Spectral Region Optimization for Raman-Based Optical Biopsy of Inflammatory Lesions

Objective: The biochemical alterations between inflammatory fibrous hyperplasia (IFH) and normal tissues of buccal mucosa were probed by using the FT-Raman spectroscopy technique. The aim was to find the minimal set of Raman bands that would furnish the best discrimination. Background: Raman-based optical biopsy is a widely recognized potential technique for noninvasive real-time diagnosis. However, few studies had been devoted to the discrimination of very common subtle or early pathologic states as inflammatory processes that are always present on, for example, cancer lesion borders. Methods: Seventy spectra of IFH from 14 patients were compared with 30 spectra of normal tissues from six patients. The statistical analysis was performed with principal components analysis and soft independent modeling class analogy cross-validated, leave-one-out methods. Results: Bands close to 574, 1,100, 1,250 to 1,350, and 1,500 cm(-1) (mainly amino acids and collagen bands) showed the main intragroup variations that are due to the acanthosis process in the IFH epithelium. The 1,200 (C-C aromatic/DNA), 1,350 (CH(2) bending/collagen 1), and 1,730 cm(-1) (collagen III) regions presented the main intergroup variations. This finding was interpreted as originating in an extracellular matrix-degeneration process occurring in the inflammatory tissues. The statistical analysis results indicated that the best discrimination capability (sensitivity of 95% and specificity of 100%) was found by using the 530-580 cm(-1) spectral region. Conclusions: The existence of this narrow spectral window enabling normal and inflammatory diagnosis also had useful implications for an in vivo dispersive Raman setup for clinical applications.

Towards the development of fiber lasers for the 2 to 4 nanom spectral region

A growing number of applications are calling for compact laser sources operating in the mid-infrared spectral region. A review of our recent work on monolithic fiber lasers (FL) based either on the use of rare-earth fluoride fibers or on Raman gain in both fluoride and chalcogenide glass fibers is presented. Accordingly, an erbium-doped double clad fluoride glass all-FL operating in the vicinity of 3 μm is shown. In addition, we present recent results on the first demonstrations of both fluoride and chalcogenide Raman fiber lasers operating at 2.23 and 3.34 μm, respectively. It is shown that based on this approach, monolithic FLs could be developed to cover the whole 2 to 4 μm spectral band.

Raman fiber source for the 1.6–1.75 μm spectral region

We propose and experimentally realize a composite Raman converter based on P-doped and Gedoped fibers. The converter has an emission wavelength of 1.649 μm and an output power of 1.2 W. Numerical simulation of the configuration suggested was performed. A similar converter scheme can be used to build sources with any emission wavelength in the range from 1.6 to 1.75 μm.

Thermomechanical sensitivity of microcantilever in the mid-infrared spectral region

This paper reports the thermomechanical sensitivity of bimaterial cantilevers over a mid-infrared (IR) spectral range (5-10 µm) that is critical both for chemical analysis via vibrational spectroscopy and for direct thermal detection in the 300-700 K range. Mechanical bending sensitivity and noise were measured and modeled for six commercially available microcantilevers, which consist of either an aluminum film on a silicon cantilever or a gold film on a silicon nitride cantilever. The spectral sensitivity of each cantilever was determined by recording cantilever deflection when illuminated with IR light from a monochromator. Rigorous modeling and systematic characterization of the optical system allowed for a quantitative estimate of IR energy incident upon the cantilever. Separately, spectral absorptance of the cantilever was measured using Fourier transform infrared (FT-IR) microscopy, which was compared with analytical models of radiation onto the cantilever and heat flow within the cantilever. The predictions of microcantilever thermomechanical bending sensitivity and noise agree well with measurements, resulting in a ranking of these cantilevers for their potential use in IR measurements.

A escolha da faixa espectral no uso combinado de métodos espectroscópicos e quimiométricos

A method is presented for the choice of spectral regions when absorption measurements are coupled to chemometric tools to perform quantitative analyses. The method is based on the spectral distribution of the relative standard deviation of concentration (s c/c). It has been applied to the development of PLS-FTNIR calibration models for the determination of density and MON of gasoline, and ethanol content and density of ethanol fuel. The new method was also compared with the correlation (R²) method and has proved to generate PLS calibration models that present better accuracy and precision than those based on R².

