Second order Coriolis resonance in the v2, v5 Raman bands of CH3F

The vibration-rotation Raman spectrum of the ν2 and ν5 fundamentals of CH3F is reported, from 1320 to 1640 cm−1, with a resolution of about 0.3 cm−1. The Coriolis resonance between the two bands leads to many perturbation-allowed transitions. Where the resonance is still sufficiently weak that the quantum number K′ retains its meaning, perturbation-allowed transitions are observed for all values of ΔK from +4 to −4; in regions of strong resonance, however, we can only say that the observed transitions obey the selection rule Δ(k−l) = 0 or ±3. The spectrum has been analyzed by band contour simulation using a computer program based on exact diagonalization of the Hamiltonian within the ν2, ν5 vibrational levels, and improved vibration-rotation constants for these bands are reported. The relative magnitudes and relative sings of polarizability derivatives involved in these vibrations are also reported.

Infrared laser photobiomodulation (lambda 830 nm) on bone tissue around dental implants: A Raman spectroscopy and scanning electronic microscopy study in rabbits

Objective: the aim of this study was to assess, through Raman spectroscopy, the incorporation of calcium hydroxyapatite (CHA; similar to 960 cm(-1)), and scanning electron microscopy (SEM), the bone quality on the healing bone around dental implants after laser photobiomodulation ( lambda 830 nm). Background Data: Laser photobiomodulation has been successfully used to improve bone quality around dental implants, allowing early wearing of prostheses. Methods: Fourteen rabbits received a titanium implant on the tibia; eight of them were irradiated with lambda 830 nm laser ( seven sessions at 48-h intervals, 21.5 J/cm(2) per point, 10 mW, phi similar to 0.0028 cm(2), 86 J per session), and six acted as control. The animals were sacrificed 15, 30, and 45 days after surgery. Specimens were routinely prepared for Raman spectroscopy and SEM. Eight readings were taken on the bone around the implant. Results: the results showed significant differences on the concentration of CHA on irradiated and control specimens at both 30 and 45 days after surgery ( p < 0.001). Conclusion: It is concluded that infrared laser photobiomodulation does improve bone healing, and this may be safely assessed by Raman spectroscopy or SEM.

Structural studies of NaPO3-MoO3 glasses by solid-state nuclear magnetic resonance and raman spectroscopy

Vitreous samples were prepared in the (100 - x)% NaPO3-x% MoO3 (0 <= x <= 70) glass-forming system by a modified melt method that allowed good optical quality samples to be obtained. The structural evolution of the vitreous network was monitored as a function of composition by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), Raman scattering, and solid-state nuclear magnetic resonance (NMR) for P-31, Na-23, and Mo-95 nuclei. Addition of MoO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures up to x = 45, suggesting a significant increase in network connectivity. For this same composition range, vibrational spectra suggest that the Mo6+ ions are bonded to some nonbridging oxygen atoms (Mo-O- or Mo=O bonded species). Mo-O-Mo bond formation occurs only at MoO3 contents exceeding x = 45. P-31 magic-angle spinning (MAS) NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. These sites are denoted as Q(2Mo)((2)), Q(1Mo)((2)), and Q(0Mo)((2)), respectively. For x < 0.45, the populations of these sites can be described along the lines of a binary model, according to which each unit of MoO3 converts two Q(nMo)((2)) sites into two Q((n+1)Mo)((2)) sites (n = 0, 1). This structural model is consistent with the presence of tetrahedral Mo(=O)(2)(O-1/2)(2) environments. Indeed, Mo-95 NMR data suggest that the majority of the molybdenum species are four-coordinated. However, the presence of additional six-coordinate molybdenum in the MAS NMR spectra indicates that the structure of these glasses may be more complicated and may additionally involve sharing of network modifier oxide between the network formers phosphorus and molybdenum. This latter hypothesis is further supported by Na-23{P-31} rotational echo double resonance (REDOR) data, which clearly reveal that the magnetic dipole-dipole interactions between P-31 and Na-23 are increasingly diminished with increasing molybdenum content. The partial transfer of modifier from the phosphate to the molybdate network former implies a partial repolymerization of the phosphate species, resulting in the formation of Q(nMo)((3)) species and accounting for the observed increase in the glass transition temperature with increasing MoO3 content that is observed in the composition range 0 <= x <= 45. Glasses with MoO3 contents beyond x = 45 show decreased thermal and crystallization stability. Their structure is characterized by isolated phosphate species [most likely of the P(OMo)(4) type] and molybdenum oxide clusters with a large extent of Mo-O-Mo connectivity.

