Deep Raman spectroscopy for the non-invasive standoff detection of concealed chemical threat agents

Deep Raman spectroscopy has been utilized for the standoff detection of concealed chemical threat agents from a distance of 15 meters under real life background illumination conditions. By using combined time and space resolved measurements, various explosive precursors hidden in opaque plastic containers were identified non-invasively. Our results confirm that combined time and space resolved Raman spectroscopy leads to higher selectivity towards the sub-layer over the surface layer as well as enhanced rejection of fluorescence from the container surface when compared to standoff spatially offset Raman spectroscopy. Raman spectra that have minimal interference from the packaging material and good signal-to-noise ratio were acquired within 5 seconds of measurement time. A new combined time and space resolved Raman spectrometer has been designed with nanosecond laser excitation and gated detection, making it of lower cost and complexity than picosecond-based laboratory systems.

Raman spectroscopy of synthetic CaHPO4•2H2O– and in comparison with the cave mineral brushite

The mineral brushite has been synthesised by mixing calcium ions and hydrogen phosphate anions to mimic the reactions in a Cave. The vibrational spectra of the synthesised brushite were compared with that of the natural Cave mineral. Bands attributable to the PO43- and HPO42- anions are observed. Brushite, both synthetic and natural, is characterised by an intense sharp band at 985 cm-1 with a shoulder at 1000 cm-1. Characteristic bending modes are observed in the 300 to 600 cm-1 region. The spectra of the synthesised brushite matches very well the spectrum of brushite from the Moorba Cave, Western Australia.

A comparative study of the number and mass of fine particles emitted with diesel fuel and marine gas oil (MGO)

The current investigation reports on diesel particulate matter emissions, with special interest in fine particles from the combustion of two base fuels. The base fuels selected were diesel fuel and marine gas oil (MGO). The experiments were conducted with a four-stroke, six-cylinder, direct injection diesel engine. The results showed that the fine particle number emissions measured by both SMPS and ELPI were higher with MGO compared to diesel fuel. It was observed that the fine particle number emissions with the two base fuels were quantitatively different but qualitatively similar. The gravimetric (mass basis) measurement also showed higher total particulate matter (TPM) emissions with the MGO. The smoke emissions, which were part of TPM, were also higher for the MGO. No significant changes in the mass flow rate of fuel and the brake-specific fuel consumption (BSFC) were observed between the two base fuels.

Evolutionary biology : mass survivals

The conclusion that the primary divergences of the modern groups of mammals occurred in the mid-Cretaceous requires fresh thinking about this facet of evolutionary history — especially in ecological terms.

Double diffusive magneto-convection fluid flow in a strong cross magnetic field with uniform surface heat and mass flux

In this study, magnetohydrodynamic natural convection boundary layer flow of an electrically conducting and viscous incompressible fluid along a heated vertical flat plate with uniform heat and mass flux in the presence of strong cross magnetic field has been investigated. For smooth integrations the boundary layer equations are transformed in to a convenient dimensionless form by using stream function formulation as well as the free variable formulation. The nonsimilar parabolic partial differential equations are integrated numerically for Pr ≪1 that is appropriate for liquid metals against the local Hartmann parameter ξ . Further, asymptotic solutions are obtained near the leading edge using regular perturbation method for smaller values of ξ . Solutions for values of ξ ≫ 1 are also obtained by employing the matched asymptotic technique. The results obtained for small, large and all ξ regimes are examined in terms of shear stress, τw, rate of heat transfer, qw, and rate of mass transfer, mw, for important physical parameter. Attention has been given to the influence of Schmidt number, Sc, buoyancy ratio parameter, N and local Hartmann parameter, ξ on velocity, temperature and concentration distributions and noted that velocity and temperature of the fluid achieve their asymptotic profiles for Sc ≥ 10:0.

Raman spectroscopy of the borate mineral ameghinite NaB3O3(OH)4

The molecular structure of the sodium borate mineral ameghinite NaB3O3(OH)4 has been determined by the use of vibrational spectroscopy. The crystal structure consists of isolated [B3O3(OH)4]- units formed by one tetrahedron and two triangles. H bonds and Na atoms link these polyanions to form a 3-dimensional framework. The Raman spectrum is dominated by an intense band at 1027 cm-1, attributed to BO stretching vibrations of both the trigonal and tetrahedral boron. A series of Raman bands at 1213, 1245 and 1281cm-1 are ascribed to BOH in-plane bending modes. The infrared spectra are characterized by strong overlap of broad multiple bands. An intense Raman band found at 620 cm-1 is attributed to the bending modes of trigonal and tetrahedral boron. Multiple Raman bands in the OH stretching region are observed at 3206, 3249 and 3385 cm-1. Raman spectroscopy coupled with infrared spectroscopy has enabled aspects about the molecular structure of the borate mineral ameghinite to be assessed.