Antarctic cloud spectral emission from ground-based measurements, a focus on far infrared signatures

The present work belongs to the PRANA project, the first extensive field campaign of observation of atmospheric emission spectra covering the Far InfraRed spectral region, for more than two years. The principal deployed instrument is REFIR-PAD, a Fourier transform spectrometer used by us to study Antarctic cloud properties. A dataset covering the whole 2013 has been analyzed and, firstly, a selection of good quality spectra is performed, using, as thresholds, radiance values in few chosen spectral regions. These spectra are described in a synthetic way averaging radiances in selected intervals, converting them into BTs and finally considering the differences between each pair of them. A supervised feature selection algorithm is implemented with the purpose to select the features really informative about the presence, the phase and the type of cloud. Hence, training and test sets are collected, by means of Lidar quick-looks. The supervised classification step of the overall monthly datasets is performed using a SVM. On the base of this classification and with the help of Lidar observations, 29 non-precipitating ice cloud case studies are selected. A single spectrum, or at most an average over two or three spectra, is processed by means of the retrieval algorithm RT-RET, exploiting some main IR window channels, in order to extract cloud properties. Retrieved effective radii and optical depths are analyzed, to compare them with literature studies and to evaluate possible seasonal trends. Finally, retrieval output atmospheric profiles are used as inputs for simulations, assuming two different crystal habits, with the aim to examine our ability to reproduce radiances in the FIR. Substantial mis-estimations are found for FIR micro-windows: a high variability is observed in the spectral pattern of simulation deviations from measured spectra and an effort to link these deviations to cloud parameters has been performed.

Spectral Reflectance Characteristics of Kimberlite Indicator Minerals and Other Selected Mineral Grains

High chromium content in kimberlite indicator minerals such as pyrope garnet and diopside is often correlated with the presence of diamonds. In this study, kimberlite indicator minerals were examined using visible light reflectance spectroscopy to determine if chromium content can be correlated with spectral absorption features. The depth of absorption features in the visible spectral region were correlated with the molecular percentage of chromium and other first series transition metal elements obtained by electron microprobe data. In the visible part of the spectrum, chromium is evident by 3 absorption features in the pyrope reflectance spectrum; one isolated and narrow feature at the wavelength 689 nm was used to correlate with the chromium mol %. The isolation of this feature in the pyrope spectra is advantageous since it is not directly affected by other proximal absorption bands that could be caused by other transition metals. Analysis of the feature indicates that as grain volume increases the depth of the absorption feature will also increase. Clustering grain volumes into fractions yields better correlation between absorption depth and mol % chromium. Other types of garnet (almandine, grossular, spessartine) and kimberlite indicator minerals (olivine, diopside, chromite, ilmenite) were analyzed to determine if other absorption features could be used to predict the proportion of specific transition metal elements. Diopside in particular illustrates the same isolated chromium absorption feature as pyrope and may indicate mol percent but needs further study with larger sample sets.

Evaluation of suitable spectral intervals for near-IR laboratory detection of water vapour continuum absorption

The water vapour continuum absorption is an important component of molecular absorption of radiation in atmosphere. However, uncertainty in knowledge of the value of the continuum absorption at present can achieve 100% in different spectral regions leading to an error in flux calculation up to 3-5 W/m2 global mean. This work uses line-by-line calculations to reveal the best spectral intervals for experimental verification of the CKD water vapour continuum models in the currently least studied near-infrared spectral region. Possible sources of errors in continuum retrieval taken into account in the simulation include the sensitivity of laboratory spectrometers and uncertainties in the spectral line parameters in HITRAN-2004 and Schwenke-Partridge database. It is shown that a number of micro-windows in near-IR can be used at present for laboratory detection of the water vapour continuum with estimated accuracy from 30 to 5%.

Assessment of the consistency of near-infrared water vapor line intensities using high-spectral-resolution ground-based Fourier transform measurements of solar radiation

Calculations of the absorption of solar radiation by atmospheric gases, and water vapor in particular, are dependent on the quality of databases of spectral line parameters. There has been increasing scrutiny of databases such as HITRAN in recent years, but this has mostly been performed on a band-by-band basis. We report nine high-spectral-resolution (0.03 cm(-1)) measurements of the solar radiation reaching the surface in southern England over the wave number range 2000 to 12,500 cm(-1) (0.8 to 5 mm) that allow a unique assessment of the consistency of the spectral line databases over this entire spectral region. The data are assessed in terms of the modeled water vapor column that is required to bring calculations and observations into agreement; for an entirely consistent database, this water vapor column should be constant with frequency. For the HITRAN01 database, the spread in water vapor column is about 11%, with distinct shifts between different spectral regions. The HITRAN04 database is in significantly better agreement (about 5% spread) in the completely updated 3000 to 8000 cm(-1) spectral region, but inconsistencies between individual spectral regions remain: for example, in the 8000 to 9500 cm(-1) spectral region, the results indicate an 18% (+/- 1%) underestimate in line intensities with respect to the 3000 to 8000 cm(-1) region. These measurements also indicate the impact of isotopic fractionation of water vapor in the 2500 to 2900 cm(-1) range, where HDO lines dominate over the lines of the most abundant isotope of H2O.