Raman Spectroscopy and Scanning Electron Microscopy Characterizations of Fission Track Method Datable Zircon Grains

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Detection of neuritic plaques in Alzheimer’s disease by magnetic resonance microscopy

Magnetic resonance microscopy (MRM) theoretically provides the spatial resolution and signal-to-noise ratio needed to resolve neuritic plaques, the neuropathological hallmark of Alzheimer’s disease (AD). Two previously unexplored MR contrast parameters, T2* and diffusion, are tested for plaque-specific contrast to noise. Autopsy specimens from nondemented controls (n = 3) and patients with AD (n = 5) were used. Three-dimensional T2* and diffusion MR images with voxel sizes ranging from 3 × 10−3 mm3 to 5.9 × 10−5 mm3 were acquired. After imaging, specimens were cut and stained with a microwave king silver stain to demonstrate neuritic plaques. From controls, the alveus, fimbria, pyramidal cell layer, hippocampal sulcus, and granule cell layer were detected by either T2* or diffusion contrast. These structures were used as landmarks when correlating MRMs with histological sections. At a voxel resolution of 5.9 × 10−5 mm3, neuritic plaques could be detected by T2*. The neuritic plaques emerged as black, spherical elements on T2* MRMs and could be distinguished from vessels only in cross-section when presented in three dimension. Here we provide MR images of neuritic plaques in vitro. The MRM results reported provide a new direction for applying this technology in vivo. Clearly, the ability to detect and follow the early progression of amyloid-positive brain lesions will greatly aid and simplify the many possibilities to intervene pharmacologically in AD.

Magnetic resonance microscopy of the equine hoof wall: a study of resolution and potential

Reasons for performing study: Obtaining magnetic resonance images of the inner hoof wall tissue at the microscopic level would enable early accurate diagnosis of laminitis and therefore more effective therapy. Objectives: To optimise magnetic resonance imaging (MRI) parameters in order to obtain the highest possible resolution of the structures beneath the equine hoof wall. Methods: Magnetic resonance microscopy (MRM) was performed in front feet from 6 cadaver horses using T-2-weighted fast spin echo (FSE-T-2), and T-1-weighted gradient echo (GRE-T-1) sequences. Results: In T-2 weighted FSE images most of the stratum medium showed no signal, however the coronary, terminal and sole papillae were visible. The stratum lamellatum was clearly visible and primary epidermal lamellae could be differentiated from dermal lamellae. Conclusion: Most structures beneath the hoof wall were differentiated. Conventional scanners for diagnostic MRI in horses are low or high field. However this study used ultra-high field scanners currently not available for clinical use. Signal-to-noise ratio (SIN) increases as a function of field strength. An increase of spatial resolution of the image results in a decreased SIN. SIN can also be improved with better coils and the resolution of high field MRI scanners will increase as technology develops and surface array coils become more readily available. Potential relevance: Although MR images with microscopic resolution were obtained ex vivo, this study demonstrates the potential for detection of lamellar pathology as it occurs. Early recognition of the development of laminitis to instigate effective therapy at an earlier stage and may improve the outcome for laminitic horses. Clinical MR is now readily available at 3 T, while 4 T, 7 T and 9 T systems are being used for human whole body applications.

Stochastic anti-resonance in a fibre Raman amplifier

Stochastic anti-resonance, that is resonant enhancement of randomness caused by polarization mode beatings, is analyzed both numerically and analytically on an example of fibre Raman amplifier with randomly varying birefringence. As a result of such anti-resonance, the polarization mode dispersion growth causes an escape of the signal state of polarization from a metastable state corresponding to the pulling of the signal to the pump state of polarization.This phenomenon reveals itself in abrupt growth of gain fluctuations as well as in dropping of Hurst parameter and Kramers length characterizing long memory in a system and noise induced escape from the polarization pulling state. The results based on analytical multiscale averaging technique agree perfectly with the numerical data obtained by direct numerical simulations of underlying stochastic differential equations. This challenging outcome would allow replacing the cumbersome numerical simulations for real-world extra-long high-speed communication systems.

