TIME-RESOLVED RESONANCE RAMAN-SPECTROSCOPY AND RAMAN SPECTROELECTROCHEMISTRY OF (CO)(5)W[4,4'-BPY]W(CO)(5), PROBED IN THE VISIBLE AND NEAR-INFRARED

Time-resolved resonance Raman spectroscopy of the lowest energy excited state of the 4,4'-bipyridyl ligand-bridged complex, [(CO)(5)W(L)W(CO5] (1), and Raman spectroscopy of electrochemically reduced 1, both give bands characteristic of the the L(.-) species. This confirms that the ligand L is negatively charged in the lowest energy exicited state which is therefore metal-ligand charge transfer (MLCT) in character. Raman spectra of the radical anion of 1 excited in the far red (800 nm) exhibited a band near 2050 cm(-1) due to a vco symmetric CO stretching mode, compared to the corresponding band at 2070 cm(-1) in the spectrum of the parent, uncharged complex. The lower vco in the reduced complex supports the recent finding by time-resolved IR spectroscopy of a similar frequency decrease for nu(CO) in the longest lived (MLCT) excited state of 1 which was attributed to electron/hole localisation in this state on the IR time scale.

Three dimensional water vapour visualization in porous packing by near-infrared diffuse transmittance tomography

Near-infrared diffuse tomography was used in order to observe dynamic behaviour of flowing gases by measuring the 3D distributions of composition and temperature in a weakly scattering packed bed reactor, subject to wall effects and non-isothermal conditions. The technique was applied to the vapour phase hydrogen isotopic exchange reaction in a hydrophobic packing of low aspect ratio made of platinum on styrene divinyl benzene sulphonate copolymer resin. The results of tomography revealed uneven temperature and composition maps of water and deuterated water vapours in the core-packed bed and in the vicinity of the wall owing to flow maldistribution. The dynamic lag between the near-wall water vapour and deuterated water vapour compositions were observed suggesting that the convective transfer which was significant near the wall at the start, owing to high porosity, was also effective at large conversions.

SN 2005cs in M51-II. Complete evolution in the optical and the near-infrared

We present the results of the one-year long observational campaign of the type 11 plateau SN 2005cs, which exploded in the nearby spiral galaxy M51 (the Whirlpool galaxy). This extensive data set makes SN 2005cs the best observed low-luminosity, Ni-56-poor type II plateau event so far and one of the best core-collapse supernovae ever. The optical and near-infrared spectra show narrow P-Cygni lines characteristic of this SN family, which are indicative of a very low expansion velocity (about 1000 km s(-1)) of the ejected material. The optical light curves cover both the plateau phase and the late-time radioactive tail, until about 380 d after core-collapse. Numerous unfiltered observations obtained by amateur astronomers give us the rare opportunity to monitor the fast rise to maximum light, lasting about 2 cl. In addition to optical observations, we also present near-infrared light curves that (together with already published ultraviolet observations) allow us to construct for the first time a reliable bolometric light Curve for an object of this class. Finally. comparing the observed data withthose derived front it semi-analytic model, we infer for SN 2005cs a Ni-56 mass of about 3 x 10(-3) M-circle dot a total ejected mass of 8-13 M-circle dot and an explosion energy of about 3 x 10(50) erg.

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.

Transient distributions of composition and temperature in a gas-solid packed bed reactor by near-infrared tomography

Near-infrared diffuse tomography was used in order to observe dynamic behaviour of flowing gases by measuring the 3D distributions of composition and temperature in a weakly scattering packed bed reactor, subject to wall effects and non-isothermal conditions. The technique was applied to the vapour phase hydrogen isotopic exchange reaction in a hydrophobic packing of low aspect ratio made of platinum on styrene divinyl benzene sulphonate copolymer resin. The results of tomography revealed uneven temperature and composition maps of water and deuterated water vapours in the core-packed bed and in the vicinity of the wall owing to flow maldistribution. The dynamic lag between the near-wall water vapour and deuterated water vapour compositions were observed suggesting that the convective transfer which was significant near the wall at the start, owing to high porosity, was also effective at large conversions. (C) 2012 Elsevier B.V. All rights reserved.

The application of Near-Infrared Reflectance Spectroscopy (NIRS) to detect melamine adulteration of soya bean meal

Soya bean products are used widely in the animal feed industry as a protein based feed ingredient and
have been found to be adulterated with melamine. This was highlighted in the Chinese scandal of
2008. Dehulled soya (GM and non-GM), soya hulls and toasted soya were contaminated with melamine
and spectra were generated using Near Infrared Reflectance Spectroscopy (NIRS). By applying chemometrics
to the spectral data, excellent calibration models and prediction statistics were obtained. The coefficients
of determination (R2) were found to be 0.89–0.99 depending on the mathematical algorithm used,
the data pre-processing applied and the sample type used. The corresponding values for the root mean
square error of calibration and prediction were found to be 0.081–0.276% and 0.134–0.368%, respectively,
again depending on the chemometric treatment applied to the data and sample type. In addition, adopting
a qualitative approach with the spectral data and applying PCA, it was possible to discriminate
between the four samples types and also, by generation of Cooman’s plots, possible to distinguish
between adulterated and non-adulterated samples.

