Rare-earth-doped optical nanothermometer in visible and near-infrared regions

With the development of optical nanothermometry in biomedical sciences, it is urgent to develop near-infrared region (NIR) nanothermometers which could detect the temperature in deep tissue levels. In this study, NaYF₄:Yb,Er@NaGdF₄:Nd nanoparticles were successfully synthesized. The luminescence properties and the mechanism of formation of dumbbell morphology of NaYF₄:Yb,Er@NaGdF₄:Nd were investigated. As a novel optical nanothermometer, dumbbell-shaped NaYF₄:Yb,Er@NaGdF₄:Nd nanoparticles exhibited high sensitivity in the visible and NIR regions. These data seem to be promising in terms of expanding the optical detection range of non-contact fluorescence temperature sensors and satisfy the requirements for temperature detection in various biological tissues.     

Stability study of flutamide in solid state and in aqueous solution

A high-performance liquid chromatography (HPLC) assay has been developed for the determination of flutamide and its degradation products. Using this method, the influence of important formulation factors on the stability of flutamide has been estimated. The stability studies have been carried out in solid state as well as in aqueous solution. The results obtained have shown a good stability for flutamide in solid state. This drug remained practically unchanged after a four-month assay in adverse temperature and humidity conditions. On the other hand, the results obtained from the stability study in solution during 12 days have shown that flutamide in aqueous solution underwent a clear degradation at mean or high temperature (22°C, 37°C) and acidic pH conditions (1.1). With respect to the influence of ionic strength, it has been found that the presence of sodium chloride prevents the degradation of flutamide in aqueous solution. The second-order kinetics model provides the best fit for highly degraded solutions.     

Diclofenac sodium: oxidative degradation in solution and solid state

The formation of two oxidative degradates of diclofenac in solution and the solid state was demonstrated.     

Ultraviolet Raman spectra and cross-sections of the G-series nerve agents

Ultraviolet (UV) Raman spectroscopy is being applied to the detection of chemical agent contamination of natural and man-made surfaces. In support of these efforts, we have measured the UV Raman signatures of the G-series nerve agents GA (tabun), GB (sarin), GD (soman), GF (cyclosarin), and the agent simulant diisopropyl methylphosphonate (DIMP) at 248 nm and 262 nm, as well as taking their UV Raman and UV absorption cross-sections. Of these chemicals, only GA exhibits any significant pre-resonance enhancement. We also show that reduction of the excitation wavelength from 262 nm to 248 nm effectively shifts the Raman spectrum away from a substantial sample fluorescence background, implying a significant improvement in detection capability.     

Optical plastic refractive measurements in the visible and the near-infrared regions

Some new refractometric results are obtained in the visible and the near-infrared spectral regions. The main optical plastics are analyzed: poly(methyl methacrylate), polystyrene, polycarbonate, and styrene acrylonitrile. New materials, such as methyl methacrylate styrene copolmer, CTE-Richardson, Zeonex, Optorez, and Bayer are examined. The refractive indices are measured for wavelengths from 435.8 to 1052 nm with a new device. Abbe constants and dispersion coefficients are calculated. The measured and computed data is intended for designers and technologists.     

Multilayer antireflection coatings for the visible and near-infrared regions

With a high-refractive-index mixed-oxide dielectric material of ZrTiO(4) and ZrO(2) [Substance H2 (Sub2) from E. Merck, Darmstadt, Germany], in combination with magnesium flouride (MgF(2)), design optimization and experimental production of low-loss antireflection (AR) coatings are carried out. Design-optimization studies that make use of these materials as constituents of a seven-layer coating system demonstrate that when the useful bandwidth of an AR coating is extended to cover a wider spectral range, the designs are in general found to have increased integrated reflection loss, higher ripple, and increased spectral instability. The experimental studies on Sub2 material show that the films have excellent optical performance over a wider process window, the advantage of which is demonstrated in the production of different AR coatings on a variety of glasses with refractive indices that range from 1.45 to 1.784 and different mechanical, thermal, and chemical properties. The manufacturing process of AR coatings shows a consistency better than 99% with respect to optical properties and durability.     