Synthesis of Fe/Ti oxides from a single source alkoxide precursor under inert atmosphere

The heterometal alkoxide [FeCl{Ti2(OPr i)9}] (1) was employed as a single source precursor for the preparation of Fe/Ti oxides under inert atmosphere. Three different synthetic procedures were adopted in the processing of 1, either employing aqueous HNO3 or HCl solutions, or in the absence of mineral acids. Products were characterised by powder X-ray diffractometry, scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM/EDS) and Raman, electron paramagnetic resonance (EPR) and Mössbauer spectroscopies. Oxide products contained titanium(IV) and either iron(III) or iron(II), depending on reaction conditions and thermal treatment temperatures. An interesting iron(III)→iron(II) reduction was observed at 1000 ºC in the HNO3-containing system, leading to the detection of ilmenite (FeTiO3). SEM/EDS studies revealed a highly heterogeneous metal distribution in all products, possibly related to the presence of a significant content of carbon and of structural defects (oxygen vacancies) in the solids.

Phase transformation and residual stress probed by Raman spectroscopy in diamond-turned single crystal silicon

Single-point diamond turning of monocrystalline semiconductors is an important field of research within brittle materials machining. Monocrystalline silicon samples with a (100) orientation have been diamond turned under different cutting conditions (feed rate and depth of cut). Micro-Raman spectroscopy and atomic force microscopy have been used to assess structural alterations and surface finish of the samples diamond turned under ductile and brittle modes. It was found that silicon undergoes a phase transformation when machined in the ductile mode. This phase transformation is evidenced by the creation of an amorphous surface layer after machining which has been probed by Raman scattering. Compressive residual stresses are estimated for the machined surface and it is observed that they decrease with an increase in the feed rate and depth of cut. This behaviour has been attributed to the formation of subsurface cracks when the feed rate is higher than or equal to 2.5 mu m/rev. The surface roughness was observed to vary with the feed rate and the depth of cut. An increase in the surface roughness was influenced by microcrack formation when the feed rate reached 5.0 mu m/rev. Furthermore, a high-pressure phase transformation induced by the tool/material interaction and responsible for the ductile response of this typical brittle material is discussed based upon the presented Raman spectra. The application of this machining technology finds use for a wide range of high quality components, for example the creation of a micrometre-range channel for microfluidic devices as well as microlenses used in the infrared spectrum range.

Surface plasmon resonance of gold nanoparticles formed by cathodic arc plasma ion implantation into polymer

Shallow subsurface layers of gold nanoclusters were formed in polymethylmethacrylate (PMMA) polymer by very low energy (49 eV) gold ion implantation. The ion implantation process was modeled by computer simulation and accurately predicted the layer depth and width. Transmission electron microscopy (TEM) was used to image the buried layer and individual nanoclusters; the layer width was similar to 6-8 nm and the cluster diameter was similar to 5-6 nm. Surface plasmon resonance (SPR) absorption effects were observed by UV-visible spectroscopy. The TEM and SPR results were related to prior measurements of electrical conductivity of Au-doped PMMA, and excellent consistency was found with a model of electrical conductivity in which either at low implantation dose the individual nanoclusters are separated and do not physically touch each other, or at higher implantation dose the nanoclusters touch each other to form a random resistor network (percolation model). (C) 2009 American Vacuum Society. [DOI: 10.1116/1.3231449]

Structural and optical properties of rare earth-doped (Ba(0.77)Ca(0.23))(1-x)(Sm, Nd, Pr, Yb)(x)TiO(3)

The structural, dielectric, and vibrational properties of pure and rare earth (RE)-doped Ba(0.77) Ca(0.23)TiO(3) (BCT23; RE = Nd, Sm, Pr, Yb) ceramics obtained via solid-state reaction were investigated. The pure and RE-doped BCT23 ceramics sintered at 1450 degrees C in air for 4 h showed a dense microstructure in all ceramics. The use of RE ions as dopants introduced lattice-parameter changes that manifested in the reduction of the volume of the unit cell. RE-doped BCT23 samples exhibit a more homogenous microstructure due to the absence of a Ti-rich phase in the grain boundaries as demonstrated by scanning electron microscopy imaging. The incorporation of REs led to perturbations of the local symmetry of TiO(6) octahedra and the creation of a new Raman mode. The results of Raman scattering measurements indicated that the Curie temperature of the ferroelectric phase transition depends on the RE ion and ion content, with the Curie temperature shifting toward lower values as the RE content increases, with the exception of Yb(3+) doping, which did not affect the ferroelectric phase transition temperature. The phase transition behavior is explained using the standard soft mode model. Electronic paramagnetic resonance measurements showed the existence of Ti vacancies in the structure of RE-doped BCT23. Defects are created via charge compensation mechanisms due to the incorporation of elements with a different valence state relative to the ions of the pure BCT23 host. It is concluded that the Ti vacancies are responsible for the activation of the Raman mode at 840 cm(-1), which is in agreement with lattice dynamics calculations. (c) 2011 American Institute of Physics. [doi:10.1063/1.3594710]