X-shooting Herbig Ae/Be stars: Accretion probed by near-infrared He I emission

The Herbig Ae/Be stars are intermediate mass pre-main sequence stars that bridge the gap between the low mass T Tauri stars and the Massive Young Stellar Objects. In this mass range, the acting star forming mechanism switches from magnetically controlled accretion to an as yet unknown mechanism, but which is likely to be direct disk accretion onto the star. We observed a large sample of Herbig Ae/Be stars with X-shooter to address this issue from a multi-wavelength perspective. It is the largest such study to date, not only because of the number of objects involved, but also because of the large wavelength coverage from the blue to the near-infrared. This allows many accretion diagnostics to be studied simultaneously. By correlating the various properties with mass, temperature and age, we aim to determine where and whether the magnetically controlled mass accretion mechanism halts and the proposed direct disk accretion takes over. Here, we will give an overview of the background, present some observations and discuss our initial results. We will introduce a new accretion diagnostic for the research of Herbig Ae/Be stars, the HeI 1.083 µm line. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nile blue-based nano-sized pH sensors for simultaneous far-red and near-infrared live bioimaging

Diblock copolymer vesicles are tagged with pH-responsive Nile Blue-based labels and used as a new type of pH-responsive colorimetric/fluorescent biosensor for far-red and near-infrared imaging of live cells. The diblock copolymer vesicles described herein are based on poly(2-(methacryloyloxy)ethyl phosphorylcholine-block-2-(diisopropylamino)ethyl methacrylate) [PMPC-PDPA]: the biomimetic PMPC block is known to facilitate rapid cell uptake for a wide range of cell lines, while the PDPA block constitutes the pH-responsive component that enables facile vesicle self-assembly in aqueous solution. These biocompatible vesicles can be utilized to detect interstitial hypoxic/acidic regions in a tumor model via a pH-dependent colorimetric shift. In addition, they are also useful for selective intracellular staining of lysosomes and early endosomes via subtle changes in fluorescence emission. Such nanoparticles combine efficient cellular uptake with a pH-responsive Nile Blue dye label to produce a highly versatile dual capability probe. This is in marked contrast to small molecule dyes, which are usually poorly uptaken by cells, frequently exhibit cytotoxicity, and are characterized by intracellular distributions invariably dictated by their hydrophilic/hydrophobic balance.

Classification the geographical origin of corn distillers dried grains with solubles by near infrared reflectance spectroscopy combined with chemometrics: A feasibility study

In this study, 137 corn distillers dried grains with solubles (DDGS) samples from a range of different geographical origins (Jilin Province of China, Heilongjiang Province of China, USA and Europe) were collected and analysed. Different near infrared spectrometers combined with different chemometric packages were used in two independent laboratories to investigate the feasibility of classifying geographical origin of DDGS. Base on the same dataset, one laboratory developed a partial least square discriminant analysis model and another laboratory developed an orthogonal partial least square discriminant analysis model. Results showed that both models could perfectly classify DDGS samples from different geographical origins. These promising results encourage the development of larger scale efforts to produce datasets which can be used to differentiate the geographical origin of DDGS and such efforts are required to provide higher level food security measures on a global scale.

Engineering of Vis-NIR Metamaterials towards Revolutionary Ultrasensitive and Versatile Plasmonic Biosensors

By enabling subwavelength light localization and strong electromagnetic field enhancement, plasmonic biosensors have opened up a new realm of possibilities for a broad range of chemical and biological sensing applications owing to their label-free and real-time attributes. Although significant progress has been made, many fundamental and practical challenges still remain to be addressed. For instance, the plasmonic biosensors are nonselective sensing platforms; they are not well-suited to provide information regarding conformation or chemical fingerprint of unknown biomolecules. Furthermore, tunability of the plasmonic resonance in visible frequency regime is still limited; this will prevent their efficient and reproducible exploitation in single-molecule sensitivity. Here, we show that by engineering geometry of plasmonic metamaterials,1 consisting of periodic arrays of artificial split-ring resonators (SRRs), the plasmonic resonance of metamaterials could be tuned to visible-near infrared regimes (Vis-NIR) such that it allows parallel acquisition of optical transmission and highly surface-enhanced Raman (SERS) spectra from large functionalized SRR arrays. The Au SRRs were designed in form of alphabet letters (U, V, S, H, Y) with various line width (from 80 to 30 nm). By tailoring their size and shape, plasmonic resonance wavelength of the SRRs could be actively tuned so that it gives the strongest SERS effect under given excitation energy and polarization for biological and organic molecules. On the other hand, the plasmonic tunability was also achieved for a given SRR pattern by tuning the laser wavelength to obtain the highest electromagnetic field enhancement. The geometry- and laser-tunable channels typically provide an electromagnetic field enhancement as high as 20 times. This will provide the basis of versatile and multichannel devices for identification of different conformational states of Guanine-rich DNA, detection of a cancer biomarker nucleolin, and femtomolar sensitivity detection of food and drink additives. These results show that the tunable Vis-IR metamaterials are very versatile biosensing platforms and suggest considerable promise in genomic research, disease diagnosis, and food safety analysis.

