Label-free detection of nanomolar unmodified single- and double-stranded dna by using surface-enhanced raman spectroscopy on Ag and Au colloids

Unlabelled single- and double-stranded DNA (ssDNA and dsDNA, respectively) has been detected at concentrations =10-9?M by surface-enhanced Raman spectroscopy. Under appropriate conditions the sequences spontaneously adsorbed to the surface of both Ag and Au colloids through their nucleobases; this allowed highly reproducible spectra with good signal-to-noise ratios to be recorded on completely unmodified samples. This eliminated the need to promote absorption by introducing external linkers, such as thiols. The spectra of model ssDNA sequences contained bands of all the bases present and showed systematic changes when the overall base composition was altered. Initial tests also showed that small but reproducible changes could be detected between oligonucleotides with the same bases arranged in a different order. The spectra of five ssDNA sequences that correspond to different strains of the Escherichia coli bacterium were found to be sufficiently composition-dependent so that they could be differentiated without the need for any advanced multivariate data analysis techniques.

Infrared and polarized Raman spectra of Cu(HSeO3)2 • H20 single crystal

Infrared and polarized Raman spectra of Cu(HSeO3) 2 - H20 single crystal have been recorded and analysed. The appearance of non-degenerate Se-OH stretching vibrations in the ~x: and ~y: polarizations of Raman spectra indicate distortion of the HSeO~- ion in the Cu(HSeO3)2 - H20 crystal. The low wavenumber values obtained for the symmetric and asymmetric stretching vibrations of the HSeO 3 ion are consistent with the strong hydrogen bonding and the influence of Jahn-Teller distortion as predicted in X-ray diffraction data. The shifting of the stretching and bending vibrations of the hydroxyl groups and water molecules from the free state values also confirms the strong hydrogen bonding in this crystal. Broad bands observed for both stretching and bending regions become sharp in the Raman spectrum recorded at 77 K. A doublet appears for the Se-OH stretching mode at this temperature indicating the settling of protons in an ordered position and the absence of intrabond proton tunnelling

Temperature dependent polarized Raman spectra of nonaaqualanthanoid (Pr) single crystal

Polarized Raman spectral changes with respect to temperature were investigated for Pr(BrO3)3·9H2O single crystals. FTIR spectra of hydrated and deuterated analogues were also recorded and analysed. Temperature dependent Raman spectral variation have been explained with the help of the thermograms recorded for the crystal. Factor group analysis could propose the appearance ofBrO3 ions at sites corresponding to C3v (4) and D3h (2). Analysis of the vibrational bands at room temperature confirms a distorted C3v symmetry for the BrO3 ion in the crystal. From the vibrations of water molecules, hydrogen bonds of varying strengths have also been identified in the crystal. The appearance υ1 mode of BrO3− anion at lower wavenumber region is attributed to the attachment of hydrogen atoms to the BrO3− anion. At high temperatures, structural rearrangement is taking place for bothH2Omolecule and BrO3 ions leading to the loss ofwater molecules and structural reorientation of bromate ions causing phase transition of the crystal at the temperature of 447 K.

Micro Far-Infrared Reflectivity of CaNb(2)O(6) Single Crystal Fibers Grown by the Laser-Heated Pedestal Growth Technique

CaNb(2)O(6) single crystal fibers were grown by the laser-heated pedestal growth technique, directly from the starting reagents. Optically transparent fibers were obtained in the form of rods with elliptical cross-section, free from cracks, impurities, and secondary phases, with an average diameter of 0.4 mm and about 20 mm of length. The fibers grew within the orthorhombic Pbcn columbite structure, with the growth axis nearly parallel to the crystallographic a-direction. The parameters b and c were parallel to the shorter and larger ellipsis axes. A special setup using a microscope was developed to obtain the far-infrared reflectivity spectra of these micrometer-sized fibers, allowing the identification and assignment of 34 of the 38 polar phonons foreseen for the material. From these phonons, the intrinsic dielectric constant ( = 18.2) and quality factor ( of 185 THz) could be estimated, showing the potential of the material for applications in microwave circuitry. These results, along with previous polarized Raman data (Cryst. Growth Des. 2010, 10, 1569), allow us to present a comprehensive set of optical phonon modes and to discuss the potential use of designed CaNb(2)O(6) microcrystals in compact optical devices.

