Alternative difference analysis scheme combining R-space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy.

PubMed

Zhan, Fei; Tao, Ye; Zhao, Haifeng

2017-07-01

Time-resolved X-ray absorption spectroscopy (TR-XAS), based on the laser-pump/X-ray-probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here, a new analysis scheme is presented for the TR-XAS difference fitting in both the extended X-ray absorption fine-structure (EXAFS) and the X-ray absorption near-edge structure (XANES) regions. R-space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non-derivative optimization algorithm and optimizes the local structure change in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen) 3 spin crossover complex and yielded reliable distance change and excitation population.

INFRARED TRANSMISSION SPECTROSCOPY OF THE EXOPLANETS HD 209458b AND XO-1b USING THE WIDE FIELD CAMERA-3 ON THE HUBBLE SPACE TELESCOPE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deming, Drake; Wilkins, Ashlee; McCullough, Peter

Exoplanetary transmission spectroscopy in the near-infrared using the Hubble Space Telescope (HST) NICMOS is currently ambiguous because different observational groups claim different results from the same data, depending on their analysis methodologies. Spatial scanning with HST/WFC3 provides an opportunity to resolve this ambiguity. We here report WFC3 spectroscopy of the giant planets HD 209458b and XO-1b in transit, using spatial scanning mode for maximum photon-collecting efficiency. We introduce an analysis technique that derives the exoplanetary transmission spectrum without the necessity of explicitly decorrelating instrumental effects, and achieves nearly photon-limited precision even at the high flux levels collected in spatial scanmore » mode. Our errors are within 6% (XO-1) and 26% (HD 209458b) of the photon-limit at a resolving power of {lambda}/{delta}{lambda} {approx} 70, and are better than 0.01% per spectral channel. Both planets exhibit water absorption of approximately 200 ppm at the water peak near 1.38 {mu}m. Our result for XO-1b contradicts the much larger absorption derived from NICMOS spectroscopy. The weak water absorption we measure for HD 209458b is reminiscent of the weakness of sodium absorption in the first transmission spectroscopy of an exoplanet atmosphere by Charbonneau et al. Model atmospheres having uniformly distributed extra opacity of 0.012 cm{sup 2} g{sup -1} account approximately for both our water measurement and the sodium absorption. Our results for HD 209458b support the picture advocated by Pont et al. in which weak molecular absorptions are superposed on a transmission spectrum that is dominated by continuous opacity due to haze and/or dust. However, the extra opacity needed for HD 209458b is grayer than for HD 189733b, with a weaker Rayleigh component.« less

Infrared Transmission Spectroscopy of the Exoplanets HD 209458b and XO-1b Using the Wide Field Camera-3 on the Hubble Space Telescope

NASA Astrophysics Data System (ADS)

Deming, Drake; Wilkins, Ashlee; McCullough, Peter; Burrows, Adam; Fortney, Jonathan J.; Agol, Eric; Dobbs-Dixon, Ian; Madhusudhan, Nikku; Crouzet, Nicolas; Desert, Jean-Michel; Gilliland, Ronald L.; Haynes, Korey; Knutson, Heather A.; Line, Michael; Magic, Zazralt; Mandell, Avi M.; Ranjan, Sukrit; Charbonneau, David; Clampin, Mark; Seager, Sara; Showman, Adam P.

2013-09-01

Exoplanetary transmission spectroscopy in the near-infrared using the Hubble Space Telescope (HST) NICMOS is currently ambiguous because different observational groups claim different results from the same data, depending on their analysis methodologies. Spatial scanning with HST/WFC3 provides an opportunity to resolve this ambiguity. We here report WFC3 spectroscopy of the giant planets HD 209458b and XO-1b in transit, using spatial scanning mode for maximum photon-collecting efficiency. We introduce an analysis technique that derives the exoplanetary transmission spectrum without the necessity of explicitly decorrelating instrumental effects, and achieves nearly photon-limited precision even at the high flux levels collected in spatial scan mode. Our errors are within 6% (XO-1) and 26% (HD 209458b) of the photon-limit at a resolving power of λ/δλ ~ 70, and are better than 0.01% per spectral channel. Both planets exhibit water absorption of approximately 200 ppm at the water peak near 1.38 μm. Our result for XO-1b contradicts the much larger absorption derived from NICMOS spectroscopy. The weak water absorption we measure for HD 209458b is reminiscent of the weakness of sodium absorption in the first transmission spectroscopy of an exoplanet atmosphere by Charbonneau et al. Model atmospheres having uniformly distributed extra opacity of 0.012 cm2 g-1 account approximately for both our water measurement and the sodium absorption. Our results for HD 209458b support the picture advocated by Pont et al. in which weak molecular absorptions are superposed on a transmission spectrum that is dominated by continuous opacity due to haze and/or dust. However, the extra opacity needed for HD 209458b is grayer than for HD 189733b, with a weaker Rayleigh component.

CuInGaSe{sub 2} nanoparticles by pulsed laser ablation in liquid medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mendivil, M.I.; García, L.V.; Krishnan, B.

2015-12-15

Highlights: • CIGS nanocolloids were synthesized using PLAL technique. • Characterized their morphology, structure, composition and optical properties. • Morphologies were dependent on ablation wavelength and liquid medium. • Optical absorption and bandgap of these nanocolloids were tunable. - Abstract: Pulsed laser ablation in liquid medium (PLALM) is a nanofabrication technique to produce complex nanostructures. CuInGaSe{sub 2} (CIGS) is an alloy with applications in photovoltaic industry. In this work, we studied the effects of laser ablation wavelength, energy fluence and liquid medium on the properties of the CIGS nanoparticles synthesized by PLALM. The nanoparticles obtained were analyzed by transmission electronmore » microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), selected area electron diffraction (SAED), X-ray photoelectron spectroscopy (XPS) and UV–vis absorption spectroscopy. XPS results confirmed the chemical states and composition of the ablated products. TEM analysis showed different morphologies for the nanomaterials obtained in different liquid media and ablation wavelengths. The optical properties for these CIGS nanocolloids were analyzed using UV–vis absorption spectroscopy. The results demonstrated the use of PLALM as a useful synthesis technique for nanoparticles of quaternary photovoltaic materials.« less

Low-lying singlet states of carotenoids having 8-13 conjugated double bonds as determined by electronic absorption spectroscopy

NASA Astrophysics Data System (ADS)

Wang, Peng; Nakamura, Ryosuke; Kanematsu, Yasuo; Koyama, Yasushi; Nagae, Hiroyoshi; Nishio, Tomohiro; Hashimoto, Hideki; Zhang, Jian-Ping

2005-07-01

Electronic absorption spectra were recorded at room temperature in solutions of carotenoids having different numbers of conjugated double bonds, n = 8-13, including a spheroidene derivatives, neurosporene, spheroidene, lycopene, anhydrorhodovibrin and spirilloxanthin. The vibronic states of 1Bu+(v=0-4), 2Ag-(v=0-3), 3Ag- (0) and 1Bu- (0) were clearly identified. The arrangement of the four electronic states determined by electronic absorption spectroscopy was identical to that determined by measurement of resonance Raman excitation profiles [K. Furuichi et al., Chem. Phys. Lett. 356 (2002) 547] for carotenoids in crystals.

Characterization and structural properties of iron in plants.

NASA Astrophysics Data System (ADS)

Dewanamuni, Udya; Dehipawala, Sunil; Gafney, Harry

Iron is one of the most abundant metals in the soil and occurs in a wide range of chemical forms. Humans receive iron through either meat products or plants. Non meat eaters depend on plant product for their daily iron requirement. The iron absorption by plants depends on other minerals present in the soil and soil pH value. The amount of iron present in plants grown with different soil compositions were investigated using X-ray absorption spectroscopy (XAS) and Mossbauer spectroscopy. Based on the X-ray absorption data, the amount of iron in plants vary significantly with soil pH value. The Mossbauer spectroscopy reveals that iron present in the samples has the form Fe3+ or electron density at the site of the iron nucleus similar to that of Fe3+. CUNY Research Scholar Program, MSEIP.

In situ differential reflectance spectroscopy of thin crystalline films of PTCDA on different substrates

NASA Astrophysics Data System (ADS)

Proehl, Holger; Nitsche, Robert; Dienel, Thomas; Leo, Karl; Fritz, Torsten

2005-04-01

We report an investigation of the excitonic properties of thin crystalline films of the archetypal organic semiconductor PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) grown on poly- and single crystalline surfaces. A sensitive setup capable of measuring the optical properties of ultrathin organic molecular crystals via differential reflectance spectroscopy (DRS) is presented. This tool allows to carry out measurements in situ, i.e., during the actual film growth, and over a wide spectral range, even on single crystalline surfaces with high symmetry or metallic surfaces, where widely used techniques like reflection anisotropy spectroscopy (RAS) or fluorescence excitation spectroscopy fail. The spectra obtained by DRS resemble mainly the absorption of the films if transparent substrates are used, which simplifies the analysis. In the case of mono- to multilayer films of PTCDA on single crystalline muscovite mica(0001) and Au(111) substrates, the formation of the solid state absorption from monomer to dimer and further to crystal-like absorption spectra can be monitored.

[Infrared spectroscopy and XRD studies of coral fossils].

PubMed

Chen, Quan-li; Zhou, Guan-min; Yin, Zuo-wei

2012-08-01

Coral fossil is an old remain of multicellular animal on the earth, and formed by various geological processes. The structural characteristics and compositions of the coral fossils with different color and radial texture on the surface were studied by infrared absorption spectroscopy and X-ray powder diffraction analyses. The results show that the studied coral fossils mainly are composed of SiO2, and the radial microstructure characterized by the calcareous coral cross-section is preserved. It is formed by metasomatism by SiO2. The infrared absorption spectra of the coral fossil with different color and texture are essentially the same, showing typical infrared absorption spectra of the quartz jade. XRD analysis shows that the main components of the coral fossils with different color and texture are consistent and mainly composed of SiO2 with a trace amount of other minerals and without CaCO3.

Investigation of periodically driven systems by x-ray absorption spectroscopy using asynchronous data collection mode

NASA Astrophysics Data System (ADS)

Singh, H.; Donetsky, D.; Liu, J.; Attenkofer, K.; Cheng, B.; Trelewicz, J. R.; Lubomirsky, I.; Stavitski, E.; Frenkel, A. I.

2018-04-01

We report the development, testing, and demonstration of a setup for modulation excitation spectroscopy experiments at the Inner Shell Spectroscopy beamline of National Synchrotron Light Source - II. A computer algorithm and dedicated software were developed for asynchronous data processing and analysis. We demonstrate the reconstruction of X-ray absorption spectra for different time points within the modulation pulse using a model system. This setup and the software are intended for a broad range of functional materials which exhibit structural and/or electronic responses to the external stimulation, such as catalysts, energy and battery materials, and electromechanical devices.

[The Study on the Far-FTIR and THz Spectra of Azitromycin Drugs with Different Physical Forms].

PubMed

Yang, Yu-ping; Fan, Li-jie; Cui, Bin; Chen, Gen-xiang; Zhang, Zhen-wei; Zhang, Cun-lin

2015-11-01

Far Fourier transform infrared spectroscopy (Far-FTIR) and terahertz time-domain spectroscopy (THz-TDS) were used to measure the fingerprint spectra of Azitromycin suspension, capsule, tablet and dispersible tablet under vacuum and nitrogen conditions, respectively. In the frequency range of 0.2-15 THz, highly resolved spectral features for Azitromycin suspension were measured and some minor differences were observed between domestic and exotic Azitromycin Suspension, such as linewidth broadening and additional peaks. As same time, for the domestic Azitromycin capsule, tablet and dispersible tablet, the absorption baselines in the range of 0.2-2.7 THz rise with the increase of frequency while absorption peaks become weaker due to the scattering of bigger particles and smaller amount of Azitromycin. Also, the additional peaks are caused by the absorption of filling materials. In parallel with the qualitative measurement, the THz absorption spectra for mixtures of polyethylene (PE) powders and exotic Azithomycin suspension with different concentrations were also measured. According to the linear correlation between the concentration and the absorption intensity, the concentration of effective component can be evaluated accurately. This means that THz-TDS method is suitable for the quality inspection and evaluation of the mixed Azithromycin system.

Basic Principles of Spectroscopy

NASA Astrophysics Data System (ADS)

Penner, Michael H.

Spectroscopy deals with the production, measurement, and interpretation of spectra arising from the interaction of electromagnetic radiation with matter. There are many different spectroscopic methods available for solving a wide range of analytical problems. The methods differ with respect to the species to be analyzed (such as molecular or atomic spectroscopy), the type of radiation-matter interaction to be monitored (such as absorption, emission, or diffraction), and the region of the electromagnetic spectrum used in the analysis. Spectroscopic methods are very informative and widely used for both quantitative and qualitative analyses. Spectroscopic methods based on the absorption or emission of radiation in the ultraviolet (UV), visible (Vis), infrared (IR), and radio (nuclear magnetic resonance, NMR) frequency ranges are most commonly encountered in traditional food analysis laboratories. Each of these methods is distinct in that it monitors different types of molecular or atomic transitions. The basis of these transitions is explained in the following sections.

Characterization of erythrosine B binding to bovine serum albumin and bilirubin displacement.

PubMed

Mathavan, Vinodaran M K; Boh, Boon Kim; Tayyab, Saad

2009-08-01

The interaction of crythrosine B (ErB), a commonly used dye for coloring foods and drinks, with bovine scrum albumin (BSA) was investigated both in the absence and presence of bilirubin (BR) using absorption and absorption difference spectroscopy. ErB binding to BSA was reflected from a significant red shift of 11 nm in the absorption maximum of ErB (527 nm) with the change in absorbance at lamdamax. Analysis of absorption difference spectroscopic titration results of BSA with increasing concentrations of ErB3 using Benesi-Hildebrand equation gave the association constant, K as 6.9 x 10(4) M(-1). BR displacing action of ErB was revealed by a significant blue shift in the absorption maximum, accompanied by a decrease in absorbance difference at lamdamax in the difference spectrum of BR-BSA complex upon addition of increasing concentrations of ErB. This was further substantiated by fluorescence spectroscopy, as addition of increasing concentrations of ErB to BR-BSA complex caused a significant decrease in fluoresccnce at 510 nm. The results suggest that ErB binds to a site in the vicinity of BR binding site on BSA. Therefore, intake of ErB may increase the risk of hyperbilirubinemia in the healthy subjects.

Applications of absorption spectroscopy using quantum cascade lasers.

PubMed

Zhang, Lizhu; Tian, Guang; Li, Jingsong; Yu, Benli

2014-01-01

Infrared laser absorption spectroscopy (LAS) is a promising modern technique for sensing trace gases with high sensitivity, selectivity, and high time resolution. Mid-infrared quantum cascade lasers, operating in a pulsed or continuous wave mode, have potential as spectroscopic sources because of their narrow linewidths, single mode operation, tunability, high output power, reliability, low power consumption, and compactness. This paper reviews some important developments in modern laser absorption spectroscopy based on the use of quantum cascade laser (QCL) sources. Among the various laser spectroscopic methods, this review is focused on selected absorption spectroscopy applications of QCLs, with particular emphasis on molecular spectroscopy, industrial process control, combustion diagnostics, and medical breath analysis.

Site partitioning of Cr3+ in the trichroic alexandrite BeAl2O4:Cr3+ crystal: contribution from x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Bordage, Amélie; Rossano, Stéphanie; Horn, Adolf Heinrich; Fuchs, Yves

2012-06-01

X-ray absorption spectroscopy measurements at the Cr K-edge of a trichroic crystal of alexandrite BeAl2O4:Cr3+ for different orientations of the crystal with respect to the polarization and direction of the x-ray incident beam have been performed. Analysis of the experimental spectra with the help of first-principles calculations of x-ray absorption spectra allowed us to estimate the proportion of chromium Cr3+ cations among the two different octahedral sites of the alexandrite structure (70% in the Cs site-30% in the Ci site). The methodology presented in this work opens up new possibilities in the field of mineralogy for the study of complex minerals containing several sites potentially occupied by several transition elements or for solid solutions.

Research on differences between 2-(2‧-pyridyl)benzimidazole and 2-(4‧-pyridyl)benzimidazole based on terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Song, Maojiang; Yang, Fei; Liu, Liping; Su, Caixia

2018-02-01

Due to the important pharmaceutical activities of benzimidazole derivatives, the differences between 2-(2‧-pyridyl)benzimidazole and 2-(4‧-pyridyl)benzimidazole were researched by terahertz time-domain spectroscopy and density functional theory systematically. Although the only difference between their molecular configurations is the different arrangement of nitrogen on pyridine ring, 2PBI and 4PBI have large differences in their experimental absorption spectra in the range of 0.2-2.5 THz, such as the amount, amplitude and frequency position of absorption peaks. The validity of these results was confirmed by the theoretical results simulated using density functional theory. The possible reasons of these differences originate from the different dihedral angles between benzimidazole ring and pyridine ring and the different hydrogen-bonding interactions within crystal cell.

Effects of γ-ray irradiation on optical absorption and laser damage performance of KDP crystals containing arsenic impurities.

PubMed

Guo, D C; Jiang, X D; Huang, J; Wang, F R; Liu, H J; Xiang, X; Yang, G X; Zheng, W G; Zu, X T

2014-11-17

The effects of γ-irradiation on potassium dihydrogen phosphate crystals containing arsenic impurities are investigated with different optical diagnostics, including UV-VIS absorption spectroscopy, photo-thermal common-path interferometer and photoluminescence spectroscopy. The optical absorption spectra indicate that a new broad absorption band near 260 nm appears after γ-irradiation. It is found that the intensity of absorption band increases with the increasing irradiation dose and arsenic impurity concentration. The simulation of radiation defects show that this absorption is assigned to the formation of AsO₄⁴⁻ centers due to arsenic ions substituting for phosphorus ions. Laser-induced damage threshold test is conducted by using 355 nm nanosecond laser pulses. The correlations between arsenic impurity concentration and laser induced damage threshold are presented. The results indicate that the damage performance of the material decreases with the increasing arsenic impurity concentration. Possible mechanisms of the irradiation-induced defects formation under γ-irradiation of KDP crystals are discussed.

The effect of water absorption on the dielectric properties of polyethylene hexagonal boron nitride nanocomposites

NASA Astrophysics Data System (ADS)

Ayoob, Raed; Alhabill, Fuad N.; Andritsch, Thomas; Vaughan, Alun S.

2018-02-01

The effect of water absorption on the dielectric response of polyethylene/hexagonal boron nitride nanocomposites has been studied by dielectric spectroscopy. The nanocomposites have been prepared with hBN concentrations ranging from 2 wt% to 30 wt%. Fourier transform infrared spectroscopy and thermogravimetric analysis revealed a very small amount of hydroxyl groups on the surface of hBN. Mass loss measurements showed that the nanocomposites did not absorb any water under ambient and dry conditions while there was some water absorption under wet conditions. The dielectric spectroscopy results showed a broad relaxation peak, indicative of different states of water with water shells of different thickness, which moved to higher frequencies with increasing water content. However, the dielectric losses were significantly lower than the losses reported in the literature of nanocomposites under wet conditions. In addition, all the absorbed water was successfully removed under vacuum conditions which demonstrated that the interactions between the water and the nanocomposites were very weak, due to the hydrophobic nature of the hBN surface. This is a highly useful property, when considering these materials for applications in electrical insulation.

Pathlength Determination for Gas in Scattering Media Absorption Spectroscopy

PubMed Central

Mei, Liang; Somesfalean, Gabriel; Svanberg, Sune

2014-01-01

Gas in scattering media absorption spectroscopy (GASMAS) has been extensively studied and applied during recent years in, e.g., food packaging, human sinus monitoring, gas diffusion studies, and pharmaceutical tablet characterization. The focus has been on the evaluation of the gas absorption pathlength in porous media, which a priori is unknown due to heavy light scattering. In this paper, three different approaches are summarized. One possibility is to simultaneously monitor another gas with known concentration (e.g., water vapor), the pathlength of which can then be obtained and used for the target gas (e.g., oxygen) to retrieve its concentration. The second approach is to measure the mean optical pathlength or physical pathlength with other methods, including time-of-flight spectroscopy, frequency-modulated light scattering interferometry and the frequency domain photon migration method. By utilizing these methods, an average concentration can be obtained and the porosities of the material are studied. The last method retrieves the gas concentration without knowing its pathlength by analyzing the gas absorption line shape, which depends upon the concentration of buffer gases due to intermolecular collisions. The pathlength enhancement effect due to multiple scattering enables also the use of porous media as multipass gas cells for trace gas monitoring. All these efforts open up a multitude of different applications for the GASMAS technique. PMID:24573311

Characterization of CuHal-intercalated carbon nanotubes with x-ray absorption spectroscopy combined with x-ray photoelectron and resonant photoemission spectroscopies

NASA Astrophysics Data System (ADS)

Brzhezinskaya, M.; Generalov, A.; Vinogdradov, A.; Eliseev, A.

2013-04-01

Encapsulated single-walled carbon nanotubes (SWCNTs) with inner channels filled by different compounds present the new class of composite materials. Such CNTs give opportunity to form 1D nanocrystals as well as quantum nanowires with new physical and chemical properties inside the tubes. The present study is aimed to characterize the possible chemical interaction between CuHal (Hal=I, Cl, Br) and SWCNTs in CuHal@SWCNTs and electronic structure of the latter using high-resolution near edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with high-resolution X-ray photoelectron spectroscopy and resonant photoemission spectroscopy. The present study has shown that there is a chemical interaction between the filler and π-electron subsystem of CNTs which is accompanied by changes of the atomic and electronic structure of the filler during the encapsulating it inside CNTs.

Disentangling atomic-layer-specific x-ray absorption spectra by Auger electron diffraction spectroscopy

NASA Astrophysics Data System (ADS)

Matsui, Fumihiko; Matsushita, Tomohiro; Kato, Yukako; Hashimoto, Mie; Daimon, Hiroshi

2009-11-01

In order to investigate the electronic and magnetic structures of each atomic layer at subsurface, we have proposed a new method, Auger electron diffraction spectroscopy, which is the combination of x-ray absorption spectroscopy (XAS) and Auger electron diffraction (AED) techniques. We have measured a series of Ni LMM AED patterns of the Ni film grown on Cu(001) surface for various thicknesses. Then we deduced a set of atomic-layer-specific AED patterns in a numerical way. Furthermore, we developed an algorithm to disentangle XANES spectra from different atomic layers using these atomic-layer-specific AED patterns. Surface and subsurface core level shift were determined for each atomic layer.

Terahertz time-domain spectroscopy of submonolayer water adsorption in hydrophilic silica aerogel.

PubMed

Zhang, Jiangquan; Grischkowsky, Daniel

2004-05-01

We report a terahertz time-domain spectroscopy study of the adsorption of water in hydrophilic silica aerogel. The adsorbed water is in submonolayer form and shows properties of index of refraction similar to those of bulk water but different absorption properties.

The influence of a salivary coating on the molecular surface composition of oral streptococci as determined by Fourier transform infrared spectroscopy

NASA Astrophysics Data System (ADS)

van der Mei, H. C.; Noordmans, J.; Busscher, H. J.

In order to determine the influence of saliva treatment on the molecular surface composition of oral streptococci, infrared transmission spectroscopy on freeze-dried cells mixed in KBr was used. All IR spectra show similar absorption bands for the saliva-coated and uncoated strains involved, with the most important absorption bands located at 2930cm -1 (CH), 1653 cm -1 (AmI), 1541 cm -1 (AmII) and two bands at 1236 cm -1 and 1082cm -1, which were assigned to phosphate and sugar groups. However, calculation of absorption band ratios normalized with respect to the CH band around 2930cm -1, showed major differences between the saliva-coated and uncoated strains. All strains demonstrated an increase in the AmI/CH and AmII/CH absorption band ratios after saliva treatment indicative for protein adsorption, except for Streptococcus mitis BA showing a small decrease in the AmI/CH absorption band ratio. Two positive relationships could furthermore be established both between the AmII/CH absorption band ratio with the N/C elemental surface concentration ratio of the strains, previously determined from X-ray Photoelectron Spectroscopy (XPS) as well as between AmI/CH with the fraction of carbon atoms at the surface involved in amide bonds, also determined by XPS. This study clearly demonstrates the possibility of IR spectroscopy to determine the molecular surface properties of freeze-dried micro-organisms, as illustrated here from a comparison between the molecular composition of untreated and saliva-treated oral streptococcal strains.

Determination of Calcium in Cereal with Flame Atomic Absorption Spectroscopy: An Experiment for a Quantitative Methods of Analysis Course

ERIC Educational Resources Information Center

Bazzi, Ali; Kreuz, Bette; Fischer, Jeffrey

2004-01-01

An experiment for determination of calcium in cereal using two-increment standard addition method in conjunction with flame atomic absorption spectroscopy (FAAS) is demonstrated. The experiment is intended to introduce students to the principles of atomic absorption spectroscopy giving them hands on experience using quantitative methods of…

A spirooxazine derivative as a highly sensitive cyanide sensor by means of UV-visible difference spectroscopy.

PubMed

Zhu, Shaoyin; Li, Minjie; Sheng, Lan; Chen, Peng; Zhang, Yumo; Zhang, Sean Xiao-An

2012-12-07

A spirooxazine derivative 2-nitro-5a-(2-(4-dimethylaminophenyl)-ethylene)-6,6-dimethyl-5a,6-dihydro-12H-indolo[2,1-b][1,3]benzooxazine (P1) was explored as a sensitive cyanide probe. Different from conventional spiropyrans, P1 avoided locating the 3H-indolium cation and the 4-nitrophenolate anion in the same conjugated structure, which enhanced the positive charge of 3H-indolium cation so that the sensitivity and reaction speed were improved highly. UV-visible difference spectroscopy using P1 detection solution as a timely reference improved the measurement accuracy, prevented the error caused by the inherent absorption change of P1 solution with time. This enabled the "positive-negative alternative absorption peaks" in difference spectrum to be used as a finger-print to distinguish whether the spectral change was caused by cyanide. Benefiting from the special design of the molecular structure and the strategy of difference spectroscopy, P1 showed high selectivity and sensitivity for CN(-). A detection limit of 0.4 μM and a rate constant of 1.1 s(-1) were achieved.

40 CFR Appendix G to Part 50 - Reference Method for the Determination of Lead in Suspended Particulate Matter Collected From...

Code of Federal Regulations, 2010 CFR

2010-07-01

... Absorption Spectroscopy.” Published by Interscience Company, New York, NY (1968). 5. Kirkbright, G. F., and Sargent, M., “Atomic Absorption and Fluorescence Spectroscopy.” Published by Academic Press, New York, NY... County, IL, by Atomic Absorption Spectroscopy.” Envir. Sci. and Tech., 3, 472-475 (1969). 7. “Proposed...

Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy

DOE PAGES

Sneeden, Eileen Y.; Hackett, Mark J.; Cotelesage, Julien J. H.; ...

2017-07-27

Sulfur-based thiyl radicals are known to be involved in a wide range of chemical and biological processes, but they are often highly reactive, which makes them difficult to observe directly. We report herein X-ray absorption spectra and analysis that support the direct observation of two different thiyl species generated photochemically by X-ray irradiation. The thiyl radical sulfur K-edge X-ray absorption spectra of both species are characterized by a uniquely low energy transition at about 2465 eV, which occurs at a lower energy than any previously observed feature at the sulfur K-edge and corresponds to a 1s → 3p transition tomore » the singly occupied molecular orbital of the free radical. In conclusion, our results constitute the first observation of substantial levels of thiyl radicals generated by X-ray irradiation and detected by sulfur K-edge X-ray absorption spectroscopy.« less

Hyperspectral photoacoustic spectroscopy of highly-absorbing samples for diagnostic ocular imaging applications

NASA Astrophysics Data System (ADS)

Lim, Hoong-Ta; Murukeshan, Vadakke Matham

2017-01-01

Photoacoustic spectroscopy has been used to measure optical absorption coefficient and the application of tens of wavelength bands in photoacoustic spectroscopy was reported. Using optical methods, absorption-related information is, generally, derived from reflectance or transmittance values. Hence measurement accuracy is limited for highly absorbing samples where the reflectance or transmittance is too low to give reasonable signal-to-noise ratio. In this context, this paper proposes and illustrates a hyperspectral photoacoustic spectroscopy system to measure the absorption-related properties of highly absorbing samples directly. The normalized optical absorption coefficient spectrum of the highly absorbing iris is acquired using an optical absorption coefficient standard. The proposed concepts and the feasibility of the developed diagnostic medical imaging system are demonstrated using fluorescent microsphere suspensions and porcine eyes as test samples.

Electrical and absorption properties of fresh cassava tubers and cassava starch

NASA Astrophysics Data System (ADS)

Harnsoongnoen, S.; Siritaratiwat, A.

2015-09-01

The objective of this study was to analyze the electrical and absorption properties of fresh cassava tubers and cassava starch at various frequencies using electric impedance spectroscopy and near-infrared spectroscopy, as well as determine the classification of the electrical parameters of both materials using the principle component analysis (PCA) method. All samples were measured at room temperature. The electrical and absorption parameters consisted of dielectric constant, dissipation factor, parallel capacitance, resistance, reactance, impedance and absorbance. It was found that the electrical and absorption properties of fresh cassava tubers and cassava starch were a function of frequency, and there were significant differences between the materials. The dielectric constant, parallel capacitance, resistance and impedance of fresh cassava tubers and cassava starch had similar dramatic decreases with increasing frequency. However, the reactance of both materials increased with an increasing frequency. The electrical parameters of both materials could be classified into two groups. Moreover, the dissipation factor and phase of impedance were the parameters that could be used in the separation of both materials. According to the absorbance patterns of the fresh cassava tubers and cassava starch, there were significant differences.

Quantitative analyses of tartaric acid based on terahertz time domain spectroscopy

NASA Astrophysics Data System (ADS)

Cao, Binghua; Fan, Mengbao

2010-10-01

Terahertz wave is the electromagnetic spectrum situated between microwave and infrared wave. Quantitative analysis based on terahertz spectroscopy is very important for the application of terahertz techniques. But how to realize it is still under study. L-tartaric acid is widely used as acidulant in beverage, and other food, such as soft drinks, wine, candy, bread and some colloidal sweetmeats. In this paper, terahertz time-domain spectroscopy is applied to quantify the tartaric acid. Two methods are employed to process the terahertz spectra of different samples with different content of tartaric acid. The first one is linear regression combining correlation analysis. The second is partial least square (PLS), in which the absorption spectra in the 0.8-1.4THz region are used to quantify the tartaric acid. To compare the performance of these two principles, the relative error of the two methods is analyzed. For this experiment, the first method does better than the second one. But the first method is suitable for the quantitative analysis of materials which has obvious terahertz absorption peaks, while for material which has no obvious terahertz absorption peaks, the second one is more appropriate.

Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering spectroscopy below 100 eV: probing first-row transition-metal M-edges in chemical complexes

PubMed Central

Wang, Hongxin; Young, Anthony T.; Guo, Jinghua; Cramer, Stephen P.; Friedrich, Stephan; Braun, Artur; Gu, Weiwei

2013-01-01

X-ray absorption and scattering spectroscopies involving the 3d transition-metal K- and L-edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M-edges, which are below 100 eV. Synchrotron-based X-ray sources can have higher energy resolution at M-edges. M-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) could therefore provide complementary information to K- and L-edge spectroscopies. In this study, M 2,3-edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M 2,3-edge RIXS on NiO, NiF2 and two other covalent complexes have been performed and different d–d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M-edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high-sensitivity and high-resolution superconducting tunnel junction X-ray detectors below 100 eV is also illustrated and discussed. PMID:23765304

Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering spectroscopy below 100 eV: probing first-row transition-metal M-edges in chemical complexes.

PubMed

Wang, Hongxin; Young, Anthony T; Guo, Jinghua; Cramer, Stephen P; Friedrich, Stephan; Braun, Artur; Gu, Weiwei

2013-07-01

X-ray absorption and scattering spectroscopies involving the 3d transition-metal K- and L-edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M-edges, which are below 100 eV. Synchrotron-based X-ray sources can have higher energy resolution at M-edges. M-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) could therefore provide complementary information to K- and L-edge spectroscopies. In this study, M2,3-edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M2,3-edge RIXS on NiO, NiF2 and two other covalent complexes have been performed and different d-d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M-edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high-sensitivity and high-resolution superconducting tunnel junction X-ray detectors below 100 eV is also illustrated and discussed.

[The Diagnostics of Detonation Flow External Field Based on Multispectral Absorption Spectroscopy Technology].

PubMed

Lü, Xiao-jing; Li, Ning; Weng, Chun-sheng

2016-03-01

Compared with traditional sampling-based sensing method, absorption spectroscopy technology is well suitable for detonation flow diagnostics, since it can provide with us fast response, nonintrusive, sensitive solution for situ measurements of multiple flow-field parameters. The temperature and concentration test results are the average values along the laser path with traditional absorption spectroscopy technology, while the boundary of detonation flow external field is unknown and it changes all the time during the detonation engine works, traditional absorption spectroscopy technology is no longer suitable for detonation diagnostics. The trend of line strength with temperature varies with different absorption lines. By increasing the number of absorption lines in the test path, more information of the non-uniform flow field can be obtained. In this paper, based on multispectral absorption technology, the reconstructed model of detonation flow external field distribution was established according to the simulation results of space-time conservation element and solution element method, and a diagnostic method of detonation flow external field was given. The model deviation and calculation error of the least squares method adopted were studied by simulation, and the maximum concentration and temperature calculation error was 20.1% and 3.2%, respectively. Four absorption lines of H2O were chosen and detonation flow was scanned at the same time. The detonation external flow testing system was set up for the valveless gas-liquid continuous pulse detonation engine with the diameter of 80 mm. Through scanning H2O absorption lines with a high frequency of 10 kHz, the on-line detection of detonation external flow was realized by direct absorption method combined with time-division multiplexing technology, and the reconstruction of dynamic temperature distribution was realized as well for the first time, both verifying the feasibility of the test method. The test results show that both of the temperature and H2O concentration rose with the arrival of detonation wave. With the increase of the vertical distance between the detonation tube nozzle and the laser path, the time of temperature and concentration coming to the peak delayed, and the temperature variation trend tended to slow down. At 20 cm from detonation tube nozzle, the maximum temperature hit 1 329 K and the maximum H2O concentration of 0.19 occurred at 4 ms after ignition. The research can provide with us the support for expanding the detonation test field with absorption spectroscopy technology, and can also help to promote the detonation mechanism research and to enhance the level of detonation engine control technology.

Quantum Cascade Laser Absorption Spectroscopy as a Plasma Diagnostic Tool: An Overview

PubMed Central

Welzel, Stefan; Hempel, Frank; Hübner, Marko; Lang, Norbert; Davies, Paul B.; Röpcke, Jürgen

2010-01-01

The recent availability of thermoelectrically cooled pulsed and continuous wave quantum and inter-band cascade lasers in the mid-infrared spectral region has led to significant improvements and new developments in chemical sensing techniques using in-situ laser absorption spectroscopy for plasma diagnostic purposes. The aim of this article is therefore two-fold: (i) to summarize the challenges which arise in the application of quantum cascade lasers in such environments, and, (ii) to provide an overview of recent spectroscopic results (encompassing cavity enhanced methods) obtained in different kinds of plasma used in both research and industry. PMID:22163581

Quantum cascade laser absorption spectroscopy as a plasma diagnostic tool: an overview.

PubMed

Welzel, Stefan; Hempel, Frank; Hübner, Marko; Lang, Norbert; Davies, Paul B; Röpcke, Jürgen

2010-01-01

The recent availability of thermoelectrically cooled pulsed and continuous wave quantum and inter-band cascade lasers in the mid-infrared spectral region has led to significant improvements and new developments in chemical sensing techniques using in-situ laser absorption spectroscopy for plasma diagnostic purposes. The aim of this article is therefore two-fold: (i) to summarize the challenges which arise in the application of quantum cascade lasers in such environments, and, (ii) to provide an overview of recent spectroscopic results (encompassing cavity enhanced methods) obtained in different kinds of plasma used in both research and industry.

Cavity-Enhanced Absorption Spectroscopy and Photoacoustic Spectroscopy for Human Breath Analysis

NASA Astrophysics Data System (ADS)

Wojtas, J.; Tittel, F. K.; Stacewicz, T.; Bielecki, Z.; Lewicki, R.; Mikolajczyk, J.; Nowakowski, M.; Szabra, D.; Stefanski, P.; Tarka, J.

2014-12-01

This paper describes two different optoelectronic detection techniques: cavity-enhanced absorption spectroscopy and photoacoustic spectroscopy. These techniques are designed to perform a sensitive analysis of trace gas species in exhaled human breath for medical applications. With such systems, the detection of pathogenic changes at the molecular level can be achieved. The presence of certain gases (biomarkers), at increased concentration levels, indicates numerous human diseases. Diagnosis of a disease in its early stage would significantly increase chances for effective therapy. Non-invasive, real-time measurements, and high sensitivity and selectivity, capable of minimum discomfort for patients, are the main advantages of human breath analysis. At present, monitoring of volatile biomarkers in breath is commonly useful for diagnostic screening, treatment for specific conditions, therapy monitoring, control of exogenous gases (such as bacterial and poisonous emissions), as well as for analysis of metabolic gases.

An effective way to reduce water absorption to terahertz

NASA Astrophysics Data System (ADS)

Wu, Yaxiong; Su, Bo; He, Jingsuo; Zhang, Cong; Zhang, Hongfei; Zhang, Shengbo; Zhang, Cunlin

2018-01-01

Since many vibrations and rotational levels of biomolecules fall within the THz band, THz spectroscopy can be used to identify biological samples. In addition, most biomolecules need to maintain their biological activity in a liquid environment, but water as polar substance has strong absorption to the THz wave. Thus, it is difficult to detect the sample information in aqueous solution using THz wave. In order to prevent the information of biological samples were masked in the solution, many research methods were used to explore how to reduce the water absorption of terahertz. In this paper, we have developed a real-time chemical methodology through transmission Terahertz time-domain spectroscopy (THz-TDS) system. The material of Zeonor 1020r is used as substrate and cover plate, and PDMS as channel interlayer. The transmission of the empty microfluidic chip is more than 80% in the range of 0.2-2.6 THz by THz-TDS system. Then, experiments were carried out using chips, which were filled with different volumes of 1, 2- propanediol, and it has been proved that the microfluidic chip could reduce the water absorption of terahertz. Finally, in order to further explore the reduction of terahertz to water absorption, we inject different concentrations of electrolyte to the chip. The results show that with the addition of different electrolytes, terahertz transmission line has evident changes. It can be taken into account that the electrolyte has different effects about the hydrogen bonds in the aqueous solution. Some of them can promote water molecules clusters, while others destroy them. Based on the basis of microfluidic chip, the discovery of this phenomenon can provide a way that reduces water absorption of terahertz. This work has laid a solid foundation for the subsequent study in reducing water absorption of terahertz.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

NASA Astrophysics Data System (ADS)

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.; Hartig, K. C.; Phillips, M. C.

2018-06-01

Rapid, in-field, and non-contact isotopic analysis of solid materials is extremely important to a large number of applications, such as nuclear nonproliferation monitoring and forensics, geochemistry, archaeology, and biochemistry. Presently, isotopic measurements for these and many other fields are performed in laboratory settings. Rapid, in-field, and non-contact isotopic analysis of solid material is possible with optical spectroscopy tools when combined with laser ablation. Laser ablation generates a transient vapor of any solid material when a powerful laser interacts with a sample of interest. Analysis of atoms, ions, and molecules in a laser-produced plasma using optical spectroscopy tools can provide isotopic information with the advantages of real-time analysis, standoff capability, and no sample preparation requirement. Both emission and absorption spectroscopy methods can be used for isotopic analysis of solid materials. However, applying optical spectroscopy to the measurement of isotope ratios from solid materials presents numerous challenges. Isotope shifts arise primarily due to variation in nuclear charge distribution caused by different numbers of neutrons, but the small proportional nuclear mass differences between nuclei of various isotopes lead to correspondingly small differences in optical transition wavelengths. Along with this, various line broadening mechanisms in laser-produced plasmas and instrumental broadening generated by the detection system are technical challenges frequently encountered with emission-based optical diagnostics. These challenges can be overcome by measuring the isotope shifts associated with the vibronic emission bands from molecules or by using the techniques of laser-based absorption/fluorescence spectroscopy to marginalize the effect of instrumental broadening. Absorption and fluorescence spectroscopy probe the ground state atoms existing in the plasma when it is cooler, which inherently provides narrower lineshapes, as opposed to emission spectroscopy which requires higher plasma temperatures to be able to detect thermally excited emission. Improvements in laser and detection systems and spectroscopic techniques have allowed for isotopic measurements to be carried out at standoff distances under ambient atmospheric conditions, which have expanded the applicability of optical spectroscopy-based isotopic measurements to a variety of scientific fields. These technological advances offer an in-situ measurement capability that was previously not available. This review will focus on isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing knowledge/technological gaps identified from the current literature and suggestions for the future work.

Depth Profiles in Maize ( Zea mays L.) Seeds Studied by Photoacoustic Spectroscopy

NASA Astrophysics Data System (ADS)

Hernández-Aguilar, C.; Domínguez-Pacheco, A.; Cruz-Orea, A.; Zepeda-Bautista, R.

2015-06-01

Photoacoustic spectroscopy (PAS) has been used to analyze agricultural seeds and can be applied to the study of seed depth profiles of these complex samples composed of different structures. The sample depth profile can be obtained through the photoacoustic (PA) signal, amplitude, and phase at different light modulation frequencies. The PA signal phase is more sensitive to changes of thermal properties in layered samples than the PA signal amplitude. Hence, the PA signal phase can also be used to characterize layers at different depths. Thus, the objective of the present study was to obtain the optical absorption spectra of maize seeds ( Zea mays L.) by means of PAS at different light modulation frequencies (17 Hz, 30 Hz, and 50 Hz) and comparing these spectra with the ones obtained from the phase-resolved method in order to separate the optical absorption spectra of seed pericarp and endosperm. The results suggest the possibility of using the phase-resolved method to obtain optical absorption spectra of different seed structures, at different depths, without damaging the seed. Thus, PAS could be a nondestructive method for characterization of agricultural seeds and thus improve quality control in the food industry.

Interaction between a cationic porphyrin and ctDNA investigated by SPR, CV and UV-vis spectroscopy.

