence of the water vapour self-continuum differs significantly in the few sets of measurements that allow an analysis. The available data also indicate that the temperature dependence differs significantly between different near-infrared windows. These pioneering measurements provide an impetus for further measurements. Improvements and/or extensions in existing techniques would aid progress to a full characterisation of the continuum – as an example, we report pilot measurements of the water vapour self-continuum using a supercontinuum laser source coupled to an FTS. Such improvements, as well as additional measurements and analyses in other laboratories, would enable the inclusion of the water vapour continuum in future spectroscopic databases, and therefore allow for a more reliable forward modelling of the radiative properties of the atmosphere. It would also allow a more confident assessment of different theoretical descriptions of the underlying cause or causes of continuum absorption.

GHASP: an H alpha kinematic survey of spiral and irregular galaxies - IX. The near-infrared, stellar and baryonic Tully-Fisher relations

We studied, for the first time, the near-infrared, stellar and baryonic Tully-Fisher relations for a sample of field galaxies taken from a homogeneous Fabry-Perot sample of galaxies [the Gassendi HAlpha survey of SPirals (GHASP) survey]. The main advantage of GHASP over other samples is that the maximum rotational velocities were estimated from 2D velocity fields, avoiding assumptions about the inclination and position angle of the galaxies. By combining these data with 2MASS photometry, optical colours, HI masses and different mass-to-light ratio estimators, we found a slope of 4.48 +/- 0.38 and 3.64 +/- 0.28 for the stellar and baryonic Tully-Fisher relation, respectively. We found that these values do not change significantly when different mass-to-light ratio recipes were used. We also point out, for the first time, that the rising rotation curves as well as asymmetric rotation curves show a larger dispersion in the Tully-Fisher relation than the flat ones or the symmetric ones. Using the baryonic mass and the optical radius of galaxies, we found that the surface baryonic mass density is almost constant for all the galaxies of this sample. In this study we also emphasize the presence of a break in the NIR Tully-Fisher relation at M(H,K) similar to -20 and we confirm that late-type galaxies present higher total-to-baryonic mass ratios than early-type spirals, suggesting that supernova feedback is actually an important issue in late-type spirals. Due to the well-defined sample selection criteria and the homogeneity of the data analysis, the Tully-Fisher relation for GHASP galaxies can be used as a reference for the study of this relation in other environments and at higher redshifts.

Near-infrared integral field spectroscopy of the Homunculus nebula around eta Carinae using Gemini/CIRPASS

This work presents the first integral field spectroscopy of the Homunculus nebula around eta Carinae in the near-infrared spectral region (J band). We confirmed the presence of a hole on the polar region of each lobe, as indicated by previous near-IR long-slit spectra and mid-IR images. The holes can be described as a cylinder of height (i.e. the thickness of the lobe) and diameter of 6.5 and 6.0 x 10(16) cm, respectively. We also mapped the blue-shifted component of He I lambda 10830 seen towards the NW lobe. Contrary to previous works, we suggested that this blue-shifted component is not related to the Paddle but it is indeed in the equatorial disc. We confirmed the claim of N. Smith and showed that the spatial extent of the Little Homunculus matches remarkably well the radio continuum emission at 3 cm, indicating that the Little Homunculus can be regarded as a small H II region. Therefore, we used the optically thin 1.3 mm radio flux to derive a lower limit for the number of Lyman-continuum photons of the central source in eta Car. In the context of a binary system, and assuming that the ionizing flux comes entirely from the hot companion star, the lower limit for its spectral type and luminosity class ranges from O5.5 III to O7 I. Moreover, we showed that the radio peak at 1.7 arcsec NW from the central star is in the same line-of-sight of the `Sr-filament` but they are obviously spatially separated, while the blue-shifted component of He I lambda 10830 may be related to the radio peak and can be explained by the ultraviolet radiation from the companion star.