Strong reduction of V(4+) amount in vanadium oxide/hexadecylamine nanotubes by doping with Co(2+) and Ni(2+) ions: Electron paramagnetic resonance and magnetic studies

In this work we present a complete characterization and magnetic study of vanadium oxide/hexadecylamine nanotubes (VO(x)/Hexa NT's) doped with Co(2)+ and Ni(2+) ions. The morphology of the NT's has been characterized by transmission electron microscopy, while the metallic elements have been quantified by the instrumental neutron activation analysis technique. The static and dynamic magnetic properties were studied by collecting data of magnetization as a function of magnetic field and temperature and by electron paramagnetic resonance. At difference of the majority reports in the literature, we do not observe magnetic dimers in vanadium oxide nanotubes. Also, we observed that the incorporation of metallic ions (Co(2+), S = 3/2 and Ni(2+), S = 1) decreases notably the amount of V(4+) ions in the system, from 14-16% (nondoped case) to 2%-4%, with respect to the total vanadium atoms (fact corroborated by XPS experiments) anyway preserving the tubular nanostructure. The method to decrease the amount of V(4+) in the nanotubes improves considerably their potential technological applications as Li-ion batteries cathodes. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3580252]

Evidences of the evolution from solid solution to surface segregation in Ni-doped SnO(2) nanoparticles using Raman spectroscopy

Ni-doped SnO(2) nanoparticles, promising for gas-sensing applications, have been synthesized by a polymer precursor method. X-ray diffraction (XRD) and transmission electron microscopy (TEM) data analyses indicate the exclusive formation of nanosized particles with rutile-type phase (tetragonal SnO(2)) for Ni contents below 10 mol%. The mean crystallite size shows a progressive reduction with the Ni content. Room-temperature Raman spectra of Ni-doped SnO(2) nanoparticles show the presence of Raman active modes and modes activated by size effects. From the evolution of the A(1g) mode with the Ni content, a solubility limit at similar to 2 mol% was estimated. Below that content, Raman results are consistent with the occurrence of solid solution (ss) and surface segregation (seg.) of Ni ions. Above similar to 2 mol% Ni, the redshift of A(1g) mode suggests that the surface segregation of Ni ions takes place. Disorder-activated bands were determined and their integrated intensity evolution with the Ni content suggest that the solid-solution regime favors the increase of disorder; meanwhile, that disorder becomes weaker as the Ni content is increased. Copyright (C) 2010 John Wiley & Sons, Ltd.

C-13-NMR, H-1-NMR, and FT-Raman study of radiation-induced modifications in radiation dosimetry polymer gels

H-1- and C-13-NMR spectroscopy and FT-Raman spectroscopy are used to investigate the properties of a polymer gel dosimeter post-irradiation. The polymer gel (PACT) is composed of acrylamide, N,N'-methylene-bisacrylamide, gelatin, and water. The formation of a polyacrylamide network within the gelatin matrix follows a dose dependence nonlinearly correlated to the disappearance of the double bonds from the dissolved monomers within the absorbed dose range of 0-50 Gy. The signal from the gelatin remains constant with irradiation. We show that the NMR spin-spin relaxation times (T-2) of PAGs irradiated to up to 50 Gy measured in a NMR spectrometer and a clinical magnetic resonance imaging scanner can be modeled using the spectroscopic intensity of the growing polymer network. More specifically, we show that the nonlinear T-2 dependence against dose can be understood in terms of the fraction of protons in three different proton pools. (C) 2000 John Wiley & Sons, Inc.

Characterization of Superparamagnetic Iron Oxide Coated with Silicone Used as Contrast Agent for Magnetic Resonance Image for the Gastrointestinal Tract

The present work is a report of the characterization of superparamagnetic iron oxide nanoparticles coated with silicone used as a contrast agent in magnetic resonance imaging of the gastrointestinal tract. The hydrodynamic size of the contrast agent is 281.2 rim, where it was determined by transmission electron microscopy and a Fe(3)O(4) crystalline structure was identified by X-ray diffraction, also confirmed by Mossbauer Spectroscopy. The blocking temperature of 190 K was determined from magnetic measurements based on the Zero Field Cooled and Field Cooled methods. The hysteresis loops were measured at different temperatures below and above the blocking temperature. Ferromagnetic resonance analysis indicated the superparamagnetic nature of the nanoparticles and a strong temperature dependence of the peak-to-peak linewidth Delta H(pp), giromagnetic factor g, number of spins N(S) and relaxation time T(2) were observed. This behavior can be attributed to an increase in the superexchange interaction.