PubMed

Xu, Zi-Qiang; Zhou, Bo; Jiang, Feng-Lei; Dai, Jie; Liu, Yi

2013-10-01

The interaction between ctDNA and a cationic porphyrin was studied in this work. The binding process was monitored by surface plasmon resonance (SPR) spectroscopy in detail. The association, dissociation rate constants and the binding constants calculated by global analysis were 2.4×10(2)±26.4M(-1)s(-1), 0.011±0.0000056s(-1) and 2.18×10(4)M(-1), respectively. And the results were confirmed by cyclic voltammetry and UV-vis absorption spectroscopy. The binding constants obtained from cyclic voltammetry and UV-vis absorption spectroscopy were 8.28×10(4)M(-1) and 6.73×10(4)M(-1) at 298K, respectively. The covalent immobilization methodology of ctDNA onto gold surface modified with three different compounds was also investigated by SPR. These compounds all contain sulfydryl but with different terminated functional groups. The results indicated that the 11-MUA (HS(CH2)10COOH)-modified gold film is more suitable for studying the DNA-drug interaction. Copyright © 2013 Elsevier B.V. All rights reserved.

Characterization of dissolved organic matter in Dongjianghu Lake by UV-visible absorption spectroscopy with multivariate analysis.

PubMed

Zhu, Yanzhong; Song, Yonghui; Yu, Huibin; Liu, Ruixia; Liu, Lusan; Lv, Chunjian

2017-08-08

UV-visible absorption spectroscopy coupled with principal component analysis (PCA) and hierarchical cluster analysis (HCA) was applied to characterize spectroscopic components, detect latent factors, and investigate spatial variations of dissolved organic matter (DOM) in a large-scale lake. Twelve surface water samples were collected from Dongjianghu Lake in China. DOM contained lignin and quinine moieties, carboxylic acid, microbial products, and aromatic and alkyl groups, which in the northern part of the lake was largely different from the southern part. Fifteen spectroscopic indices were deduced from the absorption spectra to indicate molecular weight or humification degree of DOM. The northern part of the lake presented the smaller molecular weight or the lower humification degree of DOM than the southern part. E 2/4 , E 3/4 , E 2/3 , and S 2 were latent factors of characterizing the molecular weight of DOM, while E 2/5 , E 3/5 , E 2/6 , E 4/5 , E 3/6 , and A 2/1 were latent factors of evaluating the humification degree of DOM. The UV-visible absorption spectroscopy combined with PCA and HCA may not only characterize DOM fractions of lakes, but may be transferred to other types of waterscape.

Optimizing soft X-ray NEXAFS spectroscopy in the laboratory

NASA Astrophysics Data System (ADS)

Mantouvalou, I.; Jonas, A.; Witte, K.; Jung, R.; Stiel, H.; Kanngießer, B.

2017-05-01

Near edge X-ray absorption fine structure (NEXAFS) spectroscopy in the soft X-ray range is feasible in the laboratory using laser-produced plasma sources. We present a study using seven different target materials for optimized data analysis. The emission spectra of the materials with atomic numbers ranging from Z = 6 to Z = 79 show distinct differences, rendering the adapted selection of a suitable target material for specialized experiments feasible. For NEXAFS spectroscopy a 112.5 nm thick polyimide film is investigated as a reference exemplifying the superiority of quasi-continuum like emission spectra.

Optical spectroscopy of nanoscale and heterostructured oxides

NASA Astrophysics Data System (ADS)

Senty, Tess R.

Through careful analysis of a material's properties, devices are continually getting smaller, faster and more efficient each day. Without a complete scientific understanding of material properties, devices cannot continue to improve. This dissertation uses optical spectroscopy techniques to understand light-matter interactions in several oxide materials with promising uses mainly in light harvesting applications. Linear absorption, photoluminescence and transient absorption spectroscopy are primarily used on europium doped yttrium vanadate nanoparticles, copper gallium oxide delafossites doped with iron, and cadmium selenide quantum dots attached to titanium dioxide nanoparticles. Europium doped yttrium vanadate nanoparticles have promising applications for linking to biomolecules. Using Fourier-transform infrared spectroscopy, it was shown that organic ligands (benzoic acid, 3-nitro 4-chloro-benzoic acid and 3,4-dihydroxybenzoic acid) can be attached to the surface of these molecules using metal-carboxylate coordination. Photoluminescence spectroscopy display little difference in the position of the dominant photoluminescence peaks between samples with different organic ligands although there is a strong decrease in their intensity when 3,4-dihydroxybenzoic acid is attached. It is shown that this strong quenching is due to the presence of high-frequency hydroxide vibrational modes within the organic linker. Ultraviolet/visible linear absorption measurements on delafossites display that by doping copper gallium oxide with iron allows for the previously forbidden fundamental gap transition to be accessed. Using tauc plots, it is shown that doping with iron lowers the bandgap from 2.8 eV for pure copper gallium oxide, to 1.7 eV for samples with 1 -- 5% iron doping. Using terahertz transient absorption spectroscopy measurements, it was also determined that doping with iron reduces the charge mobility of the pure delafossite samples. A comparison of cadmium selenide quantum dots, both with and without capping ligands, attached to titanium dioxide nanoparticles is performed using a new transient absorption analysis technique. Multiple exponential fit models were applied to the system and compared with the new inversion analysis technique. It is shown how the new inversion analysis can map out the charge carrier dynamics, providing carrier recombination rates and lifetimes as a function of carrier concentration, where the multiple exponential fit technique is not dependent on the carrier concentration. With the inversion analysis technique it is shown that capping ligands allow for increased charge transfer due to traps being passivated on the quantum dot surface.

Application of terahertz spectroscopy for characterization of biologically active organic molecules in natural environment

NASA Astrophysics Data System (ADS)

Karaliūnas, Mindaugas; Jakštas, Vytautas; Nasser, Kinan E.; Venckevičius, Rimvydas; Urbanowicz, Andrzej; Kašalynas, Irmantas; Valušis, Gintaras

2016-09-01

In this work, a comparative research of biologically active organic molecules in its natural environment using the terahertz (THz) time domain spectroscopy (TDS) and Fourier transform spectroscopy (FTS) systems is carried out. Absorption coefficient and refractive index of Nicotiana tabacum L. leaves containing nicotine, Cannabis sativa L. leaves containing tetrahydrocannabinol, and Humulu lupulus L. leaves containing α-acids, active organic molecules that obtain in natural environment, were measured in broad frequency range from 0.1 to 13 THz at room temperature. In the spectra of absorption coefficient the features were found to be unique for N. tabacum, C. sativa and H. lupulus. Moreover, those features can be exploited for identification of C. sativa sex and N. tabacum origin. The refractive index can be also used to characterize different species.

Application of Terahertz Attenuated Total Reflection Spectroscopy to Detect Changes in the Physical Properties of Lactose during the Lubrication Process Required for Drug Formulation.

PubMed

Dohi, Masafumi; Momose, Wataru; Yamashita, Kazunari; Hakomori, Tadashi; Sato, Shusaku; Noguchi, Shuji; Terada, Katsuhide

2017-02-01

Manufacturing the solid dosage form of an orally administered drug requires lubrication to enhance manufacturability, ensuring that critical quality attributes such as disintegration and dissolution of the drug product are maintained during manufacture. Here, to evaluate lubrication performance during manufacture, we used terahertz attenuated total reflection (THz-ATR) spectroscopy to detect differences in the physical characteristics of the lubricated powder. We applied a simple formulation prepared by blending granulated lactose as filler with magnesium stearate as lubricant. A flat tablet was prepared using the lubricated powder to acquire sharp THz-ATR absorption peaks of the samples. First, we investigated the effects of lubricant concentration and compression pressure on preparation of the tablet and then determined the effect of the pressure applied to samples in contact with the ATR prism on sample absorption amplitude. We focused on the differences in the magnitudes of spectra at the lactose-specific frequency. Second, we conducted the dynamic lubrication process using a 120-L mixer to investigate differences in the magnitudes of absorption corresponding to the lactose-specific frequency during lubrication. In both studies, enriching the lubricated powder with a higher concentration of magnesium stearate or prolonging blending time correlated with higher magnitudes of spectra at the lactose-specific frequency. Further, in the dynamic lubrication study, the wettability and disintegration time of the tablets were compared with the absorption spectra amplitudes at the lactose-specific frequency. We conclude that THz-ATR spectroscopy is useful for detecting differences in densities caused by a change in the physical properties of lactose during lubrication.

Sub-Thz Vibrational Spectroscopy for Analysis of Ovarian Cancer Cells

NASA Astrophysics Data System (ADS)

Ferrance, Jerome P.; Sizov, Igor; Jazaeri, Amir; Moyer, Aaron; Gelmont, Boris; Globus, Tatiana

2016-06-01

Sub-THz vibrational spectroscopy utilizes wavelengths in the submillimeter-wave range ( 1.5-30 wn), beyond those traditionally used for chemical and biomolecular analysis. This low energy radiation excites low-frequency internal molecular motions (vibrations) involving hydrogen bonds and other weak connections within these molecules. The ability of sub-THz spectroscopy to identify and quantify biological molecules is based on detection of signature resonance absorbance at specific frequencies between 0.05 and 1 THz, for each molecule. The long wavelengths of this radiation, mean that it can even pass through entire cells, detecting the combinations of proteins and nucleic acids that exist within the cell. This research introduces a novel sub-THz resonance spectroscopy instrument with spectral resolution sufficient to identify individual resonance absorption peaks, for the analysis of ovarian cancer cells. In vitro cell cultures of SK-OV-3 and ES-2 cells, two human ovarian cancer subtypes, were characterized and compared with a normal non-transformed human fallopian tube epithelial cell line (FT131). A dramatic difference was observed between the THz absorption spectra of the cancer and normal cell sample materials with much higher absorption intensity and a very strong absorption peak at a frequency of 13 wn dominating the cancer sample spectra. Comparison of experimental spectra with molecular dynamic simulated spectroscopic signatures suggests that the high intensity spectral peak could originate from overexpressed mi-RNA molecules specific for ovarian cancer. Ovarian cancer cells are utilized as a proof of concept, but the sub-THz spectroscopy method is very general and could also be applied to other types of cancer.

Crystallography with online optical and X-ray absorption spectroscopies demonstrates an ordered mechanism in copper nitrite reductase.

PubMed

Hough, Michael A; Antonyuk, Svetlana V; Strange, Richard W; Eady, Robert R; Hasnain, S Samar

2008-04-25

Nitrite reductases are key enzymes that perform the first committed step in the denitrification process and reduce nitrite to nitric oxide. In copper nitrite reductases, an electron is delivered from the type 1 copper (T1Cu) centre to the type 2 copper (T2Cu) centre where catalysis occurs. Despite significant structural and mechanistic studies, it remains controversial whether the substrates, nitrite, electron and proton are utilised in an ordered or random manner. We have used crystallography, together with online X-ray absorption spectroscopy and optical spectroscopy, to show that X-rays rapidly and selectively photoreduce the T1Cu centre, but that the T2Cu centre does not photoreduce directly over a typical crystallographic data collection time. Furthermore, internal electron transfer between the T1Cu and T2Cu centres does not occur, and the T2Cu centre remains oxidised. These data unambiguously demonstrate an 'ordered' mechanism in which electron transfer is gated by binding of nitrite to the T2Cu. Furthermore, the use of online multiple spectroscopic techniques shows their value in assessing radiation-induced redox changes at different metal sites and demonstrates the importance of ensuring the correct status of redox centres in a crystal structure determination. Here, optical spectroscopy has shown a very high sensitivity for detecting the change in T1Cu redox state, while X-ray absorption spectroscopy has reported on the redox status of the T2Cu site, as this centre has no detectable optical absorption.

Toroidal Optical Microresonators as Single-Particle Absorption Spectrometers

NASA Astrophysics Data System (ADS)

Heylman, Kevin D.

Single-particle and single-molecule measurements are invaluable tools for characterizing structural and energetic properties of molecules and nanomaterials. Photothermal microscopy in particular is an ultrasensitive technique capable of single-molecule resolution. In this thesis I introduce a new form of photothermal spectroscopy involving toroidal optical microresonators as detectors and a pair of non-interacting lasers as pump and probe for performing single-target absorption spectroscopy. The first three chapters will discuss the motivation, design principles, underlying theory, and fabrication process for the microresonator absorption spectrometer. With an early version of the spectrometer, I demonstrate photothermal mapping and all-optical tuning with toroids of different geometries in Chapter 4. In Chapter 5, I discuss photothermal mapping and measurement of the absolute absorption cross-sections of individual carbon nanotubes. For the next generation of measurements I incorporate all of the advances described in Chapter 2, including a double-modulation technique to improve detection limits and a tunable pump laser for spectral measurements on single gold nanoparticles. In Chapter 6 I observe sharp Fano resonances in the spectra of gold nanoparticles and describe them with a theoretical model. I continued to study this photonic-plasmonic hybrid system in Chapter 7 and explore the thermal tuning of the Fano resonance phase while quantifying the Fisher information. The new method of photothermal single-particle absorption spectroscopy that I will discuss in this thesis has reached record detection limits for microresonator sensing and is within striking distance of becoming the first single-molecule room-temperature absorption spectrometer.

Low Z elements (Mg, Al, and Si) K-edge X-ray absorption spectroscopy in minerals and disordered systems

NASA Astrophysics Data System (ADS)

Ildefonse, Ph.; Calas, G.; Flank, A. M.; Lagarde, P.

1995-05-01

Soft X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy have been performed at the Mg-, Al- and Si-K edges in order to establish the ability of this spectroscopy to derive structural information in disordered solids such as glasses and gels. Mg- and Al-K XANES are good structural probes to determine the coordination state of these elements in important minerals, glasses and gels. In a CaOsbnd MgOsbnd 2SiO2 glass Mg XANES spectra differ from that found in the crystalline equivalent, with a significant shift of the edge maxima to lower energy, consistent with a CN lower than 6. Mg-EXAFS on the same sample are in agreement and indicate the presence of 5-coordinated Mg with Mgsbnd O distances of 2.01Å. In aluminosilicate gels, Alsbnd K XANES has been used to investigate the [4]Al/Altotal ratios. These ratios increase as the Al/Si ratios decrease. Aluminosilicate and ferric-silicate gels were studied by using Sisbnd K edge XANES. XANES spectra differ significantly among the samples studied. Aluminosilicate gels with Al/Si= 1 present a different Al and Si local environment from that known in clay minerals with the same Al/Si ratio. The gel-to-mineral transformation thus implies a dissolution-recrystallization mechanism. On the contrary, ferric-silicate gel presents a Si local environment close to that found in nontronite which may be formed by a long range ordering of the initial gels.

Research on the differences between 2-(2-Chlorophenyl)benzimidazole and 2-(4-Chlorophenyl)benzimidazole based on terahertz time domain spectroscopy

NASA Astrophysics Data System (ADS)

Song, Maojiang; Yang, Fei; Liu, Liping; Shen, Li; Hu, Pengfei; Zhang, Li; Su, Caixia

2018-05-01

Due to wide variety of biological and pharmacological activities of benzimidazole derivatives, the differences between 2-(2-Chlorophenyl)benzimidazole and 2-(4-Chlorophenyl) benzimidazole were researched by employing terahertz time-domain spectroscopy and density functional theory systematically. Although the only difference between their molecular configurations is the arrangement of chlorine atom on chlorophenyl ring, there are distinctive differences in their fingerprint spectra in the range of 0.2-2.5 THz, such as amount, amplitude, and frequency position of absorption peaks. The validity of these results was confirmed by the theoretical results simulated by using density functional theory. The possible reasons of these differences originate from the different van der Waals forces and the different dihedral angles of the molecules within crystal cell. These results indicate the importance of this spectral range as a conformational fingerprint region where even minor changes in the molecular configuration lead to major differences in its THz absorption.

Excitonic Transitions and Off-resonant Optical Limiting in CdS Quantum Dots Stabilized in a Synthetic Glue Matrix

PubMed Central

2007-01-01

Stable films containing CdS quantum dots of mean size 3.4 nm embedded in a solid host matrix are prepared using a room temperature chemical route of synthesis. CdS/synthetic glue nanocomposites are characterized using high resolution transmission electron microscopy, infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis. Significant blue shift from the bulk absorption edge is observed in optical absorption as well as photoacoustic spectra indicating strong quantum confinement. The exciton transitions are better resolved in photoacoustic spectroscopy compared to optical absorption spectroscopy. We assign the first four bands observed in photoacoustic spectroscopy to 1se–1sh, 1pe–1ph, 1de–1dhand 2pe–2phtransitions using a non interacting particle model. Nonlinear absorption studies are done using z-scan technique with nanosecond pulses in the off resonant regime. The origin of optical limiting is predominantly two photon absorption mechanism.

Force-detected nanoscale absorption spectroscopy in water at room temperature using an optical trap

NASA Astrophysics Data System (ADS)

Parobek, Alexander; Black, Jacob W.; Kamenetska, Maria; Ganim, Ziad

2018-04-01

Measuring absorption spectra of single molecules presents a fundamental challenge for standard transmission-based instruments because of the inherently low signal relative to the large background of the excitation source. Here we demonstrate a new approach for performing absorption spectroscopy in solution using a force measurement to read out optical excitation at the nanoscale. The photoinduced force between model chromophores and an optically trapped gold nanoshell has been measured in water at room temperature. This photoinduced force is characterized as a function of wavelength to yield the force spectrum, which is shown to be correlated to the absorption spectrum for four model systems. The instrument constructed for these measurements combines an optical tweezer with frequency domain absorption spectroscopy over the 400-800 nm range. These measurements provide proof-of-principle experiments for force-detected nanoscale spectroscopies that operate under ambient chemical conditions.

A transmission-grating-modulated pump-probe absorption spectroscopy and demonstration of diffusion dynamics of photoexcited carriers in bulk intrinsic GaAs film.

PubMed

Chen, Ke; Wang, Wenfang; Chen, Jianming; Wen, Jinhui; Lai, Tianshu

2012-02-13

A transmission-grating-modulated time-resolved pump-probe absorption spectroscopy is developed and formularized. The spectroscopy combines normal time-resolved pump-probe absorption spectroscopy with a binary transmission grating, is sensitive to the spatiotemporal evolution of photoinjected carriers, and has extensive applicability in the study of diffusion transport dynamics of photoinjected carriers. This spectroscopy has many advantages over reported optical methods to measure diffusion dynamics, such as simple experimental setup and operation, and high detection sensitivity. The measurement of diffusion dynamics is demonstrated on bulk intrinsic GaAs films. A carrier density dependence of carrier diffusion coefficient is obtained and agrees well with reported results.

UV-VIS absorption spectroscopy: Lambert-Beer reloaded

NASA Astrophysics Data System (ADS)

Mäntele, Werner; Deniz, Erhan

2017-02-01

UV-VIS absorption spectroscopy is used in almost every spectroscopy laboratory for routine analysis or research. All spectroscopists rely on the Lambert-Beer Law but many of them are less aware of its limitations. This tutorial discusses typical problems in routine spectroscopy that come along with technical limitations or careless selection of experimental parameters. Simple rules are provided to avoid these problems.

Computationally effective solution of the inverse problem in time-of-flight spectroscopy.

PubMed

Kamran, Faisal; Abildgaard, Otto H A; Subash, Arman A; Andersen, Peter E; Andersson-Engels, Stefan; Khoptyar, Dmitry

2015-03-09

Photon time-of-flight (PTOF) spectroscopy enables the estimation of absorption and reduced scattering coefficients of turbid media by measuring the propagation time of short light pulses through turbid medium. The present investigation provides a comparison of the assessed absorption and reduced scattering coefficients from PTOF measurements of intralipid 20% and India ink-based optical phantoms covering a wide range of optical properties relevant for biological tissues and dairy products. Three different models are used to obtain the optical properties by fitting to measured temporal profiles: the Liemert-Kienle model (LKM), the diffusion model (DM) and a white Monte-Carlo (WMC) simulation-based algorithm. For the infinite space geometry, a very good agreement is found between the LKM and WMC, while the results obtained by the DM differ, indicating that the LKM can provide accurate estimation of the optical parameters beyond the limits of the diffusion approximation in a computational effective and accurate manner. This result increases the potential range of applications for PTOF spectroscopy within industrial and biomedical applications.

Extended X-ray Absorption Fine Structure Study of Bond Constraints in Ge-Sb-Te Alloys

DTIC Science & Technology

2011-02-07

Ray Absorption Spectroscopy, or EXAFS. Using the spectroscopic capabilities provided by the MCAT line at the Advanced Photon Source at Argonne...Absorption Spectroscopy, or EXAFS. Using the spectroscopic capabilities provided by the MCAT line at the Advanced Photon Source at Argonne National

An environmentally friendly method for the fabrication of reduced graphene oxide foam with a super oil absorption capacity.

PubMed

He, Yongqiang; Liu, Yue; Wu, Tao; Ma, Junkui; Wang, Xingrui; Gong, Qiaojuan; Kong, Weina; Xing, Fubao; Liu, Yu; Gao, Jianping

2013-09-15

Three kinds of graphene oxide (GO) foams were fabricated using different freezing methods (unidirectional freezing drying (UDF), non-directional freezing drying, and air freezing drying), and the corresponding reduced graphene oxide (RGO) foams were prepared by their thermal reduction of those GO foams. These RGO foams were characterized by Fourier transform infrared spectroscopy, thermal gravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The absorption process and the factors that influence the absorption capacity were investigated. The RGO foams are hydrophobic and showed extremely high absorbing abilities for organic liquids. The absorption capacity of the RGO foams made by UDF was higher than 100 g g(-1) for all the oils tested (gasoline, diesel oil, pump oil, lubricating oil and olive oil) and had the highest value of about 122 g g(-1) for olive oil. The oil absorption capacity of the GO foams was lower than that of the RGO foams, but for olive oil, the absorption capacity was still high than 70 g g(-1), which is higher than that of most oil absorbents. Copyright © 2013 Elsevier B.V. All rights reserved.

Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2018-02-01

Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.

Overtone spectroscopy of N2H+ molecular ions—application of cavity ring-down spectroscopy

NASA Astrophysics Data System (ADS)

Kálosi, Á.; Dohnal, P.; Shapko, D.; Roučka, Š.; Plašil, R.; Johnsen, R.; Glosík, J.

2017-10-01

A stationary afterglow apparatus in conjunction with a laser absorption cavity ring-down spectrometer has been employed to observe absorption lines in the P- and R-branches of the (200) <-- (000) and (2110) <-- (0110) vibrational bands of the N2H+ molecular ion as a part of an ongoing study of the electron-ion recombination of N2H+ in afterglow plasmas. The probed absorption lines lie in the near-infrared spectral region around 1580 nm. The observed transition wavenumbers were fitted to experimental accuracy and improved molecular constants for the (200) vibrational state were obtained. The employed experimental technique enables probing of the translational, rotational and vibrational temperature of the studied ions as well as the determination of the number densities of different quantum states of the ion in discharge and afterglow plasma.

Quantification of tissue oxygenation levels using diffuse reflectance spectroscopy

NASA Astrophysics Data System (ADS)

B. S., Suresh Anand; N., Sujatha

2011-08-01

Tumor growth is characterized by increased metabolic activity. The light absorption profile of hemoglobin in dysplastic tissue is different from a normal tissue. Neovascularization is a hallmark of many diseases and can serve as a predictive biomarker for the detection of cancers. Spectroscopic techniques can provide information about the metabolic and morphological changes related to the progression of neoplasia. Diffuse reflectance spectroscopy (DRS) measures the absorption and scattering properties of a biological tissue and this method can provide clinically useful information for the early diagnosis of epithelial precancers. We used tissue simulating phantoms with absorbing and scattering molecules for the determination of total hemoglobin concentration, hemoglobin oxygen saturation and intensity difference between the deoxy and oxy hemoglobin bands. The results show promising approach for the differentiating normal and malignant states of a tissue.

Lens-Aided Multi-Angle Spectroscopy (LAMAS) Reveals Small-Scale Outflow Structure in Quasars

NASA Astrophysics Data System (ADS)

Green, Paul J.

2006-06-01

Spectral differences between lensed quasar image components are common. Since lensing is intrinsically achromatic, these differences are typically explained as the effect of either microlensing, or as light path time delays sampling intrinsic quasar spectral variability. Here we advance a novel third hypothesis: some spectral differences are due to small line-of-sight differences through quasar disk wind outflows. In particular, we propose that variable spectral differences seen only in component A of the widest separation lens SDSS J1004+4112 are due to differential absorption along the sight lines. The absorber properties required by this hypothesis are akin to known broad absorption line (BAL) outflows but must have a broader, smoother velocity profile. We interpret the observed C IV emission-line variability as further evidence for spatial fine structure transverse to the line of sight. Since outflows are likely to be rotating, such absorber fine structure can consistently explain some of the UV and X-ray variability seen in AGNs. The implications are many: (1) Spectroscopic differences in other lensed objects may be due to this ``lens-aided multi-angle spectroscopy'' (LAMAS). (2) Outflows have fine structure on size scales of arcseconds, as seen from the nucleus. (3) Assuming either broad absorption line region sizes proposed in recent wind models, or typically assumed continuum emission region sizes, LAMAS and/or variability provide broadly consistent absorber size scale estimates of ~1015 cm. (4) Very broad smooth absorption may be ubiquitous in quasar spectra, even when no obvious troughs are seen.

Metal Ion Interactions with Immunoglobulin G (IgG). 1. Preliminary Studies with Electron Paramagnetic Resonance (EPR) Spectroscopy and Ultrafiltration

DTIC Science & Technology

1978-12-12

EPR and ultrafiltration studies are recommceided to conduct luture metal ion- IgG binding research. Using Scatchard plots, bind.ng levels can be...of the binding sites can be best pursued by EPR and ultrafiltration using the fragments of IgG . This report noted some difference in the binding...immunoelectrophoresis, ultrafiltration, UV spectroscopy, atomic absorption spectroscopy, and electron paramagnetic resonance (EPR). IgG used ,- ,is non

Photoacoustic spectroscopy of man infecting protozoans

NASA Astrophysics Data System (ADS)

Acosta-Avalos, D.; Alvarado-Gil, J. J.; Vargas, H.

1998-08-01

In this paper the fundamentals of photothermal spectroscopy are presented, special emphasis is done in the obtention of the optical absorption spectra. It is shown that this spectroscopy can be used successfully for the monitoring of protozoans that could infect the human. The usefulness of the technique is illustrated in the special case of Leishmania, where it is possible to find that the stage when the protozoan infect vertebrate cells show important differences in relation to the protozoans infecting insects.

High resolution x-ray fluorescence spectroscopy - a new technique for site- and spin-selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xin

1996-12-01

X-ray spectroscopy has long been used to elucidate electronic and structural information of molecules. One of the weaknesses of x-ray absorption is its sensitivity to all of the atoms of a particular element in a sample. Through out this thesis, a new technique for enhancing the site- and spin-selectivity of the x-ray absorption has been developed. By high resolution fluorescence detection, the chemical sensitivity of K emission spectra can be used to identify oxidation and spin states; it can also be used to facilitate site-selective X-ray Absorption Near Edge Structure (XANES) and site-selective Extended X-ray Absorption Fine Structure (EXAFS). Themore » spin polarization in K fluorescence could be used to generate spin selective XANES or spin-polarized EXAFS, which provides a new measure of the spin density, or the nature of magnetic neighboring atoms. Finally, dramatic line-sharpening effects by the combination of absorption and emission processes allow observation of structure that is normally unobservable. All these unique characters can enormously simplify a complex x-ray spectrum. Applications of this novel technique have generated information from various transition-metal model compounds to metalloproteins. The absorption and emission spectra by high resolution fluorescence detection are interdependent. The ligand field multiplet model has been used for the analysis of K{alpha} and K{beta} emission spectra. First demonstration on different chemical states of Fe compounds has shown the applicability of site selectivity and spin polarization. Different interatomic distances of the same element in different chemical forms have been detected using site-selective EXAFS.« less

Measurement of Absorption Coefficient of Paraformaldehyde and Metaldehyde with Terahertz Spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, J.; Xia, T.; Chen, Q.; Sun, Q.; Deng, Y.; Wang, C.

2018-03-01

The characteristic absorption spectra of paraformaldehyde and metaldehyde in the terahertz frequency region are obtained by terahertz time-domain spectroscopy (THz-TDS). In order to reduce the absorption of terahertz (THz) wave by water vapor in the air and the background noise, the measurement system was filled with dry air and the measurements were conducted at the temperature of 24°C. Meanwhile, the humidity was controlled within 10% RH. The THz frequency domain spectra of samples and their references from 0 to 2.5 THz were analyzed via Fourier transform. The refractive index and absorption coefficients of the two aldehydes were calculated by the model formulas. From 0.1 to 2.5 THz, there appear two weak absorption peaks at 1.20 and 1.66 THz in the absorption spectra of paraformaldehyde. Only one distinct absorption peak emerges at 1.83 THz for metaldehyde. There are significant differences between the terahertz absorption coefficients of paraformaldehyde and metaldehyde, which can be used as "fingerprints" to identify these substances. Furthermore, the relationship between the average absorption coefficients and mass concentrations was investigated and the average absorption coefficient-mass concentration diagrams of paraformaldehyde and metaldehyde were shown. For paraformaldehyde, there is a linear relationship between the average absorption coefficient and the natural logarithm of mass concentration. For metaldehyde, there exists a simpler linear relationship between the average absorption coefficient and the mass concentration. Because of the characteristics of THz absorption of paraformaldehyde and metaldehyde, the THz-TDS can be applied to the qualitative and quantitative detection of the two aldehydes to reduce the unpredictable hazards due to these substances.

Using high spectral resolution spectrophotometry to study broad mineral absorption features on Mars

NASA Technical Reports Server (NTRS)

Blaney, D. L.; Crisp, D.

1993-01-01

Traditionally telescopic measurements of mineralogic absorption features have been made using relatively low to moderate (R=30-300) spectral resolution. Mineralogic absorption features tend to be broad so high resolution spectroscopy (R greater than 10,000) does not provide significant additional compositional information. Low to moderate resolution spectroscopy allows an observer to obtain data over a wide wavelength range (hundreds to thousands of wavenumbers) compared to the several wavenumber intervals that are collected using high resolution spectrometers. However, spectrophotometry at high resolution has major advantages over lower resolution spectroscopy in situations that are applicable to studies of the Martian surface, i.e., at wavelengths where relatively weak surface absorption features and atmospheric gas absorption features both occur.

Development of integrated platform based on chalcogenides for sensing applications in the mid-infrared

NASA Astrophysics Data System (ADS)

Gutierrez-Arroyo, Aldo; Bodiou, Loïc.; Lemaitre, Jonathan; Baudet, Emeline; Baillieul, Marion; Hardy, Isabelle; Caillaud, Celine; Colas, Florent; Boukerma, Kada; Rinnert, Emmanuel; Michel, Karine; Bureau, Bruno; Nazabal, Virginie; Charrier, Joël.

2018-03-01

Mid-Infrared (mid-IR) spectral range, spanning from 2 μm to 20 μm, is ideal for chemical sensing using spectroscopy thanks to the presence of vibrational absorption bands of many liquid and gas substances in this wavelength range. Indeed, mid-IR spectroscopy allows simultaneous qualitative and quantitative analysis by, respectively, identifying molecules from their spectral signature and relating the concentrations of different chemical agents to their absorption coefficient according to Beer-Lambert law. In the last years, photonic integrated sensors based on mid-IR spectroscopy have emerged as a cheap, accurate, and compact solution that would enable continuous real-time on-site diagnostics and monitoring of molecular species without the need to collect samples for off-site measurements. Here, we report the design, processing and characterization of a photonic integrated transducer based on selenide ridge waveguides. Evanescent wave detection of chemical substances in liquid phase (isopropyl alcohol, C3H8O, and acetic acid, C2H4O2, both dissolved in cyclohexane) is presented using their absorption at a wavelength of 7.7 μm.

Atomically designed precursors in optical fiber amplifiers: The thermal stability of the heterobimetallic ErAl3(OPri)12 in a solution-coated silica soot

NASA Astrophysics Data System (ADS)

Engholm, M.; Lashgari, K.; Edvardsson, S.; Westin, G.; Norin, L.

2005-06-01

The thermal stability of the bimetallic alkoxide ErAl3(OPri)12 doped in an unsintered silica (soot) has been investigated. Samples have been heated to different temperatures (up to 1500°C and analyzed by using ultraviolet-visible-near infrared absorption spectroscopy, infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, thermal gravimetric analysis, and powder x-ray diffraction. It is seen that the doped samples heated up to 1000°C show broad glasslike absorption spectra, indicating an amorphous structure, while the high-temperature sample shows an ordered crystallinelike structure with sharp characteristic absorption peaks. X-ray diffraction measurements indicate the formation of an ordered structure at temperatures of 1500°C, revealing a crystal phase of silica and phases of erbium and aluminosilicate. A comparison is also made with a sample doped with aqueous ErCl3 and Al(NO3)3. It is concluded that the local structure of the ErAl3 precursor is not preserved at temperatures above 1000°C. Alternative doping procedures are discussed.

Fusion of Ultraviolet-Visible and Infrared Transient Absorption Spectroscopy Data to Model Ultrafast Photoisomerization.

PubMed

Debus, Bruno; Orio, Maylis; Rehault, Julien; Burdzinski, Gotard; Ruckebusch, Cyril; Sliwa, Michel

2017-08-03

Ultrafast photoisomerization reactions generally start at a higher excited state with excess of internal vibrational energy and occur via conical intersections. This leads to ultrafast dynamics which are difficult to investigate with a single transient absorption spectroscopy technique, be it in the ultraviolet-visible (UV-vis) or infrared (IR) domain. On one hand, the information available in the UV-vis domain is limited as only slight spectral changes are observed for different isomers. On the other hand, the interpretation of vibrational spectra is strongly hindered by intramolecular relaxation and vibrational cooling. These limitations can be circumvented by fusing UV-vis and IR transient absorption spectroscopy data in a multiset multivariate curve resolution analysis. We apply this approach to describe the spectrodynamics of the ultrafast cis-trans photoisomerization around the C-N double bond observed for aromatic Schiff bases. Twisted intermediate states could be elucidated, and isomerization was shown to occur through a continuous complete rotation. More broadly, data fusion can be used to rationalize a vast range of ultrafast photoisomerization processes of interest in photochemistry.

Spectroscopic Studies of Carotenoid-to-Bacteriochlorophyll Energy Transfer in LHRC Photosynthetic Complex from Roseiflexus castenholzii

DOE Office of Scientific and Technical Information (OSTI.GOV)

Niedzwiedzki, Dariusz; Collins, Aaron M.; LaFountain, Amy M.

Carotenoids present in the photosynthetic light-harvesting reaction center (LHRC) complex from chlorosome lacking filamentous anoxygenic phototroph, Roseiflexus castenholzii were purified and characterized for their photochemical properties. The LHRC from anaerobically grown cells contains five different carotenoids, methoxy-keto-myxocoxanthin, γ-carotene, and its three derivatives, whereas the LHRC from aerobically grown cells contains only three carotenoid pigments with methoxy-keto-myxocoxanthin being the dominant one. The spectroscopic properties and dynamics of excited singlet states of the carotenoids were studied by steady-state absorption, fluorescence and ultrafast time-resolved optical spectroscopy in organic solvent and in the intact LHRC complex. Time-resolved transient absorption spectroscopy performed in the near-infraredmore » (NIR) on purified carotenoids combined with steady-state absorption spectroscopy led to the precise determination of values of the energies of the S 1(2 1A g -) excited state. Global and single wavelength fitting of the ultrafast spectral and temporal data sets of the carotenoids in solvents and in the LHRC revealed the pathways of de-excitation of the carotenoid excited states.« less

Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene/Guanine Interface - A Proposal for High Mobility, Organic Graphene Field Effect Transistors

DTIC Science & Technology

2015-07-01

AFRL-AFOSR-UK-TR-2015-0034 Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene /Guanine...Interface – A Proposal for High Mobility, Organic Graphene Field Effect Transistors Eva Campo BANGOR UNIVERSITY COLLEGE ROAD BANGOR...April 2015 4. TITLE AND SUBTITLE Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene /Guanine Interface - A

Direct absorption spectroscopy sensor for temperature and H2O concentration of flat flame burner

NASA Astrophysics Data System (ADS)

Duan, Jin-hu; Jin, Xing; Wang, Guang-yu; Qu, Dong-sheng

2016-01-01

A tunable diode laser absorption sensor, based on direct absorption spectroscopy and time division multiplexing scheme, was developed to measure H2O concentration and temperature of flat flame burner. At the height of 15mm from the furnace surface, temperature and concentration were measured at different equivalence ratios. Then the distance between the laser and the furnace surface was changed while the equivalence ratio was fixed at 1 and experiments were performed to measure temperature and H2O concentration at every height. At last flame temperatures and H2O concentrations were obtained by simulation and computational analysis and these combustion parameters were compared with the reference. The results showed that the experimental results were in accordance with the reference values. Temperature errors were less than 4% and H2O component concentration errors were less than 5%and both of them reached their maximum when the equivalent ratio was set at 1. The temperature and H2O concentration increased with the height from furnace surface to laser when it varied from 3mm to 9mm and it decreased when it varied from 9mm to 30mm and they reached their maximum at the height of 9mm. Keywords: tunable diode laser, direct absorption spectroscopy

The water vapour self-continuum absorption in the infrared atmospheric windows: new laser measurements near 3.3 and 2.0 µm

NASA Astrophysics Data System (ADS)

Lechevallier, Loic; Vasilchenko, Semen; Grilli, Roberto; Mondelain, Didier; Romanini, Daniele; Campargue, Alain

2018-04-01

The amplitude, the temperature dependence, and the physical origin of the water vapour absorption continuum are a long-standing issue in molecular spectroscopy with direct impact in atmospheric and planetary sciences. In recent years, we have determined the self-continuum absorption of water vapour at different spectral points of the atmospheric windows at 4.0, 2.1, 1.6, and 1.25 µm, by highly sensitive cavity-enhanced laser techniques. These accurate experimental constraints have been used to adjust the last version (3.2) of the semi-empirical MT_CKD model (Mlawer-Tobin_Clough-Kneizys-Davies), which is widely incorporated in atmospheric radiative-transfer codes. In the present work, the self-continuum cross-sections, CS, are newly determined at 3.3 µm (3007 cm-1) and 2.0 µm (5000 cm-1) by optical-feedback-cavity enhanced absorption spectroscopy (OFCEAS) and cavity ring-down spectroscopy (CRDS), respectively. These new data allow extending the spectral coverage of the 4.0 and 2.1 µm windows, respectively, and testing the recently released 3.2 version of the MT_CKD continuum. By considering high temperature literature data together with our data, the temperature dependence of the self-continuum is also obtained.

Multiplexed absorption tomography with calibration-free wavelength modulation spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Weiwei; Kaminski, Clemens F., E-mail: cfk23@cam.ac.uk

2014-04-14

We propose a multiplexed absorption tomography technique, which uses calibration-free wavelength modulation spectroscopy with tunable semiconductor lasers for the simultaneous imaging of temperature and species concentration in harsh combustion environments. Compared with the commonly used direct absorption spectroscopy (DAS) counterpart, the present variant enjoys better signal-to-noise ratios and requires no baseline fitting, a particularly desirable feature for high-pressure applications, where adjacent absorption features overlap and interfere severely. We present proof-of-concept numerical demonstrations of the technique using realistic phantom models of harsh combustion environments and prove that the proposed techniques outperform currently available tomography techniques based on DAS.

X-ray absorption spectroscopy: EXAFS (Extended X-ray Absorption Fine Structure) and XANES (X-ray Absorption Near Edge Structure)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alp, E.E.; Mini, S.M.; Ramanathan, M.

1990-04-01

The x-ray absorption spectroscopy (XAS) had been an essential tool to gather spectroscopic information about atomic energy level structure in the early decades of this century. It has also played an important role in the discovery and systematization of rare-earth elements. The discovery of synchrotron radiation in 1952, and later the availability of broadly tunable synchrotron based x-ray sources have revitalized this technique since the 1970's. The correct interpretation of the oscillatory structure in the x-ray absorption cross-section above the absorption edge by Sayers et. al. has transformed XAS from a spectroscopic tool to a structural technique. EXAFS (Extended X-raymore » Absorption Fine Structure) yields information about the interatomic distances, near neighbor coordination numbers, and lattice dynamics. An excellent description of the principles and data analysis techniques of EXAFS is given by Teo. XANES (X-ray Absorption Near Edge Structure), on the other hand, gives information about the valence state, energy bandwidth and bond angles. Today, there are about 50 experimental stations in various synchrotrons around the world dedicated to collecting x-ray absorption data from the bulk and surfaces of solids and liquids. In this chapter, we will give the basic principles of XAS, explain the information content of essentially two different aspects of the absorption process leading to EXAFS and XANES, and discuss the source and samples limitations.« less

Terahertz spectroscopy of liver cirrhosis: investigating the origin of contrast

NASA Astrophysics Data System (ADS)

Sy, Stanley; Huang, Shengyang; Wang, Yi-Xiang J.; Yu, Jun; Ahuja, Anil T.; Zhang, Yuan-ting; Pickwell-MacPherson, Emma

2010-12-01

We have previously demonstrated that terahertz pulsed imaging is able to distinguish between rat tissues from different healthy organs. In this paper we report our measurements of healthy and cirrhotic liver tissues using terahertz reflection spectroscopy. The water content of the fresh tissue samples was also measured in order to investigate the correlations between the terahertz properties, water content, structural changes and cirrhosis. Finally, the samples were fixed in formalin to determine whether water was the sole source of image contrast in this study. We found that the cirrhotic tissue had a higher water content and absorption coefficient than the normal tissue and that even after formalin fixing there were significant differences between the normal and cirrhotic tissues' terahertz properties. Our results show that terahertz pulsed imaging can distinguish between healthy and diseased tissue due to differences in absorption originating from both water content and tissue structure.

[The study of CO2 cavity enhanced absorption and highly sensitive absorption spectroscopy].

PubMed

Pei, Shi-Xin; Gao, Xiao-Ming; Cui, Fen-Ping; Huang, Wei; Shao, Jie; Fan, Hong; Zhang, Wei-Jun

2005-12-01

Cavity enhanced absorption spectroscopy (CEAS) is a new spectral technology that is based on the cavity ring down absorption spectroscopy. In the present paper, a DFB encapsulation narrow line width tunable diode laser (TDL) was used as the light source. At the center output, the TDL radiation wavelength was 1.573 microm, and an optical cavity, which consisted of two high reflectivity mirrors (near 1.573 microm, the mirror reflectivity was about 0.994%), was used as a sample cell. A wavemeter was used to record the accurate frequency of the laser radiation. In the experiment, the method of scanning the optical cavity to change the cavity mode was used, when the laser frequency was coincident with one of the cavity mode; the laser radiation was coupled into the optical cavity and the detector could receive the light signals that escaped the optical cavity. As a result, the absorption spectrum of carbon dioxide weak absorption at low pressure was obtained with an absorption intensity of 1.816 x 10(-23) cm(-1) x (molecule x cm(-2)(-1) in a sample cell with a length of only 33.5 cm. An absorption sensitivity of about 3.62 x 10(-7) cm(-1) has been achieved. The experiment result indicated that the cavity enhanced absorption spectroscopy has the advantage of high sensivity, simple experimental setup, and easy operation.

Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering.

PubMed

Wu, Jinpeng; Sallis, Shawn; Qiao, Ruimin; Li, Qinghao; Zhuo, Zengqing; Dai, Kehua; Guo, Zixuan; Yang, Wanli

2018-04-17

Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid based on volatile solar and wind sources. The pressing demand of developing high-performance electrochemical energy storage solutions, i.e., batteries, relies on both fundamental understanding and practical developments from both the academy and industry. The formidable challenge of developing successful battery technology stems from the different requirements for different energy-storage applications. Energy density, power, stability, safety, and cost parameters all have to be balanced in batteries to meet the requirements of different applications. Therefore, multiple battery technologies based on different materials and mechanisms need to be developed and optimized. Incisive tools that could directly probe the chemical reactions in various battery materials are becoming critical to advance the field beyond its conventional trial-and-error approach. Here, we present detailed protocols for soft X-ray absorption spectroscopy (sXAS), soft X-ray emission spectroscopy (sXES), and resonant inelastic X-ray scattering (RIXS) experiments, which are inherently elemental-sensitive probes of the transition-metal 3d and anion 2p states in battery compounds. We provide the details on the experimental techniques and demonstrations revealing the key chemical states in battery materials through these soft X-ray spectroscopy techniques.

Incipient fire detection system

DOEpatents

Brooks, Jr., William K.

1999-01-01

A method and apparatus for an incipient fire detection system that receives gaseous samples and measures the light absorption spectrum of the mixture of gases evolving from heated combustibles includes a detector for receiving gaseous samples and subjecting the samples to spectroscopy and determining wavelengths of absorption of the gaseous samples. The wavelengths of absorption of the gaseous samples are compared to predetermined absorption wavelengths. A warning signal is generated whenever the wavelengths of absorption of the gaseous samples correspond to the predetermined absorption wavelengths. The method includes receiving gaseous samples, subjecting the samples to light spectroscopy, determining wavelengths of absorption of the gaseous samples, comparing the wavelengths of absorption of the gaseous samples to predetermined absorption wavelengths and generating a warning signal whenever the wavelengths of absorption of the gaseous samples correspond to the predetermined absorption wavelengths. In an alternate embodiment, the apparatus includes a series of channels fluidically connected to a plurality of remote locations. A pump is connected to the channels for drawing gaseous samples into the channels. A detector is connected to the channels for receiving the drawn gaseous samples and subjecting the samples to spectroscopy. The wavelengths of absorption are determined and compared to predetermined absorption wavelengths is provided. A warning signal is generated whenever the wavelengths correspond.

Stark absorption spectroscopy on the carotenoids bound to B800-820 and B800-850 type LH2 complexes from a purple photosynthetic bacterium, Phaeospirillum molischianum strain DSM120.

PubMed

Horibe, Tomoko; Qian, Pu; Hunter, C Neil; Hashimoto, Hideki

2015-04-15

Stark absorption spectroscopy was applied to clarify the structural differences between carotenoids bound to the B800-820 and B800-850 LH2 complexes from a purple photosynthetic bacterium Phaeospirillum (Phs.) molischianum DSM120. The former complex is produced when the bacteria are grown under stressed conditions of low temperature and dim light. These two LH2 complexes bind carotenoids with similar composition, 10% lycopene and 80% rhodopin, each with the same number of conjugated CC double bonds (n=11). Quantitative classical and semi-quantum chemical analyses of Stark absorption spectra recorded in the carotenoid absorption region reveal that the absolute values of the difference dipole moments |Δμ| have substantial differences (2 [D/f]) for carotenoids bound to either B800-820 or B800-850 complexes. The origin of this striking difference in the |Δμ| values was analyzed using the X-ray crystal structure of the B800-850 LH2 complex from Phs. molischianum DSM119. Semi-empirical molecular orbital calculations predict structural deformations of the major carotenoid, rhodopin, bound within the B800-820 complex. We propose that simultaneous rotations around neighboring CC and CC bonds account for the differences in the 2 [D/f] of the |Δμ| value. The plausible position of the rotation is postulated to be located around C21-C24 bonds of rhodopin. Copyright © 2014 Elsevier Inc. All rights reserved.

UV-VIS absorption spectroscopy: Lambert-Beer reloaded.

PubMed

Mäntele, Werner; Deniz, Erhan

2017-02-15

UV-VIS absorption spectroscopy is used in almost every spectroscopy laboratory for routine analysis or research. All spectroscopists rely on the Lambert-Beer Law but many of them are less aware of its limitations. This tutorial discusses typical problems in routine spectroscopy that come along with technical limitations or careless selection of experimental parameters. Simple rules are provided to avoid these problems. Copyright © 2016 Elsevier B.V. All rights reserved.

Absorption spectroscopy at the ultimate quantum limit from single-photon states

NASA Astrophysics Data System (ADS)

Whittaker, R.; Erven, C.; Neville, A.; Berry, M.; O'Brien, J. L.; Cable, H.; Matthews, J. C. F.

2017-02-01

Absorption spectroscopy is routinely used to characterise chemical and biological samples. For the state-of-the-art in laser absorption spectroscopy, precision is theoretically limited by shot-noise due to the fundamental Poisson-distribution of photon number in laser radiation. In practice, the shot-noise limit can only be achieved when all other sources of noise are eliminated. Here, we use wavelength-correlated and tuneable photon pairs to demonstrate how absorption spectroscopy can be performed with precision beyond the shot-noise limit and near the ultimate quantum limit by using the optimal probe for absorption measurement—single photons. We present a practically realisable scheme, which we characterise both the precision and accuracy of by measuring the response of a control feature. We demonstrate that the technique can successfully probe liquid samples and using two spectrally similar types of haemoglobin we show that obtaining a given precision in resolution requires fewer heralded single probe photons compared to using an idealised laser.

Light-induced radical formation and isomerization of an aromatic thiol in solution followed by time-resolved x-ray absorption spectroscopy at the sulfur K-edge

DOE PAGES

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.; ...

2017-02-20

Here, we applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ~70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemicalmore » reaction pathways and transient products of sulfur-containing molecules in solution.« less

Light-induced radical formation and isomerization of an aromatic thiol in solution followed by time-resolved x-ray absorption spectroscopy at the sulfur K-edge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.

Here, we applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ~70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemicalmore » reaction pathways and transient products of sulfur-containing molecules in solution.« less

Surface plasmon resonance near-infrared spectroscopy.

PubMed

Ikehata, Akifumi; Itoh, Tamitake; Ozaki, Yukihiro

2004-11-01

Near-infrared (NIR) spectroscopy is ill-suited to microanalysis because of its low absorptivity. We have developed a highly sensitive detection method for NIR spectroscopy based on absorption-sensitive surface plasmon resonance (SPR). The newly named SPR-NIR spectroscopy, which may open the way for NIR spectroscopy in microanalysis and surface science, is realized by an attachment of the Kretschmann configuration equipped with a mechanism for fine angular adjustment of incident light. The angular sweep of incident light enables us to make a tuning of a SPR peak for an absorption band of sample medium. From the dependences of wavelength, incident angle, and thickness of a gold film on the intensity of the SPR peak, it has been found that the absorbance can be enhanced by approximately 100 times compared with the absorbance obtained without the gold film under optimum conditions. This article reports the details of the experimental setup and the characteristics of absorption-sensitive SPR in the NIR region, together with some experimental results obtained by using it.

Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

DOE PAGES

Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; ...

2015-03-02

We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~10 6 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >10 7 laser pulses, wemore » also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.« less

Annealing induced atomic rearrangements on (Ga,In) (N,As) probed by hard X-ray photoelectron spectroscopy and X-ray absorption fine structure.

PubMed

Ishikawa, Fumitaro; Higashi, Kotaro; Fuyuno, Satoshi; Morifuji, Masato; Kondow, Masahiko; Trampert, Achim

2018-04-13

We study the effects of annealing on (Ga 0.64 ,In 0.36 ) (N 0.045 ,As 0.955 ) using hard X-ray photoelectron spectroscopy and X-ray absorption fine structure measurements. We observed surface oxidation and termination of the N-As bond defects caused by the annealing process. Specifically, we observed a characteristic chemical shift towards lower binding energies in the photoelectron spectra related to In. This phenomenon appears to be caused by the atomic arrangement, which produces increased In-N bond configurations within the matrix, as indicated by the X-ray absorption fine structure measurements. The reduction in the binding energies of group-III In, which occurs concomitantly with the atomic rearrangements of the matrix, causes the differences in the electronic properties of the system before and after annealing.

Identifying and Quantifying Adulterants in Extra Virgin Olive Oil of the Picual Varietal by Absorption Spectroscopy and Nonlinear Modeling.

PubMed

Aroca-Santos, Regina; Cancilla, John C; Matute, Gemma; Torrecilla, José S

2015-06-17

In this research, the detection and quantification of adulterants in one of the most common varieties of extra virgin olive oil (EVOO) have been successfully carried out. Visible absorption information was collected from binary mixtures of Picual EVOO with one of four adulterants: refined olive oil, orujo olive oil, sunflower oil, and corn oil. The data gathered from the absorption spectra were used as input to create an artificial neural network (ANN) model. The designed mathematical tool was able to detect the type of adulterant with an identification rate of 96% and to quantify the volume percentage of EVOO in the samples with a low mean prediction error of 1.2%. These significant results make ANNs coupled with visible spectroscopy a reliable, inexpensive, user-friendly, and real-time method for difficult tasks, given that the matrices of the different adulterated oils are practically alike.

X-ray absorption spectroscopy and X-ray photoelectron spectroscopy studies of CaSO 4:Dy thermoluminescent phosphors

NASA Astrophysics Data System (ADS)

Bakshi, A. K.; Jha, S. N.; Olivi, L.; Phase, D. M.; Kher, R. K.; Bhattacharyya, D.

2007-11-01

Extended X-ray absorption fine structure (EXAFS) measurements have been carried out on CaSO4:Dy phosphor samples at the Dy L3 edge with synchrotron radiation. Measurements were carried out on a set of samples which were subjected to post-preparation annealing at different temperatures and for different cycles. The EXAFS data have been analysed to find the Dy-S and Dy-O bond lengths in the neighbourhood of the Dy atoms in a CaSO4 matrix. The observations from EXAFS measurements were verified with XANES and XPS techniques. On the basis of these measurements, efforts were made to explain the loss of thermoluminescence sensitivity of CaSO4:Dy phosphors after repeated cycles of annealing at 400 °C in air for 1 h.

Simultaneous optimization method for absorption spectroscopy postprocessing.

PubMed

Simms, Jean M; An, Xinliang; Brittelle, Mack S; Ramesh, Varun; Ghandhi, Jaal B; Sanders, Scott T

2015-05-10

A simultaneous optimization method is proposed for absorption spectroscopy postprocessing. This method is particularly useful for thermometry measurements based on congested spectra, as commonly encountered in combustion applications of H2O absorption spectroscopy. A comparison test demonstrated that the simultaneous optimization method had greater accuracy, greater precision, and was more user-independent than the common step-wise postprocessing method previously used by the authors. The simultaneous optimization method was also used to process experimental data from an environmental chamber and a constant volume combustion chamber, producing results with errors on the order of only 1%.

High spatial resolution measurements of NO2 applying Topographic Target Light scattering-Differential Optical Absorption Spectroscopy (ToTaL-DOAS)

NASA Astrophysics Data System (ADS)

Frins, E.; Platt, U.; Wagner, T.

2008-12-01

Topographic Target Light scattering - Differential Optical Absorption Spectroscopy (ToTaL-DOAS), also called Target-DOAS, is a novel experimental procedure to retrieve trace gas concentrations present in the low atmosphere. Scattered sunlight (diffuse or specular) reflected from natural or artificial targets located at different distances are analyzed to retrieve the spatial distribution of the concentration of different trace gases like NO2, SO2 and others. We report high spatial resolution measurements of NO2 mixing ratios in the city of Montevideo (Uruguay) observing three buildings as targets with a Mini-DOAS instrument. Our instrument was 146 m, 196 m, and 280 m apart from three different buildings located along a main Avenue. We obtain temporal variation of NO2 mixing ratios between 30 ppb and 65 ppb from measurements of November 2007 and mixing ratios up to 50 ppb from measurements of August and September 2008. Our measurements demonstrate that ToTaL-DOAS observations can be made over relative short distances. In polluted air masses, the retrieved absorption signal was found to be sufficiently strong to allow measurements over distances in the range of several tens of meters.

Ultrafast quantum control of ionization dynamics in krypton.

PubMed

Hütten, Konrad; Mittermair, Michael; Stock, Sebastian O; Beerwerth, Randolf; Shirvanyan, Vahe; Riemensberger, Johann; Duensing, Andreas; Heider, Rupert; Wagner, Martin S; Guggenmos, Alexander; Fritzsche, Stephan; Kabachnik, Nikolay M; Kienberger, Reinhard; Bernhardt, Birgitta

2018-02-19

Ultrafast spectroscopy with attosecond resolution has enabled the real time observation of ultrafast electron dynamics in atoms, molecules and solids. These experiments employ attosecond pulses or pulse trains and explore dynamical processes in a pump-probe scheme that is selectively sensitive to electronic state of matter via photoelectron or XUV absorption spectroscopy or that includes changes of the ionic state detected via photo-ion mass spectrometry. Here, we demonstrate how the implementation of combined photo-ion and absorption spectroscopy with attosecond resolution enables tracking the complex multidimensional excitation and decay cascade of an Auger auto-ionization process of a few femtoseconds in highly excited krypton. In tandem with theory, our study reveals the role of intermediate electronic states in the formation of multiply charged ions. Amplitude tuning of a dressing laser field addresses different groups of decay channels and allows exerting temporal and quantitative control over the ionization dynamics in rare gas atoms.

Singularities in x-ray spectra of metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahan, G.D.

1987-08-01

The x-ray spectroscopies discussed are absorption, emission, and photoemission. The singularities show up in each of them in a different manner. In absorption and emission they show up as power law singularities at the thresholds frequencies. This review will emphasize two themes. First a simple model is proposed to describe this phenomena, which is now called the MND model after MAHAN-NOZIERES-DeDOMINICIS. Exact analytical solutions are now available for this model for the three spectroscopies discussed above. These analytical models can be evaluated numerically in a simple way. The second theme of this review is that great care must be usedmore » when comparing the theory to experiment. A number of factors influence the edge shapes in x-ray spectroscopy. The edge singularities play an important role, and are observed in many matals. Quantitative fits of the theory to experiment require the consideration of other factors. 51 refs.« less

X-ray absorption spectroscopy to determine originating depth of electrons that form an inelastic background of Auger electron spectrum

NASA Astrophysics Data System (ADS)

Isomura, Noritake; Cui, Yi-Tao; Murai, Takaaki; Oji, Hiroshi; Kimoto, Yasuji

2017-07-01

In Auger electron spectroscopy (AES), the spectral background is mainly due to inelastic scattering of Auger electrons that lose their kinetic energy in a sample bulk. To investigate the spectral components within this background for SiO2(19.3 nm)/Si(100) with known layer thickness, X-ray absorption spectroscopy (XAS) was used in the partial-electron-yield (PEY) mode at several electron kinetic energies to probe the background of the Si KLL Auger peak. The Si K-edge PEY-XAS spectra constituted of both Si and SiO2 components at each kinetic energy, and their component fractions were approximately the same as those derived from the simulated AES background for the same sample structure. The contributions of Auger electrons originating from layers at different depths to the inelastic background could thus be identified experimentally.

OH absorption spectroscopy in a flame using spatial heterodyne spectroscopy

NASA Astrophysics Data System (ADS)

Bartula, Renata J.; Ghandhi, Jaal B.; Sanders, Scott T.; Mierkiewicz, Edwin J.; Roesler, Fred L.; Harlander, John M.

2007-12-01

We demonstrate measurements of OH absorption spectra in the post-flame zone of a McKenna burner using spatial heterodyne spectroscopy (SHS). SHS permits high-resolution, high-throughput measurements. In this case the spectra span ~308-310 nm with a resolution of 0.03 nm, even though an extended source (extent of ~2×10-7 m2 rad2) was used. The high spectral resolution is important for interpreting spectra when multiple absorbers are present for inferring accurate gas temperatures from measured spectra and for monitoring weak absorbers. The present measurement paves the way for absorption spectroscopy by SHS in practical combustion devices, such as reciprocating and gas-turbine engines.

A differential optical absorption spectroscopy method for retrieval from ground-based Fourier transform spectrometers measurements of the direct solar beam

NASA Astrophysics Data System (ADS)

Huo, Yanfeng; Duan, Minzheng; Tian, Wenshou; Min, Qilong

2015-08-01

A differential optical absorption spectroscopy (DOAS)-like algorithm is developed to retrieve the column-averaged dryair mole fraction of carbon dioxide from ground-based hyper-spectral measurements of the direct solar beam. Different to the spectral fitting method, which minimizes the difference between the observed and simulated spectra, the ratios of multiple channel-pairs—one weak and one strong absorption channel—are used to retrieve from measurements of the shortwave infrared (SWIR) band. Based on sensitivity tests, a super channel-pair is carefully selected to reduce the effects of solar lines, water vapor, air temperature, pressure, instrument noise, and frequency shift on retrieval errors. The new algorithm reduces computational cost and the retrievals are less sensitive to temperature and H2O uncertainty than the spectral fitting method. Multi-day Total Carbon Column Observing Network (TCCON) measurements under clear-sky conditions at two sites (Tsukuba and Bremen) are used to derive xxxx for the algorithm evaluation and validation. The DOAS-like results agree very well with those of the TCCON algorithm after correction of an airmass-dependent bias.

A spectroscopic study of the chromatic properties of GafChromicEBT3 films.

PubMed

Callens, M; Crijns, W; Simons, V; De Wolf, I; Depuydt, T; Maes, F; Haustermans, K; D'hooge, J; D'Agostino, E; Wevers, M; Pfeiffer, H; Van Den Abeele, K

2016-03-01

This work provides an interpretation of the chromatic properties of GafChromicEBT3 films based on the chemical nature of the polydiacetylene (PDA) molecules formed upon interaction with ionizing radiation. The EBT3 films become optically less transparent with increasing radiation dose as a result of the radiation-induced polymerization of diacetylene monomers. In contrast to empirical quantification of the chromatic properties, less attention has been given to the underlying molecular mechanism that induces the strong decrease in transparency. Unlaminated GafChromicEBT3 films were irradiated with a 6 MV photon beam to dose levels up to 20 Gy. The optical absorption properties of the films were investigated using visible (vis) spectroscopy. The presence of PDA molecules in the active layer of the EBT3 films was investigated using Raman spectroscopy, which probes the vibrational modes of the molecules in the layer. The vibrational modes assigned to PDA's were used in a theoretical vis-absorption model to fit our experimental vis-absorption spectra. From the fit parameters, one can assess the relative contribution of different PDA conformations and the length distribution of PDA's in the film. Vis-spectroscopy shows that the optical density increases with dose in the full region of the visible spectrum. The Raman spectrum is dominated by two vibrational modes, most notably by the ν(C≡C) and the ν(C=C) stretching modes of the PDA backbone. By fitting the vis-absorption model to experimental spectra, it is found that the active layer contains two distinct PDA conformations with different absorption properties and reaction kinetics. Furthermore, the mean PDA conjugation length is found to be 2-3 orders of magnitude smaller than the crystals PDA's are embedded in. Vis- and Raman spectroscopy provided more insight into the molecular nature of the radiochromic properties of EBT3 films through the identification of the excited states of PDA and the presence of two PDA conformations. The improved knowledge on the molecular composition of EBT3's active layer provides a framework for future fundamental modeling of the dose-response.

Sensor for headspace pressure and H2O concentration measurements in closed vials by tunable diode laser absorption spectroscopy

NASA Astrophysics Data System (ADS)

Cai, Tingdong; Wang, Guishi; Cao, Zhensong; Zhang, Weijun; Gao, Xiaoming

2014-07-01

The concentration of H2O and the pressure in the headspace of vials are simultaneously measured by a tunable diode laser sensor based on absorption spectroscopy techniques. The 7168.437 cm-1 spectral line of H2O is chosen as the sensing transition for its strong absorption strength and being reasonably far away from its neighboring molecular transitions. In order to prevent interference absorption by ambient water vapor in the room air, a difference between the measured signal and the referenced signal is used to calculate the pressure and H2O concentration in the headspace of vials, eliminating the need for inert gas purges and calibration with known gas. The validation of the sensor is conducted in a static vial, yielding an accuracy of 1.23% for pressure and 3.81% for H2O concentration. The sensitivity of the sensor is estimated to be about 2.5 Torr for pressure and 400 ppm for H2O concentration over a 3 cm absorption path length respectively. Accurate measurements for commercial freeze-dried products demonstrate the in-line applications of the sensor for the pharmaceutical industry.

Time integrated spectroscopy of turbid media based on the microscopic beer-lambert law: application to small-size phantoms having different boundary conditions.

PubMed

Zhang, H; Urakami, T; Tsuchiya, Y; Lu, Z; Hiruma, T

1999-01-01

Continued work on time-integrated spectroscopy (TIS) is presented to quantify absorber concentrations in turbid media. We investigated the applicability of the TIS method to small-size media that have different boundary conditions by measuring two 20×20×50 mm3 cuboid liquid tissue-like phantoms at various absorption levels (absorption coefficients of the phantom from 2.5×10-3 to 4.4×10-2 mm-1 at 782 nm and from 3.1×10-3 to 2.7×10-2 mm-1 at 831 nm). The scattering and absorbing solution was filled into ordinary and black-anodized aluminum containers to provide different boundary conditions. By means of a single equation, the absorber concentrations have been recovered within errors of a few percent in both cases. This demonstrates that the TIS method can quantify absorbers in small-size media having different boundary conditions. © 1999 Society of Photo-Optical Instrumentation Engineers.

Optical absorption of suspended graphene based metal plasmonic grating in the visible range

NASA Astrophysics Data System (ADS)

Han, Y. X.; Chen, B. B.; Yang, J. B.; He, X.; Huang, J.; Zhang, J. J.; Zhang, Z. J.

2018-05-01

We employ finite-difference time-domain ( FDTD) method and Raman spectroscopy to study the properties of graphene, which is suspended on a gold/SiO2/Si grating structure with different trench depth of SiO2 layer. The absorption enhancement of suspended graphene and plasmonic resonance of metal grating are investigated in the visible range using 2D FDTD method. Moreover, it is found that the intensity of the Raman features depends very sensitively on the trench depth of SiO2 layer. Raman enhancement in our experiments is attributed to the enhanced optical absorption of graphene by near-field coupling based metal plasmonic grating. The enhanced absorption of suspended graphene modulated by localized surface plasmon resonance (LSPR) offers a potential application for opto-electromechanical devices.

The widetilde{A}←widetilde{X} ABSORPTION SPECTRUM OF 2-NITROOXYBUTYL PEROXY RADICAL

NASA Astrophysics Data System (ADS)

Eddingsaas, Nathan; Takematsu, Kana; Okumura, Mitchio

2009-06-01

The nitrate radical is an important atmospheric oxidant in the nighttime sky. Nitrate radicals react by addition to alkenes, and in the presence of oxygen form nitrooxyalkyl peroxy radicals. The peroxy radical formed from the reaction of 2-butene, nitrate radical, and oxygen was detected by cavity ringdown spectroscopy (CRDS) via its widetilde{A}←widetilde{X} electronic absorption spectrum. The widetilde{A}←widetilde{X} electronic transition is a bound-bound transition with enough structure to distinguish between different peroxy radicals as well as different conformers of the same peroxy radical. Two conformers of the nitrooxybutyl peroxy radical have been observed; the absorption features are red shifted from the same absorption features of sec-butyl peroxy radical. Calculations on the structure of nitrooxyalkyl peroxy radicals and general trends of the position of the widetilde{A}←widetilde{X} absorption transitions have also been performed and compared to those of unsubstituted peroxy radicals.

The DTIC Review: Volume 2, Number 4, Surviving Chemical and Biological Warfare

DTIC Science & Technology

1996-12-01

CHROMATOGRAPHIC ANALYSIS, NUCLEAR MAGNETIC RESONANCE, INFRARED SPECTROSCOPY , ARMY RESEARCH, DEGRADATION, VERIFICATION, MASS SPECTROSCOPY , LIQUID... mycotoxins . Such materials are not attractive as weapons of mass destruction however, as large amounts are required to produce lethal effects. In...VERIFICATION, ATOMIC ABSORPTION SPECTROSCOPY , ATOMIC ABSORPTION. AL The DTIC Review Defense Technical Information Center AD-A285 242 AD-A283 754 EDGEWOOO

Hollow waveguide cavity ringdown spectroscopy

NASA Technical Reports Server (NTRS)

Dreyer, Chris (Inventor); Mungas, Greg S. (Inventor)

2012-01-01

Laser light is confined in a hollow waveguide between two highly reflective mirrors. This waveguide cavity is used to conduct Cavity Ringdown Absorption Spectroscopy of loss mechanisms in the cavity including absorption or scattering by gases, liquid, solids, and/or optical elements.

Flameless Atomic Absorption Spectroscopy: Effects of Nitrates and Sulfates.

DTIC Science & Technology

1980-05-01

ATTACHED DDJ~P 1413 EDITION 01 INO, 6 5 IabSoLEr J UjN!LbAa~ A- i SELU 0 IONOF I tG 651 J Flameless Atomic Absorption Spectroscopy: Effects of Nitrates...analytical techniques, flameless atomic absorption is subject to matrix or interference effects. Upon heating, nitrate and sulfate salts decompose to...Eklund and J.E. Smith, Anal Chem, 51, 1205 (1979) R.H. Eklund and J.A. Holcombe, Anal Chim. Acta, 109, 97 (1979) FLAMELESS ATOMIC ABSORPTION

[Study on Identification of Three Medicinal Plant Leaves from Elaeagnus Genus by Infrared Spectroscopy].

PubMed

Zhang, Fei; Li, Lu-yang; Ding, Qi; Hu, Ji-qing; Long, Wei-fang; Wan, Ding-rong

2015-01-01

To study and identify the three species of dry medicinal plant leaves trom Elaeagnus genus (E. pungens, E. lanceolata and E. henryi) by Infrared Spectroscopy(IR). Fourier transform infrared spectroscopy and second derivative infrared spectroscopy were used to study and compare the characteristics of leaves of three Elaeagnus medicinal plants. The IR spectra and second derivative infrared spectra of the three Elaeagnus plants leaves were similar on the whole, the intensity or ratio of intensity of some absorption peaks still had certain distinctions, and the differences of the second derivative infrared spectra were more obvious. There were only slight differences between large and small leaf type of samples of Elaeagnus lanceolata; the differences of the plant leaves of one species collected in different harvest periods were far smaller than those of others belonging to the same genus. IR can be relatively reliably used for identification of the three Elaeagnus leaves.

Determination of the water vapor continuum absorption by THz-TDS and Molecular Response Theory.

PubMed

Yang, Yihong; Mandehgar, Mahboubeh; Grischkowsky, D

2014-02-24

Determination of the water vapor continuum absorption from 0.35 to 1 THz is reported. The THz pulses propagate though a 137 m long humidity-controlled chamber and are measured by THz time-domain spectroscopy (THz-TDS). The average relative humidity along the entire THz path is precisely obtained by measuring the difference between transit times of the sample and reference THz pulses to an accuracy of 0.1 ps. Using the measured total absorption and the calculated resonance line absorption with the Molecular Response Theory lineshape, based on physical principles and measurements, an accurate continuum absorption is obtained within four THz absorption windows, that agrees well with the empirical theory. The absorption is significantly smaller than that obtained using the van Vleck-Weisskopf lineshape with a 750 GHz cut-off.

Pulsatile and steady-state hemodynamics of the human patella bone by diffuse optical spectroscopy.

PubMed

Farzam, Parisa; Zirak, Peyman; Binzoni, Tiziano; Durduran, Turgut

2013-08-01

The cardiac cycle related pulsatile behavior of the absorption and scattering coefficients of diffuse light and the corresponding alterations in hemoglobin concentrations in the human patella was studied. The pulsations in scattering is considerably smaller than absorption. The difference in amplitude of absorption coefficient pulsations for different wavelengths was translated to pulsations in oxygenated and deoxygenated hemoglobin, which leads to strong pulsations in the total hemoglobin concentration and oxygen saturation. The physiological origin of the observed signals was confirmed by applying a thigh-cuff. Moreover, we have investigated the optical and physiological properties of the patella bone and their changes in response to arterial cuff occlusion.

Application of Cavity Enhanced Absorption Spectroscopy to the Detection of Nitric Oxide, Carbonyl Sulphide, and Ethane—Breath Biomarkers of Serious Diseases

PubMed Central

Wojtas, Jacek

2015-01-01

The paper presents one of the laser absorption spectroscopy techniques as an effective tool for sensitive analysis of trace gas species in human breath. Characterization of nitric oxide, carbonyl sulphide and ethane, and the selection of their absorption lines are described. Experiments with some biomarkers showed that detection of pathogenic changes at the molecular level is possible using this technique. Thanks to cavity enhanced spectroscopy application, detection limits at the ppb-level and short measurements time (<3 s) were achieved. Absorption lines of reference samples of the selected volatile biomarkers were probed using a distributed feedback quantum cascade laser and a tunable laser system consisting of an optical parametric oscillator and difference frequency generator. Setup using the first source provided a detection limit of 30 ppb for nitric oxide and 250 ppb for carbonyl sulphide. During experiments employing a second laser, detection limits of 0.9 ppb and 0.3 ppb were obtained for carbonyl sulphide and ethane, respectively. The conducted experiments show that this type of diagnosis would significantly increase chances for effective therapy of some diseases. Additionally, it offers non-invasive and real time measurements, high sensitivity and selectivity as well as minimizing discomfort for patients. For that reason, such sensors can be used in screening for early detection of serious diseases. PMID:26091398

Application of Cavity Enhanced Absorption Spectroscopy to the Detection of Nitric Oxide, Carbonyl Sulphide, and Ethane--Breath Biomarkers of Serious Diseases.

PubMed

Wojtas, Jacek

2015-06-17

The paper presents one of the laser absorption spectroscopy techniques as an effective tool for sensitive analysis of trace gas species in human breath. Characterization of nitric oxide, carbonyl sulphide and ethane, and the selection of their absorption lines are described. Experiments with some biomarkers showed that detection of pathogenic changes at the molecular level is possible using this technique. Thanks to cavity enhanced spectroscopy application, detection limits at the ppb-level and short measurements time (<3 s) were achieved. Absorption lines of reference samples of the selected volatile biomarkers were probed using a distributed feedback quantum cascade laser and a tunable laser system consisting of an optical parametric oscillator and difference frequency generator. Setup using the first source provided a detection limit of 30 ppb for nitric oxide and 250 ppb for carbonyl sulphide. During experiments employing a second laser, detection limits of 0.9 ppb and 0.3 ppb were obtained for carbonyl sulphide and ethane, respectively. The conducted experiments show that this type of diagnosis would significantly increase chances for effective therapy of some diseases. Additionally, it offers non-invasive and real time measurements, high sensitivity and selectivity as well as minimizing discomfort for patients. For that reason, such sensors can be used in screening for early detection of serious diseases.

Femtosecond spectroscopy of native and carotenoidless purple-bacterial LH2 clarifies functions of carotenoids.

PubMed

Theiss, Christoph; Leupold, Dieter; Moskalenko, Andrei A; Razjivin, Andrei P; Eichler, Hans J; Lokstein, Heiko

2008-06-01

EET between the two circular bacteriochlorophyll compartments B800 and B850 in native (containing the carotenoid rhodopin) and carotenoidless LH2 isolated from the photosynthetic purple sulfur bacterium Allochromatium minutissimum was investigated by femtosecond time-resolved transient absorption spectroscopy. Both samples were excited with 120-fs laser pulses at 800 nm, and spectral evolution was followed in the 720-955 nm range at different delay times. No dependence of transient absorption in the B800 band on the presence of the carotenoid rhodopin was found. Together with the likewise virtually unchanged absorption spectra in the bacteriochlorophyll Q(y) region, these observations suggest that absence of rhodopin does not significantly alter the structure of the pigment-protein complex including interactions between bacteriochlorophylls. Apparently, rhodopin does also not accelerate B800 to B850 EET in LH2, contrary to what has been suggested previously. Moreover, "carotenoid-catalyzed internal conversion" can also be excluded for the bacteriochlorophylls in LH2 of A. minutissimum. Together with previous results obtained with two-photon fluorescence excitation spectroscopy, it can also be concluded that there is neither EET from rhodopin to B800 nor (back-)EET from B800 to rhodopin.

Study of the Pigments in Colombian Powdered Coffee Using Photoacoustic Spectroscopy

NASA Astrophysics Data System (ADS)

Gordillo-Delgado, F.; Bedoya, A.; Marín, E.

2017-01-01

Biological pigments are chemical compounds that absorb light in the wavelength range of the visible region. They are present in all living organisms, vegetables being among their main producers. In this work, the photoacoustic spectroscopy technique was used to investigate some qualitative features related to pigments of ground and roasted coffee. The samples were collected at several Colombian commercial markets from different regions. Colombian coffee is known worldwide for its quality and flavor, being the main agricultural export product of the country. Therefore, it is important to study the composition and color of ground and roasted coffee in order to show quality and special characteristics of local varieties. Studying the content of pigments after roasting and grinding the coffee can allow a better understanding of the coloring process, which can lead to the definition of new criteria for evaluating the quality and other characteristics of the final product by comparing the optical spectra. In this work, the optical absorption spectra obtained by photoacoustic spectroscopy show absorption bands that match those of the pigments capsanthin, lutein and chlorophyll. In addition, an absorption peak in the near-infrared region was revealed, which also provides information regarding the composition of roasted and ground coffee.

High resolution infrared spectroscopy: Some new approaches and applications to planetary atmospheres

NASA Technical Reports Server (NTRS)

Mumma, M. J.

1978-01-01

The principles of spectral line formation and of techniques for retrieval of atmospheric temperature and constituent profiles are discussed. Applications to the atmospheres of Earth, Mars, Venus, and Jupiter are illustrated by results obtained with Fourier transform and infrared heterodyne spectrometers at resolving powers (lambda/delta hyperon lambda of approximately 10,000 and approximately 10 to the seventh power), respectively, showing the high complementarity of spectroscopy at these two widely different resolving powers. The principles of heterodyne spectroscopy are presented and its applications to atmospheric probing and to laboratory spectroscopy are discussed. Direct absorption spectroscopy with tuneable semiconductor lasers is discussed in terms of precision frequency-and line strength-measurements, showing substantial advances in laboratory infrared spectroscopy.

Infrared heterodyne spectroscopy of atmospheric ozone

NASA Technical Reports Server (NTRS)

Frerking, M. A.; Muehlner, D. J.

1977-01-01

The absorption spectrum of atmospheric ozone is measured within a 1/cm region at 1100/cm, using an IR heterodyne detector (spectrometer with CO2 local oscillator) developed for astronomical work. Absorption spectra obtained by passing radiation from the tunable diode laser through an absorption cell, heterodyne spectra of atmospheric ozone, and a predicted atmospheric spectrum are compared. Water vapor absorbing in the region of interest (1100/cm) is also considered. Preliminary results encourage the use of diode laser local oscillators in tunable heterodyne detector systems for spectroscopy of atmospheric ozone and remote high-resolution spectroscopy of atmospheric constituents and pollutants.

Optical remote measurement of toxic gases

NASA Technical Reports Server (NTRS)

Grant, W. B.; Kagann, R. H.; McClenny, W. A.

1992-01-01

Enactment of the Clean Air Act Amendments (CAAA) of 1990 has resulted in increased ambient air monitoring needs for industry, some of which may be met efficiently using open-path optical remote sensing techniques. These techniques include Fourier transform spectroscopy, differential optical absorption spectroscopy, laser long-path absorption, differential absorption lidar, and gas cell correlation spectroscopy. With this regulatory impetus, it is an opportune time to consider applying these technologies to the remote and/or path-averaged measurement and monitoring of toxic gases covered by the CAAA. This article reviews the optical remote sensing technology and literature for that application.

Crystal structure, Hirshfeld surfaces computational study and physicochemical characterization of the hybrid material (C7H10N)2[SnCl6]·H2O

NASA Astrophysics Data System (ADS)

BelhajSalah, S.; Abdelbaky, Mohammed S. M.; García-Granda, Santiago; Essalah, K.; Ben Nasr, C.; Mrad, M. L.

2018-01-01

A novel hybrid compound, bis(4-methylanilinium)hexachlorostannate(IV) monohydrate, formulated as (C7H10N)2[SnCl6]·H2O, has been prepared and characterized by powder and single crystal X-ray diffraction (XRD), Hirshfeld surface analysis, infrared spectroscopy (IR), optical study, differential thermal analysis(DTA) and X-ray photoelectron spectroscopy analysis (XPS). The title compound crystallizes in the monoclinic space group P21/c with a = 13.093(1)Å, b = 7.093(6)Å, c = 24.152(2)Å, β = 98.536(4)⁰ and V = 2218.4(4) Å3. Their crystal structure exhibits alternating inorganic layers parallel to the (ab) plane at z = n/2. The different entities, [SnCl6]2-, organic cations and water molecules, are connected via hydrogen bonds to form a three-dimensional network. The powder XRD data confirms the phase purity of the crystalline sample. The intermolecular interactions were investigated by Hirshfeld surfaces. The vibrational absorption bands were identified by IR spectroscopy and have been discussed. The optical properties of the crystal were studied by using optical absorption, UV-visible absorption and photoluminescence spectroscopy studies. The compound was also characterized by DTA to determine its thermal behavior with respect to the temperature. Finally, XPS technique is reported for analyzing the surface chemistry of this compound.

Improving Optical Absorption Models for Harsh Planetary Atmospheres: Laboratory Spectroscopy at Venus Surface Conditions

NASA Astrophysics Data System (ADS)

Cole, Ryan Kenneth; Schroeder, Paul James; Diego Draper, Anthony; Rieker, Gregory Brian

2018-06-01

Modelling absorption spectra in high pressure, high temperature environments is complicated by the increased relevance of higher order collisional phenomena (e.g. line mixing, collision-induced absorption, finite duration of collisions) that alter the spectral lineshape. Accurate reference spectroscopy in these conditions is of interest for mineralogy and radiative transfer studies of Venus as well as other dense planetary atmospheres. We present a new, high pressure, high temperature absorption spectroscopy facility at the University of Colorado Boulder. This facility employs a dual frequency comb absorption spectrometer to record broadband (500nm), high resolution (~0.002nm) spectra in conditions comparable to the Venus surface (730K, 90bar). Measurements of the near-infrared spectrum of carbon dioxide at high pressure and temperature will be compared to modeled spectra extrapolated from the HITRAN 2016 database as well as other published models that include additional collisional physics. This comparison gives insight into the effectiveness of existing absorption databases for modeling the lower Venus atmosphere as well as the need to expand absorption models to suit these conditions.

Operando characterization of batteries using x-ray absorption spectroscopy: advances at the beamline XAFS at synchrotron Elettra

NASA Astrophysics Data System (ADS)

Aquilanti, Giuliana; Giorgetti, Marco; Dominko, Robert; Stievano, Lorenzo; Arčon, Iztok; Novello, Nicola; Olivi, Luca

2017-02-01

X-ray absorption spectroscopy is a synchrotron radiation based technique that is able to provide information on both local structure and electronic properties in a chemically selective manner. It can be used to characterize the dynamic processes that govern the electrochemical energy storage in batteries, and to shed light on the redox chemistry and changes in structure during galvanostatic cycling to design cathode materials with improved properties. Operando XAS studies have been performed at beamline XAFS at Elettra on different systems. For Li-ion batteries, a multiedge approach revealed the role of the different cathode components during the charge and discharge of the battery. In addition, Li-S batteries for automotive applications were studied. Operando sulfur K-edge XANES and EXAFS analysis was used to characterize the redox chemistry of sulfur, and to relate the electrochemical mechanism to its local structure.

Thermal Boundary Layer Effects on Line-of-Sight Tunable Diode Laser Absorption Spectroscopy (TDLAS) Gas Concentration Measurements.

PubMed

Qu, Zhechao; Werhahn, Olav; Ebert, Volker

2018-06-01

The effects of thermal boundary layers on tunable diode laser absorption spectroscopy (TDLAS) measurement results must be quantified when using the line-of-sight (LOS) TDLAS under conditions with spatial temperature gradient. In this paper, a new methodology based on spectral simulation is presented quantifying the LOS TDLAS measurement deviation under conditions with thermal boundary layers. The effects of different temperature gradients and thermal boundary layer thickness on spectral collisional widths and gas concentration measurements are quantified. A CO 2 TDLAS spectrometer, which has two gas cells to generate the spatial temperature gradients, was employed to validate the simulation results. The measured deviations and LOS averaged collisional widths are in very good agreement with the simulated results for conditions with different temperature gradients. We demonstrate quantification of thermal boundary layers' thickness with proposed method by exploitation of the LOS averaged the collisional width of the path-integrated spectrum.

Structural properties of rutile TiO2 nanoparticles accumulated in a model of gastrointestinal epithelium elucidated by micro-beam x-ray absorption fine structure spectroscopy

NASA Astrophysics Data System (ADS)

Veronesi, G.; Brun, E.; Fayard, B.; Cotte, M.; Carrière, M.

2012-05-01

Micro-beam x-ray absorption fine structure spectroscopy was used to investigate rutile TiO2 nanoparticles internalized into gastrointestinal cells during their crossing of a gut model barrier. Nanoparticles diluted in culture medium tend to accumulate in cells after 48 h exposure; however, no spectral differences arise between particles in cellular and in acellular environments, as corroborated by quantitative analysis. This finding establishes that no modification of the lattice properties of the nanoparticles occurs upon interaction with the barrier. These measurements demonstrate the possibility of interrogating nanoparticles in situ within cells, suggesting a way to investigate their fate when incorporated in biological hosts.

Quantify Glucose Level in Freshly Diabetic's Blood by Terahertz Time-Domain Spectroscopy

NASA Astrophysics Data System (ADS)

Chen, Hua; Chen, Xiaofeng; Ma, Shihua; Wu, Xiumei; Yang, Wenxing; Zhang, Weifeng; Li, Xiao

2018-04-01

We demonstrate the capability of terahertz (THz) time-domain spectroscopy (TDS) to quantify glucose level in ex vivo freshly diabetic's blood. By investigating the THz spectra of different human blood, we find out THz absorption coefficients reflect a high sensitivity to the glucose level in blood. With a quantitative analysis of 70 patients, we demonstrate that the THz absorption coefficients and the blood glucose levels perform a linear relationship. A comparative experiment between THz measurement and glucometers is also conducted with another 20 blood samples, and the results confirm that the relative error is as less as 15%. Our ex vivo human blood study indicates that THz technique has great potential application to diagnose blood glucose level in clinical practice.