Effect of diet composition on the determination of ash and moisture content in solid cattle manure using visible and near-infrared spectroscopy

Visible and near-infrared (Vis-NIR, 350-2500 nm) diffuse reflection spectroscopy (DRS) models built from "as-collected" samples of solid cattle manure accurately predict concentrations of moisture and crude ash. Because different organic molecules emit different spectral signatures, variations in livestock diet composition may affect the predictive accuracy of these models. This study investigates how differences in livestock diet composition affect Vis-NIR DRS prediction of moisture and crude ash. Spectral signatures of solid manure samples (n = 216) from eighteen groups of cattle on six different diets were used to calibrate and validate partial least squares (PLS) regression models. Seven groups of PLS models were created and validated. In the first group, two-thirds of all samples were randomly selected as the calibration set and the remaining one-third were used for the validation set. In the remaining six groups, samples were grouped by livestock diet (ration). Each ration in turn was held out of calibrations and then used as a validation set. When predicting crude ash, the fully random calibration model produced a root mean square deviation (RMSD) of 2.5% on a dry basis (db), ratio of standard error of prediction to the root mean squared deviation (RPD) of 3.1, bias of 0.14% (db), and correlation coefficient r(2) of 0.90., When predicting moisture, an RMSD of 1.5% on a wet basis (wb), RPD of 4.3, bias of -0.09% (wb), and r(2) of 0.95 was achieved. Model accuracy and precision were not impaired by exclusion of any single ration from model calibration.     

Raman and infrared fingerprint spectroscopy of peroxide-based explosives

A comparative study of the vibrational spectroscopy of peroxide-based explosives is presented. Triacetone triperoxide (TATP) and hexamethyl-enetriperoxide-diamine (HMTD), now commonly used by terrorists, are examined as well as other peroxide-ring structures: DADP (diacetone diperoxide); TPTP [3,3,6,6,9,9-Hexaethyl-1,2,4,5,7,8-hexaoxo-nonane (tripentanone triperoxide)]; DCypDp {6,7,13,14-Tetraoxadispiro [4.2.4.2]tetradecane (dicyclopentanone diperoxide)}; TCypDp {6,7,15,16,22,23-Hexaoxatrispiro[4.2.4.2.4.2] henicosane (tricyclopentanone triperoxide)}; DCyhDp {7,8,15,16-tetraoxadispiro [5.2.5.2] hexadecane (dicyclohexanone diperoxide)}; and TCyhTp {7,8,14,15,21,22-hexaoxatrispiro [5.2.5.2.5.2] tetracosane (tricyclohexanone triperoxide)}. Both Raman and infrared (IR) spectra were measured and compared to theoretical calculations. The calculated spectra were obtained by calculation of the harmonic frequencies of the studied compounds, at the density functional theory (DFT) B3LYP/cc-pVDZ level of theory, and by the use of scaling factors. It is found that the vibrational features related to the peroxide bonds are strongly mixed. As a result, the spectrum is congested and highly sensitive to minor changes in the molecule.     

固相反应法制备纳米铈锆复合氧化物

以碳酸铈、碳酸锆、草酸为原料,机械力促进固相反应法制备了纳米级铈锆复合氧化物(CexZr1-XO2)。用TGDSC分析前驱体的热分解温度,通过XRD、TEM、BET等测试手段对产物进行了表征。结果表明:所得产物为单一的立方晶系固溶体,平均粒径<40nm,比表面积达98m2/g。采用中低温固相反应法制备纳米级铈锆复合氧化物无需溶剂,无废液且节能。     

Identification of explosives with two-dimensional ultraviolet resonance Raman spectroscopy

The first two-dimensional (2D) resonance Raman spectra of TNT, RDX, HMX, and PETN are measured with an instrument that sequentially and rapidly switches between laser wavelengths, illuminating these explosives with forty wavelengths between 210 nm and 280 nm. Two-dimensional spectra reflect variations in resonance Raman scatter with illumination wavelength, adding information not available from single or few one-dimensional spectra, thereby increasing the number of variables available for use in identification, which is especially useful in environments with contaminants and interferents. We have recently shown that 2D resonance Raman spectra can identify bacteria. Thus, a single device that identifies the presence of explosives, bacteria, and other chemicals in complex backgrounds may be feasible.     

