Characterization of the sulphate mineral coquimbite, a secondary iron sulphate from Javier Ortega mine, Lucanas Province, Peru – Using infrared, Raman spectroscopy and thermogravimetry

The mineral coquimbite has been analysed using a range of techniques including SEM with EDX, thermal analytical techniques and Raman and infrared spectroscopy. The mineral originated from the Javier Ortega mine, Lucanas Province, Peru. The chemical formula was determined as ðFe3þ 1:37; Al0:63ÞP2:00ðSO4Þ3 9H2O. Thermal analysis showed a total mass loss of 73.4% on heating to 1000 C. A mass loss of 30.43% at 641.4 C is attributed to the loss of SO3. Observed Raman and infrared bands were assigned to the stretching and bending vibrations of sulphate tetrahedra, aluminium oxide/hydroxide octahedra, water molecules and hydroxyl ions. The Raman spectrum shows well resolved bands at 2994, 3176, 3327, 3422 and 3580 cm 1 attributed to water stretching vibrations. Vibrational spectroscopy combined with thermal analysis provides insight into the structure of coquimbite.

Rapid detection of TNT in aqueous media by selective label free surface enhanced Raman spectroscopy

We report rapid and ultra-sensitive detection system for 2,4,6-trinitrotoluene (TNT) using unmodified gold nanoparticles and surface-enhanced Raman spectroscopy (SERS). First, Meisenheimer complex has been formed in aqueous solution between TNT and cysteamine in less than 15 min of mixing. The complex formation is confirmed by the development of a pink colour and a new UV–vis absorption band around 520 nm. Second, the developed Meisenheimer complex is spontaneously self-assembled onto unmodified gold nanoparticles through a stable Au–S bond between the cysteamine moiety and the gold surface. The developed mono layer of cysteamine-TNT is then screened by SERS to detect and quantify TNT. Our experimental results demonstrate that the SERS-based assay provide an ultra-sensitive approach for the detection of TNT down to 22.7 ng/L. The unambiguous fingerprint identification of TNT by SERS represents a key advantage for our proposed method. The new method provides high selectivity towards TNT over 2,4 DNT and picric acid. Therefore it satisfies the practical requirements for the rapid screening of TNT in real life samples where the interim 24-h average allowable concentration of TNT in waste water is 0.04 mg/L.

Raman spectroscopy of pyrite in marble from Chillagoe, Queensland

Samples of marble from Chillagoe, North Queensland have been analysed using scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) and Raman spectroscopy. Different types of marble were studied including soft white marble, hard white marble and a black marble. In this work, we try to ascertain why the black marble has this colour. Chemical analyses provide evidence for the presence of minerals other calcite in the marble, including the pyrite mineral. Some of these chemical analyses correspond to pyrite minerals in the black marble. The Raman spectra of these crystals were obtained and the Raman spectrum corresponds to that of pyrite from the RRUFF data base. The combination of SEM with EDS and Raman spectroscopy enables the characterisation of the mineral pyrite in Chillagoe black marble.

Eye-safe UV stand-off Raman spectroscopy for the ranged detection of explosives in the field

Increasing worldwide terrorist attacks involving explosives presents a growing need for a rapid and ranged explosive detection method that can safely be deployed in the field. Stand-off Raman spectroscopy shows great promise; however, the radiant exposures of lasers required for adequate signal generation are often much greater than what is safe for the eye or the skin, restricting use of the technique to un-populated areas. Here, by determining the safe exposure levels for lasers typically used in Raman spectroscopy, optimal parameter values are identified, which produce the largest possible detection range using power densities that do not exceed the eye-safe limit. It is shown that safe ultraviolet pulse energies can be more than three orders of magnitude greater than equivalent safe visible pulse energies. Coupling this to the 16-fold increase in Raman signal obtained in the ultraviolet at 266 nm over that at 532 nm results in a 131 times larger detection range for the eye-safe 266-nm system over an equivalent eye-safe 532-nm laser system. For the Raman system described here, this translates to a maximum range of 42 m for detecting Teflon with a 266-nm laser emitting a 100-mm diameter beam of 23.5-mJ nanosecond pulses.

Trace vapour detection at room temperature using Raman spectroscopy

A miniaturized flow-through system consisting of a gold coated silicon substrate based on enhanced Raman spectroscopy has been used to study the detection of vapour from model explosive compounds. The measurements show that the detectability of the vapour molecules at room temperature depends sensitively on the interaction between the molecule and the substrate. The results highlight the capability of a flow system combined with Raman spectroscopy for detecting low vapour pressure compounds with a limit of detection of 0.2 ppb as demonstrated by the detection of bis(2-ethylhexyl)phthalate, a common polymer additive emitted from a commercial polyvinyl chloride (PVC) tubing at room temperature.