Label-free Analysis of Conformational Dynamics and Molecular Interaction of Biomolecules by Vis-NIR Metasensor

Analysis of binding recognition and conformation of biomolecules is of paramount important in understanding of their vital functions in complex biological systems. By enabling sub-wavelength light localization and strong local field enhancement, plasmonic biosensors have become dominant tools used for such analysis owing to their label-free and real-time attributes1,2. However, the plasmonic biosensors are not well-suited to provide information regarding conformation or chemical fingerprint of biomolecules. Here, we show that plasmonic metamaterials, consisting of periodic arrays of artificial split-ring resonators (SRRs)3, can enable capabilities of both sensing and fingerprinting of biomolecules. We demonstrate that by engineering geometry of individual SRRs, localized surface plasmon resonance (LSPR) frequency of the metamaterials could be tuned to visible-near infrared regimes (Vis-NIR) such that they possess high local field enhancement for surface-enhanced Raman scattering spectroscopy (SERS). This will provide the basis for the development of a dual mode label-free conformational-resolving and quantitative detection platform. We present here the ability of each sensing mode to independently detect binding adsorption and to identify different conformational states of Guanine (G)-rich DNA monolayers in different environment milieu. Also shown is the use of the nanosensor for fingerprinting and detection of Arginine-Glycine-Glycine (RGG) peptide binding to the G-quadruplex aptamer. The dual-mode nanosensor will significantly contribute to unraveling the complexes of the conformational dynamics of biomolecules as well as to improving specificity of biodetection assays that the conventional, population-averaged plasmonic biosensors cannot achieve.

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.

The first polarimetric signatures of infrared jets in X-ray binaries

We present near-infrared linear spectropolarimetry of a sample of persistent X-ray binaries, Sco X-1, Cyg X-2, and GRS 1915+105. The slopes of the spectra are shallower than what is expected from a standard steady state accretion disk, and can be explained if the near-infrared flux contains a contribution from an optically thin jet. For the neutron star systems, Sco X-1 and Cyg X-2, the polarization levels at 2.4 mu m are 1.3% +/- 0.10% and 5.4% +/- 0.7%, respectively, which is greater than the polarization level at 1.65 mu m. This cannot be explained by interstellar polarization or electron scattering in the anisotropic environment of the accretion flow. We propose that the most likely explanation is that this is the polarimetric signature of synchrotron emission arising from close to the base of the jets in these systems. In the black hole system GRS 1915+105 the observed polarization, although high (5.0% +/- 1.2% at 2.4 mu m), may be consistent with interstellar polarization. For Sco X-1 the position angle of the radio jet on the sky is approximately perpendicular to the near-infrared position angle (electric vector), suggesting that the magnetic field is aligned with the jet. These observations may be a first step toward probing the ordering, alignment, and variability of the outflow magnetic field in a region closer to the central accreting object than is observed in the radio band.

SN 2008S: an electron-capture SN from a super-AGB progenitor?

We present comprehensive photometric and spectroscopic observations of the faint transient SN 2008S discovered in the nearby galaxy NGC 6946. SN 2008S exhibited slow photometric evolution and almost no spectral variability during the first nine months, implying a long photon diffusion time and a high-density circumstellar medium. Its bolometric luminosity (similar or equal to 10(41) erg s(-1) at peak) is low with respect to most core-collapse supernovae but is comparable to the faintest Type II-P events. Our quasi-bolometric light curve extends to 300 d and shows a tail phase decay rate consistent with that of Co-56. We propose that this is evidence for an explosion and formation of Ni-56 (0.0014 +/- 0.0003 M-circle dot). Spectra of SN 2008S show intense emission lines of H alpha, [Ca II] doublet and Ca II near-infrared (NIR) triplet, all without obvious P-Cygni absorption troughs. The large mid-infrared (MIR) flux detected shortly after explosion can be explained by a light echo from pre-existing dust. The late NIR flux excess is plausibly due to a combination of warm newly formed ejecta dust together with shock-heated dust in the circumstellar environment. We reassess the progenitor object detected previously in Spitzer archive images, supplementing this discussion with a model of the MIR spectral energy distribution. This supports the idea of a dusty, optically thick shell around SN 2008S with an inner radius of nearly 90 AU and outer radius of 450 AU, and an inferred heating source of 3000 K. The luminosity of the central star is L similar or equal to 10(4.6) L-circle dot. All the nearby progenitor dust was likely evaporated in the explosion leaving only the much older dust lying further out in the circumstellar environment. The combination of our long-term multiwavelength monitoring data and the evidence from the progenitor analysis leads us to support the scenario of a weak electron-capture supernova explosion in a super-asymptotic giant branch progenitor star (of initial mass 6-8 M-circle dot) embedded within a thick circumstellar gaseous envelope. We suggest that all of main properties of the electron-capture SN phenomenon are observed in SN 2008S and future observations may allow a definitive answer.