Real-time detection of concealed chemical hazards under ambient light conditions using Raman spectroscopy

Current concerns regarding terrorism and international crime highlight the need for new techniques for detecting unknown and hazardous substances. A novel Raman spectroscopy-based technique, spatially offset Raman spectroscopy (SORS), was recently devised for non-invasively probing the contents of diffusely scattering and opaque containers. Here, we demonstrate a modified portable SORS sensor for detecting concealed substances in-field under different background lighting conditions. Samples including explosive precursors, drugs and an organophosphate insecticide (chemical warfare agent surrogate) were concealed inside diffusely scattering packaging including plastic, paper and cloth. Measurements were carried out under incandescent and fluorescent light as well as under daylight to assess the suitability of the probe for different real-life conditions. In each case, it was possible to identify the substances against their reference Raman spectra in less than one minute. The developed sensor has potential for rapid detection of concealed hazardous substances in airports, mail distribution centers and customs checkpoints.

Environmental degradation of lignin/poly(hydroxybutyrate) blends

Blends of lignin and poly(hydroxybutyrate) (PHB) were obtained by melt extrusion. They were buried in a garden soil for up to 12 months, and the extent and mechanism of degradation were investigated by gravimetric analysis, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and Fourier transform infra-red spectroscopy (FTIR) over the entire range of compositions. The PHB films were disintegrated and lost 45 wt% of mass within 12 months. This value dropped to 12 wt% of mass when only 10 wt% of lignin was present, suggesting that lignin both inhibited and slowed down the rate of PHB degradation. TGA and DSC indicated structural changes, within the lignin/PHB matrix, with burial time, while FTIR results confirmed the fragmentation of the PHB polymer. XPS revealed an accumulation of biofilms on the surface of buried samples, providing evidence of a biodegradation mechanism. Significant surface roughness was observed with PHB films due to microbial attack caused by both loosely and strongly associated micro-organisms. The presence of lignin in the blends may have inhibited the colonisation of the micro-organisms and caused the blends to be more resistant to microbial attack. Analysis suggested that lignin formed strong hydrogen bonds with PHB in the buried samples and it is likely that the rate of breakdown of PHB is reduced, preventing rapid degradation of the blends.

Incipient neurovulnerability and neuroprotection in early psychosis : a proton spectroscopy study of the anterior hippocampus at 3Tesla

Programmed cell death (PCD) and progenitor cell generation (of glial and in some brain areas also neuronal fate) in the CNS is an active process throughout life and is generally not associated with gliosis which means that PCD can be pathologically silent. The striking discovery that progenitor cell generation (of glial and in some brain areas neuronal fate) is widespread in the adult CNS (especially the hippocampus) suggest a much more dynamic scenario than previously thought and transcends the dichotomy between neurodevelopmental and neurodegenerative models of schizophrenia and related disorders. We suggest that the regulatory processes that control the regulation of PCD and the generation of progenitor cells may be disturbed in the early phase of psychotic disorders underpinning a disconnectivity syndrom at the onset of clinically overt disorders. An ongoing 1H-MRS study of the anterior hippocampus at 3 Tesla in mostly drug-naive first-episode psychosis patients suggests no change in NAA, but significant increases in myo-inositol and lactate. The data suggests that neuronal integrity in the anterior hippocampus is still intact at the early stage of illness or mainly only functionally impaired. However the increase in lactate and myo-inositol may reflect a potential disturbance of generation and PCD of progenitor cells (of glial and in selected brain areas also neuronal fate) at the onset of psychosis. If true the use of neuroprotective agents such as lithium or eicosapentaenoic acid (which inhibit PCD and support cell generation)in the early phase of psychotic disorders may be a potent treatment avenue to explore.

Visible and near infrared spectroscopy of Hayabusa re-entry using semi-autonomous tracking

A ground-based tracking camera and co-aligned slit-less spectrograph were used to measure the spectral signature of visible radiation emitted from the Hayabusa capsule as it entered into the Earth's atmosphere in June 2010. Good quality spectra were obtained that showed the presence of radiation from the heat shield of the vehicle and the shock-heated air in front of the vehicle. An analysis of the black body nature of the radiation concluded that the peak average temperature of the surface was about (3100±100) K.

A mass spectrometric assay for the quantification of neuropeptide PYY in plasma

A multiple reaction monitoring mass spectrometric assay for the quantification of PYY in human plasma has been developed. A two stage sample preparation protocol was employed in which plasma containing the full length neuropeptide was first digested using trypsin, followed by solid-phase extraction to extract the digested peptide from the complex plasma matrix. The peptide extracts were analysed by LC-MS using multiple reaction monitoring to detect and quantify PYY. The method has been validated for plasma samples, yielding linear responses over the range 5–1,000 ng mL−1. The method is rapid, robust and specific for plasma PYY detection.