Raman spectroscopy techniques for detection of energetic materials at high and low concentration

This thesis presents the development of a rapid, sensitive and reproducible spectroscopic method for the detection of TNT in forensic and environmental applications. Simple nano sensors prepared by cost effective methods were utilized as sensitive platforms for the detection of TNT by surface enhanced Raman spectroscopy. The optimization of the substrate and the careful selection of a suitable recognition molecule contributed to the significant improvements of sensitive and selective targeting over current detection methods. The work presented in this thesis paves the way for effective detection and monitoring of explosives residues in law enforcement and environmental health applications.

High-Temperature Phase Transition Studies in a Novel Fast Ion Conductor, Na2Cd(SO4)2, Probed by Raman Spectroscopy

Temperature-dependent Raman spectroscopic studies were carried out on Na2Cd(SO4)(2) from room temperature to 600 degrees C. We observe two transitions at around 280 and 565 degrees C. These transitions are driven by the change in the SO4 ion. On the basis of these studies, one can explain the changes in the conductivity data observed around 280 and 565 degrees C. At 280 degrees C, spontaneous tilting of the SO4 ion leads to restriction of Na+ mobility. Above 565 degrees C, the SO4 ion starts to rotate freely, leading to increased mobility of Na+ ion in the channel.

Syntheses and characterization of trans-[NiL2(NCS)2][L = 2-(aminomethyl) pyridine], trans-[NiL02(NSC)2][L0 = 2-(2-aminoethyl)pyridine] and trans-[NiL00 2(NSC)2] [L00 = 2-(2-methylaminoethyl)pyridine] complexes: X-ray single crystal structure of trans-[NiL02(NSC)2] [L0 = 2-(2-aminoethyl)pyridine]

[NiL2(NCS)2] (1) [L = 2-(aminomethyl)pyridine], [NiL02(NCS)2] (2) [(L0) = 2-(2-aminoethyl)pyridine and [NiL00 2(NCS)2] (3) [L00 = 2-(2-methylaminoethyl)pyridine] have been synthesized from solution. All the complexes possess trans geometry as is evident from solid state UV–Vis spectral study and X-ray single crystal structure analysis of complex 2 unambiguously proves trans geometry of the species.

Determination of beta-turn conformation by laser Raman spectroscopy

To correlate the Raman frequencies of the amide I and III bands to beta-turn structures, three peptides shown to contain beta-turn structure by x-ray diffraction and NMR were examined. The compounds examined were tertiary (formula: see text). The amide I band of these compounds is seen at 1,668, 1,665, and 1,677 cm-1, and the amide III band appears at 1,267, 1,265, and 1,286 cm-1, respectively. Thus, it is concluded that the amide I band for type III beta-turn structure appears in the range between 1,665 and 1,677 cm-1 and the amide III band between 1,265 and 1,286 cm-1.

Rapid isolation and detection of erythropoietin in blood plasma by magnetic core gold nanoparticles and portable Raman spectroscopy

Isolating, purifying, and identifying proteins in complex biological matrices is often difficult, time consuming, and unreliable. Herein we describe a rapid screening technique for proteins in biological matrices that combines selective protein isolation with direct surface enhanced Raman spectroscopy (SERS) detection. Magnetic core gold nanoparticles were synthesised, characterised, and subsequently functionalized with recombinant human erythropoietin (rHuEPO)-specific antibody. The functionalized nanoparticles were used to capture rHuEPO from horse blood plasma within 15 minutes. The selective binding between the protein and the functionalized nanoparticles was monitored by SERS. The purified protein was then released from the nanoparticles’ surface and directly spectroscopically identified on a commercial nanopillar SERS substrate. ELISA independently confirmed the SERS identification and quantified the released rHuEPO. Finally, the direct SERS detection of the extracted protein was successfully demonstrated for in-field screening by a handheld Raman spectrometer within 1 minute sample measurement time.

Observation of kink shear bands in an aluminium single crystal fracture specimen

The near-tip deformation field in a high-constraint three-point bend specimen of pure aluminium single crystal is studied using in situ electron back-scattered diffraction and optical metallography. The orientation considered has the notch lying on the (0 1 0) plane and the notch front along direction. Results clearly show the occurrence of a kink shear sector boundary at 90° to the notch line on the specimen free surface as predicted by the analytical model of Rice [J.R. Rice, Mech. Mater. 6 (1987) 317].