Modelling the warm H(2) infrared emission of the Helix nebula cometary knots

Molecular hydrogen emission is commonly observed in planetary nebulae. Images taken in infrared H(2) emission lines show that at least part of the molecular emission is produced inside the ionized region. In the best studied case, the Helix nebula, the H(2) emission is produced inside cometary knots (CKs), comet-shaped structures believed to be clumps of dense neutral gas embedded within the ionized gas. Most of the H(2) emission of the CKs seems to be produced in a thin layer between the ionized diffuse gas and the neutral material of the knot, in a mini-photodissociation region (mini-PDR). However, PDR models published so far cannot fully explain all the characteristics of the H(2) emission of the CKs. In this work, we use the photoionization code AANGABA to study the H(2) emission of the CKs, particularly that produced in the interface H(+)/H(0) of the knot, where a significant fraction of the H(2) 1-0 S(1) emission seems to be produced. Our results show that the production of molecular hydrogen in such a region may explain several characteristics of the observed emission, particularly the high excitation temperature of the H(2) infrared lines. We find that the temperature derived from H(2) observations, even of a single knot, will depend very strongly on the observed transitions, with much higher temperatures derived from excited levels. We also proposed that the separation between the H alpha and [N II] peak emission observed in the images of CKs may be an effect of the distance of the knot from the star, since for knots farther from the central star the [N II] line is produced closer to the border of the CK than H alpha.

Nuclear and extended spectra of NGC 1068-I. Hints from near-infrared spectroscopy

We report the first simultaneous zJHK spectroscopy on the archetypical Seyfert 2 galaxy NGC 1068 covering the wavelength region 0.9-2.4 mu m. The slit, aligned in the north-south direction and centred in the optical nucleus, maps a region 300 pc in radius at subarcsec resolution, with a spectral resolving power of 360 km s-1. This configuration allows us to study the physical properties of the nuclear gas including that of the north side of the ionization cone, map the strong excess of continuum emission in the K band and attributed to dust and study the variations, both in flux and profile, in the emission lines. Our results show the following. (1) Mid- to low-ionization emission lines are split into two components, whose relative strengths vary with the position along the slit and seem to be correlated with the jet. (2) The coronal lines are single-peaked and are detected only in the central few hundred of pc from the nucleus. (3) The absorption lines indicate the presence of intermediate age stellar population, which might be a significant contributor to the continuum in the near-IR spectra. (4) Through some simple photoionization models we find photoionization as the main mechanism powering the emitting gas. (5) Calculations using stellar features point to a mass concentration inside the 100-200 pc of about 1010 M(circle dot).

Nuclear and extended spectra of NGC 1068-II. Near-infrared stellar population synthesis

We performed stellar population synthesis on the nuclear and extended regions of NGC 1068 by means of near-infrared spectroscopy to disentangle their spectral energy distribution components. This is the first time that such a technique is applied to the whole 0.8-2.4 mu m wavelength interval in this galaxy. NGC 1068 is one of the nearest and probably the most studied Seyfert 2 galaxy, becoming an excellent laboratory to study the interaction between black holes, the jets that they can produce and the medium in which they propagate. Our main result is that traces of young stellar population are found at similar to 100 pc south of the nucleus. The contribution of a power-law continuum in the centre is about 25 per cent, which is expected if the light is scattered from a Seyfert 1 nucleus. We find peaks in the contribution of the featureless continuum about 100-150 pc from the nucleus on both sides. They might be associated with regions where the jet encounters dense clouds. Further support to this scenario is given by the peaks of hot dust distribution found around these same regions and the H(2) emission-line profile, leading us to propose that the peaks might be associated to regions where stars are being formed. Hot dust also has an important contribution to the nuclear region, reinforcing the idea of the presence of a dense, circumnuclear torus in this galaxy. Cold dust appears mostly in the south direction, which supports the view that the south-west emission is behind the plane of the galaxy and is extinguished very likely by dust in the plane. Intermediate-age stellar population contributes significantly to the continuum, especially in the inner 200 pc.