Synthesis, characterization, and single crystal X-ray structure of the 1-furoyl-3-cyclohexylthiourea cadmium chloride complex, Cd[C4H3OC(O)NHC(S)NHC6H11]4Cl2

Cadmium chloride complex of 1-furoyl-3-cyclohexylthiourea (CyTu) was prepared and characterized by elemental analysis, IR, and Raman spectroscopy. The structure of the complex was determined by single crystal X-ray methods (space group Bbab, a = 20.918(1), b = 23.532(1), c = 23.571(1) angstrom, = = , Z = 8). Each cadmium has distorted octahedral geometry, coordinated by two chlorides and the thiocarbonyl sulfurs from four CyTu molecules. All the spectroscopic data are consistent with coordination of CyTu by sulfur to cadmium.

Charge-transfer behavior of polyaniline single wall carbon nanotubes nanocomposites monitored by resonance Raman spectroscopy

Highly dispersed nanocomposites of polyaniline(PANI) and oxidized single wall carbon nanotubes(SWNTs) have been prepared using dodecylbenzenesulfonic acid as dispersant. The materials were characterized via resonance Raman and electronic absorption spectroscopies. The behavior of the composites as a function of the applied potential was also investigated using in situ Raman electrochemical measurements. The results obtained at E(laser) = 1.17 eV suggest that a charge-transfer process occur between PANI and semiconducting nanotubes for samples where the metallic tubes are previously oxidized. The spectroelectrochemical data show that the presence of SWNTs prevents the oxidation of PANI rings. Copyright (C) 2010 John Wiley & Sons, Ltd.

In silico infrared and Raman spectroscopy under pressure: The case of CaSnO3 perovskite

The CaSnO3 perovskite is investigated under geochemical pressure, up to 25 GPa, by means of periodic ab initio calculations performed at B3LYP level with local Gaussian-type orbital basis sets. Structural, elastic, and spectroscopic (phonon wave-numbers, infrared and Raman intensities) properties are fully characterized and discussed. The evolution of the Raman spectrum of CaSnO3 under pressure is reported to remarkably agree with a recent experimental determination [J. Kung, Y. J. Lin, and C. M. Lin, J. Chem. Phys. 135, 224507 (2011)] as regards both wave-number shifts and intensity changes. All phonon modes are symmetry-labeled and bands assigned. The single-crystal total spectrum is symmetry-decomposed into the six directional spectra related to the components of the polarizability tensor. The infrared spectrum at increasing pressure is reported for the first time and its main features discussed. All calculations are performed using the CRYSTAL14 program, taking advantage of the new implementation of analytical infrared and Raman intensities for crystalline materials. (C) 2015 AIP Publishing LLC.

Dependence of brittle-to-ductile transition on crystallographic direction in diamond turning of single-crystal silicon

The objective of this paper is to show the dependence relationship between the crystallographic orientations upon brittle-to-ductile transition during diamond turning of monocrystalline silicon. Cutting tests were performed using a -5 degrees rake angle round nose diamond tool at different machining scales. At the micrometre level, the feedrate was kept constant at 2.5 micrometres per revolution (mu m/r), and the depth of cut was varied from 1 to 5 mu m. At the submicrometre level, the depth of cut was kept constant at 500 nm and the feedrate varied from 5 to 10 mu m/r. At the micrometre level, the uncut shoulder generated with an interrupted cutting test procedure provided a quantitative measurement of the ductile-to-brittle transition. Results show that the critical chip thickness in silicon for ductile material removal reaches a maximum of 285 nm in the [100] direction and a minimum of 115 nm in the [110] direction, when the depth of cut was 5 mu m. It was found that when a submicrometre depth of cut was applied, microcracks were revealed in the [110] direction, which is the softer direction in silicon. Micro Raman spectroscopy was used to estimate surface residual stress after machining. Compressive residual stress in the range 142 MPa and smooth damage free surface finish was probed in the [100] direction for a depth of cut of 5 mu m, whereas residual stresses in the range 350 MPa and brittle damage was probed in the [110] direction for a depth of cut of 500 nm.

Single-wall carbon nanotube interactions with copper-oxamato building block of molecule-based magnets probed by resonance Raman spectroscopy

The electronic interactions between the [Cu(opba)]2- anions (where opba is orthophenylenebis (oxamato)) and single-wall carbon nanotubes (SWCNTs) were investigated by resonance Raman spectroscopy. The opba can form molecular magnets, and the interactions of opba with SWCNTs can produce materials with very different magnetic/electronic properties. It is observed that the electronic interaction shows a dependence on the SWCNT diameter independent of whether they are metallic or semiconducting, although the interaction is stronger for metallic tubes. The interaction also is dependent on the amount of complex that is probably adsorbed on the carbon surface of the SWCNTs. Some charge transfer can be also occurring between the metallic complex and the SWCNTs. Copyright (c) 2012 John Wiley & Sons, Ltd.

