Near-infrared spectroscopy of PKS 1549-79: a protoquasar revealed?

We present a near-infrared (near-IR) spectrum of the nearby radio galaxy PKS 1549-79 (z = 0.153). These data were taken with the aim of testing the idea that this object contains a quasar nucleus that is moderately extinguished, despite evidence that its radio jet points close to our line of sight. We detect broad Paalpha emission (FWHM 1745 +/- 40 km s(-1)), relatively bright continuum emission, and a continuum slope consistent with a reddened quasar spectrum (3.1 <A(V) <7.3), all emitted by an unresolved point source. Therefore we conclude that we have, indeed, detected a hidden quasar nucleus in PKS 1549-79. Combined with previous results, these observations are consistent with the idea that PKS 1549-79 is a young radio source in which the cocoon of debris left over from the triggering events has not yet been swept aside by circumnuclear outflows.

Determination of higher heating value of petro-diesels using mid-infrared spectroscopy and chemometry

Higher heating value (HHV) is probably the most important property of the fuels. Bomb calorimeter and derived empirical formulae are often used for accurate determination of HHV of fuels. A useful empirical equation was derived to estimate HHV of petro-diesels from their C and H contents: HHV (in MJ/kg) = 0.3482(C) + 1.1887(H), r (2) = 0.9956. The derived correlation was validated against the most common formulae in the literature, Boie and Channiwala-Parikh correlations. Accordingly, accurate determination of C and H contents is essential for estimation of HHV and avoids using a bomb calorimeter. However, accurate estimation of C and H contents requires using expensive and laborious gas chromatographic techniques. In this work, chemometry offered a simple method for HHV determination of petro-diesels without using bomb calorimeter or even gas chromatography. PLS-1 calibration was used instead of gas chromatography to find C and H contents from the non-selective mid-infrared (MIR) spectra of petro-diesels, HHV was then estimated from the earlier empirical equation. The proposed method predicts HHV of petro-diesels with high accuracy and precision, with modest analysis costs. The present method may be extended to other fuels.

Optical and infrared spectroscopy of the type IInSN1998S: days 3-127

We present contemporary optical and infrared spectroscopic observations of the type IIn SN 1998S covering the period between 3 and 127 days after discovery. During the first week the spectra are characterized by prominent broad H, He and C III/N III emission lines with narrow peaks, superimposed on a very blue continuum (T similar to 24 000 K). In the following two weeks the C III/N III emission vanished, together with the broad emission components of the H and He lines. Broad, blueshifted absorption components appeared in the spectra. The temperature of the continuum also dropped to similar to 14000 K. By the end of the first month the spectrum comprised broad, blueshifted absorptions in H, He, Si II, Fe II and Sc II. By day 44, broad emission components in H and He reappeared in the spectra. These persisted to as late as days similar to 100-130, becoming increasingly asymmetric. We agree with Leonard et al. that the broad emission lines indicate interaction between the ejecta and circumstellar material (CSM) emitted by the progenitor. We also agree that the progenitor of SN 1998S appears to have gone through at least two phases of mass-loss, giving rise to two CSM zones. Examination of the spectra indicates that the inner zone extended to less than or equal to 90 au, while the outer CSM extended from 185 an to over 1800 au.

The prediction of intake potential and organic matter digestibility of grass silages by near infrared spectroscopy analysis of undried samples