A best-case probe, light source, and database for H2O absorption thermometry to 2100 K and 50 bar

NASA Astrophysics Data System (ADS)

Brittelle, Mack S.

This work aspired to improve the ability of forthcoming researchers to utilize near IR H2O absorption spectroscopy for thermometry with development of three best-case techniques: the design of novel high temperature sapphire optical access probes, the construction of a fixed-wavelength H 2O absorption spectroscopy system enhanced by an on-board external-cavity diode laser, and the creation of an architecture for a high-temperature and -pressure H2O absorption cross-section database. Each area's main goal was to realize the best-case for direct absorption spectroscopy H2O vapor thermometry at combustion conditions. Optical access to combustion devices is explored through the design and implementation of two versions of novel high-temperature (2000 K) sapphire immersion probes (HTSIPs) for use in ambient flames and gas turbine combustors. The development and evaluation of a fixed wavelength H2O absorption spectroscopy (FWAS) system that is demonstrates how the ECDL allows the system to operate in multiple modes that enhance FWAS measurement accuracy by improving wavelength position monitoring, and reducing non-absorption based contamination in spectral scans. The architecture of a high temperature (21000 K) and pressure (50 bar) database (HTPD) is developed that can enhance absorption spectroscopy based thermometry. The HTPD formation is developed by the evaluation of two approaches, a line-by-line (LBL) approach, where transition lineshape parameters are extracted from spectra and used along with a physics based model to allow the simulation of spectra over a wide range of temperatures and pressures, or an absorption cross-section (sigmaabs) approach, where spectra generated from a high temperature and pressure furnace are catalog spectra at various conditions forming a database of absorption cross-sections that is then interpolated to provide a simulated absorbance spectra based on measured reference grade spectra. Utilizing near future reference grade H2O absorption spectra, generated by the Sanders Group by means of an ECDL and a high temperature and pressure furnace, a unique opportunity is taken to provide the research community with a database that can be utilized for optical thermometry.

In Situ Industrial Bimetallic Catalyst Characterization using Scanning Transmission Electron Microscopy and X-ray Absorption Spectroscopy at One Atmosphere and Elevated Temperature.

PubMed

Prestat, Eric; Kulzick, Matthew A; Dietrich, Paul J; Smith, Mr Matthew; Tien, Mr Eu-Pin; Burke, M Grace; Haigh, Sarah J; Zaluzec, Nestor J

2017-08-18

We have developed a new experimental platform for in situ scanning transmission electron microscope (STEM) energy dispersive X-ray spectroscopy (EDS) which allows real time, nanoscale, elemental and structural changes to be studied at elevated temperature (up to 1000 °C) and pressure (up to 1 atm). Here we demonstrate the first application of this approach to understand complex structural changes occurring during reduction of a bimetallic catalyst, PdCu supported on TiO 2 , synthesized by wet impregnation. We reveal a heterogeneous evolution of nanoparticle size, distribution, and composition with large differences in reduction behavior for the two metals. We show that the data obtained is complementary to in situ STEM electron energy loss spectroscopy (EELS) and when combined with in situ X-ray absorption spectroscopy (XAS) allows correlation of bulk chemical state with nanoscale changes in elemental distribution during reduction, facilitating new understanding of the catalytic behavior for this important class of materials. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Non-uniform temperature and species concentration measurements in a laminar flame using multi-band infrared absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ma, Liu Hao; Lau, Lok Yin; Ren, Wei

2017-03-01

We report in situ measurements of non-uniform temperature, H2O and CO2 concentration distributions in a premixed methane-air laminar flame using tunable diode laser absorption spectroscopy (TDLAS). A mid-infrared, continuous-wave, room-temperature interband cascade laser (ICL) at 4183 nm was used for the sensitive detection of CO2 at high temperature.The H2O absorption lines were exploited by one distributed feedback (DFB) diode laser at 1343 nm and one ICL at 2482 nm to achieve multi-band absorption measurements with high species concentration sensitivity, high temperature sensitivity, and immunity to variations in ambient conditions. A novel profile-fitting function was proposed to characterize the non-uniform temperature and species concentrations along the line-of-sight in the flame by detecting six absorption lines of CO2 and H2O simultaneously. The flame temperature distribution was measured at different heights above the burner (5-20 mm), and compared with the thermocouple measurement with heat-transfer correction. Our TDLAS measured temperature of the central flame was in excellent agreement (<1.5% difference) with the thermocouple data.The TDLAS results were also compared with the CFD simulations using a detailed chemical kinetics mechanism (GRI 3.0) and considering the heat loss to the surroundings.The current CFD simulation overpredicted the flame temperature in the gradient region, but was in excellent agreement with the measured temperature and species concentration in the core of the flame.

Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge.

PubMed

Schreck, Simon; Wernet, Philippe

2016-09-14

The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

Atmospheric absorption of terahertz radiation and water vapor continuum effects

NASA Astrophysics Data System (ADS)

Slocum, David M.; Slingerland, Elizabeth J.; Giles, Robert H.; Goyette, Thomas M.

2013-09-01

The water vapor continuum absorption spectrum was investigated using Fourier Transform Spectroscopy. The transmission of broadband terahertz radiation from 0.300 to 1.500 THz was recorded for multiple path lengths and relative humidity levels. The absorption coefficient as a function of frequency was determined and compared with theoretical predictions and available water vapor absorption data. The prediction code is able to separately model the different parts of atmospheric absorption for a range of experimental conditions. A variety of conditions were accurately modeled using this code including both self and foreign gas broadening for low and high water vapor pressures for many different measurement techniques. The intensity and location of the observed absorption lines were also in good agreement with spectral databases. However, there was a discrepancy between the resonant line spectrum simulation and the observed absorption spectrum in the atmospheric transmission windows caused by the continuum absorption. A small discrepancy remained even after using the best available data from the literature to account for the continuum absorption. From the experimental and resonant line simulation spectra the air-broadening continuum parameter was calculated and compared with values available in the literature.

Femtosecond transient absorption, Raman, and electrochemistry studies of tetrasulfonated copper phthalocyanine in water solutions.

PubMed

Abramczyk, H; Brozek-Płuska, B; Kurczewski, K; Kurczewska, M; Szymczyk, I; Krzyczmonik, P; Błaszczyk, T; Scholl, H; Czajkowski, W

2006-07-20

Ultrafast time-resolved electronic spectra of the primary events induced in the copper tetrasulfonated phthalocyanine Cu(tsPc)4-) in aqueous solution has been measured by femtosecond pump-probe transient absorption spectroscopy. The primary events initiated by the absorption of a photon occurring within the femtosecond time scale are discussed on the basis of the electron transfer mechanism between the adjacent phthalocyanine rings proposed recently in our laboratory. The femtosecond transient absorption results are compared with the low temperature emission spectra obtained with Raman spectroscopy and the voltammetric curves.

X-Ray Absorption near Edge Structure Spectroscopy of Nanodiamonds from the Allende Meteorite

NASA Technical Reports Server (NTRS)

Flynn, G. J.; Keller, L. P.; Hill, H.; Jacobsen, C.; Wirick, S.

2000-01-01

Carbon X-ray Absorption Near Edge Structure Spectroscopy shows Allende DM nanodiamonds have two pre-edge peaks, consistent with other small diamonds, but fail to show a diamond exciton which is seen in 3.6 nm diamond thin films.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wojciech, Blachucki

This work treats of the high energy resolution off-resonant X-ray spectroscopy (HEROS) method of determining the density of unoccupied electronic states in the vicinity of the absorption edge. HEROS is an alternative to the existing X-ray absorption spectroscopy (XAS) methods and opens the way for new studies not achievable before.

DETERMINING BERYLLIUM IN DRINKING WATER BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROSCOPY

EPA Science Inventory

A direct graphite furnace atomic absorption spectroscopy method for the analysis of beryllium in drinking water has been derived from a method for determining beryllium in urine. Ammonium phosphomolybdate and ascorbic acid were employed as matrix modifiers. The matrix modifiers s...

Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com; Yadav, A. K.

2016-04-04

This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It ismore » a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.« less

Prospects for laser-induced breakdown spectroscopy for biomedical applications: a review.

PubMed

Singh, Vivek Kumar; Rai, Awadhesh Kumar

2011-09-01

We review the different spectroscopic techniques including the most recent laser-induced breakdown spectroscopy (LIBS) for the characterization of materials in any phase (solid, liquid or gas) including biological materials. A brief history of the laser and its application in bioscience is presented. The development of LIBS, its working principle and its instrumentation (different parts of the experimental set up) are briefly summarized. The generation of laser-induced plasma and detection of light emitted from this plasma are also discussed. The merit and demerits of LIBS are discussed in comparison with other conventional analytical techniques. The work done using the laser in the biomedical field is also summarized. The analysis of different tissues, mineral analysis in different organs of the human body, characterization of different types of stone formed in the human body, analysis of biological aerosols using the LIBS technique are also summarized. The unique abilities of LIBS including detection of molecular species and calibration-free LIBS are compared with those of other conventional techniques including atomic absorption spectroscopy, inductively coupled plasma atomic emission spectroscopy and mass spectroscopy, and X-ray fluorescence.

Environmentally Controlled Infrared Spectroscopy System for Fundamental Studies of Polymer Electrolyte Membranes

DTIC Science & Technology

2015-10-15

to state-of- hydration . Polarization modulated infrared reflection- absorption spectroscopy experiments are enabled by the use of a spin-coater to coat...NAME(S) AND ADDRESS (ES) U.S. Army Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 SPEEK, Nafion, Ionomers, state-of- hydration ...enabled correlation of the exchange site structure to state-of- hydration . Polarization modulated infrared reflection-absorption spectroscopy experiments

Single-tone and two-tone AM-FM spectral calculations for tunable diode laser absorption spectroscopy

NASA Technical Reports Server (NTRS)

Chou, Nee-Yin; Sachse, Glen W.

1987-01-01

A generalized theory for optical heterodyne spectroscopy with phase modulated laser radiation is used which allows the calculation of signal line shapes for frequency modulation spectroscopy of Lorentzian gas absorption lines. In particular, synthetic spectral line shapes for both single-tone and two-tone modulation of lead-salt diode lasers are presented in which the contributions from both amplitude and frequency modulations are included.

Spectroelectrochemistry: The Combination of Optical and Electrochemical Techniques.

ERIC Educational Resources Information Center

Heineman, William R.

1983-01-01

Two different techniques, electrochemistry and spectroscopy, can be combined for studying the redox chemistry of inorganic, organic, and biological molecules. Several commonly used spectroelectrochemical methods and their applications are described. Includes discussions of optically transparent electrodes, optical absorption/fluorescence…

X-Ray Absorption Spectroscopy As a Probe of Microbial Sulfur Biochemistry: the Nature of Bacterial Sulfur Globules Revisited

DOE Office of Scientific and Technical Information (OSTI.GOV)

George, G.N.; Gnida, M.; Bazylinski, D.A.

2009-05-18

The chemical nature of the sulfur in bacterial sulfur globules has been the subject of controversy for a number of years. Sulfur K-edge X-ray absorption spectroscopy (XAS) is a powerful technique for probing the chemical forms of sulfur in situ, but two groups have used it with very different conclusions. The root of the controversy lies with the different detection strategies used by the two groups, which result in very different spectra. This paper seeks to resolve the controversy. We experimentally demonstrate that the use of transmittance detection for sulfur K-edge XAS measurements is highly prone to spectroscopic distortions andmore » that much of the published work on sulfur bacteria is very likely based on distorted data. We also demonstrate that all three detection methods used for X-ray absorption experiments yield essentially identical spectra when the measurements are carried out under conditions where no experimental distortions are expected. Finally, we turn to the original question--the chemical nature of bacterial sulfur. We examine isolated sulfur globules of Allochromatium vinosum and intact cells of a strain of magnetotactic coccus and show that XAS indicates the presence of a chemical form of sulfur resembling S{sub 8}.« less

Diamond sensors and polycapillary lenses for X-ray absorption spectroscopy.

PubMed

Ravel, B; Attenkofer, K; Bohon, J; Muller, E; Smedley, J

2013-10-01

Diamond sensors are evaluated as incident beam monitors for X-ray absorption spectroscopy experiments. These single crystal devices pose a challenge for an energy-scanning experiment using hard X-rays due to the effect of diffraction from the crystalline sensor at energies which meet the Bragg condition. This problem is eliminated by combination with polycapillary lenses. The convergence angle of the beam exiting the lens is large compared to rocking curve widths of the diamond. A ray exiting one capillary from the lens meets the Bragg condition for any reflection at a different energy from the rays exiting adjacent capillaries. This serves to broaden each diffraction peak over a wide energy range, allowing linear measurement of incident intensity over the range of the energy scan. Extended X-ray absorption fine structure data are measured with a combination of a polycapillary lens and a diamond incident beam monitor. These data are of comparable quality to data measured without a lens and with an ionization chamber monitoring the incident beam intensity.

Spectroscopic Studies on the Effect of Some Ferrocene Derivatives in the Formation of Silver Nanoparticles.

PubMed

Sanyal, Manik Kumar; Biswas, Bipul; Chowdhury, Avijit; Mallik, Biswanath

2016-06-01

Silver nanoparticles were prepared by microwave assisted method using silver nitrate as precursor in the presence of some ferrocene derivatives. The formation of the silver nanoparticles was monitored using UV-Vis spectroscopy. The UV-Vis spectroscopy revealed the formation of silver nanoparticles by exhibiting typical surface plasmon absorption band. The position of plasmon band (406-429 nm) was observed to depend on the nature of a particular ferrocene derivative used. TEM images indicated that the nanoparticles were spherical in shape and well-dispersed. Quantum dots (3.2 nm) were prepared by using ferrocenecarboxylic acid. The surface plasmon absorption band has shown red shift with increasing concentration of ferrocene derivative. For different duration of microwave heating time, intensity of absorption spectra in general was found to increase except in presence of ferrocene carbaldehyde where it decreased. Time-dependent spectra have indicated almost stable position of the surface plasmon band with increasing time of observation confirming that the as prepared silver nanoparticles did not aggregate with lapse of time.

Measurement of Electronic States of PbS Nanocrystal Quantum Dots Using Scanning Tunneling Spectroscopy: The Role of Parity Selection Rules in Optical Absorption

NASA Astrophysics Data System (ADS)

Diaconescu, Bogdan; Padilha, Lazaro A.; Nagpal, Prashant; Swartzentruber, Brian S.; Klimov, Victor I.

2013-03-01

We study the structure of electronic states in individual PbS nanocrystal quantum dots by scanning tunneling spectroscopy (STS) using one-to-two monolayer nanocrystal films treated with 1, 2-ethanedithiols (EDT). Up to six individual valence and conduction band states are resolved for a range of quantum dot sizes. The measured states’ energies are in good agreement with calculations using the k·p four-band envelope function formalism. A comparison of STS and optical absorption spectra indicates that some of the absorption features can only be explained by asymmetric transitions involving the states of different symmetries (e.g., S and P or P and D), which points towards the relaxation of the parity selection rules in these nanostructures. STS measurements also reveal a midgap feature, which is likely similar to one observed in previous charge transport studies of EDT-treated quantum dot films.

Intracavity Laser Absorption Spectroscopy of Platinum Nitride in the Near Infrared

NASA Astrophysics Data System (ADS)

O'Brien, Leah C.; Harris, Rachel A.; Whittemore, Sean; O'Brien, James J.

2009-06-01

A new electronic transition of PtN has been recorded using intracavity laser absorption spectroscopy. Four red-degraded branches are observed, with a bandheads located at 11733 and 11725 wn. The results of the analysis will be presented and compared with ab initio calculations.

Atomic Absorption Spectroscopy. The Present and the Future.

ERIC Educational Resources Information Center

Slavin, Walter

1982-01-01

The status of current techniques and methods of atomic absorption (AA) spectroscopy (flame, hybrid, and furnace AA) is discussed, including limitations. Technological opportunities and how they may be used in AA are also discussed, focusing on automation, microprocessors, continuum AA, hybrid analyses, and others. (Author/JN)

Determination of copper binding in Pseudomonas putida CZ1 by chemical modifications and X-ray absorption spectroscopy.

PubMed

Chen, XinCai; Shi, JiYan; Chen, YingXu; Xu, XiangHua; Chen, LiTao; Wang, Hui; Hu, TianDou

2007-03-01

Previously performed studies have shown that Pseudomonas putida CZ1 biomass can bind an appreciable amount of Cu(II) and Zn(II) ions from aqueous solutions. The mechanisms of Cu- and Zn-binding by P. putida CZ1 were ascertained by chemical modifications of the biomass followed by Fourier transform infrared and X-ray absorption spectroscopic analyses of the living or nonliving cells. A dramatic decrease in Cu(II)- and Zn(II)-binding resulted after acidic methanol esterification of the nonliving cells, indicating that carboxyl functional groups play an important role in the binding of metal to the biomaterial. X-ray absorption spectroscopy was used to determine the speciation of Cu ions bound by living and nonliving cells, as well as to elucidate which functional groups were involved in binding of the Cu ions. The X-ray absorption near-edge structure spectra analysis showed that the majority of the Cu was bound in both samples as Cu(II). The fitting results of Cu K-edge extended X-ray absorption fine structure spectra showed that N/O ligands dominated in living and nonliving cells. Therefore, by combining different techniques, our results indicate that carboxyl functional groups are the major ligands responsible for the metal binding in P. putida CZ1.

In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts.

PubMed

Polovov, Ilya B; Volkovich, Vladimir A; Charnock, John M; Kralj, Brett; Lewin, Robert G; Kinoshita, Hajime; May, Iain; Sharrad, Clint A

2008-09-01

Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molten LiCl-KCl eutectic was used to determine the immediate coordination environment about the uranium. The dominant species in the melt was [UO 2Cl 4] (2-). Further analysis of the extended X-ray absorption fine structure data and Raman spectroscopy of the melts quenched back to room temperature indicated the possibility of ordering beyond the first coordination sphere of [UO 2Cl 4] (2-). The electrolytic generation of uranium(III) in a molten LiCl-KCl eutectic was also investigated. Anodic dissolution of uranium metal was found to be more efficient at producing uranium(III) in high-temperature melts than the cathodic reduction of uranium(IV). These high-temperature electrolytic processes were studied by in situ electronic absorption spectroelectrochemistry, and we have also developed in situ X-ray absorption spectroelectrochemistry techniques to probe both the uranium oxidation state and the uranium coordination environment in these melts.

Diffuse-light absorption spectroscopy by fiber optics for detecting and quantifying the adulteration of extra virgin olive oil

NASA Astrophysics Data System (ADS)

Mignani, A. G.; Ciaccheri, L.; Ottevaere, H.; Thienpont, H.; Conte, L.; Marega, M.; Cichelli, A.; Attilio, C.; Cimato, A.

2010-09-01

A fiber optic setup for diffuse-light absorption spectroscopy in the wide 400-1700 nm spectral range is experimented for detecting and quantifying the adulteration of extra virgin olive oil caused by lower-grade olive oils. Absorption measurements provide spectral fingerprints of authentic and adulterated oils. A multivariate processing of spectroscopic data is applied for discriminating the type of adulterant and for predicting its fraction.

Portable, Fiber-Based, Diffuse Reflection Spectroscopy (DRS) Systems for Estimating Tissue Optical Properties.

PubMed

Vishwanath, Karthik; Chang, Kevin; Klein, Daniel; Deng, Yu Feng; Chang, Vivide; Phelps, Janelle E; Ramanujam, Nimmi

2011-02-01

Steady-state diffuse reflection spectroscopy is a well-studied optical technique that can provide a noninvasive and quantitative method for characterizing the absorption and scattering properties of biological tissues. Here, we compare three fiber-based diffuse reflection spectroscopy systems that were assembled to create a light-weight, portable, and robust optical spectrometer that could be easily translated for repeated and reliable use in mobile settings. The three systems were built using a broadband light source and a compact, commercially available spectrograph. We tested two different light sources and two spectrographs (manufactured by two different vendors). The assembled systems were characterized by their signal-to-noise ratios, the source-intensity drifts, and detector linearity. We quantified the performance of these instruments in extracting optical properties from diffuse reflectance spectra in tissue-mimicking liquid phantoms with well-controlled optical absorption and scattering coefficients. We show that all assembled systems were able to extract the optical absorption and scattering properties with errors less than 10%, while providing greater than ten-fold decrease in footprint and cost (relative to a previously well-characterized and widely used commercial system). Finally, we demonstrate the use of these small systems to measure optical biomarkers in vivo in a small-animal model cancer therapy study. We show that optical measurements from the simple portable system provide estimates of tumor oxygen saturation similar to those detected using the commercial system in murine tumor models of head and neck cancer.

Performance of a lookup table-based approach for measuring tissue optical properties with diffuse optical spectroscopy

NASA Astrophysics Data System (ADS)

Nichols, Brandon S.; Rajaram, Narasimhan; Tunnell, James W.

2012-05-01

Diffuse optical spectroscopy (DOS) provides a powerful tool for fast and noninvasive disease diagnosis. The ability to leverage DOS to accurately quantify tissue optical parameters hinges on the model used to estimate light-tissue interaction. We describe the accuracy of a lookup table (LUT)-based inverse model for measuring optical properties under different conditions relevant to biological tissue. The LUT is a matrix of reflectance values acquired experimentally from calibration standards of varying scattering and absorption properties. Because it is based on experimental values, the LUT inherently accounts for system response and probe geometry. We tested our approach in tissue phantoms containing multiple absorbers, different sizes of scatterers, and varying oxygen saturation of hemoglobin. The LUT-based model was able to extract scattering and absorption properties under most conditions with errors of less than 5 percent. We demonstrate the validity of the lookup table over a range of source-detector separations from 0.25 to 1.48 mm. Finally, we describe the rapid fabrication of a lookup table using only six calibration standards. This optimized LUT was able to extract scattering and absorption properties with average RMS errors of 2.5 and 4 percent, respectively.

Photothermal microfluidic cantilever deflection spectroscopy reflecting clustering mechanism of ethanol water mixtures

NASA Astrophysics Data System (ADS)

Ghoraishi, Maryam; Hawk, John; Thundat, Thomas

Aqueous mixture of alcohol is a typical prototype for biomolecules, micelle formation, and structural stability of proteins. Therefore, Short chain alcohols such as EtOH have been used as a simple model for understanding of more complex aqueous biomolecules. Here we study vibrational energy peaks of EtOH water binary mixtures using micromechanical calorimetric spectroscopy using bimaterial microfluidic cantilevers (BMC). The IR spectra of EtOH-water are experimentally collected employing a BMC as concentration of EtOH changes from 20-100 wt%. As concentration of EtOH varies in the mixture, considerable shifts in the wavenumber at IR absorption peak maxima are reported. The experimentally measured shifts in the wavenumber at IR absorption peak maxima are related to changes in dipole moment (μ) of EtOH at different concentration. The relationship between IR absorption wavenumber for both anti and gauche conformers of EtOH, and inverse dipole moment, 1/ μ, of EtOH at different concentrations follows a power law dependence. Our technique offers a platform to investigate dipole effect on molecular vibrations of mixtures in confined picoliter volumes, previously unexplored with other analytical techniques due to limitations of volume under study.

High spatial resolution measurements of NO2 applying Topographic Target Light scattering-Differential Optical Absorption Spectroscopy (ToTaL-DOAS)

NASA Astrophysics Data System (ADS)

Frins, E.; Platt, U.; Wagner, T.

2008-06-01

Tomographic Target Light scattering - Differential Optical Absorption Spectroscopy (ToTaL-DOAS), also called Target-DOAS, is a novel experimental procedure to retrieve trace gas concentrations present in the low atmosphere. Scattered sunlight (partially or totally) reflected from natural or artificial targets of similar albedo located at different distances is analyzed to retrieve the concentration of different trace gases like NO2, SO2 and others. We report high spatial resolution measurements of NO2 mixing ratios in the city of Montevideo (Uruguay) observing three buildings as targets with a Mini-DOAS instrument. Our instrument was 146 m apart from the first building, 196 m from the second and 286 m from the third one. All three buildings are located along a main Avenue. We obtain temporal variation of NO2 mixing ratios between 30 ppb and 65 ppb (±2 ppb). Our measurements demonstrate that ToTaL-DOAS measurements can be made over very short distances. In polluted air masses, the retrieved absorption signal was found to be strong enough to allow measurements over distances in the range of several ten meters, and achieve a spatial resolution of 50 m approximately.

Time-temperature dependent variations in beta-carotene contents in carrot using different spectrophotometric techniques

NASA Astrophysics Data System (ADS)

Ullah, Rahat; Khan, Saranjam; Shah, Attaullah; Ali, Hina; Bilal, Muhammad

2018-05-01

The current study presents time dependent variations in the concentration of beta-carotene in carrot under different storage-temperature conditions using UV–VIS and Raman spectrophotometric techniques. The UV–VIS absorption spectra of beta-carotene extracted from carrot shows three distinct absorption peaks at 442, 467, and 500 nm with maximum absorption at 467 nm. These absorption peaks are very much reproducible and are assigned to β-carotene. Similarly, Raman spectra of carrot samples also confirmed the three main Raman peaks of beta-carotene at shift positions 1003, 1150, and 1515 cm‑1. An overall decrease in beta-carotene content has been observed for time-temperature conditions. These results depict a decrease of about 40% in the content of beta-carotene when carrot samples were stored in a refrigerator (4 °C) for the first 20 d, whereas a decrease of about 25% was observed when carrot samples were stored in a freezer (‑16 °C) for the same period. The objective of this study is to investigate the possible use of Raman spectroscopy and UV–VIS spectroscopy for quick and detailed analysis of changes (degradation) in beta-carotene content associated with time and temperature in storage (frozen foods) in order to promote quality foods for consumers. Future study with a greater focus on the concentration/content of beta-carotene in other fruits/vegetables is also desirable.

Adsorption and photodecomposition of Mo(CO)[sub 6] on Si(111) 7[times]7: An infrared reflection absorption spectroscopy study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Richter, L.J.; Buntin, S.A.; Chu, P.M.

1994-02-15

The adsorption and photodecomposition of Mo(CO)[sub 6] adsorbed on Si(111) 7[times]7 surfaces has been studied with Auger electron spectroscopy, temperature programmed desorption, low energy electron diffraction and infrared reflection absorption spectroscopy in a single external reflection configuration. The external-reflection technique is demonstrated to have adequate sensitivity to characterize submonolayer coverages of photogenerated Mo(CO)[sub [ital x

Visualizing the Solute Vaporization Interference in Flame Atomic Absorption Spectroscopy

ERIC Educational Resources Information Center

Dockery, Christopher R.; Blew, Michael J.; Goode, Scott R.

2008-01-01

Every day, tens of thousands of chemists use analytical atomic spectroscopy in their work, often without knowledge of possible interferences. We present a unique approach to study these interferences by using modern response surface methods to visualize an interference in which aluminum depresses the calcium atomic absorption signal. Calcium…

Analysis of fingerprints features of infrared spectra of various processed products of Radix Aconiti kusnezoffii

NASA Astrophysics Data System (ADS)

Tu-ya; Yang, Ping; Sun, Su-qin; Zhou, Qun; Bao, Xiao-hua; Noda, Isao

2010-06-01

Fourier-transform infrared spectroscopy (FTIR) and two-dimensional correlation infrared spectroscopy (2D-IR)) are employed to analyze various processed products and ether extracts of Radix Aconiti kusnezoffii. There is a resemblance among the spectra of different processed products. The major difference lies in the absorption peak at 1641 cm -1 in the IR spectra, which reflects the transformation of raw aconite to the processed products. There are distinctive differences in the absorption peaks in the range of 1800-1500 cm -1 in the second derivative spectra, which has better resolution, of different processed products. 2D-IR spectra, which elevate the resolution further, can present even more differences among the products in the range of 1800-800 cm -1. Analysis of ether extracts of various processed products proves that there are alcohols, esters, carboxylic acids or ketones in all of them. However, their contents in different samples have obvious differences. With the advantages of high resolution, high-speed and convenience, IR can quickly and precisely distinguish various processed products of Radix A. kusnezoffii, and can be applied to predict the tendency of transformation of the complicated chemical mixture systems under heat perturbation.

Green biochemistry approach for synthesis of silver and gold nanoparticles using Ficus racemosa latex and their pH-dependent binding study with different amino acids using UV/Vis absorption spectroscopy.

PubMed

Tetgure, Sandesh R; Borse, Amulrao U; Sankapal, Babasaheb R; Garole, Vaman J; Garole, Dipak J

2015-04-01

Simple and eco-friendly biosynthesis approach was developed to synthesize silver nanoparticles (SNPs) and gold nanoparticles (GNPs) using Ficus racemosa latex as reducing agent. The presence of sunlight is utilized with latex and achieved the nanoparticles whose average size was in the range of 50-120 nm for SNPs and 20-50 nm for GNPs. The synthesized nanoparticles were characterized by UV/Visible absorption spectroscopy, X-ray diffraction, and field emission-scanning electron microscopy techniques toget understand the obtained nanoparticles. The pH-dependent binding studies of SNPs and GNPs with four amino acids, namely L-lysine, L-arginine, L-glutamine and glycin have been reported.

Improved detection sensitivity of D-mannitol crystalline phase content using differential spectral phase shift terahertz spectroscopy measurements.

PubMed

Allard, Jean-François; Cornet, Alain; Debacq, Christophe; Meurens, Marc; Houde, Daniel; Morris, Denis

2011-02-28

We report quantitative measurement of the relative proportion of δ- and β-D-mannitol crystalline phases inserted into polyethylene powder pellets, obtained by time-domain terahertz spectroscopy. Nine absorption bands have been identified from 0.2 THz to 2.2 THz. The best quantification of the δ-phase proportion is made using the 1.01 THz absorption band. Coherent detection allows using the spectral phase shift of the transmitted THz waveform to improve the detection sensitivity of the relative δ-phase proportion. We argue that differential phase shift measurements are less sensitive to samples' defects. Using a linear phase shift compensation for pellets of slightly different thicknesses, we were able to distinguish a 0.5% variation in δ-phase proportion.

Application of MCD spectroscopy and TD-DFT to endohedral metallofullerenes for characterization of their electronic transitions.

PubMed

Yamada, Michio; Slanina, Zdenek; Mizorogi, Naomi; Muranaka, Atsuya; Maeda, Yutaka; Nagase, Shigeru; Akasaka, Takeshi; Kobayashi, Nagao

2013-03-14

We describe, for the first time, the application of magnetic circular dichroism (MCD) spectroscopy and time-dependent density functional theory (TD-DFT) calculations using B3LYP and M06-2X functionals to characterize the electronic transitions of endohedral metallofullerenes (EMFs). Results revealed that the electronic transitions of La@C(2v)-C(82), La(2)@I(h)-C(80), and Sc(3)N@I(h)-C(80) can be assigned using these techniques. Particularly, a difference in the electronic transitions between La(2)@I(h)-C(80) and Sc(3)N@I(h)-C(80), which is invisible in absorption spectra, was observed clearly in MCD spectra. The observed MCD bands agree well with the oscillator strengths calculated using the B3LYP functional. In addition, the MCD bands of La(2)@I(h)-C(80) were altered upon [5,6]-addition, demonstrating that the MCD spectroscopy is sensitive to chemical functionalization of EMFs, and that it is therefore powerful to distinguish [5,6]-adducts from pristine La(2)@I(h)-C(80), although no marked difference exists in their absorption spectra.

Terahertz time-domain spectroscopy and quantitative analysis of metal gluconates.

PubMed

Li, Shaoxian; Yang, Jingqi; Zhao, Hongwei; Yang, Na; Jing, Dandan; Zhang, Jianbing; Li, Qingnuan; Han, Jiaguang

2015-01-01

A series of metal gluconates (Na(+), K(+), Mg(2+), Ca(2+), Fe(2+), Cu(2+), and Zn(2+)) were investigated by terahertz (THz) time-domain spectroscopy. The absorption coefficients and refractive indices of the samples were obtained in the frequency range of 0.5-2.6 THz. The gluconates showed distinct THz characteristic fingerprints, and the dissimilarities reflect their different structures, hydrogen-bond networks, and molecular interactions. In addition, some common features were observed among these gluconates, and the similarities probably come from the similar carbohydrate anion group. The X-ray powder diffraction measurements of these metal gluconates were performed, and the copper(II) gluconate was found to be amorphous, corresponding to the monotonic increase feature in the THz absorption spectrum. The results suggest that THz spectroscopy is sensitive to molecular structure and physical form. Binary and ternary mixtures of different gluconates were quantitatively analyzed based on the Beer-Lambert law. A chemical map of a tablet containing calcium D-gluconate monohydrate and α-lactose in the polyethylene host was obtained by THz imaging. The study shows that THz technology is a useful tool in pharmaceutical research and quality control applications.

Wafer-scale metasurface for total power absorption, local field enhancement and single molecule Raman spectroscopy

PubMed Central

Wang, Dongxing; Zhu, Wenqi; Best, Michael D.; Camden, Jon P.; Crozier, Kenneth B.

2013-01-01

The ability to detect molecules at low concentrations is highly desired for applications that range from basic science to healthcare. Considerable interest also exists for ultrathin materials with high optical absorption, e.g. for microbolometers and thermal emitters. Metal nanostructures present opportunities to achieve both purposes. Metal nanoparticles can generate gigantic field enhancements, sufficient for the Raman spectroscopy of single molecules. Thin layers containing metal nanostructures (“metasurfaces”) can achieve near-total power absorption at visible and near-infrared wavelengths. Thus far, however, both aims (i.e. single molecule Raman and total power absorption) have only been achieved using metal nanostructures produced by techniques (high resolution lithography or colloidal synthesis) that are complex and/or difficult to implement over large areas. Here, we demonstrate a metasurface that achieves the near-perfect absorption of visible-wavelength light and enables the Raman spectroscopy of single molecules. Our metasurface is fabricated using thin film depositions, and is of unprecedented (wafer-scale) extent. PMID:24091825

Efficient encapsulation of chloroform with cryptophane-M and the formation of exciplex studied by fluorescence spectroscopy.

PubMed

Shi, Yanqi; Li, Xueming; Yang, Jianchun; Gao, Fang; Tao, Chuanyi

2011-03-01

Efficient encapsulation of small molecules with supermolecules is one of significantly important subjects due to strong application potentials. This article presents the interaction between cryptophane-M and chloroform by fluorescence spectroscopy. The sonicated cryptophane-M solution exhibits light green color in chloroform, and the solid obtained from the evaporation of chloroform also has different color from that of cryptophane-M. In contrast, the sonicated cryptophane-M solutions in other solvents are colorless, and the solid obtained from the evaporation of these solvents has the same color as that of cryptophane-M. Furthermore, the freshly prepared cryptophane-M solution in different solvents is almost colorless, and the solid obtained from the evaporation of these solvents displays the same color as that of cryptophane-M. Although the sonicated cryptophane-M solutions in different solvents have very similar absorption spectra, they exhibit quite different emission spectra in chloroform. In contrast, the freshly-prepared cryptophane-M solutions show similar absorption and emission spectroscopy in various solvents. The variation of the fluorescence spectroscopy in binary solvents with the increasing chloroform ratio suggests that cryptophane-M and chloroform form a 1:1 exciplex, and the binding constant is estimated to be 292.95 M(-1). Although all solvents are able to enter into the cavity of cryptophane-M, only chloroform can stay in the cavity of cryptophane-M for a while, which is mostly due to the strong intermolecular interaction between cryptophane-M and chloroform, and this results in the formation of the exciplex between them. © Springer Science+Business Media, LLC 2010

Nonlinear femtosecond pump-probe spectroscopy using a power-encoded soliton delay line.

PubMed

Saint-Jalm, Sarah; Andresen, Esben Ravn; Bendahmane, Abdelkrim; Kudlinski, Alexandre; Rigneault, Hervé

2016-01-01

We show femtosecond time-resolved nonlinear pump-probe spectroscopy using a fiber soliton as the probe pulse. Furthermore, we exploit soliton dynamics to record an entire transient trace with a power-encoded delay sweep. The power-encoded delay line takes advantage of the dependency of the soliton trajectory in the (λ,z) space upon input power; the difference in accumulated group delay between trajectories converts a fast power sweep into a fast delay sweep. We demonstrate the concept by performing transient absorption spectroscopy in a test sample and validate it against a conventional pump-probe setup.

Analyte-induced spectral filtering in femtosecond transient absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

Here, we discuss the influence of spectral filtering by samples in femtosecond transient absorption measurements. Commercial instruments for transient absorption spectroscopy (TA) have become increasingly available to scientists in recent years and TA is becoming an established technique to measure the dynamics of photoexcited systems. Furthermore, we show that absorption of the excitation pulse by the sample can severely alter the spectrum and consequently the temporal pulse shape. This “spectral self-filtering” effect can lead to systematic errors and misinterpretation of data, most notably in concentration dependent measurements. Finally, the combination of narrow absorption peaks in the sample with ultrafast broadbandmore » excitation pulses is especially prone to this effect.« less

Analyte-induced spectral filtering in femtosecond transient absorption spectroscopy

DOE PAGES

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

2017-03-06

Here, we discuss the influence of spectral filtering by samples in femtosecond transient absorption measurements. Commercial instruments for transient absorption spectroscopy (TA) have become increasingly available to scientists in recent years and TA is becoming an established technique to measure the dynamics of photoexcited systems. Furthermore, we show that absorption of the excitation pulse by the sample can severely alter the spectrum and consequently the temporal pulse shape. This “spectral self-filtering” effect can lead to systematic errors and misinterpretation of data, most notably in concentration dependent measurements. Finally, the combination of narrow absorption peaks in the sample with ultrafast broadbandmore » excitation pulses is especially prone to this effect.« less

The interaction of copper ions with Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli: an X-ray absorption near-edge structure (XANES) spectroscopy study.

PubMed

Zanzen, Ulrike; Bovenkamp-Langlois, Lisa; Klysubun, Wantana; Hormes, Josef; Prange, Alexander

2018-04-01

The antimicrobial properties of copper ions have been known for a long time. However, the exact mechanism of action of the transition metal on microorganisms has long been unclear. X-ray absorption near-edge structure (XANES) spectroscopy at the Cu K edge allows the determination of copper speciation in Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa that have been treated with Cu(II) and Cu(I) solutions. The death/inactivation of the bacteria was observed using plate counting and light microscopy. The Cu K-XANES spectra of the two Gram-negative bacteria are different than those of the Gram-positive strain. The results clearly show that the Cu + -S bond contributes to the antibacterial activity of copper, as in the case of silver. The detailed evaluation of the differentiated absorption spectra shows that Cu + (not Cu 2+ ) is the dominant ion that binds to the bacteria. Because Cu + is not the most common copper ion, copper is not as effective an antibacterial agent as silver, whose common valency is actually + 1. Any reaction of copper with phosphorus from the bacteria can be excluded after the evaluation of the absorption spectra.

Strong Impact of an Axial Ligand on the Absorption by Chlorophyll a and b Pigments Determined by Gas-Phase Ion Spectroscopy Experiments.

PubMed

Kjær, Christina; Stockett, Mark H; Pedersen, Bjarke M; Nielsen, Steen Brøndsted

2016-12-01

The microenvironments in photosynthetic proteins affect the absorption by chlorophyll (Chl) pigments. It is, however, a challenge to disentangle the impact on the transition energies of different perturbations, for example, the global electrostatics of the protein (nonbonded environmental effects), exciton coupling between Chl's, conformational variations, and binding of an axial ligand to the magnesium center. This is needed to distinguish between the two most commonly proposed mechanisms for energy transport in photosynthetic proteins, relying on either weakly or strongly coupled pigments. Here, on the basis of photodissociation action spectroscopy, we establish that the redshift of the Soret absorption band due to binding of a negatively charged carboxylate (as present in aspartic acid and glutamic acid residues) is 0.1-0.2 eV for Chl a and b. This effect is almost enough to reproduce the well-known green color of plants and can account for the strong spectral variation between Chl's. The experimental data serve to benchmark future high-level calculations of excited-state energies. Finally, we demonstrate that complexes between Chl a and histidine, tagged by a quaternary ammonium ion, can be made in the gas phase by electrospray ionization, but more work is needed to produce enough ions for gas-phase spectroscopy.

Far Ultraviolet Spectroscopy of Saturn's Icy Moon Rhea

NASA Astrophysics Data System (ADS)

Elowitz, Mark; Hendrix, Amanda; Mason, Nigel J.; Sivaraman, Bhalamurugan

2018-01-01

We present an analysis of spatially resolved, far-UV reflectance spectra of Saturn’s icy satellite Rhea, collected by the Cassini Ultraviolet Imaging Spectrograph (UVIS). In recent years ultraviolet spectroscopy has become an important tool for analysing the icy satellites of the outer solar system (1Hendrix & Hansen, 2008). Far-UV spectroscopy provides unique information about the molecular structure and electronic transitions of chemical species. Many molecules that are suspected to be present in the icy surfaces of moons in the outer solar system have broad absorption features due to electronic transitions that occur in the far-UV portion of the spectrum. The studies show that Rhea, like the other icy satellites of the Saturnian system are dominated by water-ice as evident by the 165-nm absorption edge, with minor UV absorbing contaminants. Far-UV spectra of several Saturnian icy satellites, including Rhea and Dione, show an unexplained weak absorption feature centered near 184 nm. To carry out the geochemical survey of Rhea’s surface, the UVIS observations are compared with vacuum-UV spectra of thin-ice samples measured in laboratory experiments. Thin film laboratory spectra of water-ice and other molecular compounds in the solid phase were collected at near-vacuum conditions and temperatures identical to those at the surface of Rhea. Comparison between the observed far-UV spectra of Rhea’s surface ice and modelled spectra based on laboratory absorption measurements of different non-water-ice compounds show that two possible chemical compounds could explain the 184-nm absorption feature. The two molecular compounds include simple chlorine molecules and hydrazine monohydrate. Attempts to explain the source(s) of these compounds on Rhea and the scientific implications of their possible discovery will be summarized.[1] Hendrix, A. R. & Hansen, C. J. (2008). Icarus, 193, pp. 323-333.

Absorption and emission spectroscopic characterisation of 8-amino-riboflavin

NASA Astrophysics Data System (ADS)

Tyagi, A.; Zirak, P.; Penzkofer, A.; Mathes, T.; Hegemann, P.; Mack, M.; Ghisla, S.