Comparison of the binding stoichiometries of positively charged DNA-binding drugs using positive and negative ion electrospray ionization mass spectrometry

Positive and negative ion electrospray ionization (ESI) mass spectra of complexes of positively charged small molecules (distamycin, Hoechst 33258, [Ru(phen)2dpq]Cl2 and [Ru(phen)2dpqC]Cl2) have been compared. [Ru(phen)2dpq]Cl2 and [Ru(phen)2dpqC]Cl2 bind to DNA by intercalation. Negative ion ESI mass spectra of mixtures of [Ru(phen)2dpq]Cl2 or [Ru(phen)2dpqC]Cl2 with DNA showed ions from DNA-ligand complexes consistent with solution studies. In contrast, only ions from freeDNAwere present in positive ion ESI mass spectra of mixtures of [Ru(phen)2dpq]Cl2 or [Ru(phen)2dpqC]Cl2 with DNA, highlighting the need for obtaining ESI mass spectra of non-covalent complexes under a range of experimental conditions. Negative ion spectra of mixtures of the minor groove binder Hoechst 33258 with DNA containing a known minor groove binding sequence were dominated by ions from a 1:1 complex. In contrast, in positive ion spectra there were also ions present from a 2:1 (Hoechst 33258: DNA) complex, suggesting an alternative binding mode was possible either in solution or in the gas phase. When Hoechst 33258 was mixed with a DNA sequence lacking a high affinity minor groove binding site, the negative ion ESI mass spectra showed that 1:1 and 2:1 complexes were formed, consistent with existence of binding modes other than minor groove binding. The data presented suggest that comparison of positive and negative ion ESI-MS spectra might provide an insight into various binding modes in both solution and the gas phase.

Non-destructive evaluation of articular cartilage defects using near-infrared (NIR) spectroscopy in osteoarthritic rat models and its direct relation to Mankin Score

Objective The aim of this study was to demonstrate the potential of near-infrared (NIR) spectroscopy for categorizing cartilage degeneration induced in animal models. Method Three models of osteoarthritic degeneration were induced in laboratory rats via one of the following methods: (i) menisectomy (MSX); (ii) anterior cruciate ligament transaction (ACLT); and (iii) intra-articular injection of mono-ido-acetete (1 mg) (MIA), in the right knee joint, with 12 rats per model group. After 8 weeks, the animals were sacrificed and tibial knee joints were collected. A custom-made nearinfrared (NIR) probe of diameter 5 mm was placed on the cartilage surface and spectral data were acquired from each specimen in the wavenumber range 4 000 – 12 500 cm−1. Following spectral data acquisition, the specimens were fixed and Safranin–O staining was performed to assess disease severity based on the Mankin scoring system. Using multivariate statistical analysis based on principal component analysis and partial least squares regression, the spectral data were then related to the Mankinscores of the samples tested. Results Mild to severe degenerative cartilage changes were observed in the subject animals. The ACLT models showed mild cartilage degeneration, MSX models moderate, and MIA severe cartilage degenerative changes both morphologically and histologically. Our result demonstrate that NIR spectroscopic information is capable of separating the cartilage samples into different groups relative to the severity of degeneration, with NIR correlating significantly with their Mankinscore (R2 = 88.85%). Conclusion We conclude that NIR is a viable tool for evaluating articularcartilage health and physical properties such as change in thickness with degeneration.

Challenges in mass spectrometry-based quantification of bioactive peptides: A case study exploring the neuropeptide Y family

The study of biologically active peptides is critical to the understanding of physiological pathways, especially those involved in the development of disease. Historically, the measurement of biologically active endogenous peptides has been undertaken by radioimmunoassay, a highly sensitive and robust technique that permits the detection of physiological concentrations in different biofluid and tissue extracts. Over recent years, a range of mass spectrometric approaches have been applied to peptide quantification with limited degrees of success. Neuropeptide Y (NPY), peptide YY (PYY), and pancreatic polypeptide (PP) belong to the NPY family exhibiting regulatory effects on appetite and feeding behavior. The physiological significance of these peptides depends on their molecular forms and in vivo concentrations systemically and at local sites within tissues. In this report, we describe an approach for quantification of individual peptides within mixtures using high-performance liquid chromatography electrospray ionization tandem mass spectrometry analysis of the NPY family peptides. Aspects of quantification including sample preparation, the use of matrix-matched calibration curves, and internal standards will be discussed. This method for the simultaneous determination of NPY, PYY, and PP was accurate and reproducible but lacks the sensitivity required for measurement of their endogenous concentration in plasma. The advantages of mass spectrometric quantification will be discussed alongside the current obstacles and challenges. © 2012 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 98: 357–366, 2012.