A study was undertaken to examine a range of sample preparation and near infrared reflectance spectroscopy (NIPS) methodologies, using undried samples, for predicting organic matter digestibility (OMD g kg(-1)) and ad libitum intake (g kg(-1) W-0.75) of grass silages. A total of eight sample preparation/NIRS scanning methods were examined involving three extents of silage comminution, two liquid extracts and scanning via either external probe (1100-2200 nm) or internal cell (1100-2500 nm). The spectral data (log 1/R) for each of the eight methods were examined by three regression techniques each with a range of data transformations. The 136 silages used in the study were obtained from farms across Northern Ireland, over a two year period, and had in vivo OMD (sheep) and ad libitum intake (cattle) determined under uniform conditions. In the comparisons of the eight sample preparation/scanning methods, and the differing mathematical treatments of the spectral data, the sample population was divided into calibration (n = 91) and validation (n = 45) sets. The standard error of performance (SEP) on the validation set was used in comparisons of prediction accuracy. Across all 8 sample preparation/scanning methods, the modified partial least squares (MPLS) technique, generally minimized SEP's for both OMD and intake. The accuracy of prediction also increased with degree of comminution of the forage and with scanning by internal cell rather than external probe. The system providing the lowest SEP used the MPLS regression technique on spectra from the finely milled material scanned through the internal cell. This resulted in SEP and R-2 (variance accounted for in validation set) values of 24 (g/kg OM) and 0.88 (OMD) and 5.37 (g/kg W-0.75) and 0.77 (intake) respectively. These data indicate that with appropriate techniques NIRS scanning of undried samples of grass silage can produce predictions of intake and digestibility with accuracies similar to those achieved previously using NIRS with dried samples. (C) 1998 Elsevier Science B.V.

Use of Short Time-on-Stream Attenuated Total Internal Reflection Infrared Spectroscopy To Probe Changes in Adsorption Geometry for Determination of Selectivity in the Hydrogenation of Citral

Abstract Image

A new experimental procedure based on attenuated total reflection infrared spectroscopy has been developed to investigate surface species under liquid phase reaction conditions. The technique has been tested by investigating the enhanced selectivity in the hydrogenation of α,β-unsaturated aldehyde citral over a 5% Pt/SiO2 catalyst toward unsaturated alcohols geraniol/nerol, which occurs when citronellal is added to the reaction. The change in selectivity is proposed to be the result of a change in the citral adsorption mode in the presence of citronellal. Short time on stream attenuated total internal reflection infrared spectroscopy has allowed identification of the adsorption modes of citral. With no citronellal, citral adsorbs through both the C═C and C═O groups; however, in the presence of citronellal, citral adsorption occurs through the C═O group only, which is proposed to be the cause of the altered reaction selectivity.

TIME-RESOLVED ABSORPTION, INFRARED, AND RESONANCE RAMAN-SPECTRA OF THE COMPLEXES [RU(X)(R)(CO)(2)(ALPHA-DIIMINE)] (X=HALIDE R=ALKYL) - INFLUENCE OF X ON THE CHARGE-TRANSFER CHARACTER OF THE LOWEST EXCITED-STATE

Nanosecond time-resolved absorption (TA), resonance Raman (TR(3)), and infrared (TRIR) spectra are reported for several complexes [Ru(X)(R)(CO)(2)(alpha-diimine)] (X = Cl, Br, I; R = Me, Et; alpha-diimine = N,N'-diisopropyl-1,4-diaza-1,3-butadiene (iPr-DAB), pyridine-2-carbaldehyde-N-isopropylimine (iPr-PyCa), 2,2'-bipyridine (bpy)). This is the first instance in which the TA, TR(3), and TRIR techniques have been used to probe excited states in the same series of complexes. The TA spectra of the iodide complexes show a transient absorption between 550 and 700 nm, which does not depend on the solvent but shifts to lower energy in the order iPr-DAB > bpy > iPr-PyCa. This band is assigned to an intraligand transition. For the corresponding chloride and bromide complexes this band occurs at higher energy, most probably because of a change of character of the lowest excited state from XLCT to MLCT. The TRIR spectra show an increase in v(CO) (and k(CO)) on promotion to the excited state; however, the shifts Delta v(CO) show a decrease in the order Cl- > Br- > I-. The TR(3) spectra of the excited complexes [Ru(X)(R)(Co)(2)(iPr-DAB)] show v(s)(CN) of the iPr-DAB ligand 50-80 cm(-1) lower in frequency than for the complexes in their ground state. This frequency shift decreases in the order Cl- > Br- > I-, indicating a decrease of CT character of the lowest excited state in this order. However, going from X = Br to I, the effect on Delta v(CO) is much larger than the decrease of Delta v(s)(CN). This different effect on the CO- and CN-stretching frequencies is assigned to a gradual change in character of the lowest excited state from MLCT to XLCT when Cl- is replaced by Br- and I-. This result confirms a similar conclusion derived from previous resonance Raman and emission experiments on these complexes.