2009-10-01

The flavin dye 8-amino-8-demethyl- D-riboflavin (AF) in the solvents water, DMSO, methanol, and chloroform/DMSO was studied by absorption and fluorescence spectroscopy. The first absorption band is red-shifted compared to riboflavin, and blue-shifted compared to roseoflavin (8-dimethylamino-8-demethyl-D-riboflavin). The fluorescence quantum yield of AF in the studied solvents varies between 20% and 50%. The fluorescence lifetimes were found to be in the 2-5 ns range. AF is well soluble in DMSO, weakly soluble in water and methanol, and practically insoluble in chloroform. The limited solubility causes AF aggregation, which was seen in differences between measured absorption spectra and fluorescence excitation spectra. Light scattering in the dye absorption region is discussed and approximate absorption cross-section spectra are determined from the combined measurement of transmission and fluorescence excitation spectra. The photo-stability of AF was studied by prolonged light exposure. The photo-degradation routes of AF are discussed.

Phase-resolved reflectance spectroscopy on layered turbid media

NASA Astrophysics Data System (ADS)

Hielscher, Andreas H.; Liu, Hanli; Chance, Britton; Tittel, Frank K.; Jacques, Steven L.

1995-05-01

In this study, we investigate the influence of layered tissue structures on the phase-resolved reflectance. As a particular example, we consider the affect of the skin, skull, and meninges on noninvasive blood oxygenation determination of the brain. In this case, it's important to know how accurate one can measure the absorption coefficient of the brain through the enclosing layers of different tissues. Experiments were performed on layered gelatin tissue phantoms and the results compared to diffusion theory. It is shown that when a high absorbing medium is placed on top of a low absorbing medium, the absorption coefficient of the lower layer is accessible. In the inverse case, where a low absorbing medium is placed on top of a high absorbing medium, the absorption coefficient of the underlying medium can only be determined if the differences in the absorption coefficient are small, or the top layer is very thin. Investigations on almost absorption and scattering free layers, like the cerebral fluid filled arachnoid, reveal that the determination of the absorption coefficient is barely affected by these kinds of structures.

Application of far-infrared spectroscopy to the structural identification of protein materials.

PubMed

Han, Yanchen; Ling, Shengjie; Qi, Zeming; Shao, Zhengzhong; Chen, Xin

2018-05-03

Although far-infrared (IR) spectroscopy has been shown to be a powerful tool to determine peptide structure and to detect structural transitions in peptides, it has been overlooked in the characterization of proteins. Herein, we used far-IR spectroscopy to monitor the structure of four abundant non-bioactive proteins, namely, soybean protein isolate (SPI), pea protein isolate (PPI) and two types of silk fibroins (SFs), domestic Bombyx mori and wild Antheraea pernyi. The two globular proteins SPI and PPI result in broad and weak far-IR bands (between 50 and 700 cm-1), in agreement with those of some other bioactive globular proteins previously studied (lysozyme, myoglobin, hemoglobin, etc.) that generally only have random amino acid sequences. Interestingly, the two SFs, which are characterized by a structure composed of highly repetitive motifs, show several sharp far-IR characteristic absorption peaks. Moreover, some of these characteristic peaks (such as the peaks at 260 and 428 cm-1 in B. mori, and the peaks at 245 and 448 cm-1 in A. pernyi) are sensitive to conformational changes; hence, they can be directly used to monitor conformational transitions in SFs. Furthermore, since SF absorption bands clearly differ from those of globular proteins and different SFs even show distinct adsorption bands, far-IR spectroscopy can be applied to distinguish and determine the specific SF component within protein blends.

A sole multi-analyte receptor responds with three distinct fluorescence signals: traffic signal like sensing of Al(3+), Zn(2+) and F(-).

PubMed

Datta, Barun Kumar; Thiyagarajan, Durairaj; Ramesh, Aiyagari; Das, Gopal

2015-08-07

A dialdehyde-based multi-analyte sensor renders distinctive emission spectra for Al(3+), Zn(2+) and F(-) ions. The ligand exhibited different types of interactions with these three different ions resulting in the enhancement of fluorescence intensity at three different wavelengths. All the sensing processes were studied in detail by absorption spectroscopy, emission spectroscopy and (1)H-NMR titration experiment. The ligand has the working ability in a wide pH range including the physiological pH. The ligand is non-toxic and amicable for sensing intracellular Al(3+) and Zn(2+) in live HeLa cells.

Circuit Board Analysis for Lead by Atomic Absorption Spectroscopy in a Course for Nonscience Majors

ERIC Educational Resources Information Center

Weidenhammer, Jeffrey D.

2007-01-01

A circuit board analysis of the atomic absorption spectroscopy, which is used to measure lead content in a course for nonscience majors, is being presented. The experiment can also be used to explain the potential environmental hazards of unsafe disposal of various used electronic equipments.

Laser-based absorption spectroscopy as a technique for rapid in-line analysis of respired gas concentrations of O2 and CO2

PubMed Central

Cummings, Beth; Hamilton, Michelle L.; Ciaffoni, Luca; Pragnell, Timothy R.; Peverall, Rob; Ritchie, Grant A. D.; Hancock, Gus

2011-01-01

The use of sidestream analyzers for respired gas analysis is almost universal. However, they are not ideal for measurements of respiratory gas exchange because the analyses are both temporally dissociated from measurements of respiratory flow and also not generally conducted under the same physical conditions. This study explores the possibility of constructing an all optical, fast response, in-line breath analyzer for oxygen and carbon dioxide. Using direct absorption spectroscopy with a diode laser operating at a wavelength near 2 μm, measurements of expired carbon dioxide concentrations were obtained with an absolute limit of detection of 0.04% at a time resolution of 10 ms. Simultaneously, cavity enhanced absorption spectroscopy at a wavelength near 760 nm was employed to obtain measurements of expired oxygen concentrations with an absolute limit of detection of 0.26% at a time resolution of 10 ms. We conclude that laser-based absorption spectroscopy is a promising technology for in-line analysis of respired carbon dioxide and oxygen concentrations. PMID:21512147

Laser-based absorption spectroscopy as a technique for rapid in-line analysis of respired gas concentrations of O2 and CO2.

PubMed

Cummings, Beth; Hamilton, Michelle L; Ciaffoni, Luca; Pragnell, Timothy R; Peverall, Rob; Ritchie, Grant A D; Hancock, Gus; Robbins, Peter A

2011-07-01

The use of sidestream analyzers for respired gas analysis is almost universal. However, they are not ideal for measurements of respiratory gas exchange because the analyses are both temporally dissociated from measurements of respiratory flow and also not generally conducted under the same physical conditions. This study explores the possibility of constructing an all optical, fast response, in-line breath analyzer for oxygen and carbon dioxide. Using direct absorption spectroscopy with a diode laser operating at a wavelength near 2 μm, measurements of expired carbon dioxide concentrations were obtained with an absolute limit of detection of 0.04% at a time resolution of 10 ms. Simultaneously, cavity enhanced absorption spectroscopy at a wavelength near 760 nm was employed to obtain measurements of expired oxygen concentrations with an absolute limit of detection of 0.26% at a time resolution of 10 ms. We conclude that laser-based absorption spectroscopy is a promising technology for in-line analysis of respired carbon dioxide and oxygen concentrations.

Raman structural studies of the nickel electrode

NASA Technical Reports Server (NTRS)

Cornilsen, Bahne C.

1994-01-01

The objectives of this investigation have been to define the structures of charged active mass, discharged active mass, and related precursor materials (alpha-phases), with the purpose of better understanding the chemical and electrochemical reactions, including failure mechanisms and cobalt incorporation, so that the nickel electrode may be improved. Although our primary tool has been Raman spectroscopy, the structural conclusions drawn from the Raman data have been supported and augmented by three other analysis methods: infrared spectroscopy, powder X-ray Diffraction (XRD), and x-ray absorption spectroscopy (in particular EXAFS, Extended X-ray Absorption Fine Structure spectroscopy).

Optical Detection and Probing of Single Dopant Molecules of Pentacene in a p-Terphenyl Crystal by Means of Absorption Spectroscopy

DTIC Science & Technology

1989-08-31

Pentacene in a p-Terphenyl Host Crystal bY !eT=s of bsorotion Spectroscopy 12 PERSONAl AU- OR(S) L. Kador, W.E. Moerner & D.E. Horne 1 3a 7 P; OF REPORT...G(OP SUB-GROUP Single Molecule Detection FM Spectroscopy Pentacene in p-terphenyl 19 AtiSTRACT {Continue on reverse it necessary and identity Oy block...OF PENTACENE IN A p-TERPIIENYL IIOST CRYSTAL BY MEANS OF ABSORPTION SPECTROSCOPY L. Kador , 1). E. I lorne, and W. lF. Moerner IM Research )ivision

Terahertz spectral characteristics of two kinds of important functional oligosaccharides

NASA Astrophysics Data System (ADS)

Li, Ge; Liu, Wei; Wang, Wenai

2018-01-01

The absorption spectra of two kinds of important functional oligosaccharides were firstly acquired based on Fourier transform infrared spectroscopy in the range of 0.15-10THz. The simulation results of their infrared spectra were given based on Gaussian software, which were in good agreement with the experiment results. The rotation spectra and some perssad vibration spectra of these molecules were analyzed, and their absorption peaks were exactly identified. The components information was obtained by comparing the simulation results of different molecules.

Energy-absorption spectroscopy of unitary Fermi gases in a uniform potential

NASA Astrophysics Data System (ADS)

Zhang, Pengfei; Yu, Zhenhua

2018-04-01

We propose to use the energy absorption spectroscopy to measure the kinetic coefficients of unitary Fermi gases in a uniform potential. We show that, in our scheme, the energy absorption spectrum is proportional to the dynamic structure factor of the system. The profile of the spectrum depends on the shear viscosity η , the thermal conductivity κ , and the superfluid bulk viscosity ξ3. We show that extraction of these coefficients from the spectrum is achievable in present experiments.

X-ray absorption spectroscopy investigations on oxidized Ni/Au contacts to p-GaN.

PubMed

Jan, J C; Asokan, K; Chiou, J W; Pong, W F; Tseng, P K; Chen, L C; Chen, F R; Lee, J F; Wu, J S; Lin, H J; Chen, C T

2001-03-01

X-ray absorption spectroscopy was used to investigate the electronic structure of as-deposited and oxidized Ni/Au contacts to p-GaN and to elucidate the mechanism responsible for low impedance. X-ray absorption near edge spectra of Ni K- and L3,2-edges clearly indicate formation of NiO on the sample surface after annealing. The reason for low impedance may be attributed to increase in hole concentration and existence of p-NiO layer on the surface.

Actively coupled cavity ringdown spectroscopy with low-power broadband sources.

PubMed

Petermann, Christian; Fischer, Peer

2011-05-23

We demonstrate a coupling scheme for cavity enhanced absorption spectroscopy that makes use of an intracavity acousto-optical modulator to actively switch light into (and out of) a resonator. This allows cavity ringdown spectroscopy (CRDS) to be implemented with broadband nonlaser light sources with spectral power densities of less than 30μW/nm. Although the acousto-optical element reduces the ultimate detection limit by introducing additional losses, it permits absorptivities to be measured with a high dynamic range, especially in lossy environments. Absorption measurements for the forbidden transition of gaseous oxygen in air at ∼760nm are presented using a low-coherence cw-superluminescent diode. The same setup was electronically configured to cover absorption losses from 1.8×10^-8cm^-1 to 7.5% per roundtrip. This could be of interest in process analytical applications.

Infrared Spectroscopy of Carbonaceous-chondrite Inclusions in the Kapoeta Meteorite: Discovery of Nanodiamonds with New Spectral Features and Astrophysical Implications

NASA Astrophysics Data System (ADS)

Abdu, Yassir A.; Hawthorne, Frank C.; Varela, Maria E.

2018-03-01

We report the finding of nanodiamonds, coexisting with amorphous carbon, in carbonaceous-chondrite (CC) material from the Kapoeta achondritic meteorite by Fourier-transform infrared (FTIR) spectroscopy and micro-Raman spectroscopy. In the C–H stretching region (3100–2600 cm‑1), the FTIR spectrum of the Kapoeta CC material (KBr pellet) shows bands attributable to aliphatic CH2 and CH3 groups, and is very similar to IR spectra of organic matter in carbonaceous chondrites and the diffuse interstellar medium. Nanodiamonds, as evidenced by micro-Raman spectroscopy, were found in a dark region (∼400 μm in size) in the KBr pellet. Micro-FTIR spectra collected from this region are dramatically different from the KBr-pellet spectrum, and their C–H stretching region is dominated by a strong and broad absorption band centered at ∼2886 cm‑1 (3.47 μm), very similar to that observed in IR absorption spectra of hydrocarbon dust in dense interstellar clouds. Micro-FTIR spectroscopy also indicates the presence of an aldehyde and a nitrile, and both of the molecules are ubiquitous in dense interstellar clouds. In addition, IR peaks in the 1500–800 cm‑1 region are also observed, which may be attributed to different levels of nitrogen aggregation in diamonds. This is the first evidence for the presence of the 3.47 μm interstellar IR band in meteorites. Our results further support the assignment of this band to tertiary CH groups on the surfaces of nanodiamonds. The presence of the above interstellar bands and the absence of shock features in the Kapoeta nanodiamonds, as indicated by Raman spectroscopy, suggest formation by a nebular-condensation process similar to chemical-vapor deposition.

Molecular dispersion spectroscopy based on Fabry-Perot quantum cascade lasers.

PubMed

Sterczewski, Lukasz A; Westberg, Jonas; Wysocki, Gerard

2017-01-15

Two Fabry-Perot quantum cascade lasers are used in a differential dual comb configuration to perform rapidly swept dispersion spectroscopy of low-pressure nitrous oxide with <1  ms acquisition time. Active feedback control of the laser injection current enables simultaneous wavelength modulation of both lasers at kilohertz rates. The system demonstrates similar performance in both absorption and dispersion spectroscopy modes and achieves a noise-equivalent absorption figure of merit in the low 10^-4/Hz range.

Physicochemical, nutritional and infrared spectroscopy evaluation of an optimized soybean/corn flour extrudate

USDA-ARS?s Scientific Manuscript database

A central composite design using RMS successfully described the effect of independent variables (feed moisture, die temperature and soybean proportion) on the specific parameters of product quality (expansion index, water absorption index, water solubility index and total color difference) studied. ...

Separating melanin from hemodynamics in nevi using multimode hyperspectral dermoscopy and spatial frequency domain spectroscopy

NASA Astrophysics Data System (ADS)

Vasefi, Fartash; MacKinnon, Nicholas; Saager, Rolf; Kelly, Kristen M.; Maly, Tyler; Booth, Nicholas; Durkin, Anthony J.; Farkas, Daniel L.

2016-11-01

Changes in the pattern and distribution of both melanocytes (pigment producing) and vasculature (hemoglobin containing) are important in distinguishing melanocytic proliferations. The ability to accurately measure melanin distribution at different depths and to distinguish it from hemoglobin is clearly important when assessing pigmented lesions (benign versus malignant). We have developed a multimode hyperspectral dermoscope (SkinSpect™) able to more accurately image both melanin and hemoglobin distribution in skin. SkinSpect uses both hyperspectral and polarization-sensitive measurements. SkinSpect's higher accuracy has been obtained by correcting for the effect of melanin absorption on hemoglobin absorption in measurements of melanocytic nevi. In vivo human skin pigmented nevi (N=20) were evaluated with the SkinSpect, and measured melanin and hemoglobin concentrations were compared with spatial frequency domain spectroscopy (SFDS) measurements. We confirm that both systems show low correlation of hemoglobin concentrations with regions containing different melanin concentrations (R=0.13 for SFDS, R=0.07 for SkinSpect).

Separating melanin from hemodynamics in nevi using multimode hyperspectral dermoscopy and spatial frequency domain spectroscopy

PubMed Central

Vasefi, Fartash; MacKinnon, Nicholas; Saager, Rolf; Kelly, Kristen M.; Maly, Tyler; Booth, Nicholas; Durkin, Anthony J.; Farkas, Daniel L.

2016-01-01

Abstract. Changes in the pattern and distribution of both melanocytes (pigment producing) and vasculature (hemoglobin containing) are important in distinguishing melanocytic proliferations. The ability to accurately measure melanin distribution at different depths and to distinguish it from hemoglobin is clearly important when assessing pigmented lesions (benign versus malignant). We have developed a multimode hyperspectral dermoscope (SkinSpect™) able to more accurately image both melanin and hemoglobin distribution in skin. SkinSpect uses both hyperspectral and polarization-sensitive measurements. SkinSpect’s higher accuracy has been obtained by correcting for the effect of melanin absorption on hemoglobin absorption in measurements of melanocytic nevi. In vivo human skin pigmented nevi (N=20) were evaluated with the SkinSpect, and measured melanin and hemoglobin concentrations were compared with spatial frequency domain spectroscopy (SFDS) measurements. We confirm that both systems show low correlation of hemoglobin concentrations with regions containing different melanin concentrations (R=0.13 for SFDS, R=0.07 for SkinSpect). PMID:27830262

Separating melanin from hemodynamics in nevi using multimode hyperspectral dermoscopy and spatial frequency domain spectroscopy.

PubMed

Vasefi, Fartash; MacKinnon, Nicholas; Saager, Rolf; Kelly, Kristen M; Maly, Tyler; Booth, Nicholas; Durkin, Anthony J; Farkas, Daniel L

2016-11-01

Changes in the pattern and distribution of both melanocytes (pigment producing) and vasculature (hemoglobin containing) are important in distinguishing melanocytic proliferations. The ability to accurately measure melanin distribution at different depths and to distinguish it from hemoglobin is clearly important when assessing pigmented lesions (benign versus malignant). We have developed a multimode hyperspectral dermoscope (SkinSpect™) able to more accurately image both melanin and hemoglobin distribution in skin. SkinSpect uses both hyperspectral and polarization-sensitive measurements. SkinSpect’s higher accuracy has been obtained by correcting for the effect of melanin absorption on hemoglobin absorption in measurements of melanocytic nevi. In vivo human skin pigmented nevi (N=20) were evaluated with the SkinSpect, and measured melanin and hemoglobin concentrations were compared with spatial frequency domain spectroscopy (SFDS) measurements. We confirm that both systems show low correlation of hemoglobin concentrations with regions containing different melanin concentrations (R=0.13 for SFDS, R=0.07 for SkinSpect).

Optical spectroscopy of interplanetary dust collected in the earth's stratosphere

NASA Technical Reports Server (NTRS)

Fraundorf, P.; Patel, R. I.; Shirck, J.; Walker, R. M.; Freeman, J. J.

1980-01-01

Optical absorption spectra of interplanetary dust particles 2-30 microns in size collected in the atmosphere at an altitude of 20 km by inertial impactors mounted on NASA U-2 aircraft are reported. Fourier transform absorption spectroscopy of crushed samples of the particles reveals a broad feature in the region 1300-800 kaysers which has also been found in meteorite and cometary dust spectra, and a weak iron crystal field absorption band at approximately 9800 kaysers, as is observed in meteorites. Work is currently in progress to separate the various components of the interplanetary dust particles in order to evaluate separately their contributions to the absorption.

Time-Resolved IR-Absorption Spectroscopy of Hot-Electron Dynamics in Satellite and Upper Conduction Bands in GaP

NASA Technical Reports Server (NTRS)

Cavicchia, M. A.; Alfano, R. R.

1995-01-01

The relaxation dynamics of hot electrons in the X6 and X7 satellite and upper conduction bands in GaP was directly measured by femtosecond UV-pump-IR-probe absorption spectroscopy. From a fit to the induced IR-absorption spectra the dominant scattering mechanism giving rise to the absorption at early delay times was determined to be intervalley scattering of electrons out of the X7 upper conduction-band valley. For long delay times the dominant scattering mechanism is electron-hole scattering. Electron transport dynamics of the upper conduction band of GaP has been time resolved.

Photoacoustic spectroscopy and thermal relaxation method to evaluate corn moisture content

NASA Astrophysics Data System (ADS)

Pedrochi, F.; Medina, A. N.; Bento, A. C.; Baesso, M. L.; Luz, M. L. S.; Dalpasquale, V. A.

2005-06-01

In this study, samples of popcorn with different degrees of moisture were analyzed. The optical absorption bands at the mid infrared were measured using photoacoustic spectroscopy and were correlated to the sample moisture. The results were in agreement with moisture data determined by the well known reference method, the Karl Fischer. In addition, the thermal relaxation method was used to determine the sample specific heat as a function of the moisture content. The results were also in agreement with the two mentioned methods.

New photocycle intermediates in the photoactive yellow protein from Ectothiorhodospira halophila: picosecond transient absorption spectroscopy.

PubMed

Ujj, L; Devanathan, S; Meyer, T E; Cusanovich, M A; Tollin, G; Atkinson, G H

1998-07-01

Previous studies have shown that the room temperature photocycle of the photoactive yellow protein (PYP) from Ectothiorhodospira halophila involves at least two intermediate species: I1, which forms in <10 ns and decays with a 200-micros lifetime to I2, which itself subsequently returns to the ground state with a 140-ms time constant at pH 7 (Genick et al. 1997. Biochemistry. 36:8-14). Picosecond transient absorption spectroscopy has been used here to reveal a photophysical relaxation process (stimulated emission) and photochemical intermediates in the PYP photocycle that have not been reported previously. The first new intermediate (I0) exhibits maximum absorption at approximately 510 nm and appears in

Influence of multiple scattering and absorption on the full scattering profile and the isobaric point in tissue

NASA Astrophysics Data System (ADS)

Duadi, Hamootal; Fixler, Dror

2015-05-01

Light reflectance and transmission from soft tissue has been utilized in noninvasive clinical measurement devices such as the photoplethysmograph (PPG) and reflectance pulse oximeter. Incident light on the skin travels into the underlying layers and is in part reflected back to the surface, in part transferred and in part absorbed. Most methods of near infrared (NIR) spectroscopy focus on the volume reflectance from a semi-infinite sample, while very few measure transmission. We have previously shown that examining the full scattering profile (angular distribution of exiting photons) provides more comprehensive information when measuring from a cylindrical tissue. Furthermore, an isobaric point was found which is not dependent on changes in the reduced scattering coefficient. The angle corresponding to this isobaric point depends on the tissue diameter. We investigated the role of multiple scattering and absorption on the full scattering profile of a cylindrical tissue. First, we define the range in which multiple scattering occurs for different tissue diameters. Next, we examine the role of the absorption coefficient in the attenuation of the full scattering profile. We demonstrate that the absorption linearly influences the intensity at each angle of the full scattering profile and, more importantly, the absorption does not change the position of the isobaric point. The findings of this work demonstrate a realistic model for optical tissue measurements such as NIR spectroscopy, PPG, and pulse oximetery.

Direct determination and speciation of mercury compounds in environmental and biological samples by carbon bed atomic absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skelly, E.M.

A method was developed for the direct determination of mercury in water and biological samples using a unique carbon bed atomizer for atomic absorption spectroscopy. The method avoided sources of error such as loss of volatile mercury during sample digestion and contamination of samples through added reagents by eliminating sample pretreatment steps. The design of the atomizer allowed use of the 184.9 nm mercury resonance line in the vacuum ultraviolet region, which increased sensitivity over the commonly used spin-forbidden 253.7 nm line. The carbon bed atomizer method was applied to a study of mercury concentrations in water, hair, sweat, urine,more » blood, breath and saliva samples from a non-occupationally exposed population. Data were collected on the average concentration, the range and distribution of mercury in the samples. Data were also collected illustrating individual variations in mercury concentrations with time. Concentrations of mercury found were significantly higher than values reported in the literature for a ''normal'' population. This is attributed to the increased accuracy gained by eliminating pretreatment steps and increasing atomization efficiency. Absorption traces were obtained for various solutions of pure and complexed mercury compounds. Absorption traces of biological fluids were also obtained. Differences were observed in the absorption-temperatures traces of various compounds. The utility of this technique for studying complexation was demonstrated.« less

Investigation of Diode Pumped Alkali Laser Atmospheric Transmission Using Tunable Diode Laser Absorption Spectroscopy

DTIC Science & Technology

2012-09-01

atmosphere”. Applied Physics B: Lasers and Optics, 82(1):133–140, 2006. 11. Barrass, S., Y. Grard, R.J. Holdsworth, and P.A. Martin . “Near-infrared tun...15. Brown, M. S., S. Williams, C. D. Lindstrom , and D. L. Barone. Progress in Applying Tunable Diode Laser Absorption Spectroscopy to Scramjet

A Simplified Digestion Protocol for the Analysis of Hg in Fish by Cold Vapor Atomic Absorption Spectroscopy

ERIC Educational Resources Information Center

Kristian, Kathleen E.; Friedbauer, Scott; Kabashi, Donika; Ferencz, Kristen M.; Barajas, Jennifer C.; O'Brien, Kelly

2015-01-01

Analysis of mercury in fish is an interesting problem with the potential to motivate students in chemistry laboratory courses. The recommended method for mercury analysis in fish is cold vapor atomic absorption spectroscopy (CVAAS), which requires homogeneous analyte solutions, typically prepared by acid digestion. Previously published digestion…

Development of picosecond time-resolved X-ray absorption spectroscopy by high-repetition-rate laser pump/X-ray probe at Beijing Synchrotron Radiation Facility.

PubMed

Wang, Hao; Yu, Can; Wei, Xu; Gao, Zhenhua; Xu, Guang Lei; Sun, Da Rui; Li, Zhenjie; Zhou, Yangfan; Li, Qiu Ju; Zhang, Bing Bing; Xu, Jin Qiang; Wang, Lin; Zhang, Yan; Tan, Ying Lei; Tao, Ye

2017-05-01

A new setup and commissioning of transient X-ray absorption spectroscopy are described, based on the high-repetition-rate laser pump/X-ray probe method, at the 1W2B wiggler beamline at the Beijing Synchrotron Radiation Facility. A high-repetition-rate and high-power laser is incorporated into the setup with in-house-built avalanche photodiodes as detectors. A simple acquisition scheme was applied to obtain laser-on and laser-off signals simultaneously. The capability of picosecond transient X-ray absorption spectroscopy measurement was demonstrated for a photo-induced spin-crossover iron complex in 6 mM solution with 155 kHz repetition rate.

Laser absorption spectroscopy of oxygen confined in highly porous hollow sphere xerogel.

PubMed

Yang, Lin; Somesfalean, Gabriel; He, Sailing

2014-02-10

An Al2O3 xerogel with a distinctive microstructure is studied for the application of laser absorption spectroscopy of oxygen. The xerogel has an exceptionally high porosity (up to 88%) and a large pore size (up to 3.6 µm). Using the method of gas-in-scattering media absorption spectroscopy (GASMAS), a long optical path length (about 3.5m) and high enhancement factor (over 300 times) are achieved as the result of extremely strong multiple-scattering when the light is transmitted through the air-filled, hollow-sphere alumina xerogel. We investigate how the micro-physical feature influences the optical property. As part of the optical sensing system, the material's gas exchange dynamics are also experimentally studied.

Quantitative detection of melamine based on terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Zhao, Xiaojing; Wang, Cuicui; Liu, Shangjian; Zuo, Jian; Zhou, Zihan; Zhang, Cunlin

2018-01-01

Melamine is an organic base and a trimer of cyanamide, with a 1, 3, 5-triazine skeleton. It is usually used for the production of plastics, glue and flame retardants. Melamine combines with acid and related compounds to form melamine cyanurate and related crystal structures, which have been implicated as contaminants or biomarkers in protein adulterations by lawbreakers, especially in milk powder. This paper is focused on developing an available method for quantitative detection of melamine in the fields of security inspection and nondestructive testing based on THz-TDS. Terahertz (THz) technology has promising applications for the detection and identification of materials because it exhibits the properties of spectroscopy, good penetration and safety. Terahertz time-domain spectroscopy (THz-TDS) is a key technique that is applied to spectroscopic measurement of materials based on ultrafast femtosecond laser. In this study, the melamine and its mixture with polyethylene powder in different consistence are measured using the transmission THz-TDS. And we obtained the refractive index spectra and the absorption spectrum of different concentrations of melamine on 0.2-2.8THz. In the refractive index spectra, it is obvious to see that decline trend with the decrease of concentration; and in the absorption spectrum, two peaks of melamine at 1.98THz and 2.28THz can be obtained. Based on the experimental result, the absorption coefficient and the consistence of the melamine in the mixture are determined. Finally, methods for quantitative detection of materials in the fields of nondestructive testing and quality control based on THz-TDS have been studied.

Local atomic and electronic structures of epitaxial strained LaCoO3 thin films

NASA Astrophysics Data System (ADS)

Sterbinsky, G. E.; Ryan, P. J.; Kim, J.-W.; Karapetrova, E.; Ma, J. X.; Shi, J.; Woicik, J. C.

2012-01-01

We have examined the atomic and electronic structures of perovskite lanthanum cobaltite (LaCoO3) thin films using Co K-edge x-ray absorption fine structure (XAFS) spectroscopy. Extended XAFS (EXAFS) demonstrates that a large difference between in-plane and out-of-plane Co-O bond lengths results from tetragonal distortion in highly strained films. The structural distortions are strongly coupled to the hybridization between atomic orbitals of the Co and O atoms, as shown by x-ray absorption near edge spectroscopy (XANES). Our results indicate that increased hybridization is not the cause of ferromagnetism in strained LaCoO3 films. Instead, we suggest that the strain-induced distortions of the oxygen octahedra increase the population of eg electrons and concurrently depopulate t2g electrons beyond a stabilization threshold for ferromagnetic order.

Comment on ``(Au-Ag)144(SR)60 alloy nanomolecules'' by C. Kumara and A. Dass, Nanoscale, 2011, 3, 3064

NASA Astrophysics Data System (ADS)

Barcaro, Giovanni; Sementa, Luca; Fortunelli, Alessandro; Stener, Mauro

2015-04-01

A recent paper in this journal reported the synthesis and characterization via electrospray ionization mass spectroscopy and UV-vis spectroscopy of (Au-Ag)144(SR)60 alloy nanomolecules with different compositions, ranging from 1 : 0 to 1 : 0.75 Au : Ag ratios. The UV-vis spectra of such systems were found to exhibit absorption peaks at 310 nm, 425 nm and 560 nm, interpreted as reminiscent of the silver surface plasmon resonance band due to simple atomic replacement of Au by Ag atoms in a fixed structural framework. On the basis of a comparison of experimentally observed and theoretically simulated optical absorption spectra, we conclude that the experimental situation must be more complicated, and that further work is needed to achieve atomistic insight into these fascinating systems.

X-ray absorption spectroscopy characterization of embedded and extracted nano-oxides

DOE PAGES

Stan, Tiberiu; Sprouster, David J.; Ofan, Avishai; ...

2016-12-29

Here, the chemistries and structures of both embedded and extracted Ysingle bondTisingle bondO nanometer-scale oxides in a nanostructured ferritic alloy (NFA) were probed by x-ray absorption spectroscopy (XAS). Y 2Ti 2O 7 is the primary embedded phase, while the slightly larger extracted oxides are primarily Y 2TiO 5. Analysis of the embedded nano-oxides is difficult partly due to the multiple Ti environments associated with different oxides and those still residing in matrix lattice sites. Thus, bulk extraction followed by selective filtration was used to isolate the larger Y 2TiO 5 oxides for XAS, while the smaller predominant embedded phase Ymore » 2Ti 2O 7 oxides passed through the filters and were analyzed using the log-ratio method.« less

Gas exchange in fruits related to skin condition and fruit ripening studied with diode laser spectroscopy

NASA Astrophysics Data System (ADS)

Huang, Jing; Zhang, Hao; Lin, Huiying; Li, Tianqi; Mei, Liang; Svanberg, Katarina; Svanberg, Sune

2016-12-01

The concentration of the biologically active molecular oxygen gas is of crucial importance for fruits in the metabolic respiration, maturation, and ripening processes. In our study, oxygen content and oxygen transport in fruits, exemplified by apples and guavas, were studied noninvasively by gas in scattering media absorption spectroscopy. The technique is based on the fact that free gases typically have 10,000 times narrower absorption features than the bulk material. The technique was demonstrated in studies of the influence of the fruit skin in regulating the internal oxygen balance, by observing the signal response of the internal oxygen gas to a transient change in the ambient gas concentration on peeled and unpeeled fruits. In addition, the gas exchange rate at different ripening stages was also studied in intact guavas.

The Optical Absorption Coefficient of Maize Grains Investigated by Photoacoustic Spectroscopy

NASA Astrophysics Data System (ADS)

Rodríguez-Páez, C. L.; Carballo-Carballo, A.; Rico-Molina, R.; Hernández-Aguilar, C.; Domínguez-Pacheco, A.; Cruz-Orea, A.; Moreno-Martínez, E.

2017-01-01

In the maize and tortilla industry, it is important to characterize the color of maize ( Zea mays L.) grain, as it is one of the attributes that directly affect the quality of the tortillas consumed by the population. For this reason, the availability of alternative techniques for assessing and improving the quality of grain is valued. Photoacoustic spectroscopy has proven to be a useful tool for characterizing maize grain. So, the objective of the present study was to determine the optical absorption coefficient β of the maize grain used to make tortillas from two regions of Mexico: (a) Valles Altos, 2012-2013 production cycle and (b) Guasave, Sinaloa, 2013-2014 production cycle. Traditional reflectance measurements, physical characteristics of the grain and nutrient content were also calculated. The experimental results show different characteristics for maize grains.

Gas exchange in fruits related to skin condition and fruit ripening studied with diode laser spectroscopy.

PubMed

Huang, Jing; Zhang, Hao; Lin, Huiying; Li, Tianqi; Mei, Liang; Svanberg, Katarina; Svanberg, Sune

2016-12-01

The concentration of the biologically active molecular oxygen gas is of crucial importance for fruits in the metabolic respiration, maturation, and ripening processes. In our study, oxygen content and oxygen transport in fruits, exemplified by apples and guavas, were studied noninvasively by gas in scattering media absorption spectroscopy. The technique is based on the fact that free gases typically have 10,000 times narrower absorption features than the bulk material. The technique was demonstrated in studies of the influence of the fruit skin in regulating the internal oxygen balance, by observing the signal response of the internal oxygen gas to a transient change in the ambient gas concentration on peeled and unpeeled fruits. In addition, the gas exchange rate at different ripening stages was also studied in intact guavas.

Cavity ring-down spectroscopy (CRDS) system for measuring atmospheric mercury using differential absorption

NASA Astrophysics Data System (ADS)

Pierce, A.; Obrist, D.; Moosmuller, H.; Moore, C.

2012-04-01

Atmospheric elemental mercury (Hg0) is a globally pervasive element that can be transported and deposited to remote ecosystems where it poses — particularly in its methylated form — harm to many organisms including humans. Current techniques for measurement of atmospheric Hg0 require several liters of sample air and several minutes for each analysis. Fast-response (i.e., 1 second or faster) measurements would improve our ability to understand and track chemical cycling of mercury in the atmosphere, including high frequency Hg0 fluctuations, sources and sinks, and chemical transformation processes. We present theory, design, challenges, and current results of our new prototype sensor based on cavity ring-down spectroscopy (CRDS) for fast-response measurement of Hg0 mass concentrations. CRDS is a direct absorption technique that implements path-lengths of multiple kilometers in a compact absorption cell using high-reflectivity mirrors, thereby improving sensitivity and reducing sample volume compared to conventional absorption spectroscopy. Our sensor includes a frequency-doubled, dye-laser emitting laser pulses tunable from 215 to 280 nm, pumped by a Q-switched, frequency tripled Nd:YAG laser with a pulse repetition rate of 50 Hz. We present how we successfully perform automated wavelength locking and stabilization of the laser to the peak Hg0 absorption line at 253.65 nm using an external isotopically-enriched mercury (202Hg0) cell. An emphasis of this presentation will be on the implementation of differential absorption measurement whereby measurements are alternated between the peak Hg0 absorption wavelength and a nearby wavelength "off" the absorption line. This can be achieved using a piezo electric tuning element that allows for pulse-by-pulse tuning and detuning of the laser "online" and "offline" of the Hg absorption line, and thereby allows for continuous correction of baseline extinction losses. Unexpected challenges with this approach included different efficiencies of laser performance (e.g., frequency doubling) at the two wavelengths and temperature dependence. We will discuss improvements on the control of our system to eliminate drift due to conversion efficiency and temperature dependence. We will detail complications with operating this instrument from a mobile platform for in situ measurements in the field. Finally, we will present data acquisition and processing approaches along with results of calibration curves, and comparisons to conventional mercury analyzers (i.e., a Tekran 2537 mercury vapor analyzer) during ambient air measurements.

Micro-X-Ray Fluorescence, Micro-X-Ray Absorption Spectroscopy, and Micro-X-Ray Diffraction Investigation of Lead Speciation after the Addition of Different Phosphorus Amendments to a Smelter-Contaminated Soil

EPA Science Inventory

The stabilization of Pb on additions of P to contaminated soils and mine spoil materials has been well documented. It is clear from the literature that different P sources result in different efficacies of Pb stabilization in the same contaminated material. We hypothesized that...

Structural determination of individual chemical species in a mixed system by iterative transformation factor analysis-based X-ray absorption spectroscopy combined with UV-visible absorption and quantum chemical calculation.

PubMed

Ikeda, Atsushi; Hennig, Christoph; Rossberg, André; Tsushima, Satoru; Scheinost, Andreas C; Bernhard, Gert

2008-02-15

A multitechnique approach using extended X-ray absorption fine structure (EXAFS) spectroscopy based on iterative transformation factor analysis (ITFA), UV-visible absorption spectroscopy, and density functional theory (DFT) calculations has been performed in order to investigate the speciation of uranium(VI) nitrate species in acetonitrile and to identify the complex structure of individual species in the system. UV-visible spectral titration suggests that there are four different species in the system, that is, pure solvated species, mono-, di-, and trinitrate species. The pure EXAFS spectra of these individual species are extracted by ITFA from the measured spectral mixtures on the basis of the speciation distribution profile calculated from the UV-visible data. Data analysis of the extracted EXAFS spectra, with the help of DFT calculations, reveals the most probable complex structures of the individual species. The pure solvated species corresponds to a uranyl hydrate complex with an equatorial coordination number (CNeq) of 5, [UO2(H2O)5]2+. Nitrate ions tend to coordinate to the uranyl(VI) ion in a bidentate fashion rather than a unidentate one in acetonitrile for all the nitrate species. The mononitrate species forms the complex of [UO2(H2O)3NO3]+ with a CNeq value of 5, while the di- and trinitrate species have a CNeq value of 6, corresponding to [UO2(H2O)2(NO3)2]0 (D2h) and [UO2(NO3)3]- (D3h), respectively.

Identification of different forms of cocaine and substances used in adulteration using near-infrared Raman spectroscopy and infrared absorption spectroscopy.

PubMed

Penido, Ciro A F O; Pacheco, Marcos Tadeu T; Zângaro, Renato A; Silveira, Landulfo

2015-01-01

Identification of cocaine and subsequent quantification immediately after seizure are problems for the police in developing countries such as Brazil. This work proposes a comparison between the Raman and FT-IR techniques as methods to identify cocaine, the adulterants used to increase volume, and possible degradation products in samples seized by the police. Near-infrared Raman spectra (785 nm excitation, 10 sec exposure time) and FT-IR-ATR spectra were obtained from different samples of street cocaine and some substances commonly used as adulterants. Freebase powder, hydrochloride powder, and crack rock can be distinguished by both Raman and FT-IR spectroscopies, revealing differences in their chemical structure. Most of the samples showed characteristic peaks of degradation products such as benzoylecgonine and benzoic acid, and some presented evidence of adulteration with aluminum sulfate and sodium carbonate. Raman spectroscopy is better than FT-IR for identifying benzoic acid and inorganic adulterants in cocaine. © 2014 American Academy of Forensic Sciences.

Non-Destructive and Discriminating Identification of Illegal Drugs by Transient Absorption Spectroscopy in the Visible and Near-IR Wavelength Range

NASA Astrophysics Data System (ADS)

Sato, Chie; Furube, Akihiro; Katoh, Ryuzi; Nonaka, Hidehiko; Inoue, Hiroyuki

2008-11-01

We have tested the possibility of identifying illegal drugs by means of nanosecond transient absorption spectroscopy with a 10-ns UV-laser pulse for the excitation light and visible-to-near-IR light for the probe light. We measured the transient absorption spectra of acetonitrile solutions of d-methamphetamine, dl-3,4-methylenedioxymethamphetamine hydrochloride (MDMA), and dl-N-methyl-1-(1,3-benzodioxol-5-yl)-2-butanamine hydrochloride (MBDB), which are illegal drugs widely consumed in Japan. Transient absorption signals of these drugs were observed between 400 and 950 nm, a range in which they are transparent in the ground state. By analyzing the spectra in terms of exponential and Gaussian functions, we could identify the drugs and discriminate them from chemical substances having similar structures. We propose that transient absorption spectroscopy will be a useful, non-destructive method of inspecting for illegal drugs, especially when they are dissolved in liquids. Such a method may even be used for drugs packed in opaque materials if it is further extended to utilize intense femtosecond laser pulses.

Spectral heterogeneity and carotenoid-to-bacteriochlorophyll energy transfer in LH2 light-harvesting complexes from Allochromatium vinosum.

PubMed

Magdaong, Nikki M; LaFountain, Amy M; Hacking, Kirsty; Niedzwiedzki, Dariusz M; Gibson, George N; Cogdell, Richard J; Frank, Harry A

2016-02-01

Photosynthetic organisms produce a vast array of spectral forms of antenna pigment-protein complexes to harvest solar energy and also to adapt to growth under the variable environmental conditions of light intensity, temperature, and nutrient availability. This behavior is exemplified by Allochromatium (Alc.) vinosum, a photosynthetic purple sulfur bacterium that produces different types of LH2 light-harvesting complexes in response to variations in growth conditions. In the present work, three different spectral forms of LH2 from Alc. vinosum, B800-820, B800-840, and B800-850, were isolated, purified, and examined using steady-state absorption and fluorescence spectroscopy, and ultrafast time-resolved absorption spectroscopy. The pigment composition of the LH2 complexes was analyzed by high-performance liquid chromatography, and all were found to contain five carotenoids: lycopene, anhydrorhodovibrin, spirilloxanthin, rhodopin, and rhodovibrin. Spectral reconstructions of the absorption and fluorescence excitation spectra based on the pigment composition revealed significantly more spectral heterogeneity in these systems compared to LH2 complexes isolated from other species of purple bacteria. The data also revealed the individual carotenoid-to-bacteriochlorophyll energy transfer efficiencies which were correlated with the kinetic data from the ultrafast transient absorption spectroscopic experiments. This series of LH2 complexes allows a systematic exploration of the factors that determine the spectral properties of the bound pigments and control the rate and efficiency of carotenoid-to-bacteriochlorophyll energy transfer.