CHANDRA AND SPITZER IMAGING OF THE INFRARED CLUSTER IN NGC 2071

We present results of a sensitive Chandra X-ray observation and Spitzer mid-infrared (mid-IR) observations of the IR cluster lying north of the NGC 2071 reflection nebula in the Orion B molecular cloud. We focus on the dense cluster core known as NGC 2071-IR, which contains at least nine IR sources within a 40 `` x 40 `` region. This region shows clear signs of active star formation including powerful molecular outflows, Herbig-Haro objects, and both OH and H(2)O masers. We use Spitzer Infrared Array Camera (IRAC) images to aid in X-ray source identification and to determine young stellar object (YSO) classes using mid-IR colors. Spitzer IRAC colors show that the luminous source IRS 1 is a class I protostar. IRS 1 is believed to be driving a powerful bipolar molecular outflow and may be an embedded B-type star or its progenitor. Its X-ray spectrum reveals a fluorescent Fe emission line at 6.4 keV, arising in cold material near the protostar. The line is present even in the absence of large flares, raising questions about the nature of the ionizing mechanism responsible for producing the 6.4 keV fluorescent line. Chandra also detects X-ray sources at or near the positions of IRS 2, IRS 3, IRS 4, and IRS 6 and a variable X-ray source coincident with the radio source VLA 1, located just 2 `` north of IRS 1. No IR data are yet available to determine a YSO classification for VLA 1, but its high X-ray absorption shows that it is even more deeply embedded than IRS 1, suggesting that it could be an even younger, less-evolved protostar.

GEMINI near-infrared spectroscopic observations of young massive stars embedded in molecular clouds

K-band spectra of young stellar candidates in four Southern hemisphere clusters have been obtained with the Gemini Near-Infrared Spectrograph in Gemini South. The clusters are associated with IRAS sources that have colours characteristic of ultracompact H II regions. Spectral types were obtained by comparison of the observed spectra with those of a near-infrared (NIR) library; the results include the spectral classification of nine massive stars and seven objects confirmed as background late-type stars. Two of the studied sources have K-band spectra compatible with those characteristic of very hot stars, as inferred from the presence of C IV, N III and N V emission lines at 2.078, 2.116 and 2.100 mu m, respectively. One of them, I16177_IRS1, has a K-band spectrum similar to that of Cyg OB2 7, an O3If* supergiant star. The nebular K-band spectrum of the associated Ultra-Compact (UC) H II region shows the s-process [Kr III] and [Se IV] high excitation emission lines, previously identified only in planetary nebula. One young stellar object was found in each cluster, associated with either the main IRAS source or a nearby resolved Midecourse Space eXperiment (MSX) component, confirming the results obtained from previous NIR photometric surveys. The distances to the stars were derived from their spectral types and previously determined JHK magnitudes; they agree well with the values obtained from the kinematic method, except in the case of IRAS 15408-5356, for which the spectroscopic distance is about a factor of 2 smaller than the kinematic value.

Metallicity gradients at large galactocentric radii using the near-infrared Calcium triplet

We describe a new spectroscopic technique for measuring radial metallicity gradients out to large galactocentric radii. We use the DEep Imaging Multi-Object Spectrograph (DEIMOS) on the Keck telescope and the galaxy spectrum extraction technique of Proctor et al. We also make use of the metallicity sensitive near-infrared Calcium ii triplet (CaT) features together with single stellar population models to obtain metallicities. Our technique is applied as a pilot study to a sample of three relatively nearby (< 30 Mpc) intermediate-mass to massive early-type galaxies. Results are compared with previous literature inner region values and generally show good agreement. We also include a comparison with profiles from dissipational disc-disc major merger simulations. Based on our new extended metallicity gradients combined with other observational evidence and theoretical predictions, we discuss possible formation scenarios for the galaxies in our sample. The limitations of our new technique are also discussed.

All-optical switching device for infrared based on PbTe quantum dots

Multilayers of PbTe quantum dots embedded in SiO2 were fabricated by alternate use of Pulsed Laser Deposition (PLD) and Plasma Enhanced Chemical Vapor Deposition (PECVD) techniques. The morphological properties of the nanostructured material were studied by means of High Resolution Transmission Electron Microscopy (HRTEM), Grazing-Incidence Small-Angle X-ray scattering (GISAXS) and X-ray Reflectometry (XRR) techniques. A preliminary analysis of the GISAXS spectra provided information about the multilayer periodicity and its relationship to the size of the deposited PbTe nanoparticles. Finally multilayers were fabricated inside a Fabry-Perot cavity. The device was characterized by means of Scanning Electron Microscopy (SEM). Transmittance measurements show the device functionality in the infrared region. (C) 2007 Elsevier Ltd. All rights reserved.