Polymorphic-induced transformations in CaTa2O6 single-crystal fibers obtained by laser-heated pedestal growth

Calcium tantalite (CaTa2O6) single crystal fibers were obtained by the laser-heated pedestal growth method (LHPG). At room temperature, this material can present three polymorphic modifications. The rapid crystallization inherent to the LHPG method produced samples within the Pm3 space group, with some chemical disorder. In order to check for polymorphic-induced transformations, the CaTa2O6 fibers have been submitted to different thermal treatments and investigated by micro-Raman spectroscopy. For short annealing times (15 min) at 1200 °C, the cubic modification was maintained, though with an improved crystalline quality, as evidenced by the enhanced inelastic scattered intensity (by ca. 250%) and narrowing of Raman bands. The polarized Raman spectra respected very well the predicted symmetries and the selection rules for this cubic modification. On the other hand, long annealing times (24 h) at 1200 °C led to a complete (irreversible) polymorphic transformation. The Raman bands became still more intense (ca. 15 times larger than for the as-grown fibers), narrower, and several new modes appeared. Also, the spectra became unpolarized, demonstrating a polycrystalline nature of the transformed crystals. The observed Raman modes could be fully assigned to an orthorhombic modification of CaTa2O6 belonging to the Pnma space group.

In Situ SHINERS at Electrochemical Single-Crystal Electrode/Electrolyte Interfaces: Tuning Preparation Strategies and Selected Applications

We have studied Au(55 nm)@SiO2 nanoparticles (NPs) on two low-index phases of gold and platinum single crystal electrodes in ClO4– and SO42– ion-containing electrolytes by both electrochemical methods and in-situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS). We showed the blocking of the electrode with surfactants originating from the synthesis of as-prepared SHINERS NPs. We introduce an efficient procedure to overcome this problem, which provides a fundamental platform for the application of SHINERS in surface electrochemistry and beyond. Our method is based on a hydrogen evolution treatment of the SHINERS-NP-modified single-crystal surfaces. The reliability of our preparation strategy is demonstrated in electrochemical SHINERS experiments on the potential-controlled adsorption and phase formation of pyridine on Au(hkl) and Pt(hkl). We obtained high-quality Raman spectra on these well-defined and structurally carefully characterized single-crystal surfaces. The analysis of the characteristic A1 vibrational modes revealed perfect agreement with the interpretation of single-crystal voltammetric and chronoamperometric experiments. Our study demonstrates that the SHINERS protocol developed in this work qualifies this Raman method as a pioneering approach with unique opportunities for in situ structure and reactivity studies at well-defined electrochemical solid/liquid interfaces.

Characterization of a zeolite-templated carbon by electrochemical quartz crystal microbalance and in situ Raman spectroscopy

Electrochemical quartz crystal microbalance was used to monitor the mass changes during the electrochemical characterization of a zeolite-templated carbon (ZTC) in 1 M H2SO4 medium. Under electrochemical oxidation conditions, a high anodic current and a net mass increase were recorded, resulting in the increase of the specific capacitance owing to the contribution of the pseudocapacitance, mainly derived from the hydroquinone–quinone redox couple. Under more severe electrochemical conditions, a net mass loss was observed, revealing that electrochemical gasification took place. Surface chemistry, before and after the electrochemical treatments, was analyzed through temperature programmed desorption experiments. Furthermore, in situ Raman spectroscopy was used to further characterize the structural changes produced in ZTC under the electrochemical conditions applied, supporting that high potential values produce the electrochemical oxidation and degradation of the carbon material.

Raman spectroscopy of hydrogene-arsenate group (AsO3OH) in solid-state compounds: cobalt mineral phase burgessite Co2(H2O)4[AsO3OH]2•H2O

Raman spectrum of burgessite, Co2(H2O)4[AsO3OH]2.H2O was studied, interpreted and compared with its infrared spectrum. The stretching and bending vibrations of (AsO3) and As-OH units together with the stretching, bending and libration modes of water molecules and hydroxyl ions were assigned. The range of O-H...O hydrogen bond lengths was inferred from the Raman and infrared spectra of burgessite. The presence of (AsO3OH)2- units in the crystal structure of burgessite was proved in agreement with its recently solved crystal structure. Raman and infrared spectra of erythrite inferred from the RRUFF database are used for comparison.