The water vapour continuum in near-infrared windows - Current understanding and prospects for its inclusion in spectroscopic databases

NASA Astrophysics Data System (ADS)

Shine, Keith P.; Campargue, Alain; Mondelain, Didier; McPheat, Robert A.; Ptashnik, Igor V.; Weidmann, Damien

2016-09-01

Spectroscopic catalogues, such as GEISA and HITRAN, do not yet include information on the water vapour continuum that pervades visible, infrared and microwave spectral regions. This is partly because, in some spectral regions, there are rather few laboratory measurements in conditions close to those in the Earth's atmosphere; hence understanding of the characteristics of the continuum absorption is still emerging. This is particularly so in the near-infrared and visible, where there has been renewed interest and activity in recent years. In this paper we present a critical review focusing on recent laboratory measurements in two near-infrared window regions (centred on 4700 and 6300 cm-1) and include reference to the window centred on 2600 cm-1 where more measurements have been reported. The rather few available measurements, have used Fourier transform spectroscopy (FTS), cavity ring down spectroscopy, optical-feedback - cavity enhanced laser spectroscopy and, in very narrow regions, calorimetric interferometry. These systems have different advantages and disadvantages. Fourier Transform Spectroscopy can measure the continuum across both these and neighbouring windows; by contrast, the cavity laser techniques are limited to fewer wavenumbers, but have a much higher inherent sensitivity. The available results present a diverse view of the characteristics of continuum absorption, with differences in continuum strength exceeding a factor of 10 in the cores of these windows. In individual windows, the temperature dependence of the water vapour self-continuum differs significantly in the few sets of measurements that allow an analysis. The available data also indicate that the temperature dependence differs significantly between different near-infrared windows. These pioneering measurements provide an impetus for further measurements. Improvements and/or extensions in existing techniques would aid progress to a full characterisation of the continuum - as an example, we report pilot measurements of the water vapour self-continuum using a supercontinuum laser source coupled to an FTS. Such improvements, as well as additional measurements and analyses in other laboratories, would enable the inclusion of the water vapour continuum in future spectroscopic databases, and therefore allow for a more reliable forward modelling of the radiative properties of the atmosphere. It would also allow a more confident assessment of different theoretical descriptions of the underlying cause or causes of continuum absorption.

Reflectance spectroscopy (0.35-8 μm) of ammonium-bearing minerals and qualitative comparison to Ceres-like asteroids

NASA Astrophysics Data System (ADS)

Berg, Breanne L.; Cloutis, Edward A.; Beck, Pierre; Vernazza, Pierre; Bishop, Janice L.; Takir, Driss; Reddy, Vishnu; Applin, Daniel; Mann, Paul

2016-02-01

Ammonium-bearing minerals have been suggested to be present on Mars, Ceres, and various asteroids and comets. We undertook a systematic study of the spectral reflectance properties of ammonium-bearing minerals and compounds that have possible planetary relevance (i.e., ammonium carbonates, chlorides, nitrates, oxalates, phosphates, silicates, and sulfates). Various synthetic and natural NH4+-bearing minerals were analyzed using reflectance spectroscopy in the long-wave ultraviolet, visible, near-infrared, and mid-infrared regions (0.35-8 μm) in order to identify spectral features characteristic of the NH4+ molecule, and to evaluate if and how these features vary among different species. Mineral phases were confirmed through structural and compositional analyses using X-ray diffraction, X-ray fluorescence, and elemental combustion analysis. Characteristic absorption features associated with NH4 can be seen in the reflectance spectra at wavelengths as short as ∼1 μm. In the near-infrared region, the most prominent absorption bands are located near 1.6, 2.0, and 2.2 μm. Absorption features characteristic of NH4+ occurred at slightly longer wavelengths in the mineral-bound NH4+ spectra than for free NH4+ for most of the samples. Differences in wavelength position are attributable to various factors, including differences in the type and polarizability of the anion(s) attached to the NH4+, degree and type of hydrogen bonding, molecule symmetry, and cation substitutions. Multiple absorption features, usually three absorption bands, in the mid-infrared region between ∼2.8 and 3.8 μm were seen in all but the most NH4-poor sample spectra, and are attributed to fundamentals, combinations, and overtones of stretching and bending vibrations of the NH4+ molecule. These features appear even in reflectance spectra of water-rich samples which exhibit a strong 3 μm region water absorption feature. While many of the samples examined in this study have NH4 absorption bands at unique wavelength positions, in order to discriminate between different NH4+-bearing phases, absorption features corresponding to molecules other than NH4+ should be included in spectral analysis. A qualitative comparison of the laboratory results to telescopic spectra of Asteroids 1 Ceres, 10 Hygiea, and 324 Bamberga for the 3 μm region demonstrates that a number of NH4-bearing phases are consistent with the observational data in terms of exhibiting an absorption band in the 3.07 μm region.

Reflectance spectroscopy (0.35–8 μm) of ammonium-bearing minerals and qualitative comparison to Ceres-like asteroids

USGS Publications Warehouse

Berg, Breanne L.; Cloutis, Edward A.; Beck, P.; Vernazza, P.; Bishop, Janice L; Takir, Driss; Reddy, V.; Applin, D.; Mann, Paul

2016-01-01

Ammonium-bearing minerals have been suggested to be present on Mars, Ceres, and various asteroids and comets. We undertook a systematic study of the spectral reflectance properties of ammonium-bearing minerals and compounds that have possible planetary relevance (i.e., ammonium carbonates, chlorides, nitrates, oxalates, phosphates, silicates, and sulfates). Various synthetic and natural NH4+-bearing minerals were analyzed using reflectance spectroscopy in the long-wave ultraviolet, visible, near-infrared, and mid-infrared regions (0.35–8 μm) in order to identify spectral features characteristic of the NH4+ molecule, and to evaluate if and how these features vary among different species. Mineral phases were confirmed through structural and compositional analyses using X-ray diffraction, X-ray fluorescence, and elemental combustion analysis. Characteristic absorption features associated with NH4 can be seen in the reflectance spectra at wavelengths as short as ∼1 μm. In the near-infrared region, the most prominent absorption bands are located near 1.6, 2.0, and 2.2 μm. Absorption features characteristic of NH4+ occurred at slightly longer wavelengths in the mineral-bound NH4+ spectra than for free NH4+ for most of the samples. Differences in wavelength position are attributable to various factors, including differences in the type and polarizability of the anion(s) attached to the NH4+, degree and type of hydrogen bonding, molecule symmetry, and cation substitutions. Multiple absorption features, usually three absorption bands, in the mid-infrared region between ∼2.8 and 3.8 μm were seen in all but the most NH4-poor sample spectra, and are attributed to fundamentals, combinations, and overtones of stretching and bending vibrations of the NH4+ molecule. These features appear even in reflectance spectra of water-rich samples which exhibit a strong 3 μm region water absorption feature. While many of the samples examined in this study have NH4 absorption bands at unique wavelength positions, in order to discriminate between different NH4+-bearing phases, absorption features corresponding to molecules other than NH4+ should be included in spectral analysis. A qualitative comparison of the laboratory results to telescopic spectra of Asteroids 1 Ceres, 10 Hygiea, and 324 Bamberga for the 3 μm region demonstrates that a number of NH4-bearing phases are consistent with the observational data in terms of exhibiting an absorption band in the 3.07 μm region.

The extraction of gold nanoparticles from oat and wheat biomasses using sodium citrate and cetyltrimethylammonium bromide, studied by x-ray absorption spectroscopy, high-resolution transmission electron microscopy, and UV-visible spectroscopy.

PubMed

Armendariz, Veronica; Parsons, Jason G; Lopez, Martha L; Peralta-Videa, Jose R; Jose-Yacaman, Miguel; Gardea-Torresdey, Jorge L

2009-03-11

Gold (Au) nanoparticles can be produced through the interaction of Au(III) ions with oat and wheat biomasses. This paper describes a procedure to recover gold nanoparticles from oat and wheat biomasses using cetyltrimethylammonium bromide or sodium citrate. Extracts were analyzed using UV-visible spectroscopy, high-resolution transmission electron microscopy (HRTEM), and x-ray absorption spectroscopy. The HRTEM data demonstrated that smaller nanoparticles are extracted first, followed by larger nanoparticles. In the fourth extraction, coating of chelating agents is visible on the extracted nanoparticles.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole

Here, we demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole L.

We demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security applications.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

DOE PAGES

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole; ...

2017-06-19

Here, we demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

SPECTROSCOPY ALONG MULTIPLE, LENSED SIGHT LINES THROUGH OUTFLOWING WINDS IN THE QUASAR SDSS J1029+2623

DOE Office of Scientific and Technical Information (OSTI.GOV)

Misawa, Toru; Inada, Naohisa; Ohsuga, Ken

2013-02-01

We study the origin of absorption features on the blue side of the C IV broad emission line of the large-separation lensed quasar SDSS J1029+2623 at z{sub em} {approx} 2.197. The quasar images, produced by a foreground cluster of galaxies, have a maximum separation angle of {theta} {approx} 22.''5. The large angular separation suggests that the sight lines to the quasar central source can go through different regions of outflowing winds from the accretion disk of the quasar, providing a unique opportunity to study the structure of outflows from the accretion disk, a key ingredient for the evolution of quasarsmore » as well as for galaxy formation and evolution. Based on medium- and high-resolution spectroscopy of the two brightest images conducted at the Subaru telescope, we find that each image has different intrinsic levels of absorptions, which can be attributed either to variability of absorption features over the time delay between the lensed images, {Delta}t {approx} 744 days, or to the fine structure of quasar outflows probed by the multiple sight lines toward the quasar. While both these scenarios are consistent with the current data, we argue that they can be distinguished with additional spectroscopic monitoring observations.« less

Application of time-division-multiplexed lasers for measurements of gas temperature and CH4 and H2O concentrations at 30 kHz in a high-pressure combustor.

PubMed

Caswell, Andrew W; Kraetschmer, Thilo; Rein, Keith; Sanders, Scott T; Roy, Sukesh; Shouse, Dale T; Gord, James R

2010-09-10

Two time-division-multiplexed (TDM) sources based on fiber Bragg gratings were applied to monitor gas temperature, H(2)O mole fraction, and CH(4) mole fraction using line-of-sight absorption spectroscopy in a practical high-pressure gas turbine combustor test article. Collectively, the two sources cycle through 14 wavelengths in the 1329-1667 nm range every 33 μs. Although it is based on absorption spectroscopy, this sensing technology is fundamentally different from typical diode-laser-based absorption sensors and has many advantages. Specifically, the TDM lasers allow efficient, flexible acquisition of discrete-wavelength information over a wide spectral range at very high speeds (typically 30 kHz) and thereby provide a multiplicity of precise data at high speeds. For the present gas turbine application, the TDM source wavelengths were chosen using simulated temperature-difference spectra. This approach is used to select TDM wavelengths that are near the optimum values for precise temperature and species-concentration measurements. The application of TDM lasers for other measurements in high-pressure, turbulent reacting flows and for two-dimensional tomographic reconstruction of the temperature and species-concentration fields is also forecast.

Characterisation of historic plastics using terahertz time-domain spectroscopy and pulsed imaging.

PubMed

Pastorelli, Gianluca; Trafela, Tanja; Taday, Phillip F; Portieri, Alessia; Lowe, David; Fukunaga, Kaori; Strlič, Matija

2012-05-01

Terahertz (THz) time-domain spectroscopy and 3D THz pulsed imaging have been explored with regard to polymer materials, both commodity and historic polymers. A systematic spectroscopic study of a wide range of different polymer materials showed significant differences in their spectra. Polyolefins and polystyrenes generally exhibit lower absorption than other examined polymers, various cellulose derivates, poly(vinyl chloride), poly(methyl methacrylate), polyamide, hard rubber and phenol formaldehyde resin, the last of these exhibiting the most intense absorption over the entire range, 0.15-4.2 THz. It was also examined how the presence of plasticisers in poly(vinyl chloride), the presence of fillers in polypropylene, and the degree of branching in polyethylene and polystyrene affect the spectra; inorganic fillers in polypropylene affected the absorption most. With 3D THz pulsed imaging, features in polymer objects were explored, appearing either as integral parts of the material (coatings and pores in foams) or as a consequence of physical deterioration (cracks, delamination). All of these features of various complexities can be successfully imaged in 3D. Terahertz technology is thus shown to have significant potential for both chemical and structural characterisation of polymers, which will be of interest to heritage science, but also to the polymer industry and development of analytical technologies in general.

Photoionization and electron radical recombination dynamics in photoactive yellow protein investigated by ultrafast spectroscopy in the visible and near-infrared spectral region.

PubMed

Zhu, Jingyi; Paparelli, Laura; Hospes, Marijke; Arents, Jos; Kennis, John T M; van Stokkum, Ivo H M; Hellingwerf, Klaas J; Groot, Marie Louise

2013-09-26

Photoinduced ionization of the chromophore inside photoactive yellow protein (PYP) was investigated by ultrafast spectroscopy in the visible and near-infrared spectral regions. An absorption band that extended from around 550 to 850 nm was observed and ascribed to solvated electrons, ejected from the p-hydroxycinnamic acid anion chromophore upon the absorption of two 400 nm photons. Global kinetic analysis showed that the solvated electron absorption decayed in two stages: a shorter phase of around 10 ps and a longer phase of more than 3 ns. From a simulation based on a diffusion model we conclude that the diffusion rate of the electron is about 0.8 Å(2)/ps in wild type PYP, and that the electron is ejected to a short distance of only several angstroms away from the chromophore. The chromophore-protein pocket appears to provide a water-similar local environment for the electron. Because mutations at different places around the chromophore have different effect on the electron recombination dynamics, we suggest that solvated electrons could provide a new method to investigate the local dielectric environment inside PYP and thus help to understand the role of the protein in the photoisomerization process.

Accurate quantum yields by laser gain vs absorption spectroscopy - Investigation of Br/Br(asterisk) channels in photofragmentation of Br2 and IBr

NASA Technical Reports Server (NTRS)

Haugen, H. K.; Weitz, E.; Leone, S. R.

1985-01-01

Various techniques have been used to study photodissociation dynamics of the halogens and interhalogens. The quantum yields obtained by these techniques differ widely. The present investigation is concerned with a qualitatively new approach for obtaining highly accurate quantum yields for electronically excited states. This approach makes it possible to obtain an accuracy of 1 percent to 3 percent. It is shown that measurement of the initial transient gain/absorption vs the final absorption in a single time-resolved signal is a very accurate technique in the study of absolute branching fractions in photodissociation. The new technique is found to be insensitive to pulse and probe laser characteristics, molecular absorption cross sections, and absolute precursor density.

Direct Absorption Spectroscopy with Electro-Optic Frequency Combs

NASA Astrophysics Data System (ADS)

Fleisher, Adam J.; Long, David A.; Plusquellic, David F.; Hodges, Joseph T.

2017-06-01

The application of electro-optic frequency combs to direct absorption spectroscopy has increased research interest in high-agility, modulator-based comb generation. This talk will review common architectures for electro-optic frequency comb generators as well as describe common self-heterodyne and multi-heterodyne (i.e., dual-comb) detection approaches. In order to achieve a sufficient signal-to-noise ratio on the recorded interferogram while allowing for manageable data volumes, broadband electro-optic frequency combs require deep coherent averaging, preferably in real-time. Applications such as cavity-enhanced spectroscopy, precision atomic and molecular spectroscopy, as well as time-resolved spectroscopy will be introduced. D.A. Long et al., Opt. Lett. 39, 2688 (2014) A.J. Fleisher et al., Opt. Express 24, 10424 (2016)

Structural and Spectral Characterization of Co2+- and Ni2+-DOPED CdO Powder Prepared From Solution at Room Temperature

NASA Astrophysics Data System (ADS)

Reddy, C. V.; Rao, L. V. Krishna; Satish, D. V.; Shim, J.; Ravikumar, R. V. S. S. N.

2015-11-01

The mild and simple solution method was used for the synthesis of Co2+- and Ni2+-doped CdO powders at room temperature. The prepared powders were characterized using powder X-ray diffraction, scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), optical absorption, and Fourier transform infrared spectroscopy (FTIR). From the powder X-ray diffraction patterns, it has been observed that the prepared Co2+ and Ni2+ ion-doped CdO powders belong to the cubic phase, and the evaluated average crystalline sizes of the powders are 20 and 14 nm, respectively. The SEM images and the EDS spectra show that the prepared powders are distributed over different sizes in the grain boundaries. Optical absorption studies allow determination of site symmetry of the metal ion with its ligands. The crystal field (Dq) and inter-electronic repulsion (B and C) parameters have been evaluated from the optical absorption spectra. The FTIR spectra show the characteristic fundamental vibrations of the metal oxide and CdO.

Multispecies breath analysis faster than a single respiratory cycle by optical-feedback cavity-enhanced absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ventrillard-Courtillot, Irene; Gonthiez, Thierry; Clerici, Christine; Romanini, Daniel

2009-11-01

We demonstrate a first application, of optical-feedback cavity-enhanced absorption spectroscopy (OF-CEAS) to breath analysis in a medical environment. Noninvasive monitoring of trace species in exhaled air was performed simultaneous to spirometric measurements on patients at Bichat Hospital (Paris). The high selectivity of the OF-CEAS spectrometer and a time response of 0.3 s (limited by sample flow rate) allowed following the evolution of carbon monoxide and methane concentrations during individual respiratory cycles, and resolving variations among different ventilatory patterns. The minimum detectable absorption on this time scale is about 3×10-10 cm-1. At the working wavelength of the instrument (2.326 μm), this translates to concentration detection limits of ~1 ppbv (45 picomolar, or ~1.25 μg/m3) for CO and 25 ppbv for CH4, well below concentration values found in exhaled air. This same instrument is also able to provide measurement of NH3 concentrations with a detection limit of ~10 ppbv however, at present, memory effects do not allow its measurement on fast time scales.

Modeling L2,3-Edge X-ray Absorption Spectroscopy with Real-Time Exact Two-Component Relativistic Time-Dependent Density Functional Theory.

PubMed

Kasper, Joseph M; Lestrange, Patrick J; Stetina, Torin F; Li, Xiaosong

2018-04-10

X-ray absorption spectroscopy is a powerful technique to probe local electronic and nuclear structure. There has been extensive theoretical work modeling K-edge spectra from first principles. However, modeling L-edge spectra directly with density functional theory poses a unique challenge requiring further study. Spin-orbit coupling must be included in the model, and a noncollinear density functional theory is required. Using the real-time exact two-component method, we are able to variationally include one-electron spin-orbit coupling terms when calculating the absorption spectrum. The abilities of different basis sets and density functionals to model spectra for both closed- and open-shell systems are investigated using SiCl 4 and three transition metal complexes, TiCl 4 , CrO 2 Cl 2 , and [FeCl 6 ] 3- . Although we are working in the real-time framework, individual molecular orbital transitions can still be recovered by projecting the density onto the ground state molecular orbital space and separating contributions to the time evolving dipole moment.

Probing the electronic structure of platinum(II) chromophores: crystal structures, NMR structures, and photophysical properties of six new bis- and di- phenolate/thiolate Pt(II)diimine chromophores.

PubMed

Weinstein, Julia A; Tierney, Mark T; Davies, E Stephen; Base, Karel; Robeiro, Anthony A; Grinstaff, Mark W

2006-05-29

A general route for synthesis of six structurally similar Pt(II) diimine thiolate/phenolates chromophores possessing bulky phenolate or thiolate ligands is reported. The Pt chromophores were characterized using an array of techniques including 1H, 13C, and 195Pt NMR, absorption, emission, (spectro)electrochemistry, and EPR spectroscopy. Systematic variation of the electronic structure of the Pt(II) chromophores studied was achieved by (i) changing solvent polarity; (ii) substituting oxygen for sulfur in the donor ligand; (iii) alternating donor ligands from bis- to di-coordination; and (iv) changing the electron donating/withdrawing properties of the ligand(s). The lowest excited state in these new chromophores was assigned to a [charge-transfer-to-diimine] transition from the HOMO of mixed Pt/S (or Pt/O) character on the basis of absorption and emission spectroscopy, UV/vis (spectro)electrochemistry, and EPR spectroscopy. One of the chromophores, Pt(dpphen)(3,5-di-tert-butyl-catecholate) represents an example of a Pt(II) diimine phenolate chromophore that possesses a reversible oxidation centered predominantly on the donor ligand. Results from EPR spectroscopy indicate participation of the Pt(II) orbitals in the HOMO. There is a dramatic difference in the photophysical properties of carborane complexes compared to other mixed-ligand Pt(II) compounds, which includes room-temperature emission and photostability. The charge-transfer character of the lowest excited state in this series of chromophores is maintained throughout. Moreover, the absorption and emission energies and the redox properties of the excited state can be significantly tuned.

Discrimination of Medicine Radix Astragali from Different Geographic Origins Using Multiple Spectroscopies Combined with Data Fusion Methods

NASA Astrophysics Data System (ADS)

Wang, Hai-Yan; Song, Chao; Sha, Min; Liu, Jun; Li, Li-Ping; Zhang, Zheng-Yong

2018-05-01

Raman spectra and ultraviolet-visible absorption spectra of four different geographic origins of Radix Astragali were collected. These data were analyzed using kernel principal component analysis combined with sparse representation classification. The results showed that the recognition rate reached 70.44% using Raman spectra for data input and 90.34% using ultraviolet-visible absorption spectra for data input. A new fusion method based on Raman combined with ultraviolet-visible data was investigated and the recognition rate was increased to 96.43%. The experimental results suggested that the proposed data fusion method effectively improved the utilization rate of the original data.

Quantification and parametrization of non-linearity effects by higher-order sensitivity terms in scattered light differential optical absorption spectroscopy

NASA Astrophysics Data System (ADS)

Puķīte, Jānis; Wagner, Thomas

2016-05-01

We address the application of differential optical absorption spectroscopy (DOAS) of scattered light observations in the presence of strong absorbers (in particular ozone), for which the absorption optical depth is a non-linear function of the trace gas concentration. This is the case because Beer-Lambert law generally does not hold for scattered light measurements due to many light paths contributing to the measurement. While in many cases linear approximation can be made, for scenarios with strong absorptions non-linear effects cannot always be neglected. This is especially the case for observation geometries, for which the light contributing to the measurement is crossing the atmosphere under spatially well-separated paths differing strongly in length and location, like in limb geometry. In these cases, often full retrieval algorithms are applied to address the non-linearities, requiring iterative forward modelling of absorption spectra involving time-consuming wavelength-by-wavelength radiative transfer modelling. In this study, we propose to describe the non-linear effects by additional sensitivity parameters that can be used e.g. to build up a lookup table. Together with widely used box air mass factors (effective light paths) describing the linear response to the increase in the trace gas amount, the higher-order sensitivity parameters eliminate the need for repeating the radiative transfer modelling when modifying the absorption scenario even in the presence of a strong absorption background. While the higher-order absorption structures can be described as separate fit parameters in the spectral analysis (so-called DOAS fit), in practice their quantitative evaluation requires good measurement quality (typically better than that available from current measurements). Therefore, we introduce an iterative retrieval algorithm correcting for the higher-order absorption structures not yet considered in the DOAS fit as well as the absorption dependence on temperature and scattering processes.

Using of laser spectroscopy and chemometrics methods for identification of patients with lung cancer, patients with COPD and healthy people from absorption spectra of exhaled air

NASA Astrophysics Data System (ADS)

Bukreeva, Ekaterina B.; Bulanova, Anna A.; Kistenev, Yury V.; Kuzmin, Dmitry A.; Nikiforova, Olga Yu.; Ponomarev, Yurii N.; Tuzikov, Sergei A.; Yumov, Evgeny L.

2014-11-01

The results of application of the joint use of laser photoacoustic spectroscopy and chemometrics methods in gas analysis of exhaled air of patients with chronic respiratory diseases (chronic obstructive pulmonary disease and lung cancer) are presented. The absorption spectra of exhaled breath of representatives of the target groups and healthy volunteers were measured; the selection by chemometrics methods of the most informative absorption coefficients in scan spectra in terms of the separation investigated nosology was implemented.

Measurements of CO2, CH4, H2O, and HDO over a 2-km Outdoor Path with Dual-Comb Spectroscopy

NASA Astrophysics Data System (ADS)

Rieker, G. B.; Giorgetta, F. R.; Coddington, I.; Swann, W. C.; Sinclair, L. C.; Cromer, C.; Baumann, E.; Newbury, N. R.; Kofler, J.; Petron, G.; Sweeney, C.; Tans, P. P.

2013-12-01

We demonstrate simultaneous sensing of CO2, CH4, H2O, and HDO over a 2-km outdoor open air path using dual-frequency-comb absorption spectroscopy (DCS). Our implementation of the DCS technique simultaneously offers broad spectral coverage (>8 THz, 267 cm-1) and fine spectral point spacing (100 MHz, 0.0033 cm-1) with a coherent eye-safe beam. The spectrometer, which is adapted from [Zolot et al., 2012], consists of two mutually coherent Erbium-doped fiber frequency-comb lasers which create a broad spectrum of perfectly spaced narrow linewidth frequency elements (';comb teeth') near 1.6 μm. The comb light is transmitted by a telescope and active steering mirrors from the roof of the NIST Boulder laboratory to a 50-cm flat mirror located 1 km away. The return light is received by a second telescope and carried via multimode fiber to a detector. The greenhouse gas absorption attenuates the teeth from the two combs that are coincident with the relevant molecular resonant frequencies. We purposefully offset the frequencies between the two frequency combs in a Vernier-like fashion so that each pair of comb teeth from the two combs results in a unique rf heterodyne beat frequency on the photodiode. The spectral spacing between subsequent comb teeth pairs is 100 MHz, far lower than the ~4 GHz linewidths of small molecule absorption features in the atmosphere. Because of the narrow comb linewidth, there is an essentially negligible instrument lineshape. The measured absorption spectrum can thus resolve neighboring absorption features of different species, and can be compared directly with HITRAN and recent greenhouse gas absorption models developed for satellite- and ground-based carbon observatories to determine the path-integrated concentrations of the absorbing species. Measurements covering the complete 30013←00001 absorption band of CO2 and absorption features of CH4, H2O and HDO between 1.6-1.67 μm were performed under a variety of atmospheric conditions. During windy conditions when the atmosphere is well-mixed and species concentrations are stable, long-time-average data (240 min) are used to achieve high signal-to-noise ratio for careful comparisons of different spectral absorption models to the measured spectrum. Shorter five minute time resolution spectra are used to track fluctuations in atmospheric greenhouse gas concentrations over diurnal cycles and different weather conditions, and compared with simultaneous point-sampled measurements using a commercial cavity ringdown-based gas sensor. A. M. Zolot, F. R. Giorgetta, E. Baumann, J. W. Nicholson, W. C. Swann, I. Coddington, and N. R. Newbury (2012), Direct-Comb Molecular Spectroscopy with Accurate, Resolved Comb Teeth over 43 THz, Opt. Lett., 37(4), 638-640. a) Transmitted intensity spectrum over the 2-km outdoor path showing the spectral intensity variations of the combs and fine structure from gas absorption. b) Background-corrected absorbance of CO2 (blue) fitted with a Hitran model (red). The CO2 concentration measured from the fit is 408 ppm.

Probing Exciton and Charge Dynamics in Organic Thin Films and Photovoltaics with Nonlinear Spectroscopy

NASA Astrophysics Data System (ADS)

McDonough, Thomas J.

Emerging organic solar cell technologies offer unique advantages over silicon solar cells, such as solution processability and the use of flexible substrates, but the efficiencies of these devices do not yet match the efficiency of silicon. Ultrafast nonlinear spectroscopies can probe the fates of photoexcited species on timescales in which these species are lost to channels that do not result in electric current. In the first study, I compare the ultrafast dynamics of singlet fission and charge generation in pentacene films grown on glass and graphene. The molecular orientation is different on the two substrates: the long axis of the pentacene molecules are "standing-up" (normal to the surface) on glass and "lying-down" (parallel to the surface) on graphene. By studying the fluence and polarization dependence of the transient absorption of pentacene on these two substrates, I am able to clarify previous spectral assignments. I identify a broad, isotropic absorption at 853 nm as due in significant part to hole absorption, in contrast to this feature's typical assignment to T1-T2 absorption. At high fluence, additional peaks at 614 and 688 (on glass) nm appear, whose kinetics and anisotropies are not explained by heating, which I assign to charge generation. In the second study, I utilize two-dimensional white-light spectroscopy to study the morphology dependence of exciton diffusion in semiconducting carbon nanotubes. I analyze the spectral diffusion of the S 1-S1 2D-WL lineshape via the center line slope method to separate the homogeneous and inhomogeneous contributions to the lineshape in each sample. I determine a morphology independent homogeneous linewidth of 10 meV, but I find that the inhomogeneous linewidth is sensitive to the particular sample environment. I model our experimental spectra with kinetic Monte Carlo simulations of exciton diffusion in a 1D potential. I also present preliminary bias-dependent transient absorption and 2D-WL measurements of carbon nanotube solar cell devices. I observe increasing positive trion absorption with increasing forward bias. The kinetics in the device are much different than the kinetics in the thin film, and there is an interesting change in kinetics with bias voltage that requires further investigation.

Characterizing the Circumgalactic Medium of Nearby Galaxies with HST/COS and HST/STIS Absorption-line Spectroscopy. II. Methods and Models

NASA Astrophysics Data System (ADS)

Keeney, Brian A.; Stocke, John T.; Danforth, Charles W.; Shull, J. Michael; Pratt, Cameron T.; Froning, Cynthia S.; Green, James C.; Penton, Steven V.; Savage, Blair D.

2017-05-01

We present basic data and modeling for a survey of the cool, photoionized circumgalactic medium (CGM) of low-redshift galaxies using far-UV QSO absorption-line probes. This survey consists of “targeted” and “serendipitous” CGM subsamples, originally described in Stocke et al. (Paper I). The targeted subsample probes low-luminosity, late-type galaxies at z< 0.02 with small impact parameters (< ρ > =71 kpc), and the serendipitous subsample probes higher luminosity galaxies at z≲ 0.2 with larger impact parameters (< ρ > =222 kpc). Hubble Space Telescope and FUSE UV spectroscopy of the absorbers and basic data for the associated galaxies, derived from ground-based imaging and spectroscopy, are presented. We find broad agreement with the COS-Halos results, but our sample shows no evidence for changing ionization parameter or hydrogen density with distance from the CGM host galaxy, probably because the COS-Halos survey probes the CGM at smaller impact parameters. We find at least two passive galaxies with H I and metal-line absorption, confirming the intriguing COS-Halos result that galaxies sometimes have cool gas halos despite no on-going star formation. Using a new methodology for fitting H I absorption complexes, we confirm the CGM cool gas mass of Paper I, but this value is significantly smaller than that found by the COS-Halos survey. We trace much of this difference to the specific values of the low-z metagalactic ionization rate assumed. After accounting for this difference, a best-value for the CGM cool gas mass is found by combining the results of both surveys to obtain {log}(M/{M}⊙ )=10.5+/- 0.3, or ˜30% of the total baryon reservoir of an L≥slant {L}* , star-forming galaxy. Based on observations with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by AURA, Inc., under NASA contract NAS 5-26555.

Tuning the nonlinear optical absorption in Au/BaTiO3 nanocomposites with gold nanoparticle concentration

NASA Astrophysics Data System (ADS)

Bijeesh, M. M.; Shakhi, P. K.; Varier, Geetha K.; Nandakumar, P.

2018-06-01

We report on the nonlinear optical absorption coefficient of Au/BaTiO3 nanocomposite films and its dependence on gold nanoparticle concentration. Au/BaTiO3 nanocomposite films with different molar ratio of Au/Ba are prepared by sol-gel technique and characterized by X-ray diffraction, UV Visible absorption spectroscopy and high resolution transmission electron microscopy. An open aperture Z-scan technique is employed to study the third order nonlinear optical properties of Au/BaTiO3 thin films. An Nd:YAG laser operating at 532 nm wavelength having a pulse width of 5 ns is used for the measurements. The two-photon absorption coefficient of the films increases linearly with gold nanoparticle concentration and significant enhancement of nonlinear optical absorption is observed. This ability to fine tune the nonlinear optical coefficients of Au/BaTiO3 films would be handy in optical device applications.

Developing a Transdisciplinary Teaching Implement for Atomic Absorption Spectroscopy

ERIC Educational Resources Information Center

Drew, John

2008-01-01

In this article I explain why I wrote the set of teaching notes on Atomic Absorption Spectroscopy (AAS) and why they look the way they do. The notes were intended as a student reference to question, highlight and write over as much as they wish during an initial practical demonstration of the threshold concept being introduced, in this case…

The Use of a Microprocessor-Controlled, Video Output Atomic Absorption Spectrometer as an Educational Tool in a Two-Year Technical Curriculum.

ERIC Educational Resources Information Center

Kerfoot, Henry B.

Based on instructional experiences at Charles County Community College, Maryland, this report examines the pedagogical advantage of teaching atomic absorption (AA) spectroscopy with an AA spectrophotometer that is equipped with a microprocessor and video output mechanism. The report first discusses the growing importance of AA spectroscopy in…

Preliminary study on quality evaluation of pecans with terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Li, Bin; Cao, Wei; Mathanker, Sunil; Zhang, Weili; Wang, Ning

2010-11-01

This paper reports a preliminary work on a feasibility study of applying terahertz (THz) technology for pecan quality evaluation. A set of native pecan nuts collected in 2009 were used during the experiment. Each pecan nutmeat was manually sliced at a thickness of about 1mm, 2mm, and 3mm and a size of about 2cm (length) ×1cm (width). Pecan shell and inner separator were also cut into the same size. The absorption spectra for the nutmeat slices, shell, and inner separator were collected using a THz time-domain spectroscopy (THz-TDS) developed by a group of researchers at Oklahoma State University. The test results show that nutmeat, shell, and inner separator had different absorption characteristics within the bandwidth of 0.2-2.0 THz. To study the capability of insect damage detection of the THz spectroscopy, the absorption spectra of insects (living manduca sexta and dry pecan weevil) were also collected. Due to high water contents in the insects, very obvious spectral characteristics were found. The results from the preliminary study show a potential of THz technology applied for quality detection of bio-products. However, since bio-products mostly have high water content and are handled under an environment with certain levels of water content, practical issues needs to be further investigated to make the THz technology a feasible tool for quality evaluation.

Role of the Cu-ZrO 2 Interfacial Sites for Conversion of Ethanol to Ethyl Acetate and Synthesis of Methanol from CO 2 and H 2 [The Role of the Cu-ZrO 2 Interfacial Sites for Ethanol Conversion to Ethyl Acetate and Methanol Synthesis from CO 2 and H 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ro, Insoo; Liu, Yifei; Ball, Madelyn R.

Well-defined Cu catalysts containing different amounts of zirconia were synthesized by controlled surface reactions (CSRs) and atomic layer deposition methods and studied for the selective conversion of ethanol to ethyl acetate and for methanol synthesis. Selective deposition of ZrO 2 on undercoordinated Cu sites or near Cu nanoparticles via the CSR method was evidenced by UV–vis absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The concentrations of Cu and Cu-ZrO 2 interfacial sites were quantified using a combination of subambient CO Fourier transform infrared spectroscopy and reactive N 2O chemisorption measurements. The oxidation states ofmore » the Cu and ZrO 2 species for these catalysts were determined using X-ray absorption near edge structure measurements, showing that these species were present primarily as Cu 0 and Zr 4+, respectively. Here, it was found that the formation of Cu-ZrO 2 interfacial sites increased the turnover frequency by an order of magnitude in both the conversion of ethanol to ethyl acetate and the synthesis of methanol from CO 2 and H 2.« less

Role of the Cu-ZrO 2 Interfacial Sites for Conversion of Ethanol to Ethyl Acetate and Synthesis of Methanol from CO 2 and H 2 [The Role of the Cu-ZrO 2 Interfacial Sites for Ethanol Conversion to Ethyl Acetate and Methanol Synthesis from CO 2 and H 2

DOE PAGES

Ro, Insoo; Liu, Yifei; Ball, Madelyn R.; ...

2016-09-06

Well-defined Cu catalysts containing different amounts of zirconia were synthesized by controlled surface reactions (CSRs) and atomic layer deposition methods and studied for the selective conversion of ethanol to ethyl acetate and for methanol synthesis. Selective deposition of ZrO 2 on undercoordinated Cu sites or near Cu nanoparticles via the CSR method was evidenced by UV–vis absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The concentrations of Cu and Cu-ZrO 2 interfacial sites were quantified using a combination of subambient CO Fourier transform infrared spectroscopy and reactive N 2O chemisorption measurements. The oxidation states ofmore » the Cu and ZrO 2 species for these catalysts were determined using X-ray absorption near edge structure measurements, showing that these species were present primarily as Cu 0 and Zr 4+, respectively. Here, it was found that the formation of Cu-ZrO 2 interfacial sites increased the turnover frequency by an order of magnitude in both the conversion of ethanol to ethyl acetate and the synthesis of methanol from CO 2 and H 2.« less

Infrared Spectroscopy on Smoke Produced by Cauterization of Animal Tissue

PubMed Central

Gianella, Michele; Sigrist, Markus W.

2010-01-01

In view of in vivo surgical smoke studies a difference-frequency-generation (DFG) laser spectrometer (spectral range 2900–3144 cm−1) and a Fourier-transform infrared (FTIR) spectrometer were employed for infrared absorption spectroscopy. The chemical composition of smoke produced in vitro with an electroknife by cauterization of different animal tissues in different atmospheres was investigated. Average concentrations derived are: water vapor (0.87%), methane (20 ppm), ethane (4.8 ppm), ethene (17 ppm), carbon monoxide (190 ppm), nitric oxide (25 ppm), nitrous oxide (40 ppm), ethyne (50 ppm) and hydrogen cyanide (25 ppm). No correlation between smoke composition and the atmosphere or the kind of cauterized tissue was found. PMID:22319267

Optical study of plasma sprayed hydroxyapatite coatings deposited at different spray distance

NASA Astrophysics Data System (ADS)

Belka, R.; Kowalski, S.; Żórawski, W.

2017-08-01

Series of hydroxyapatite (HA) coatings deposited on titanium substrate at different spray (plasma gun to workpiece) distance were investigated. The optical methods as dark field confocal microscopy, Raman/PL and UV-VIS spectroscopy were used for study the influence of deposition process on structural degradation of HA precursor. The hydroxyl group concentration was investigated by study the OH mode intensity in the Raman spectra. Optical absorption coefficients at near UV region were analyzed by Diffuse Reflectance Spectroscopy. PL intensity observed during Raman measurement was also considered as relation to defects concentration and degradation level. It was confirmed the different gunsubstrate distance has a great impact on structure of deposited HA ceramics.

Probing the influence of the center atom coordination structure in iron phthalocyanine multi-walled carbon nanotube-based oxygen reduction reaction catalysts by X-ray absorption fine structure spectroscopy

NASA Astrophysics Data System (ADS)

Peng, Yingxiang; Li, Zhipan; Xia, Dingguo; Zheng, Lirong; Liao, Yi; Li, Kai; Zuo, Xia

2015-09-01

Three different pentacoordinate iron phthalocyanine (FePc) electrocatalysts with an axial ligand (pyridyl group, Py) anchored to multi-walled carbon nanotubes (MWCNTs) are prepared by a microwave method as high performance composite electrocatalysts (FePc-Py/MWCNTs) for the oxygen reduction reaction (ORR). For comparison, tetracoordinate FePc electrocatalysts without an axial ligand anchored to MWCNTs (FePc/MWCNTs) are assembled in the same way. Ultraviolet-visible spectrophotometry (UV-Vis), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HRTEM) are used to characterize the obtained electrocatalysts. The electrocatalytic activity of the samples is measured by linear sweep voltammetry (LSV), and the onset potential of all of the FePc-Py/MWCNTs electrocatalysts is found to be more positive than that of their FePc/MWCNTs counterparts. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy are employed to elucidate the relationship between molecular structure and electrocatalytic activity. XPS indicates that higher concentrations of Fe3+ and pyridine-type nitrogen play critical roles in determining the electrocatalytic ORR activity of the samples. XAFS spectroscopy reveals that the FePc-Py/MWCNTs electrocatalysts have a coordination geometry around Fe that is closer to the square pyramidal structure, a higher concentration of Fe3+, and a smaller phthalocyanine ring radius compared with those of FePc/MWCNTs.

Intercomparison of measurements of NO2 concentrations in the atmosphere simulation chamber SAPHIR during the NO3Comp campaign

NASA Astrophysics Data System (ADS)

Fuchs, H.; Ball, S. M.; Bohn, B.; Brauers, T.; Cohen, R. C.; Dorn, H.-P.; Dubé, W. P.; Fry, J. L.; Häseler, R.; Heitmann, U.; Jones, R. L.; Kleffmann, J.; Mentel, T. F.; Müsgen, P.; Rohrer, F.; Rollins, A. W.; Ruth, A. A.; Kiendler-Scharr, A.; Schlosser, E.; Shillings, A. J. L.; Tillmann, R.; Varma, R. M.; Venables, D. S.; Villena Tapia, G.; Wahner, A.; Wegener, R.; Wooldridge, P. J.; Brown, S. S.

2010-01-01

NO2 concentrations were measured by various instruments during the NO3Comp campaign at the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich, Germany, in June 2007. Analytical methods included photolytic conversion with chemiluminescence (PC-CLD), broadband cavity ring-down spectroscopy (BBCRDS), pulsed cavity ring-down spectroscopy (CRDS), incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS), and laser-induced fluorescence (LIF). All broadband absorption spectrometers were optimized for the detection of the main target species of the campaign, NO3, but were also capable of detecting NO2 simultaneously with reduced sensitivity. NO2 mixing ratios in the chamber were within a range characteristic of polluted, urban conditions, with a maximum mixing ratio of approximately 75 ppbv. The overall agreement between measurements of all instruments was excellent. Linear fits of the combined data sets resulted in slopes that differ from unity only within the stated uncertainty of each instrument. Possible interferences from species such as water vapor and ozone were negligible under the experimental conditions.

Intercomparison of measurements of NO2 concentrations in the atmosphere simulation chamber SAPHIR during the NO3Comp campaign

NASA Astrophysics Data System (ADS)

Fuchs, H.; Ball, S. M.; Bohn, B.; Brauers, T.; Cohen, R. C.; Dorn, H.-P.; Dubé, W. P.; Fry, J. L.; Häseler, R.; Heitmann, U.; Jones, R. L.; Kleffmann, J.; Mentel, T. F.; Müsgen, P.; Rohrer, F.; Rollins, A. W.; Ruth, A. A.; Kiendler-Scharr, A.; Schlosser, E.; Shillings, A. J. L.; Tillmann, R.; Varma, R. M.; Venables, D. S.; Villena Tapia, G.; Wahner, A.; Wegener, R.; Wooldridge, P. J.; Brown, S. S.