Noninvasive detection of concealed liquid explosives using Raman spectroscopy

We present a Raman spectroscopic method for the noninvasive detection of liquid explosives within bottles, and other packaging, of substantially higher sensitivity and wider applicability than that currently available via conventional Raman spectroscopy. The approach uses a modification of the spatially offset Raman spectroscopy (SORS) concept, which permits the interrogation of a wide range of containers, including transparent, colored, and diffusely scattering plastic and glass beverage, medicine, and cosmetic bottles, with no change in experimental geometry. The enhanced sensitivity is achieved by the technique's inherent ability to effectively suppress fluorescence and Raman contributions originating from the wall of the container. The application is demonstrated on the noninvasive detection of hydrogen peroxide solution, a critical component of a number of liquid explosives. In contrast to conventional Raman spectroscopy, the modified SORS concept enables the detection of concealed hydrogen peroxide solution in all the studied cases.     

Characterization of solution and solid state properties of polyaniline processed from trifluoroacetic acid

In this work are reported properties of polyaniline processed from trifluoroacetic acid. Films obtained by simple drop casting were smooth and defectless. Features like absorption in range of UV–vis-NIR, mid-IR and electrical conductivity are discussed. The highest electrical conductivity of such films was found equal to 65?S/cm. It was observed a striking feature—successive colour transition from cyan to deep green when the solvent was dried out from the cast film.     

Application of near-infrared spectroscopy in the pharmaceutical solid dosage form

Near-infrared (NIR) spectroscopy, one of the most rapidly growing methodologies in pharmaceutical analysis, has been used to analyze the pharmaceutical solid dosage form. The objective of this study was to examine the information that can be gathered from NIR spectroscopy and demonstrate the potential utility of the technique as an alternative to current methods of tablet performance testing. The tablet formulation included active drug (acetaminophen or theophylline), binder (hydroxyethylcellulose), filler (lactose, calcium sulfate, dibasic calcium phosphate dihydrate, or microcrystalline cellulose), and lubricant (magnesium stearate). The compression forces were varied from 5 to 25 kN. A Foss/NIRSystems scanning near-infrared spectrometer was used to measure the diffuse reflectance from the tablet surface. Each tablet was scanned on opposite sides to reduce the effects of positioning. First derivative and multiplicative scatter correction data treatments were explored. A calibration for compression force, independent of the filler, was developed. In addition, the spectra were able to distinguish among the fillers used. A comparison of these spectra with data collected earlier suggests that the technique could differentiate among drugs as well. Near-infrared diffuse reflection spectroscopy, when properly calibrated, can determine the compression force used to prepare a tablet. This measurement may be independent of the different active drugs or fillers used in the tablet formulations.     

Multispectral decomposition for the removal of out-of-band effects of visible/infrared imaging radiometer suite visible and near-infrared bands

The visible/infrared imaging radiometer suite (VIIRS) is now onboard the first satellite platform managed by the Joint Polar Satellite System of the National Oceanic and Atmospheric Administration and NASA. It collects scientific data from an altitude of approximately 830 km in 22 narrow bands located in the 0.4-12.5 μm range. The seven visible and near-infrared (VisNIR) bands in the wavelength interval between 0.4-0.9 μm are known to suffer from the out-of-band (OOB) responses--a small amount of radiances far away from the center of a given band that can pass through the filter and reach detectors in the focal plane. A proper treatment of the OOB effects is necessary in order to obtain calibrated at-sensor radiance data [referred to as the Sensor Data Records (SDRs)] from measurements with these bands and subsequently to derive higher-level data products [referred to as the Environmental Data Records (EDRs)]. We have recently developed a new technique, called multispectral decomposition transform (MDT), which can be used to correct/remove the OOB effects of VIIRS VisNIR bands and to recover the true narrow band radiances from the measured radiances containing OOB effects. An MDT matrix is derived from the laboratory-measured filter transmittance functions. The recovery of the narrow band signals is performed through a matrix multiplication--the production between the MDT matrix and a multispectral vector. Hyperspectral imaging data measured from high altitude aircraft and satellite platforms, the complete VIIRS filter functions, and the truncated VIIRS filter functions to narrower spectral intervals, are used to simulate the VIIRS data with and without OOB effects. Our experimental results using the proposed MDT method have demonstrated that the average errors after decomposition are reduced by more than one order of magnitude.     