Recent applications of Chemical Imaging to pharmaceutical process monitoring and quality control

Chemical Imaging (CI) is an emerging platform technology that integrates conventional imaging and spectroscopy to attain both spatial and spectral information from an object. Vibrational spectroscopic methods, such as Near Infrared (NIR) and Raman spectroscopy, combined with imaging are particularly useful for analysis of biological/pharmaceutical forms. The rapid, non-destructive and non-invasive features of CI mark its potential suitability as a process analytical tool for the pharmaceutical industry, for both process monitoring and quality control in the many stages of drug production. This paper provides an overview of CI principles, instrumentation and analysis. Recent applications of Raman and NIR-CI to pharmaceutical quality and process control are presented; challenges facing Cl implementation and likely future developments in the technology are also discussed. (C) 2007 Elsevier B.V. All rights reserved.

Reduction of Staphylococcus aureus and Pseudomonas aeruginosa colonisation on PVC through covalent surface attachment of fluorinated thiols

OBJECTIVES: This study reports the development, characterisation and microbiological testing of surface-modified polyvinylchloride (PVC) films for the purpose of reducing bacterial adherence.

METHODS: Irreversible covalent surface modification was achieved via nucleophilic substitution of fluorinated thiol-terminated compounds onto the polymer backbone. Four fluorinated modifiers, 2,3,5,6-tetrafluorothiophenol (TFTP), 4-(trifluoromethyl)thiophenol (TFMTP), 3,5-bis(trifluoromethyl)benzenethiol (BTFMBT) and 3,3,4,4,5,5,6,6,7, 7,8,8,9,9,10,10,10-heptadecafluoro-decane-1-thiol (HDFDT), were investigated. Modification was confirmed using attenuated total reflectance infrared spectroscopy; Raman mapping demonstrated that modification was homogenous on the macroscopic scale. The influence of fluorination on surface hydrophobicity was studied by contact angle analysis. The effect on microbial adherence was examined using Pseudomonas aeruginosa and Staphylococcus aureus.

KEY FINDINGS: The resultant changes in contact angle relative to control PVC ranged from -4 degrees to +14 degrees . In all cases, adherence of P. aeruginosa and S. aureus was significantly reduced relative to control PVC, with adherence levels ranging from 62% and 51% for TFTP-modified PVC to 32% and 7% for TFMTP-modified PVC.

CONCLUSIONS: These results demonstrate an important method in reducing the incidence of bacterial infection in PVC medical devices without compromising mechanical properties.

Characterization of silica-supported dodecatungstic heteropolyacids as a function of their dehydroxylation temperature

Dodecatungsto-silicic H4SiW12O40 and -phosphoric acids H3PW12O40 were deposited on silica by a classical impregnation technique. The resulting materials were studied by in situ Raman and infrared spectroscopy, XPS and by solid-state H-1 MAS NMR as a function of their dehydroxylation temperature. The data show that in the case of H3PW12O40 three silanol groups are protonated while in the case of H4SiW12O40 at least one acidic proton remains. Upon heating this proton reacts leading to a disordered structure and a broadening of the W-O Raman bands.

Perturbed frequency-selective surfaces fabricated on large thin polymer membranes for multiband infrared applications

The design, fabrication, and characterization of single-screen perturbed frequency-selective surfaces (FSS) at infrared frequencies for single and multiband applications are reported. Single-band FSS based on parallel strips have been perturbed by decreasing the length of every second strip within the array in order to achieve dual band-stop responses. The same principle has been extended to design FSS exhibiting tri- and quadreflection bands. In addition, strip FSSs have been perturbed by replacing every second strip for a metallic ring, resulting in dual-band filters with different polarization responses of the bands. These designs have been fabricated on large thin polyimide membranes using sacrificial silicon wafers. An oxide interlayer between the sacrificial silicon wafer and the polyimide membrane is employed to stop the silicon etching and is wet etched subsequently by a solution of ammonium fluoride and acetic acid that does not attack either the polyimide membrane or the aluminium FSS elements. Fourier transform infrared spectroscopy measurements are presented to validate the predicted responses of the fabricated prototypes.