2009-10-01

NO2 concentrations were measured by various instruments during the NO3Comp campaign at the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich, Germany, in June 2007. Analytic methods included photolytic conversion with chemiluminescence (PC-CLD), broadband cavity ring-down spectroscopy (BBCRDS), pulsed cavity ring-down spectroscopy (CRDS), incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS), and laser-induced fluorescence (LIF). All broadband absorption spectrometers were optimized for the detection of the main target species of the campaign, NO2, but were also capable of detecting NO2 simultaneously with reduced sensitivity. NO2 mixing ratios in the chamber were within a range characteristic of polluted, urban conditions, with a maximum mixing ratio of approximately 75 ppbv. The overall agreement between measurements of all instruments was excellent. Linear fits of the combined data sets resulted in slopes that differ from unity only within the stated uncertainty of each instrument. Possible interferences from species such as water vapor and ozone were negligible under the experimental conditions.

Distributed information system on molecular spectroscopy

NASA Astrophysics Data System (ADS)

Bykov, A. D.; Fazliev, A. Z.; Kozodoev, A. V.; Privezentsev, A. I.; Sinitsa, L. N.; Tonkov, M. V.; Filippov, N. N.; Tretyakov, M. Yu.

2006-12-01

The urgency of creating the information-computational systems (ICS) on molecular spectroscopy follows from the circumstance that for some molecules the number of calculated energy levels counts hundreds of thousands, and the number of spectral lines sometimes reaches hundreds of millions. Publication of such data volumes in regular journals is inappropriate. Comparison of different calculated spectral characteristics or their comparison with experimental data beyond computer processing is hopeless. We find information systems to be an adequate form for holding such data volumes and a toolkit for handling them. Correct digital data processing requires appropriate sets of metadata arranged in the form of ontology of molecular spectroscopy. Our information system provides the data on spectral line parameters, water molecule energy levels, and absorption coefficients. Within this distributed IS one can solve two types of problems: manipulation with data and calculation of spectral functions. Among the latest experimental data in the IS there are data obtained at the Institute of Applied Physics RAS. To calculate the absorption coefficients for the molecules of carbonic acid gas, we take into consideration spectral line interference.

Optical and structural behaviors of crosslinked polyvinyl alcohol thin films

NASA Astrophysics Data System (ADS)

Pandit, Subhankar; Kundu, Sarathi

2018-04-01

Polyvinyl Alcohol (PVA) has excellent properties like uniaxial tensile stress, chemical resistance, biocompatibility, etc. The properties of PVA further can be tuned by crosslinking process. In this work, a simple heat treatment method is used to find out the optimum crosslinking of PVA and the corresponding structural and optical responses are explored. The PVA crosslinking is done by exposing the films at different temperatures and time intervals. The optical property of pure and heat treated PVA films are investigated by UV-Vis absorption and photoluminescence emission spectroscopy and structural modifications are studied by Fourier Transform Infrared Spectroscopy (FTIR). The absorption peaks of pure PVA are observed at ≈ 280 and 335 nm and the corresponding emission is observed at ≈ 424 nm. The pure PVA showed modified optical behaviors after the heat treatment. In addition, dipping the PVA films in hot water (85°C) for nearly 20 minutes also show impact on both structural and optical properties. From FTIR spectroscopy, the changes in vibrational band positions confirm the structural modifications of PVA films.

Rapid, Time-Division Multiplexed, Direct Absorption- and Wavelength Modulation-Spectroscopy

PubMed Central

Klein, Alexander; Witzel, Oliver; Ebert, Volker

2014-01-01

We present a tunable diode laser spectrometer with a novel, rapid time multiplexed direct absorption- and wavelength modulation-spectroscopy operation mode. The new technique allows enhancing the precision and dynamic range of a tunable diode laser absorption spectrometer without sacrificing accuracy. The spectroscopic technique combines the benefits of absolute concentration measurements using calibration-free direct tunable diode laser absorption spectroscopy (dTDLAS) with the enhanced noise rejection of wavelength modulation spectroscopy (WMS). In this work we demonstrate for the first time a 125 Hz time division multiplexed (TDM-dTDLAS-WMS) spectroscopic scheme by alternating the modulation of a DFB-laser between a triangle-ramp (dTDLAS) and an additional 20 kHz sinusoidal modulation (WMS). The absolute concentration measurement via the dTDLAS-technique allows one to simultaneously calibrate the normalized 2f/1f-signal of the WMS-technique. A dTDLAS/WMS-spectrometer at 1.37 μm for H2O detection was built for experimental validation of the multiplexing scheme over a concentration range from 50 to 3000 ppmV (0.1 MPa, 293 K). A precision of 190 ppbV was achieved with an absorption length of 12.7 cm and an averaging time of two seconds. Our results show a five-fold improvement in precision over the entire concentration range and a significantly decreased averaging time of the spectrometer. PMID:25405508

Real-time trace gas sensor using a multimode diode laser and multiple-line integrated cavity enhanced absorption spectroscopy.

PubMed

Karpf, Andreas; Rao, Gottipaty N

2015-07-01

We describe and demonstrate a highly sensitive trace gas sensor based on a simplified design that is capable of measuring sub-ppb concentrations of NO2 in tens of milliseconds. The sensor makes use of a relatively inexpensive Fabry-Perot diode laser to conduct off-axis cavity enhanced spectroscopy. The broad frequency range of a multimode Fabry-Perot diode laser spans a large number of absorption lines, thereby removing the need for a single-frequency tunable laser source. The use of cavity enhanced absorption spectroscopy enhances the sensitivity of the sensor by providing a pathlength on the order of 1 km in a small volume. Off-axis alignment excites a large number of cavity modes simultaneously, thereby reducing the sensor's susceptibility to vibration. Multiple-line integrated absorption spectroscopy (where one integrates the absorption spectra over a large number of rovibronic transitions of the molecular species) further improves the sensitivity of detection. Relatively high laser power (∼400  mW) is used to compensate for the low coupling efficiency of a broad linewidth laser to the optical cavity. The approach was demonstrated using a 407 nm diode laser to detect trace quantities of NO2 in zero air. Sensitivities of 750 ppt, 110 ppt, and 65 ppt were achieved using integration times of 50 ms, 5 s, and 20 s respectively.

Attosecond XUV absorption spectroscopy of doubly excited states in helium atoms dressed by a time-delayed femtosecond infrared laser

NASA Astrophysics Data System (ADS)

Yang, Z. Q.; Ye, D. F.; Ding, Thomas; Pfeifer, Thomas; Fu, L. B.

2015-01-01

In the present paper, we investigate the time-resolved transient absorption spectroscopy of doubly excited states of helium atoms by solving the time-dependent two-electron Schrödinger equation numerically based on a one-dimensional model. The helium atoms are subjected to an extreme ultraviolet (XUV) attosecond pulse and a time-delayed infrared (IR) few-cycle laser pulse. A superposition of doubly excited states populated by the XUV pulse is identified, which interferes with the direct ionization pathway leading to Fano resonance profiles in the photoabsorption spectrum. In the presence of an IR laser, however, the Fano line profiles are strongly modified: A shifting, splitting, and broadening of the original absorption lines is observed when the XUV attosecond pulse and infrared few-cycle laser pulse overlap in time, which is in good agreement with recent experimental results. At certain time delays, we observe symmetric Lorentz, inverted Fano profiles, and even negative absorption cross sections indicating that the XUV light can be amplified during the interaction with atoms. We further prove that the above pictures are general for different doubly excited states by suitably varying the frequency of the IR field to coherently couple the corresponding states.

XAS Studies of Se Speciation in Selenite-Fed Rats

PubMed Central

Weekley, Claire M.; Aitken, Jade B.; Witting, Paul K.; Harris, Hugh H.

2014-01-01

The biological activity of selenium is dependent on its chemical form. Therefore, knowledge of Se chemistry in vivo is required for efficacious use of selenium compounds in disease prevention and treatment. Using X-ray absorption spectroscopy, Se speciation in the kidney, liver, heart, spleen, testis and red blood cells of rats fed control (~0.3 ppm Se) or selenite-supplemented (1 ppm or 5 ppm Se) diets for 3 or 6 weeks, was investigated. X-ray absorption spectroscopy revealed the presence of Se–Se and Se–C species in the kidney and liver, and Se–S species in the kidney, but not the liver. X-ray absorption near edge structure (XANES) spectra showed that there was variation in speciation in the liver and kidneys, but Se speciation was much more uniform in the remaining organs. Using principal component analysis (PCA) to interpret the Se K-edge X-ray absorption spectra, we were able to directly compare the speciation of Se in two different models of selenite metabolism – human lung cancer cells and rat tissues. The effects of Se dose, tissue type and duration of diet on selenium speciation in rat tissues were investigated, and a relationship between the duration of the diet (3 weeks versus 6 weeks) and selenium speciation was observed. PMID:25363824

Absorption Peaks: α, β, γ and Their Covariance with Age and Hemoglobin in Human Blood Samples Using Photoacoustic Spectroscopy

NASA Astrophysics Data System (ADS)

González-Domínguez, J. L.; Hernández-Aguilar, C.; Domínguez-Pacheco, F. A.; Martínez-Ortiz, E.; Cruz-Orea, A.; Sánchez-Sinencio, F.

2012-11-01

This study reports the absorption peaks α, β, γ in the Soret band of photoacoustic (PA) signals and their covariance with age and hemoglobin in human blood samples through PA spectroscopy. Samples were taken randomly from a masculine population grouped in three categories according to age: infants, young adults, and senior adults. Samples were prepared with two drops of blood from a 0.5 mL insulin syringe with a needle gauge 31G over 5 mm circles of filter paper. It was observed that the PA signal, the amplitude as a function of the wavelength, has a behavior as that reported for human blood for the three absorption peaks α, β, γ. In particular, the ratio γ/ β is due to electronic transitions associated with charge-transfer interactions of iron orbitals with the ligand states. Through an evaluation of optical absorption peaks in blood samples and their covariance with age and hemoglobin concentration, a relationship was found for the ratio peaks γ/ β and γ/ α with such parameters. Specifically, a negative covariance in the Soret band of the ratio peaks γ/ β and γ/ α with respect to both age and hemoglobin was found. This showed a tendency in their behavior. Further experiments of different populations may corroborate these conclusions.

New approaches to photothermal spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amer, N.M.

1984-02-01

In recent years, the small rise in temperature associated with the absorption of light has provided the basis for a new class of spectrotroscopy which can be loosely called photothermal spectroscopy. Until recently, the more familiar member of this family has been photoacoustic spectroscopy where the optical heating is converted into sound and is detected with a suitable transducer. Although this approach has proven to be useful, the ultimate sensitivity of photoacoustics can be limited by the scattering of light on the transducer. Furthermore, in the case of experiments requiring a wide range of temperatures and pressures, or involving hostilemore » environment, both microphone and piezoelectric photoacoustic detections cannot be employed. To overcome these limitations the optical heating has to be exploited in different ways. The principles of photothermal deflection spectroscopy and photothermal displacement spectroscopy are described.« less

Quantification of zinc-porphyrin in dry-cured ham products by spectroscopic methods Comparison of absorption, fluorescence and X-ray fluorescence spectroscopy.

PubMed

Laursen, Kristoffer; Adamsen, Christina E; Laursen, Jens; Olsen, Karsten; Møller, Jens K S

2008-03-01

Zinc-protoporphyrin (Zn-pp), which has been identified as the major pigment in certain dry-cured meat products, was extracted with acetone/water (75%) and isolated from the following meat products: Parma ham, Iberian ham and dry-cured ham with added nitrite. The quantification of Zn-pp by electron absorption, fluorescence and X-ray fluorescence (XRF) spectroscopy was compared (concentration range used [Zn-pp]=0.8-9.7μM). All three hams were found to contain Zn-pp, and the results show no significant difference among the content of Zn-pp quantified by fluorescence, absorbance and X-ray fluorescence spectroscopy for Parma ham and Iberian ham. All three methods can be used for quantification of Zn-pp in acetone/water extracts of different ham types if the content is higher than 1.0ppm. For dry-cured ham with added nitrite, XRF was not applicable due to the low content of Zn-pp (<0.1ppm). In addition, XRF spectroscopy provides further information regarding other trace elements and can therefore be advantageous in this aspect. This study also focused on XRF determination of Fe in the extracts and as no detectable Fe was found in the three types of ham extracts investigated (limit of detection; Fe⩽1.8ppm), it allows the conclusion that iron containing pigments, e.g., heme, do not contribute to the noticeable red colour observed in some of the extracts.

THz Time-Domain Spectroscopy of Interstellar Ice Analogs

NASA Astrophysics Data System (ADS)

Ioppolo, Sergio; McGuire, Brett A.; de Vries, Xander; Carroll, Brandon; Allodi, Marco; Blake, Geoffrey

2015-08-01

The unambiguous identification of nearly 200 molecular species in different astronomical environments proves that our cosmos is a ‘Molecular Universe’. The cumulative outcome of recent observations, laboratory studies, and astrochemical models indicates that there is a strong interplay between the gas and the solid phase throughout the process of forming molecules in space. Observations of interstellar ices are generally limited to lines-of-sight along which infrared absorption spectroscopy is possible. Therefore, the identification of more complex prebiotic molecules in the mid-IR is difficult because of their low expected interstellar abundances and the overlap of their absorption features with those from the more abundant species. In the THz region, telescopes can detect Interstellar ices in emission or absorption against dust continuum. Thus, THz searches do not require a background point source. Moreover, since THz spectra are the fingerprint of inter- and intramolecular forces, complex species can present unique modes that do not overlap with those from simpler, more abundant molecules. THz modes are also sensitive to temperature and phase changes in the ice. Therefore, spectroscopy at THz frequencies has the potential to better characterize the physics and chemistry of the ISM. Currently, the Herschel Space Telescope, SOFIA, and ALMA databases contain a vast amount of new THz spectral data that require THz laboratory spectra for interpretation. The latter, however, are largely lacking. We have recently constructed a new THz time-domain spectroscopy system operating in the range between 0.3 - 7.5 THz. This work focuses on the laboratory investigation of the composition and structure of the most abundant interstellar ice analogs compared to some more complex species. Different temperatures, mixing ratios, and matrix isolation experiments will be shown. The ultimate goal of this research is to provide the scientific community with an extensive THz ice-database, which will allow quantitative studies of the ISM, and guide future astronomical observations of species in the solid phase.

Phase-resolved two-dimensional terahertz spectroscopy - a probe of highly nonlinear light-matter interactions

NASA Astrophysics Data System (ADS)

Elsaesser, Thomas

Terahertz (THz) spectroscopy gives insight into low-frequency excitations and charge dynamics in condensed matter. So far, most experiments in a frequency range from 0.5 to 30 THz have focused on the linear THz response to determine linear absorption and disperion spectra, and/or electric conductivities. The generation of ultrashort THz transients with peak electric fields up to megavolts/cm has allowed for addressing nonlinear light-matter interactions and inducing excitations far from equilibrium. The novel method of two-dimensional THz (2D-THz) spectroscopy allows for mapping ultrafast dynamics and couplings of elementary excitations up to arbitrary nonlinear order in the electric field, both under resonant and nonresonant excitation conditions. In particular, different contributions to the overall nonlinear response are separated by dissecting it as a function of excitation and detection frequencies and for different waiting times after excitation. This talk gives an introduction in 2D-THz spectroscopy, including its recent extension to 3-pulse sequences and interaction schemes. To illustrate the potential of the method, recent results on two-phonon coherences and high-order interband excitations in the semiconductor InSb will be presented. Nonlinear THz excitation of two-phonon coherences exploits a resonance enhancement by the large electronic interband dipole of InSb and is, thus, far more efficient than linear excitation via resonant two-phonon absorption. As a second application, the nonlinear softmode response in a crystal consisting of aspirin molecules will be discussed. At moderate THz driving fields, the pronounced correlation of rotational modes of CH3 groups with collective oscillations of π-electrons drives the system into the regime of nonperturbative light-matter interaction. Nonlinear absorption around 1.1 THz leads to a blue-shifted coherent emission at 1.5 THz, revealing a dynamic breakup of the strong electron-phonon correlations.

Characterizing caged molecules through flash photolysis and transient absorption spectroscopy.

PubMed

Kao, Joseph P Y; Muralidharan, Sukumaran

2013-01-01

Caged molecules are photosensitive molecules with latent biological activity. Upon exposure to light, they are rapidly transformed into bioactive molecules such as neurotransmitters or second messengers. They are thus valuable tools for using light to manipulate biology with exceptional spatial and temporal resolution. Since the temporal performance of the caged molecule depends critically on the rate at which bioactive molecules are generated by light, it is important to characterize the kinetics of the photorelease process. This is accomplished by initiating the photoreaction with a very brief but intense pulse of light (i.e., flash photolysis) and monitoring the course of the ensuing reactions through various means, the most common of which is absorption spectroscopy. Practical guidelines for performing flash photolysis and transient absorption spectroscopy are described in this chapter.

Intensity-Stabilized Fast-Scanned Direct Absorption Spectroscopy Instrumentation Based on a Distributed Feedback Laser with Detection Sensitivity down to 4 × 10−6

PubMed Central

Zhao, Gang; Tan, Wei; Jia, Mengyuan; Hou, Jiajuan; Ma, Weiguang; Dong, Lei; Zhang, Lei; Feng, Xiaoxia; Wu, Xuechun; Yin, Wangbao; Xiao, Liantuan; Axner, Ove; Jia, Suotang

2016-01-01

A novel, intensity-stabilized, fast-scanned, direct absorption spectroscopy (IS-FS-DAS) instrumentation, based on a distributed feedback (DFB) diode laser, is developed. A fiber-coupled polarization rotator and a fiber-coupled polarizer are used to stabilize the intensity of the laser, which significantly reduces its relative intensity noise (RIN). The influence of white noise is reduced by fast scanning over the spectral feature (at 1 kHz), followed by averaging. By combining these two noise-reducing techniques, it is demonstrated that direct absorption spectroscopy (DAS) can be swiftly performed down to a limit of detection (LOD) (1σ) of 4 × 10−6, which opens up a number of new applications. PMID:27657082

Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

PubMed Central

Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

2015-01-01

The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples. PMID:26098075

Characterization of the physico-chemical properties of polymeric materials for aerospace flight. [differential thermal and atomic absorption spectroscopic analysis of nickel cadmium batteries

NASA Technical Reports Server (NTRS)

Rock, M.

1981-01-01

Electrodes and electrolytes of nickel cadmium sealed batteries were analyzed. Different thermal analysis of negative and positive battery electrodes was conducted and the temperature ranges of occurrence of endotherms indicating decomposition of cadmium hydroxide and nickel hydroxide are identified. Atomic absorption spectroscopy was used to analyze electrodes and electrolytes for traces of nickel, cadmium, cobalt, and potassium. Calibration curves and data are given for each sample analyzed. Instrumentation and analytical procedures used for each method are described.

Some aspects of pulsed laser deposition of Si nanocrystalline films

NASA Astrophysics Data System (ADS)

Polyakov, B.; Petruhins, A.; Butikova, J.; Kuzmin, A.; Tale, I.

2009-11-01

Nanocrystalline silicon films were deposited by a picosecond laser ablation on different substrates in vacuum at room temperature. A nanocrystalline structure of the films was evidenced by atomic force microscopy (AFM), optical and Raman spectroscopies. A blue shift of the absorption edge was observed in optical absorption spectra, and a decrease of the optical phonon energy at the Brillouin zone centre was detected by Raman scattering. Early stages of nanocrystalline film formation on mica and HOPG substrates were studied by AFM. Mechanism of nanocrystal growth on substrate is discussed. in here

Investigating the Implementation of ZnO Nanoparticles as a Tunable UV Detector for Different Skin Types

NASA Astrophysics Data System (ADS)

Mosayebi, Pegah; Dorranian, Davoud; Behzad, Kasra

A facile chemical reduction method was used to synthesize ZnO nanoparticles (NPs) in ethylene glycol solvent at two different calcination temperatures. As a result of variation in the calcination temperature, ZnO NPs with two different sizes were achieved. The NPs were investigated for their structural and optical characteristics using X-ray diffraction and ultraviolet (UV)-Vis spectroscopy. The synthesized ZnO NPs exhibited a hexagonal structure with sizes of 46 and 65nm. The synthesized NPs were then used to investigate dye photocatalytic behavior of products as a tunable UV detector for different skin types. The dye degradation and decolorization of methylene blue in the presence of ZnO NP, following UV radiation as a function of time, were studied at different pH levels. The optical absorption spectra were then taken every 15min for all samples. The UV-Vis spectroscopy spectra revealed that optical absorption of solution was decreased upon UV exposure as a function of time. Photocatalytic reaction indicated that the dye degradation and decolorization rate were accelerated with the increase of pH level. Therefore, a tunable UV detector for different skin types could be engineered by varying the pH level of solution to avoid human skin burning.

Measurements of the weak UV absorptions of isoprene and acetone at 261-275 nm using cavity ringdown spectroscopy for evaluation of a potential portable ringdown breath analyzer.

PubMed

Sahay, Peeyush; Scherrer, Susan T; Wang, Chuji

2013-06-26

The weak absorption spectra of isoprene and acetone have been measured in the wavelength range of 261-275 nm using cavity ringdown spectroscopy. The measured absorption cross-sections of isoprene in the wavelength region of 261-266 nm range from 3.65 × 10⁻²¹ cm².molecule⁻¹ at 261 nm to 1.42 × 10⁻²¹ cm².molecule⁻¹ at 266 nm; these numbers are in good agreement with the values reported in the literature. In the longer wavelength range of 270-275 nm, however, where attractive applications using a single wavelength compact diode laser operating at 274 nm is located, isoprene has been reported in the literature to have no absorption (too weak to be detected). Small absorption cross-sections of isoprene in this longer wavelength region are measured using cavity ringdown spectroscopy for the first time in this work, i.e., 6.20 × 10⁻²³ cm².molecule⁻¹ at 275 nm. With the same experimental system, wavelength-dependent absorption cross-sections of acetone have also been measured. Theoretical detection limits of isoprene and comparisons of absorbance of isoprene, acetone, and healthy breath gas in this wavelength region are also discussed.

Laser-based measurements of pressure broadening and pressure shift coefficients of combustion-relevant absorption lines in the near-infrared region

NASA Astrophysics Data System (ADS)

Bürkle, Sebastian; Walter, Nicole; Wagner, Steven

2018-06-01

A set of high-resolution absorption spectrometers based on TDLAS was used to determine the impact of combustion-relevant gases on the pressure shift and broadening of H2O, CO2, C2H2 and CH4 absorption lines in the near-infrared spectral region. In particular, self- and foreign-broadening coefficients induced by CO2, N2, O2, air, C2H2 and CH4 were measured. The absorption lines under investigation are suitable to measure the respective species in typical combustion environments via laser absorption spectroscopy. Additionally, species-dependent self- and foreign-induced pressure shift coefficients were measured and compared to the literature. The experiments were performed in two specifically designed absorption cells over a wide pressure range from 5 to 180 kPa. Different sources of uncertainty were identified and quantified to achieve relative measurement uncertainties of 0.7-1.5% for broadening coefficients and 0.6-1.6% for pressure shift coefficients.

Glassy dynamics of sorbitol solutions at terahertz frequencies.

PubMed

Sibik, Juraj; Shalaev, Evgenyi Y; Zeitler, J Axel

2013-07-28

The absorption spectra of D-sorbitol and a range of its concentrated aqueous solutions were studied by terahertz spectroscopy over the temperature interval of 80 K < T < 310 K. It is shown that the slow-down of molecules at around the glass transition temperature, Tg, dramatically influences the thermal dependence of the absorption at terahertz frequencies. Furthermore, two different absorption regimes are revealed below Tg: at temperatures well below Tg, the absorption resembles the coupling of terahertz radiation to the vibrational density of states (VDOS); above these temperatures, between 160 K and Tg, in the sample of pure sorbitol and the sample of a solution of 70 wt% sorbitol in water, another type of absorption is observed at terahertz frequencies. Several possibilities of the physical origin of this absorption are discussed and based on the experimental data this process is tentatively assigned to the Johari-Goldstein β-relaxation processes shifting to lower frequencies at temperatures below Tg leaving behind a spectrum largely dominated by losses into the VDOS.

X-ray absorption spectroscopy using a self-seeded soft X-ray free-electron laser

DOE PAGES

Kroll, Thomas; Kern, Jan; Kubin, Markus; ...

2016-09-19

X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. But, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. We compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based onmore » self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. Lastly, we show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements.« less

X-ray absorption spectroscopy using a self-seeded soft X-ray free-electron laser

PubMed Central

Kroll, Thomas; Kern, Jan; Kubin, Markus; Ratner, Daniel; Gul, Sheraz; Fuller, Franklin D.; Löchel, Heike; Krzywinski, Jacek; Lutman, Alberto; Ding, Yuantao; Dakovski, Georgi L.; Moeller, Stefan; Turner, Joshua J.; Alonso-Mori, Roberto; Nordlund, Dennis L.; Rehanek, Jens; Weniger, Christian; Firsov, Alexander; Brzhezinskaya, Maria; Chatterjee, Ruchira; Lassalle-Kaiser, Benedikt; Sierra, Raymond G.; Laksmono, Hartawan; Hill, Ethan; Borovik, Andrew; Erko, Alexei; Föhlisch, Alexander; Mitzner, Rolf; Yachandra, Vittal K.; Yano, Junko; Wernet, Philippe; Bergmann, Uwe

2016-01-01

X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. However, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. Here we compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based on self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. We show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements. PMID:27828320

The temperature measurement research for high-speed flow based on tunable diode laser absorption spectroscopy

NASA Astrophysics Data System (ADS)

Di, Yue; Jin, Yi; Jiang, Hong-liang; Zhai, Chao

2013-09-01

Due to the particularity of the high-speed flow, in order to accurately obtain its' temperature, the measurement system should has some characteristics of not interfereing with the flow, non-contact measurement and high time resolution. The traditional measurement method cannot meet the above requirements, however the measurement method based on tunable diode laser absorption spectroscopy (TDLAS) technology can meet the requirements for high-speed flow temperature measurement. When the near-infared light of a specific frequency is through the media to be measured, it will be absorbed by the water vapor molecules and then the transmission light intensity is detected by the detector. The temperature of the water vapor which is also the high-speed flow temperature, can be accurately obtained by the Beer-Lambert law. This paper focused on the research of absorption spectrum method for high speed flow temperature measurement with the scope of 250K-500K. Firstly, spectral line selection method for low temperature measurement of high-speed flow is discussed. Selected absorption lines should be isolated and have a high peak absorption within the range of 250-500K, at the same time the interference of the other lines should be avoided, so that a high measurement accuracy can be obtained. According to the near-infrared absorption spectra characteristics of water vapor, four absorption lines at the near 1395 nm and 1409 nm are selected. Secondly, a system for the temperature measurement of the water vapor in the high-speed flow is established. Room temperature are measured through two methods, direct absorption spectroscopy (DAS) and wavelength modulation spectroscopy (WMS) ,the results show that this system can realize on-line measurement of the temperature and the measurement error is about 3%. Finally, the system will be used for temperature measurement of the high-speed flow in the shock tunnel, its feasibility of measurement is analyzed.

X-ray Absorption Spectroscopy Characterization of a Li/S Cell

PubMed Central

Ye, Yifan; Kawase, Ayako; Song, Min-Kyu; Feng, Bingmei; Liu, Yi-Sheng; Marcus, Matthew A.; Feng, Jun; Cairns, Elton J.; Guo, Jinghua; Zhu, Junfa

2016-01-01

The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We have investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH3(CH2)15N+(CH3)3Br−) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na2Sx solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfur reaction products on the cathode surface during the charge/discharge processes make the capacity decay. A modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies. PMID:28344271

Noninvasive evaluation of collagen and hemoglobin contents and scattering property of in vivo keloid scars and normal skin using diffuse reflectance spectroscopy: pilot study

NASA Astrophysics Data System (ADS)

Tseng, Sheng-Hao; Hsu, Chao-Kai; Yu-Yun Lee, Julia; Tzeng, Shih-Yu; Chen, Wan-Rung; Liaw, Yu-Kai

2012-07-01

Collagen is a rich component in skin that provides skin structure integrity; however, its contribution to the absorption and scattering properties of various types of skin has not been extensively studied. We considered the contribution of the collagen to the absorption spectrum of in vivo normal skin and keloids of 12 subjects derived from our diffuse reflectance spectroscopy (DRS) system in the wavelength range from 550 to 860 nm. It was found that the collagen concentration, the hemoglobin oxygen saturation, and the reduced scattering coefficient of keloids were remarkably different from that of normal skin. Our results suggest that our DRS system could assist clinicians in understanding the functional and structural condition of keloid scars. In the future, we will evaluate the accuracy of our system in the keloid diagnosis and investigate the applicability of our system for other skin-collagen-related studies.

Structures and Optical Properties of Hydrazones Derived from Biological Polyenes

NASA Astrophysics Data System (ADS)

Nakashima, Takayasu; Yamada, Takashi; Hashimoto, Hideki; Kobayashi, Takayoshi

2001-08-01

A set of hydrazone molecules was derived from a series of biological polyenes that have different polyene chain-lengths with common substituent group of 2,4-dinitrophenylhydrazine. Their structures were determined by high-resolution NMR spectroscopy as well as X-ray crystallography, and their optical properties were investigated by room and low temperature optical absorption spectroscopy. Among the derivatives so far synthesized, the one that has the shortest polyene chain (C13-DNPH) afforded single crystals without inversion symmetry, hence applicable for the second-order nonlinear optical devices. Molecular structures in the crystals were closely inspected in order to explain the cause to violate the inversion symmetry. Hydrazones derived in this study gave rise to two transition moments along the molecular axis. Comparison of the optical absorption spectra among the derivatives showed a unique phenomenon that could be attributed to the crossover of the excited state potential energy surfaces along the elongation of the polyene chain-lengths.

Structures and Optical Properties of Hydrazones Derived from Biological Polyenes

NASA Astrophysics Data System (ADS)

Nakashima, Takayasu; Yamada, Takashi; Hashimoto, Hideki; Kobayashi, Takayoshi

A set of hydrazone molecules was derived from a series of biological polyenes that have different polyene chain-lengths with common substituent group of 2,4-dinitrophenylhydrazine. Their structures were determined by high-resolution NMR spectroscopy as well as X-ray crystallography, and their optical properties were investigated by room and low temperature optical absorption spectroscopy. Among the derivatives so far synthesized, the one that has the shortest polyene chain (C13-DNPH) afforded single crystals without inversion symmetry, hence applicable for the second-order nonlinear optical devices. Molecular structures in the crystals were closely inspected in order to explain the cause to violate the inversion symmetry. Hydrazones derived in this study gave rise to two transition moments along the molecular axis. Comparison of the optical absorption spectra among the derivatives showed a unique phenomenon that could be attributed to the crossover of the excited state potential energy surfaces along the elongation of the polyene chain-lengths.

X-ray Absorption Spectroscopy Characterization of a Li/S Cell

DOE PAGES

Ye, Yifan; Kawase, Ayako; Song, Min-Kyu; ...

2016-01-11

The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH 3(CH 2) 15N+(CH 3) 3Br₋) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na 2S x solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfurmore » reaction products on the cathode surface during the charge/discharge processes make the capacity decay. Lastly, a modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies.« less

Portable ultrahigh-vacuum sample storage system for polarization-dependent total-reflection fluorescence x-ray absorption fine structure spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Watanabe, Yoshihide, E-mail: e0827@mosk.tytlabs.co.jp; Nishimura, Yusaku F.; Suzuki, Ryo

A portable ultrahigh-vacuum sample storage system was designed and built to investigate the detailed geometric structures of mass-selected metal clusters on oxide substrates by polarization-dependent total-reflection fluorescence x-ray absorption fine structure spectroscopy (PTRF-XAFS). This ultrahigh-vacuum (UHV) sample storage system provides the handover of samples between two different sample manipulating systems. The sample storage system is adaptable for public transportation, facilitating experiments using air-sensitive samples in synchrotron radiation or other quantum beam facilities. The samples were transferred by the developed portable UHV transfer system via a public transportation at a distance over 400 km. The performance of the transfer system was demonstratedmore » by a successful PTRF-XAFS study of Pt{sub 4} clusters deposited on a TiO{sub 2}(110) surface.« less

Two-dimensional Fano lineshapes: Excited-state absorption contributions

NASA Astrophysics Data System (ADS)

Finkelstein-Shapiro, Daniel; Pullerits, Tõnu; Hansen, Thorsten

2018-05-01

Fano interferences in nanostructures are influenced by dissipation effects as well as many-body interactions. Two-dimensional coherent spectroscopies have just begun to be applied to these systems where the spectroscopic signatures of a discrete-continuum structure are not known. In this article, we calculate the excited-state absorption contribution for different models of higher lying excited states. We find that the characteristic asymmetry of one-dimensional spectroscopies is recovered from the many-body contributions and that the higher lying excited manifolds have distorted lineshapes that are not anticipated from discrete-level Hamiltonians. We show that the Stimulated Emission cannot have contributions from a flat continuum of states. This work completes the Ground-State Bleach and Stimulated Emission signals that were calculated previously [D. Finkelstein-Shapiro et al., Phys. Rev. B 94, 205137 (2016)]. The model reproduces the observations reported for molecules on surfaces probed by 2DIR.

Small hydrocarbons on metal surfaces: adsorption-induced changes in electronic and geometric structure as seen by X-ray absorption spectroscopy.

PubMed

Wöll, C

2001-03-01

Monolayers of several unsaturated and saturated hydrocarbons (ethylene, acetylene, benzene, n-hexane, cyclohexane, n-octane, n-hexatriacontane) adsorbed on a number of different metal surfaces [Cu(111), Au(111), Ru(0001) and Pt(111)] have been investigated by carbon K-edge X-ray absorption spectroscopy (XAS). Whereas the corresponding multilayer data qualitatively resemble the core-excitation spectra observed for the free molecules, generally significant modifications are observed in the monolayer data. For the saturated hydrocarbons, a strong quenching of the Rydberg R resonance at 287.7 eV and the appearance of a new broad feature at around 285.1 eV (M resonance) is observed for molecules in direct contact with the metal surfaces. In the case of the unsaturated hydrocarbons, for a number of metals, distinct new features are seen in the XAS data, revealing significant intramolecular distortions.

Identification of effective exciton-exciton annihilation in squaraine-squaraine copolymers.

PubMed

Hader, Kilian; May, Volkhard; Lambert, Christoph; Engel, Volker

2016-05-11

Ultrafast time-resolved transient absorption spectroscopy is able to monitor the fate of the excited state population in molecular aggregates or polymers. Due to many competing decay processes, the identification of exciton-exciton annihilation (EEA) is difficult. Here, we use a microscopic model to describe exciton annihilation processes in squaraine-squaraine copolymers. Transient absorption time traces measured at different laser powers exhibit an unusual time-dependence. The analysis points towards dynamics taking place on three time-scales. Immediately after laser-excitation a localization of excitons takes place within the femtosecond time-regime. This is followed by exciton-exciton annihilation which is responsible for a fast decay of the exciton population. At later times, excitations being localized on units which are not directly connected remain so that diffusion dominates the dynamics and leads to a slower decay. We thus provide evidence for EEA tracked by time-resolved spectroscopy which has not been reported that clearly before.

NO binding kinetics in myoglobin investigated by picosecond Fe K-edge absorption spectroscopy

PubMed Central

Silatani, Mahsa; Lima, Frederico A.; Penfold, Thomas J.; Rittmann, Jochen; Reinhard, Marco E.; Rittmann-Frank, Hannelore M.; Borca, Camelia; Grolimund, Daniel; Milne, Christopher J.; Chergui, Majed

2015-01-01

Diatomic ligands in hemoproteins and the way they bind to the active center are central to the protein’s function. Using picosecond Fe K-edge X-ray absorption spectroscopy, we probe the NO-heme recombination kinetics with direct sensitivity to the Fe-NO binding after 532-nm photoexcitation of nitrosylmyoglobin (MbNO) in physiological solutions. The transients at 70 and 300 ps are identical, but they deviate from the difference between the static spectra of deoxymyoglobin and MbNO, showing the formation of an intermediate species. We propose the latter to be a six-coordinated domed species that is populated on a timescale of ∼200 ps by recombination with NO ligands. This work shows the feasibility of ultrafast pump–probe X-ray spectroscopic studies of proteins in physiological media, delivering insight into the electronic and geometric structure of the active center. PMID:26438842

Two-dimensional Fano lineshapes: Excited-state absorption contributions.

PubMed

Finkelstein-Shapiro, Daniel; Pullerits, Tõnu; Hansen, Thorsten

2018-05-14

Fano interferences in nanostructures are influenced by dissipation effects as well as many-body interactions. Two-dimensional coherent spectroscopies have just begun to be applied to these systems where the spectroscopic signatures of a discrete-continuum structure are not known. In this article, we calculate the excited-state absorption contribution for different models of higher lying excited states. We find that the characteristic asymmetry of one-dimensional spectroscopies is recovered from the many-body contributions and that the higher lying excited manifolds have distorted lineshapes that are not anticipated from discrete-level Hamiltonians. We show that the Stimulated Emission cannot have contributions from a flat continuum of states. This work completes the Ground-State Bleach and Stimulated Emission signals that were calculated previously [D. Finkelstein-Shapiro et al., Phys. Rev. B 94, 205137 (2016)]. The model reproduces the observations reported for molecules on surfaces probed by 2DIR.

Comparison of soil organic carbon speciation using C NEXAFS and CPMAS 13C NMR spectroscopy.

PubMed

Prietzel, Jörg; Müller, Svenja; Kögel-Knabner, Ingrid; Thieme, Jürgen; Jaye, Cherno; Fischer, Daniel

2018-07-01

We compared synchrotron-based C near-edge X-ray absorption fine structure (NEXAFS) and CPMAS 13 C nuclear magnetic resonance (NMR) spectroscopy with respect to their precision and accuracy to quantify different organic carbon (OC) species in defined mixtures of soil organic matter source compounds. We also used both methods to quantify different OC species in organic surface horizons of a Histic Leptosol as well as in mineral topsoil and subsoil horizons of two soils with different parent material, stage of pedogenesis, and OC content (Cambisol: 15-30 OC mgg -1 , Podzol: 0.9-7 OC mgg -1 ). CPMAS 13 C NMR spectroscopy was more accurate and precise (mean recovery of different C functional groups 96-103%) than C NEXAFS spectroscopy (mean recovery 92-113%). For organic surface and topsoil samples, NMR spectroscopy consistently yielded larger O-alkyl C percentages and smaller alkyl C percentages than C NEXAFS spectroscopy. For the Cambisol subsoil samples both methods performed well and showed similar C speciation results. NEXAFS spectroscopy yielded excellent spectra with a high signal-to-noise ratio also for OC-poor Podzol subsoil samples, whereas this was not the case for CPMAS 13 C NMR spectroscopy even after sample treatment with HF. Our results confirm the analytical power of CPMAS 13 C NMR spectroscopy for a reliable quantitative OC speciation in soils with >10mgOCg -1 . Moreover, they highlight the potential of synchrotron-based C NEXAFS spectroscopy as fast, non-invasive method to semi-quantify different C functional groups in soils with low C content (0.9-10mgg -1 ). Copyright © 2018 Elsevier B.V. All rights reserved.

Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study

DOE PAGES

Chuang, Cheng-Hao; Ray, Sekhar C.; Mazumder, Debarati; ...

2017-02-10

Nitrogen-doped graphene oxides (GO:N x) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH 2) 2 ]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:N x synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in whichmore » each N-atom trigonally bonds to three distinct sp 2 -hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:N x . The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.« less

Investigation of nanoparticulate silicon as printed layers using scanning electron microscopy, transmission electron microscopy, X-ray absorption spectroscopy and X-ray photoelectron spectroscopy

DOE PAGES

Unuigbe, David M.; Harting, Margit; Jonah, Emmanuel O.; ...

2017-08-21

The presence of native oxide on the surface of silicon nanoparticles is known to inhibit charge transport on the surfaces. Scanning electron microscopy (SEM) studies reveal that the particles in the printed silicon network have a wide range of sizes and shapes. High-resolution transmission electron microscopy reveals that the particle surfaces have mainly the (111)- and (100)-oriented planes which stabilizes against further oxidation of the particles. X-ray absorption spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) measurements at the O 1s-edge have been utilized to study the oxidation and local atomic structure of printed layers of silicon nanoparticles which were milledmore » for different times. XANES results reveal the presence of the +4 (SiO 2) oxidation state which tends towards the +2 (SiO) state for higher milling times. Si 2pXPS results indicate that the surfaces of the silicon nanoparticles in the printed layers are only partially oxidized and that all three sub-oxide, +1 (Si 2O), +2 (SiO) and +3 (Si 2O 3), states are present. The analysis of the change in the sub-oxide peaks of the silicon nanoparticles shows the dominance of the +4 state only for lower milling times.« less

Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study

NASA Astrophysics Data System (ADS)

Chuang, Cheng-Hao; Ray, Sekhar C.; Mazumder, Debarati; Sharma, Surbhi; Ganguly, Abhijit; Papakonstantinou, Pagona; Chiou, Jau-Wern; Tsai, Huang-Ming; Shiu, Hung-Wei; Chen, Chia-Hao; Lin, Hong-Ji; Guo, Jinghua; Pong, Way-Faung

2017-02-01

Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.

The use of C-near edge X-ray absorption fine structure spectroscopy for the elaboration of chemistry in lignocellulosics

Treesearch

Lucian A. Lucia; Hiroki Nanko; Alan W. Rudie; Doug G. Mancosky; Sue Wirick

2006-01-01

The research presented elucidates the oxidation chemistry occurring in hydrogen peroxide bleached kraft pulp fibers by employing carbon near edge x-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft x-ray technique that selectively interrogates atomic moieties using photoelectrons (Xrays) of variable energies. The X1A beam line at the National...

Revealing electronic structure changes in Chevrel phase cathodes upon Mg insertion using X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wan, Liwen F.; Wright, Joshua; Perdue, Brian R.

Following previous work predicting the electronic response of the Chevrel phase Mo6S8 upon Mg insertion (Thole et al., Phys. Chem. Chem. Phys., 2015, 17, 22548), we provide the experimental proof, evident in X-ray absorption spectroscopy, to illustrate the charge compensation mechanism of the Chevrel phase compound during Mg insertion and de-insertion processes.

Analysis of an Air Conditioning Coolant Solution for Metal Contamination Using Atomic Absorption Spectroscopy: An Undergraduate Instrumental Analysis Exercise Simulating an Industrial Assignment

ERIC Educational Resources Information Center

Baird, Michael J.

2004-01-01

A real-life analytical assignment is presented to students, who had to examine an air conditioning coolant solution for metal contamination using an atomic absorption spectroscopy (AAS). This hands-on access to a real problem exposed the undergraduate students to the mechanism of AAS, and promoted participation in a simulated industrial activity.