High-Throughput Prediction of Acacia and Eucalypt Lignin Syringyl/Guaiacyl Content Using FT-Raman Spectroscopy and Partial Least Squares Modeling

High-throughput techniques are necessary to efficiently screen potential lignocellulosic feedstocks for the production of renewable fuels, chemicals, and bio-based materials, thereby reducing experimental time and expense while supplanting tedious, destructive methods. The ratio of lignin syringyl (S) to guaiacyl (G) monomers has been routinely quantified as a way to probe biomass recalcitrance. Mid-infrared and Raman spectroscopy have been demonstrated to produce robust partial least squares models for the prediction of lignin S/G ratios in a diverse group of Acacia and eucalypt trees. The most accurate Raman model has now been used to predict the S/G ratio from 269 unknown Acacia and eucalypt feedstocks. This study demonstrates the application of a partial least squares model composed of Raman spectral data and lignin S/G ratios measured using pyrolysis/molecular beam mass spectrometry (pyMBMS) for the prediction of S/G ratios in an unknown data set. The predicted S/G ratios calculated by the model were averaged according to plant species, and the means were not found to differ from the pyMBMS ratios when evaluating the mean values of each method within the 95 % confidence interval. Pairwise comparisons within each data set were employed to assess statistical differences between each biomass species. While some pairwise appraisals failed to differentiate between species, Acacias, in both data sets, clearly display significant differences in their S/G composition which distinguish them from eucalypts. This research shows the power of using Raman spectroscopy to supplant tedious, destructive methods for the evaluation of the lignin S/G ratio of diverse plant biomass materials.

Drift mobility of holes in single-crystal beta-AgI

The drift mobility of photoexcited holes in single-crystal beta-AgI has been measured between 260 and 312 °K. In this range the drift mobility µd increased with temperature due to trap-limited behavior. At 300 °K µd=12 cm2/V sec, the concentration and energy of the dominant traps being given by Nt=3×109 to 5×109/cm3 and Et=0.52 to 0.50 eV, respectively. Electron drift mobilities could not be determined due to low electron lifetimes. Journal of Applied Physics is copyrighted by The American Institute of Physics.

Large Low-Frequency Fluctuations in the Velocity of a Driven Vortex Lattice in a Single Crystal of 2H-NbSe2 Superconductor

The driven state of a well-ordered flux line lattice in a single crystal of 2H-NbSe2 in the time domain has revealed the presence of substantial fluctuations in velocity, with large and distinct time periods (similar to seconds). A superposition of a periodic drive in the driven vortex lattice causes distinct changes in these fluctuations. We propose that prior to the onset of the peak effect there exists a heretofore unexplored regime of coherent dynamics, with unexpected behavior in velocity fluctuations.

Co(II) and Cr(III) complexes of formate-formamide mixed ligands: synthesis, structures, single crystal-to-single crystal transformation and magnetic behaviour

Solvothermal treatment of an equimolar mixture of Co(NO3)(2)center dot 6H(2)O, HCONH2 and NaN3 in MeOH at 100 degrees C yielded a three-dimensional NaCl type network Co(HCOO)(2)(HCONH2)(2) center dot HCONH2 (1a) containing formamides in the pores of the structure. Solvated pink 1a undergoes single crystal-to-single crystal (SCSC) transformation at 215 degrees C to form the desolvated dark brown product Co(HCOO)(2)-( HCONH2)(2) (1b) with the retention of the original framework. Reversible single crystal-to-single crystal transformation of 1b (brown) to 1a (pink) in the presence of excess formamide was also established at room temperature. The coordination environment around Co(II) in both 1a and 1b is octahedral with a CoN2O4 coordination composition. A similar reaction replacing Co(II) by Cr(III) produced a heterometallic 3D extended network Na[Cr(HCOO)(4)(HCONH2)(2)]center dot 2H(2)O (2a) at 100 degrees C. An increase in reaction temperature to 150 degrees C produced a simple mononuclear complex Cr(HCOO)(3)(HCONH2)(3) center dot 3H(2)O (2b). Variable temperature magnetic studies revealed the presence of a canting phenomena in both 1a and 1b, and hysteresis loop in the field dependent magnetisation plot at 2 K whereas complex 2a is simply paramagnetic in nature.