Derivation of an urban materials spectral library through emittance and reflectance spectroscopy

Recent advances in thermal infrared remote sensing include the increased availability of airborne hyperspectral imagers (such as the Hyperspectral Thermal Emission Spectrometer, HyTES, or the Telops HyperCam and the Specim aisaOWL), and it is planned that an increased number spectral bands in the long-wave infrared (LWIR) region will soon be measured from space at reasonably high spatial resolution (by imagers such as HyspIRI). Detailed LWIR emissivity spectra are required to best interpret the observations from such systems. This includes the highly heterogeneous urban environment, whose construction materials are not yet particularly well represented in spectral libraries. Here, we present a new online spectral library of urban construction materials including LWIR emissivity spectra of 74 samples of impervious surfaces derived using measurements made by a portable Fourier Transform InfraRed (FTIR) spectrometer. FTIR emissivity measurements need to be carefully made, else they are prone to a series of errors relating to instrumental setup and radiometric calibration, which here relies on external blackbody sources. The performance of the laboratory-based emissivity measurement approach applied here, that in future can also be deployed in the field (e.g. to examine urban materials in situ), is evaluated herein. Our spectral library also contains matching short-wave (VIS–SWIR) reflectance spectra observed for each urban sample. This allows us to examine which characteristic (LWIR and) spectral signatures may in future best allow for the identification and discrimination of the various urban construction materials, that often overlap with respect to their chemical/mineralogical constituents. Hyperspectral or even strongly multi-spectral LWIR information appears especially useful, given that many urban materials are composed of minerals exhibiting notable reststrahlen/absorption effects in this spectral region. The final spectra and interpretations are included in the London Urban Micromet data Archive (LUMA; http://LondonClimate.info/LUMA/SLUM.html).

Study of Blood Porphyrin Spectral Profile for Diagnosis of Chronic Renal Failure

The progression to end-stage renal failure is independent of the initial pathogenic mechanism. Metabolic acidosis is a common consequence of chronic renal failure that results from inadequate ammonium excretion and decreased tubular bicarbonate reabsorption. Protoporphyrin IX (PpIX) is the immediate metabolic precursor of the heme molecule. The purpose of this study was to evaluate the levels of erythrocytes protoporphyrin IX at an animal model during progressive renal disease. A total of 36 eight-week-old male Wistar rats were divided into six groups: Normal, 4 and 8 weeks after 5/6 nephrectomy (NX). Renal function was evaluated by creatinine clearance and plasma creatinine levels. The autofluorescence of erythrocytes porphyrin of healthy and NX rats was analyzed using fluorescence spectroscopy. Emission spectra were obtained by exciting the samples at 405 nm. Significant differences between normal and NX rats autofluorescence shape occurred in the 600-700 nm spectral region. A correlation was observed between emission band intensity at 635 nm and progression of renal disease.

Desenvolvimento de um código computacional para simulação e análise de espectros atômicos

The aim of this work was the development a computer code for simulation and analysis of atomic spectra from databases constructed from the literature. There were created four routines that can be useful for spectroscopic studies in the atomic processes of laser isotope separation. In the first routine, Possible Transitions, the program checks the possible electron transitions from an energy level of the atom present in the database considering the selection rules for an electric dipole transition. The second routine, Locator Transitions, checks the possible electronic transitions within a user-specified spectral region. The routine Spectra Simulator creates simulated spectra using the graphical application gnuplot through lorentzian curve and finally, the routine Electronic Temperature determines the temperature of electronic excitation of the atom, thought the Boltzmann Plot Method. To test the reliability of the program there were obtained experimental emission spectra of a hollow cathode discharge of dysprosium and argon as a buffer gas. The hollow cathode discharge has been subjected to different values of operating currents and pressure of inert gas. The spectra obtained were treated with the assistance of program routines developed (Transition Locator and Spectra Simulator) and temperatures electronic excitation of the atoms of dysprosium in the different discharge conditions were calculated (routine Electronic Temperature). The results showed that the electronic excitation temperature of the neutral dysprosium atoms in the hollow cathode discharge increases with increasing current applied to the cathode and also by increasing the gas pressure buffer. The determination coefficients, R2, obtained by the Electronic Temperature routine using the linear adjust of the Boltzmann Plot Method were greater... (Complete abstract click electronic access below)

Analysis Of The Dna Fourier Transform-infrared Microspectroscopic Signature Using An All-reflecting Objective.

The Fourier transform-infrared (FT-IR) signature of dry samples of DNA and DNA-polypeptide complexes, as studied by IR microspectroscopy using a diamond attenuated total reflection (ATR) objective, has revealed important discriminatory characteristics relative to the PO2(-) vibrational stretchings. However, DNA IR marks that provide information on the sample's richness in hydrogen bonds have not been resolved in the spectral profiles obtained with this objective. Here we investigated the performance of an all reflecting objective (ARO) for analysis of the FT-IR signal of hydrogen bonds in DNA samples differing in base richness types (salmon testis vs calf thymus). The results obtained using the ARO indicate prominent band peaks at the spectral region representative of the vibration of nitrogenous base hydrogen bonds and of NH and NH2 groups. The band areas at this spectral region differ in agreement with the DNA base richness type when using the ARO. A peak assigned to adenine was more evident in the AT-rich salmon DNA using either the ARO or the ATR objective. It is concluded that, for the discrimination of DNA IR hydrogen bond vibrations associated with varying base type proportions, the use of an ARO is recommended.