In-plane switching of cholesteric liquid crystals for visible and near-infrared applications

We have investigated the in-plane switching of cholesteric liquid crystals for reflective wavelength shifters for visible and near-infrared applications. These devices are based on the elongation of the cholesteric pitch by an electric field perpendicular to the helical axis. The transmission notch-reflection peak position can be tuned continuously to a longer wavelength (redshift) by application of an in-plane electric field. The helix is completely unwound when the electric field is higher than the cholesteric-to-nematic transition field, and the sample is transformed to a transparent state. We have investigated the electro-optic performance of in-plane switching of cholesteric samples and developed a simple phenomenological model to describe the underlying electro-optic phenomena.     

Stand-off detection of explosives particles by multispectral imaging Raman spectroscopy

A Raman multispectral imaging technique is presented, which can be used for stand-off detection of single explosives particles. A frequency-doubled Nd:YAG laser operating at 10 Hz illuminates the surface under investigation. The backscattered Raman signal is collected by a receiver subsystem consisting of a 150 mm Schmidt-Cassegrain telescope, a laser line edge filter, a liquid-crystal tunable filter, and a gated intensified charge-coupled device (ICCD) detector. A sequence of images is recorded by the ICCD, where, for each recording, a different wavelength is selected by the tunable filter. By this, a Raman spectrum is recorded for each pixel, which makes it possible to detect even single particles when compared to known spectra for possible explosives. The comparison is made using correlation and least-square fitting. The system is relatively insensitive to environment and light variations. Multispectral Raman images of sulfur, ammonium nitrate, 2,4-dinitrotoluene, and 2,4,6-trinitrotoluene were acquired at a stand-off distance of 10 m. Detection of sulfur particles was done at a distance of 10 m.     

Temperature-dependent refractive index of potassium acid phthalate (KAP) in the visible and near-infrared

We report an investigation of the temperature-dependence of the refractive index of potassium acid phthalate (KAP) crystal. Refractive index measurements are based on a refractometer setup operating in a temperature range from 25 °C to 200 °C and using five different laser wavelengths in the visible and near-infrared. Temperature-dependent dispersion relations are proposed, with an average fitting quality that exceeds experimental accuracy, and compared to previous room-temperature Sellmeier equations. Consequently, the new relations are employed for the calculation of various linear and nonlinear optical properties of KAP.     

Comparison of near-infrared and laser-induced breakdown spectroscopy for determination of magnesium stearate in pharmaceutical powders and solid dosage forms

Near-infrared (NIR) spectroscopy has become well established in both the pharmaceutical arena and other areas as a useful technique for rapid quantitative analysis of solid materials. Though laser-induced breakdown spectroscopy (LIBS) has not been widely applied in the pharmaceutical industry, the technique has been used for rapid quantitative analysis of solids in many other applications. One analysis amenable to each technique is the determination of magnesium stearate in solids during the lubrication blending unit operation of pharmaceutical processing. A comparative study of the utility of these two techniques for this application will be presented. Necessary sample preparations and the extent and type of matrix effects will be discussed. Additionally, it will be shown that NIR provides better accuracy and precision than LIBS with the experimental parameters used; however, LIBS showed superior selectivity as it was demonstrated to be more robust to sample matrix perturbations. Examples of blending applications will also be presented.