Determination of Fe Content of Some Food Items by Flame Atomic Absorption Spectroscopy (FAAS): A Guided-Inquiry Learning Experience in Instrumental Analysis Laboratory

ERIC Educational Resources Information Center

Fakayode, Sayo O.; King, Angela G.; Yakubu, Mamudu; Mohammed, Abdul K.; Pollard, David A.

2012-01-01

This article presents a guided-inquiry (GI) hands-on determination of Fe in food samples including plantains, spinach, lima beans, oatmeal, Frosted Flakes cereal (generic), tilapia fish, and chicken using flame atomic absorption spectroscopy (FAAS). The utility of the GI experiment, which is part of an instrumental analysis laboratory course,…

[Possibilities of ultrasonic spectroscopy of the blood in the diagnosis of early postoperative inflammatory complications in patients with stomach cancer].

PubMed

Moskalenko, O V

1998-01-01

The indexes of ultrasound wave absorption in the blood serum of patients with gastric cancer were studied using ultrasound spectroscopy method. The coefficient of absorption (CA) changes were registered 1-2 days before the first clinical signs occurrence. While inflammatory complications presence CA had lowered, the daily gradient of lowering had raised.

Speciation and Lability of Ag-, AgCl- and Ag2S-Nanoparticles in Soil Determined by X-ray Absorption Spectroscopy and Diffusive Gradients in Thin Films

EPA Science Inventory

Long-term speciation and lability of silver (Ag-), silver chloride (AgCl-) and silver sulfide nanoparticles (Ag₂S-NPs) in soil were studied by X-ray absorption spectroscopy (XAS), and newly developed "nano" Diffusive Gradients in Thin Films (DGT) devices. These nano-D...

Study of nonlinear absorption properties of reduced graphene oxide by Z-scan technique

NASA Astrophysics Data System (ADS)

Sreeja, V. G.; Vinitha, G.; Reshmi, R.; Anila, E. I.; Jayaraj, M. K.

2017-05-01

Graphene has generated enormous research interest during the last decade due to its significant unique properties and wide applications in the field of optoelectronics and photonics. This research studied the structural and nonlinear absorption properties of reduced graphene oxide (rGO) synthesized by Modified Hummer's method. Structural and physiochemical properties of the rGO were explored with the help of Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy (Raman). Nonlinear absorption property in rGO, was investigated by open aperture Z-scan technique by using a continuous wave (CW) laser. The Z-scan results demonstrate saturable absorption property of rGO with a nonlinear absorption coefficient, β, of -2.62 × 10-4 cm/W, making it suitable for applications in Q switching, generation of ultra-fast high energy pulses in laser cavity and mode lockers.

Structural study of aggregated β-carotene by absorption spectroscopy

NASA Astrophysics Data System (ADS)

Lu, Li Ping; Wei, Liang Shu

2017-10-01

By UV-visible absorption spectroscope, the aggregated β-carotene in hydrated ethanol was studied in the temperature range of 5 55°C, with different ethanol/water ratio. And the structural evolutions of these aggregates with time were detected. The spectrophotometric analysis showed that the aggregate of β-carotene formed in 1:1 ethanol/water solution transfered from H-type to J-type with temperature increase. In 2:1 ethanol/water solution a new type of aggregate with strong coupling was predicated by the appearing absorption peak located at about 550 nm. In the time scales of 48 houses all the aggregated structures were stable, but the absorption intensity decreased with time. It was concluded that the types of aggregated β-carotene which wouldn't change with time depended on the solvent composition and temperature.

Mid-infrared laser absorption spectroscopy of NO2 at elevated temperatures

NASA Astrophysics Data System (ADS)

Sur, Ritobrata; Peng, Wen Yu; Strand, Christopher; Mitchell Spearrin, R.; Jeffries, Jay B.; Hanson, Ronald K.; Bekal, Anish; Halder, Purbasha; Poonacha, Samhitha P.; Vartak, Sameer; Sridharan, Arun K.

2017-01-01

A mid-infrared quantum cascade laser absorption sensor was developed for in-situ detection of NO2 in high-temperature gas environments. A cluster of spin-split transitions near 1599.9 cm-1 from the ν3 absorption band of NO2 was selected due to the strength of these transitions and the low spectral interference from water vapor within this region. Temperature- and species-dependent collisional broadening parameters of ten neighboring NO2 transitions with Ar, O2, N2, CO2 and H2O were measured and reported. The spectral model was validated through comparisons with direct absorption spectroscopy measurements of NO2 seeded in various bath gases. The performance of the scanned wavelength modulation spectroscopy (WMS)-based sensor was demonstrated in a combustion exhaust stream seeded with varying flow rates of NO2, achieving reliable detection of 1.45 and 1.6 ppm NO2 by mole at 600 K and 800 K, respectively, with a measurement uncertainty of ±11%. 2σ noise levels of 360 ppb and 760 ppb were observed at 600 K and 800 K, respectively, in an absorption path length of 1.79 m.

Nanoscale infrared absorption spectroscopy of individual nanoparticles enabled by scattering-type near-field microscopy.

PubMed

Stiegler, Johannes M; Abate, Yohannes; Cvitkovic, Antonija; Romanyuk, Yaroslav E; Huber, Andreas J; Leone, Stephen R; Hillenbrand, Rainer

2011-08-23

Infrared absorption spectroscopy is a powerful and widely used tool for analyzing the chemical composition and structure of materials. Because of the diffraction limit, however, it cannot be applied for studying individual nanostructures. Here we demonstrate that the phase contrast in substrate-enhanced scattering-type scanning near-field optical microscopy (s-SNOM) provides a map of the infrared absorption spectrum of individual nanoparticles with nanometer-scale spatial resolution. We succeeded in the chemical identification of silicon nitride nanoislands with heights well below 10 nm, by infrared near-field fingerprint spectroscopy of the Si-N stretching bond. Employing a novel theoretical model, we show that the near-field phase spectra of small particles correlate well with their far-field absorption spectra. On the other hand, the spectral near-field contrast does not scale with the volume of the particles. We find a nearly linear scaling law, which we can attribute to the near-field coupling between the near-field probe and the substrate. Our results provide fundamental insights into the spectral near-field contrast of nanoparticles and clearly demonstrate the capability of s-SNOM for nanoscale chemical mapping based on local infrared absorption. © 2011 American Chemical Society

XAS Studies of Arsenic in the Environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charnock, J. M.; School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Oxford Road, Manchester, M13 9PL; Polya, D. A.

2007-02-02

Arsenic is present in low concentrations in much of the Earth's crust and changes in its speciation are vital to understanding its transport and toxicity in the environment. We have used X-ray absorption spectroscopy to investigate the coordination sites of arsenic in a wide variety of samples, including soil and earthworm tissues from arsenic-contaminated land, and human hair and nail samples from people exposed to arsenic in Cambodia. Our results confirm the effectiveness of using X-ray absorption near edge structure (XANES) and X-ray absorption fine structure (EXAFS) spectroscopy to determine speciation changes in environmental samples.

Terahertz optical properties of nonlinear optical CdSe crystals

NASA Astrophysics Data System (ADS)

Yan, Dexian; Xu, Degang; Li, Jining; Wang, Yuye; Liang, Fei; Wang, Jian; Yan, Chao; Liu, Hongxiang; Shi, Jia; Tang, Longhuang; He, Yixin; Zhong, Kai; Lin, Zheshuai; Zhang, Yingwu; Cheng, Hongjuan; Shi, Wei; Yao, Jianquan; Wu, Yicheng

2018-04-01

We investigate the optical properties of cadmium selenide (CdSe) crystals in a wide terahertz (THz) range from 0.2 to 6 THz by THz time-domain spectroscopy (THz-TDS) and Fourier transform infrared spectroscopy (FTIR). The refractive index, absorption coefficient and transmittance are measured and analyzed. The properties are characterized by several absorption peaks which represent the relevant phonon vibrations modes. The experimental results are in agreement with the theoretical results. The dispersion and absorption properties of CdSe crystal are analyzed in THz range. These properties indicate a good potential for THz sources and THz modulated devices.

Internal standards in fluorescent X-ray spectroscopy1 1 Publication authorized by the Director, U.S. Geological Survey.

USGS Publications Warehouse

Adler, I.; Axelrod, J.M.

1955-01-01

The use of internal standards in the analysis of ores and minerals of widely-varying matrix by means of fluorescent X-ray spectroscopy is frequently the most practical approach. Internal standards correct for absorption and enhancement effects except when an absorption edge falls between the comparison lines or a very strong emission line falls between the absorption edges responsible for the comparison lines. Particle size variations may introduce substantial errors. One method of coping with the particle size problem is grinding the sample with an added abrasive. ?? 1955.

[Purification and structural identification of herbicides from Botrytis cinerea].

PubMed

Zheng, Meng; Xu, Kuo; Dong, Jingao

2008-10-01

Toxin produced by phytopathogenic fungi is one of the important microbial herbicides. We found a new compound with herbicidal activity. Five different ultraviolet absorption components were isolated from the filtrate of Botrytis cinerea isolate 7-3 culture. Of the five components, one showed strong inhibitory to Digitaria sanguinalis. The pure fraction with high herbicidal activity was obtained by HPLC purification. Its structure was identified as 10-syn-dihydrobotrydial by Ultraviolet and Visible Spectroscopy, Infrared Spectrum, Nuclear Magnetic Resonance Spectroscopy analysis. The findings are important for future preparation and application of the herbicide.

Variability of the health effects of crystalline silica: Fe speciation in industrial quartz reagents and suspended dusts—insights from XAS spectroscopy

NASA Astrophysics Data System (ADS)

Di Benedetto, Francesco; D'Acapito, Francesco; Capacci, Fabio; Fornaciai, Gabriele; Innocenti, Massimo; Montegrossi, Giordano; Oberhauser, Werner; Pardi, Luca A.; Romanelli, Maurizio

2014-03-01

We investigated the speciation of Fe in bulk and in suspended respirable quartz dusts coming from ceramic and iron-casting industrial processes via X-ray absorption spectroscopy, with the aim of contributing to a better understanding of the variability of crystalline silica toxicity. Four different bulk industrial quartz powders, nominally pure quartz samples with Fe contents below 200 ppm, and three respirable dusts filters were selected. Fe speciation was determined in all samples through a coupled study of the X-ray absorption near-edge structure and extended X-ray absorption fine structure regions, operating at the Fe-K edge. Fe speciation revealed common features at the beginning of the different production processes, whereas significant differences were observed on both respirable dusts and bulk dusts exiting from the production process. Namely, a common pollution of the raw quartz dusts by elemental Fe was evidenced and attributed to residuals of the industrial production of quartz materials. Moreover, the respirable samples indicated that reactivity occurs after the suspension of the powders in air. The gravitational selection during the particle suspension consistently allowed us to clearly discriminate between suspended and bulk dusts. On the basis of the obtained results, we provide an apparent spectroscopic discrimination between the raw materials used in the considered industrial processes, and those that are effectively inhaled by workers. In particular, an amorphous FeIII oxide, with an unsaturated coordination sphere, can be related to silica reactivity (and health consequences).

Structural and luminescence properties of Dy3+ doped bismuth phosphate glasses for greenish yellow light applications

NASA Astrophysics Data System (ADS)

Damodaraiah, S.; Reddy Prasad, V.; Babu, S.; Ratnakaram, Y. C.

2017-05-01

Different compositions of (5, 10, 15 and 20 mol%) of bismuth and different concentrations (0.5, 1.0, 1.5 and 2.0 mol%) of Dy3+ ion doped bismuth phosphate (BiP) glasses were synthesized by melt-quenching technique. The structural characterization was accomplished by XRD, SEM with EDS, FTIR, FT-Raman and 31P MAS NMR spectroscopy. The optical properties were studied using absorption and photoluminescence spectroscopy. Different structural groups were identified using FTIR and FT-Raman spectra. The depolymerization of metaphosphate chains are described by the decrease of Q2 tetrahedral sites allowing the formation of pyrophosphate groups (Q1) revealed by 31P MAS NMR spectroscopic investigations. Judd-Ofelt intensity parameters Ωλ (λ = 2, 4 and 6) were evaluated from absorption spectra. Radiative parameters such as radiative lifetimes (τR), integrated absorption cross-sections (Σ) and branching ratios (βR) were calculated using Judd-Ofelt intensity parameters. From photoluminescence spectra, experimental branching ratios (βexp) and stimulated emission cross-sections (σP) were calculated for all the observed emission transitions of prepared glasses. The decay profiles for 4F9/2 level were recorded and fit exponential for 0.5 mol% and non-exponential for higher concentrations of Dy3+ due to non-radiative energy transfer among excited Dy3+ ions. The CIE chromaticity co-ordinates have been calculated from the luminescence spectra which confirmed greenish yellow light emission.

Intercomparison of field measurements of nitrous acid (HONO) during the SHARP campaign

NASA Astrophysics Data System (ADS)

Pinto, J. P.; Dibb, J.; Lee, B. H.; Rappenglück, B.; Wood, E. C.; Levy, M.; Zhang, R.-Y.; Lefer, B.; Ren, X.-R.; Stutz, J.; Tsai, C.; Ackermann, L.; Golovko, J.; Herndon, S. C.; Oakes, M.; Meng, Q.-Y.; Munger, J. W.; Zahniser, M.; Zheng, J.

2014-05-01

Because of the importance of HONO as a radical reservoir, consistent and accurate measurements of its concentration are needed. As part of SHARP (Study of Houston Atmospheric Radical Precursors), time series of HONO were obtained by six different measurement techniques on the roof of the Moody Tower at the University of Houston. Techniques used were long path differential optical absorption spectroscopy (DOAS), stripping coil-visible absorption photometry (SC-AP), long path absorption photometry (LOPAP®), mist chamber/ion chromatography (MC-IC), quantum cascade-tunable infrared laser differential absorption spectroscopy (QC-TILDAS), and ion drift-chemical ionization mass spectrometry (ID-CIMS). Various combinations of techniques were in operation from 15 April through 31 May 2009. All instruments recorded a similar diurnal pattern of HONO concentrations with higher median and mean values during the night than during the day. Highest values were observed in the final 2 weeks of the campaign. Inlets for the MC-IC, SC-AP, and QC-TILDAS were collocated and agreed most closely with each other based on several measures. Largest differences between pairs of measurements were evident during the day for concentrations < 100 parts per trillion (ppt). Above 200 ppt, concentrations from the SC-AP, MC-IC, and QC-TILDAS converged to within about 20%, with slightly larger discrepancies when DOAS was considered. During the first 2 weeks, HONO measured by ID-CIMS agreed with these techniques, but ID-CIMS reported higher values during the afternoon and evening of the final 4 weeks, possibly from interference from unknown sources. A number of factors, including building related sources, likely affected measured concentrations.

Intrinsic Raman spectroscopy for quantitative biological spectroscopy Part II

PubMed Central

Bechtel, Kate L.; Shih, Wei-Chuan; Feld, Michael S.

2009-01-01

We demonstrate the effectiveness of intrinsic Raman spectroscopy (IRS) at reducing errors caused by absorption and scattering. Physical tissue models, solutions of varying absorption and scattering coefficients with known concentrations of Raman scatterers, are studied. We show significant improvement in prediction error by implementing IRS to predict concentrations of Raman scatterers using both ordinary least squares regression (OLS) and partial least squares regression (PLS). In particular, we show that IRS provides a robust calibration model that does not increase in error when applied to samples with optical properties outside the range of calibration. PMID:18711512

Indirect absorption spectroscopy using quantum cascade lasers: mid-infrared refractometry and photothermal spectroscopy.

PubMed

Pfeifer, Marcel; Ruf, Alexander; Fischer, Peer

2013-11-04

We record vibrational spectra with two indirect schemes that depend on the real part of the index of refraction: mid-infrared refractometry and photothermal spectroscopy. In the former, a quantum cascade laser (QCL) spot is imaged to determine the angles of total internal reflection, which yields the absorption line via a beam profile analysis. In the photothermal measurements, a tunable QCL excites vibrational resonances of a molecular monolayer, which heats the surrounding medium and changes its refractive index. This is observed with a probe laser in the visible. Sub-monolayer sensitivities are demonstrated.

Characterization of photo-induced valence tautomerism in a cobalt-dioxolene complex by ultrafast spectroscopy

NASA Astrophysics Data System (ADS)

Beni, A.; Bogani, L.; Bussotti, L.; Dei, A.; Gentili, P. L.; Righini, R.

2005-01-01

The valence tautomerism of low-spin CoIII(Cat-N-BQ)(Cat-N-SQ) was investigated by means of UV-vis pump-probe transient absorption spectroscopy in chloroform. By exciting the CT transition of the complex at 480 nm, an intramolecular electron transfer process is selectively triggered. The photo-induced charge transfer is pursued by a cascade of two main molecular events characterized by the ultrafast transient absorption spectroscopy: the first gives rise to the metastable high-spin CoII(Cat-N-BQ)2 that, secondly, reaches the chemical equilibrium with the reactant species.

Ultrafast relaxation dynamics of nitric oxide synthase studied by visible broadband transient absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hung, Chih-Chang; Yabushita, Atsushi; Kobayashi, Takayoshi; Chen, Pei-Feng; Liang, Keng S.

2017-09-01

Ultrafast dynamics of endothelial nitric oxide synthase (eNOS) oxygenase domain was studied by transient absorption spectroscopy pumping at Soret band. The broadband visible probe spectrum has visualized the relaxation dynamics from the Soret band to Q-band and charge transfer (CT) band. Supported by two-dimensional correlation spectroscopy, global fitting analysis has successfully concluded the relaxation dynamics from the Soret band to be (1) electronic transition to Q-band (0.16 ps), (2) ligand dissociation and CT (0.94 ps), (3) relaxation of the CT state (4.0 ps), and (4) ligand rebinding (59 ps).

Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy

DOE PAGES

Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2016-06-06

Copper ferrite, CuFe 2 O 4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe 2 O 4. A phase pure tetragonal CuFe 2 O 4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. We used ex situ X-ray absorption spectroscopy (XAS) measurements to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structuremore » (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(II) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(III) cations to octahedral positions previously occupied by copper(II). Then, upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(III) was achieved. Our results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.« less

Redox chemistry of a binary transition metal oxide (AB2O4): a study of the Cu(2+)/Cu(0) and Fe(3+)/Fe(0) interconversions observed upon lithiation in a CuFe2O4 battery using X-ray absorption spectroscopy.

PubMed

Cama, Christina A; Pelliccione, Christopher J; Brady, Alexander B; Li, Jing; Stach, Eric A; Wang, Jiajun; Wang, Jun; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C

2016-06-22

Copper ferrite, CuFe2O4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2O4. A phase pure tetragonal CuFe2O4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. Ex situ X-ray absorption spectroscopy (XAS) measurements were used to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(ii) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(iii) cations to octahedral positions previously occupied by copper(ii). Upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(iii) was achieved. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.

Structural anisotropy in amorphous SnO2 film probed by X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Zhu, Q.; Ma, Q.; Buchholz, D. B.; Chang, R. P. H.; Bedzyk, M. J.; Mason, T. O.

2013-07-01

Polarization-dependent X-ray absorption measurements reveal the existence of structural anisotropy in amorphous (a-) SnO2 film. The anisotropy is readily seen for the second neighbor interaction whose magnitude differs along three measured directions. The differences can be well accounted for by 10%-20% variation in the Debye-Waller factor. Instead of a single Gaussian distribution found in crystalline SnO2, the Sn-O bond distribution is bimodal in a-SnO2 whose separation shows a weak angular dependence. The oxygen vacancies, existing in the a-SnO2 film in the order of 1021 cm-3, distribute preferentially along the film surface direction.

Ultrasensitive detection of atmospheric trace gases using frequency modulation spectroscopy

NASA Technical Reports Server (NTRS)

Cooper, David E.

1986-01-01

Frequency modulation (FM) spectroscopy is a new technique that promises to significantly extend the state-of-the-art in point detection of atmospheric trace gases. FM spectroscopy is essentially a balanced bridge optical heterodyne approach in which a small optical absorption or dispersion from an atomic or molecular species of interest generates an easily detected radio frequency (RF) signal. This signal can be monitored using standard RF signal processing techniques and is, in principle, limited only by the shot noise generated in the photodetector by the laser source employed. The use of very high modulation frequencies which exceed the spectral width of the probed absorption line distinguishes this technique from the well-known derivative spectroscopy which makes use of low (kHz) modulation frequencies. FM spectroscopy was recently extended to the 10 micron infrared (IR) spectral region where numerous polyatomic molecules exhibit characteristic vibrational-rotational bands. In conjunction with tunable semiconductor diode lasers, the quantum-noise-limited sensitivity of the technique should allow for the detection of absorptions as small as .00000001 in the IR spectral region. This sensitivity would allow for the detection of H2O2 at concentrations as low as 1 pptv with an integration time of 10 seconds.

SPECIATION OF ORGANOTINS IN POLY VINYL CHLORIDE PIPE VIA X-RAY ABSORPTION SPECTROSCOPY AND IN LEACHATES USING GC-PFPD AFTER DERIVATISATION

EPA Science Inventory

Three different polyvinyl chloride (PVC) pipe types were subjected to de–ionized water exposures over the course of at least 180 days. Water exposed to the pipe was analyzed for organotin speciation and concentration. Organotin concentrations were the highest during the fir...

Determination of chromium in treated crayfish, Procambarus clarkii, by electrothermal ASS: study of chromium accumulation in different tissues

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hernandez, F.; Diaz, J.; Medina, J.

1986-06-01

In the present study, the authors investigated the accumulation of chromium in muscle, hepatopancreas, antennal glands, and gills of Procambarus clarkii (Girard) from Lake Albufera following Cr(VI)-exposure. Determinations of chromium were made by using Electrothermal Atomic Absorption Spectroscopy and the standard additions method.

SPECIATION OF ORGANOTINS IN POLY VINYL PIPE VIA X-RAY ABSORPTION SPECTROSCOPY AND IN LEACHATES BY ELTHYLATION/DERIVITIZATION

EPA Science Inventory

Three different polyvinyl chloride (PVC) pipe types were subjected to de-ionized water exposures over the course of at least 180 days. Water exposed to the pipe was analyzed for organotin speciation and concentration. Organotin concentrations were the highest during the first 1-5...

Novel visualization studies of lignocellulosic oxidation chemistry by application of C-near edge X-ray absorption fine structure spectroscopy

Treesearch

Douglas G. Mancosky; Lucian A. Lucia; Hiroki Nanko; Sue Wirick; Alan W. Rudie; Robert Braun

2005-01-01

The research presented herein is the first attempt to probe the chemical nature of lignocellulosic samples by the application of carbon near edge X-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft X-ray technique that principally provides selective interrogation of discrete atomic moieties using photoelectrons of variable energies. The X1A beam...

Optical signature of nerve tissue-Exploratory ex vivo study comparing optical, histological, and molecular characteristics of different adipose and nerve tissues.

PubMed

Balthasar, Andrea J R; Bydlon, Torre M; Ippel, Hans; van der Voort, Marjolein; Hendriks, Benno H W; Lucassen, Gerald W; van Geffen, Geert-Jan; van Kleef, Maarten; van Dijk, Paul; Lataster, Arno

2018-05-14

During several anesthesiological procedures, needles are inserted through the skin of a patient to target nerves. In most cases, the needle traverses several tissues-skin, subcutaneous adipose tissue, muscles, nerves, and blood vessels-to reach the target nerve. A clear identification of the target nerve can improve the success of the nerve block and reduce the rate of complications. This may be accomplished with diffuse reflectance spectroscopy (DRS) which can provide a quantitative measure of the tissue composition. The goal of the current study was to further explore the morphological, biological, chemical, and optical characteristics of the tissues encountered during needle insertion to improve future DRS classification algorithms. To compare characteristics of nerve tissue (sciatic nerve) and adipose tissues, the following techniques were used: histology, DRS, absorption spectrophotometry, high-resolution magic-angle spinning nuclear magnetic resonance (HR-MAS NMR) spectroscopy, and solution 2D 13 C- 1 H heteronuclear single-quantum coherence spectroscopy. Tissues from five human freshly frozen cadavers were examined. Histology clearly highlights a higher density of cellular nuclei, collagen, and cytoplasm in fascicular nerve tissue (IFAS). IFAS showed lower absorption of light around 1200 nm and 1750 nm, higher absorption around 1500 nm and 2000 nm, and a shift in the peak observed around 1000 nm. DRS measurements showed a higher water percentage and collagen concentration in IFAS and a lower fat percentage compared to all other tissues. The scattering parameter (b) was highest in IFAS. The HR-MAS NMR data showed three extra chemical peak shifts in IFAS tissue. Collagen, water, and cellular nuclei concentration are clearly different between nerve fascicular tissue and other adipose tissue and explain some of the differences observed in the optical absorption, DRS, and HR-NMR spectra of these tissues. Some differences observed between fascicular nerve tissue and adipose tissues cannot yet be explained but may be helpful in improving the discriminatory capabilities of DRS in anesthesiology procedures. Lasers Surg. Med. 9999:1-13, 2018. © 2018 The Authors. Lasers in Surgery and Medicine Published by Wiley Periodicals, Inc. © 2018 The Authors. Lasers in Surgery and Medicine Published by Wiley Periodicals, Inc.

Temperature effect on laser-induced breakdown spectroscopy spectra of molten and solid salts

NASA Astrophysics Data System (ADS)

Hanson, Cynthia; Phongikaroon, Supathorn; Scott, Jill R.

2014-07-01

Laser-induced breakdown spectroscopy (LIBS) has been investigated as a potential analytical tool to improve operations and safeguards for electrorefiners, such as those used in processing spent nuclear fuel. This study set out to better understand the effect of sample temperature and physical state on LIBS spectra of molten and solid salts by building calibration curves of cerium and assessing self-absorption, plasma temperature, electron density, and local thermal equilibrium (LTE). Samples were composed of a LiCl-KCl eutectic salt, an internal standard of MnCl2, and varying concentrations of CeCl3 (0.1, 0.3, 0.5, 0.8, and 1.0 wt.% Ce) under different temperatures (773, 723, 673, 623, and 573 K). Analysis of salts in their molten form is preferred as plasma plumes from molten samples experienced less self-absorption, less variability in plasma temperature, and higher clearance of the minimum electron density required for local thermal equilibrium. These differences are attributed to plasma dynamics as a result of phase changes. Spectral reproducibility was also better in the molten state due to sample homogeneity.

X-ray magnetic circular dichroism measured at the Fe K-edge with a reduced intrinsic broadening: x-ray absorption spectroscopy versus resonant inelastic x-ray scattering measurements

NASA Astrophysics Data System (ADS)

Juhin, Amélie; Sainctavit, Philippe; Ollefs, Katharina; Sikora, Marcin; Filipponi, Adriano; Glatzel, Pieter; Wilhelm, Fabrice; Rogalev, Andrei

2016-12-01

X-ray magnetic circular dichroism is measured at the Fe K pre-edge in yttrium iron garnet using two different procedures that allow reducing the intrinsic broadening due to the 1s corehole lifetime. First, deconvolution of XMCD data measured in total fluorescence yield (TFY) with an extremely high signal-to-noise ratio enables a factor of 2.4 to be gained in the XMCD intensity. Ligand field multiplet calculations performed with different values of intrinsic broadening show that deconvolving such high quality XMCD data is similar to reducing the lifetime broadening from a 1s corehole to a 2p corehole. Second, MCD is measured by resonant inelastic x-ray scattering spectroscopy as a function of incident energy and emission energy. Selection of a fixed emission energy, instead of using the TFY, allows enhancing the MCD intensity up to a factor of  ˜4.7. However, this significantly changes the spectral shape of the XMCD signal, which cannot be interpreted any more as an absorption spectrum.

The relationship between structural and optical properties of Se-Ge-As glasses

NASA Astrophysics Data System (ADS)

Ghayebloo, M.; Rezvani, M.; Tavoosi, M.

2018-05-01

In this study, the structural and optical characterization of bulk Se-Ge-As glasses has been investigated. In this regards, six different Se60Ge40-xAsx (0 ≤ x ≤ 25) glasses were prepared by conventional melt quenching technique in quartz ampoule. The produced samples were characterized using X-ray diffraction (XRD), Raman spectroscopy, differential thermal analysis (DTA), ultraviolet-visible (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. The fundamental absorption edge for all the glasses was analyzed in terms of the theory proposed by Davis and Mott. According to achieved results, fully amorphous phase can easily form in different Se-Ge-As systems. The thermal and optical characteristic of Se60Ge40-xAsx glasses shows anomalous behavior at 5 mol% of As for the glass transition temperature, transmittance, absorption edge, optical energy gap and Urbach energy. The highest glass transition temperature, transmittance, optical energy gap and Urbach energy properties were achieved in Se60Ge35As5 glass as a result of the highest connectivity of cations and anions in glass network.

Third-harmonic generation susceptibility spectroscopy in free fatty acids

NASA Astrophysics Data System (ADS)

Chen, Yu-Cheng; Hsu, Hsun-Chia; Lee, Chien-Ming; Sun, Chi-Kuang

2015-09-01

Lipid-correlated disease such as atherosclerosis has been an important medical research topic for decades. Many new microscopic imaging techniques such as coherent anti-Stokes Raman scattering and third-harmonic generation (THG) microscopy were verified to have the capability to target lipids in vivo. In the case of THG microscopy, biological cell membranes and lipid bodies in cells and tissues have been shown as good sources of contrast with a laser excitation wavelength around 1200 nm. We report the THG excitation spectroscopy study of two pure free fatty acids including oleic acid and linoleic acid from 1090 to 1330 nm. Different pure fatty acids presented slightly-different THG χ(3) spectra. The measured peak values of THG third-order susceptibility χ(3) in both fatty acids were surprisingly found not to match completely with the resonant absorption wavelengths around 1190 to 1210 nm, suggesting possible wavelengths selection for enhanced THG imaging of lipids while avoiding laser light absorption. Along with the recent advancement in THG imaging, this new window between 1240 to 1290 nm may offer tremendous new opportunities for sensitive label-free lipid imaging in biological tissues.

Spectroscopic studies on the interaction of chromium (VI) and chromium (III) with keyhole limpet hemocyanin.

PubMed

Fan, Yulan; Zeng, Guidi; Liu, Jingyi; Chen, Huifang; Xue, Jun; Wu, Yongquan; Li, Xun

2017-03-01

The interactions of keyhole limpet hemocyanin (KLH) with chromium nitrate, potassium dichromate, and chromate were investigated using fluorescence, UV-vis absorption and circular dichroism (CD) spectroscopy under simulated physiological conditions. The experimental results showed that the different forms of chromium could quench the intrinsic fluorescence of KLH following a static quenching mechanism rather than by dynamic collision, which indicated that a Cr-KLH complex was formed. The Stern-Volmer quenching constants for the interaction indicated that the binding reaction of KLH with Cr(VI) was stronger the binding of KLH with Cr(III). The thermodynamic values for binding of Cr(VI) to KLH are ΔH > 0 and ΔS > 0. By contrast, the values for the interaction of Cr(III) with KLH are ΔH < 0 and ΔS < 0. The results of synchronous fluorescence, UV-vis absorption and CD spectroscopy showed that the α-helical secondary structure and conformation of KLH were altered by different forms of chromium. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Tunable diode laser absorption spectroscopy as method of choice for non-invasive and automated detection of microbial growth in media fills.

PubMed

Brueckner, David; Roesti, David; Zuber, Ulrich; Sacher, Meik; Duncan, Derek; Krähenbühl, Stephan; Braissant, Olivier

2017-05-15

Tunable diode laser absorption spectroscopy (TDLAS) was evaluated on its potential to detect bacterial growth of contaminated media fill vials. The target was a replacement/ automation of the traditional visual media fill inspection. TDLAS was used to determine non-invasively O 2 and/or CO 2 changes in headspaces of such vials being induced by metabolically active microorganisms. Four different vial formats, 34 microorganisms (inoculation volume<10 cells) and two different media (TSB/FTM) were tested. Applying parallel CO 2 and O 2 headspace measurements all format-organism combinations were detected within <11 days reliably with reproducible results. False negatives were exclusively observed for samples that were intentionally breached with syringes of 0.3mm in diameter. Overall it was shown that TDLAS functionality for a replacement of the visual media fill inspection is given and that investing in further validation and implementation studies is valuable. Nevertheless, some small but vincible challenges remain to have this technology in practical use. Copyright © 2017 Elsevier B.V. All rights reserved.

Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

PubMed

Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

2013-01-15

The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.

Label free detection of phospholipids by infrared absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ahmed, Tahsin; Foster, Erick; Vigil, Genevieve; Khan, Aamir A.; Bohn, Paul; Howard, Scott S.

2014-08-01

We present our study on compact, label-free dissolved lipid sensing by combining capillary electrophoresis separation in a PDMS microfluidic chip online with mid-infrared (MIR) absorption spectroscopy for biomarker detection. On-chip capillary electrophoresis is used to separate the biomarkers without introducing any extrinsic contrast agent, which reduces both cost and complexity. The label free biomarker detection could be done by interrogating separated biomarkers in the channel by MIR absorption spectroscopy. Phospholipids biomarkers of degenerative neurological, kidney, and bone diseases are detectable using this label free technique. These phospholipids exhibit strong absorption resonances in the MIR and are present in biofluids including urine, blood plasma, and cerebrospinal fluid. MIR spectroscopy of a 12-carbon chain phosphatidic acid (PA) (1,2-dilauroyl-snglycero- 3-phosphate (sodium salt)) dissolved in N-methylformamide, exhibits a strong amide peak near wavenumber 1660 cm-1 (wavelength 6 μm), arising from the phosphate headgroup vibrations within a low-loss window of the solvent. PA has a similar structure to many important phospholipids molecules like phosphatidylcholine (PC), phosphatidylinositol (PI), phosphatidylethanolamine (PE), phosphatidylglycerol (PG), and phosphatidylserine (PS), making it an ideal molecule for initial proof-of-concept studies. This newly proposed detection technique can lead us to minimal sample preparation and is capable of identifying several biomarkers from the same sample simultaneously.

Solid-state cocrystal formation between acyclovir and fumaric acid: Terahertz and Raman vibrational spectroscopic studies.

PubMed

Cai, Qiang; Xue, Jiadan; Wang, Qiqi; Du, Yong

2017-11-05

The vibrational spectra of solid-state acyclovir, fumaric acid and their cocrystal have been investigated by using terahertz time-domain spectroscopy (THz-TDS) and Raman spectroscopy at room temperature. In experimental THz spectra, the cocrystal has absorption peaks in 0.65, 0.94 and 1.10THz respectively, while the raw materials are absolutely different in this region. Raman spectra also show similar results about differences between the cocrystal and raw materials. Density functional theory (DFT) was performed to simulate vibrational modes of different theoretical forms between acyclovir and fumaric acid. The calculation of theoretical THz spectra shows that O8C7N1H27 and the carboxyl group COOH establish a dimer theoretical cocrystal form by the hydrogen bonding effect, which makes contributions to the formation of absorption peaks in 0.70, 1.01 and 1.34THz, and agrees well with experimental observations. The theoretical Raman result also indicates that this dimer form matches with experimental results. The characteristic bands of the cocrystal between acyclovir and fumaric acid are also assigned based on the simulation results from the DFT calculation. Copyright © 2017 Elsevier B.V. All rights reserved.

Solid-state cocrystal formation between acyclovir and fumaric acid: Terahertz and Raman vibrational spectroscopic studies

NASA Astrophysics Data System (ADS)

Cai, Qiang; Xue, Jiadan; Wang, Qiqi; Du, Yong

2017-11-01

The vibrational spectra of solid-state acyclovir, fumaric acid and their cocrystal have been investigated by using terahertz time-domain spectroscopy (THz-TDS) and Raman spectroscopy at room temperature. In experimental THz spectra, the cocrystal has absorption peaks in 0.65, 0.94 and 1.10 THz respectively, while the raw materials are absolutely different in this region. Raman spectra also show similar results about differences between the cocrystal and raw materials. Density functional theory (DFT) was performed to simulate vibrational modes of different theoretical forms between acyclovir and fumaric acid. The calculation of theoretical THz spectra shows that O8dbnd C7sbnd N1sbnd H27 and the carboxyl group sbnd COOH establish a dimer theoretical cocrystal form by the hydrogen bonding effect, which makes contributions to the formation of absorption peaks in 0.70, 1.01 and 1.34 THz, and agrees well with experimental observations. The theoretical Raman result also indicates that this dimer form matches with experimental results. The characteristic bands of the cocrystal between acyclovir and fumaric acid are also assigned based on the simulation results from the DFT calculation.

Hydrogen/deuterium (H/D) exchange of gelatinized starch studied by two-dimensional (2D) near-infrared (NIR) correlation spectroscopy

NASA Astrophysics Data System (ADS)

Shinzawa, Hideyuki; Mizukado, Junji

2018-05-01

Hydrogen/deuterium (H/D) exchange of gelatinized starch was probed by in-situ near-infrared (NIR) monitoring coupled with two-dimensional (2D) correlation spectroscopy. Gelatinized starch undergoes spontaneous H/D exchange in D2O. During the substitution, the exchange rate essentially becomes different depending on solvent accessibility of various parts of the molecule. Thus, by analyzing the change in the NIR feature observed during the substitution, it becomes possible to sort out local structure and dynamics of the system. 2D correlation analysis of the time-dependent NIR spectra reveals the presence of different local structure of the starch, each having different solvent accessibility. For example, during the H/D exchange, the D2O is first absorbed by starch molecules especially around the surface area between the starch and water, where the water molecules are weakly interacted with the starch molecules. This absorption is quickly followed by the development of HDO species. Further absorption of the D2O results in the penetration of the molecules inside the starch and eventually develops the relatively strong interaction between the HDO and starch molecules because of the presence of dominant starch molecules.

Characterization of Lignin in Situ by Photoacoustic Spectroscopy

PubMed Central

Gould, J. Michael

1982-01-01

Photoacoustic spectroscopy is a recently developed nondestructive analytical technique that provides ultraviolet, visible, and infrared absorption spectra from intensely light scattering, solid, and/or optically opaque materials not suitable for conventional spectrophotometric analysis. In wood and other lignocellulosics, the principal ultraviolet absorption bands, in the absence of photosynthetic pigments, arise from the aromatic lignin component of the cell walls. Photoacoustic spectra of extracted lignin fragments (milled wood lignin) and synthetic lignin-like polymers contain a single major absorption band at 280 nanometers with an absorption tail extending beyond 400 nanometers. Photoacoustic spectra of pine, maple, and oak lignin in situ contain a broad primary absorption band at 300 nanometers and a longer wavelength shoulder around 370 nanometers. Wheat lignin in situ, on the other hand, exhibits two principle absorption peaks, at 280 nanometers and 320 nanometers. The presence of absorption bands at wavelengths greater than 300 nanometers in intact lignin could result from (a) interacting, nonconjugated chromophores, or (b) the presence of more highly conjugated structural components formed as the result of oxidation of the polymer. Evidence for the latter comes from the observation that, on the outer surface of senescent, field-dried wheat culms (stems), new absorption bands in the 350 to 400 nanometer region predominate. These new bands are less apparent on the outer surface of presenescent wheat culms and are virtually absent on the inner surface of either senescent or presenescent culms, suggesting that the appearance of longer wavelength absorption bands in senescent wheat is the result of accumulated photochemical modifications of the ligin polymer. These studies also demonstrate photoacoustic spectroscopy to be an important new tool for the investigation of insoluble plant components. PMID:16662709

Laser absorption spectroscopy applied to monitoring of short-lived climate pollutants (SLCPs)

NASA Astrophysics Data System (ADS)

Wang, Gaoxuan; Shen, Fengjiao; Yi, Hongming; Hubert, Patrice; Deguine, Alexandre; Petitprez, Denis; Maamary, Rabih; Augustin, Patrick; Fourmentin, Marc; Fertein, Eric; Sigrist, Markus W.; Ba, Tong-Nguyen; Chen, Weidong

2018-06-01

Enhanced mitigation of short-lived climate pollutants (SLCPs) has been recently paid more attention in order to provide more sizeable short-term reductions of global warming effects over the next several decades. We overview in this article our recent progress in the development of spectroscopic instruments for optical monitoring of major SLCPs based on laser absorption spectroscopy. Methane (CH4) and black carbon (BC) are the most important SLCPs contributing to the human enhancement of the global greenhouse effect after CO2. We present optical sensing of these two climate-change related atmospheric species to illustrate how "classical" spectroscopy can help to address today's challenging issues: (1) Photoacoustic measurements of BC optical absorption coefficient in order to determine its radiative-forcing related optical parameters (such as mass absorption coefficient, absorption Ångström coefficient) with higher precision (∼7.4% compared to 12-30% for filter-based methods routinely used nowadays). The 1σ (SNR = 1) minimum measurable volumetric mass density of 21 ng/m3 (in 60 s) for black carbon. (2) Direct absorption spectroscopy-based monitoring of methane (CH4) in field campaign to identify pollution source in conjunction with air mass back-trajectory modeling. Using a White-type multipass cell (an effective path-length of 175 m), a 1σ detection limit of 33.3 ppb in 218 s was achieved with a relative measurement precision of 1.1% and an overall measurement uncertainty of about 5.1%. Performance of the custom, lab-based instruments (in terms of detection limits, measurement precision, temporal response, etc.), spectroscopic measurement aspects, experimental details, spectral data processing, analysis and modeling of the observed environmental episode will be presented and discussed.

Photodissociation Spectroscopy of Cold Protonated Synephrine: Surprising Differences between IR-UV Hole-Burning and IR Photodissociation Spectroscopy of the O-H and N-H Modes.

PubMed

Nieuwjaer, N; Desfrançois, C; Lecomte, F; Manil, B; Soorkia, S; Broquier, M; Grégoire, G

2018-04-19

We report the UV and IR photofragmentation spectroscopies of protonated synephrine in a cryogenically cooled Paul trap. Single (UV or IR) and double (UV-UV and IR-UV) resonance spectroscopies have been performed and compared to quantum chemistry calculations, allowing the assignment of the lowest-energy conformer with two rotamers depending on the orientation of the phenol hydroxyl (OH) group. The IR-UV hole burning spectrum exhibits the four expected vibrational modes in the 3 μm region, i.e., the phenol OH, C β -OH, and two NH 2 + stretches. The striking difference is that, among these modes, only the free phenol OH mode is active through IRPD. The protonated amino group acts as a proton donor in the internal hydrogen bond and displays large frequency shifts upon isomerization expected during the multiphoton absorption process, leading to the so-called IRMPD transparency. More interestingly, while the C β -OH is a proton acceptor group with moderate frequency shift for the different conformations, this mode is still inactive through IRPD.

Using mid-Infrared External Reflectance Spectroscopy to Distinguish Between Different Commercially Produced Poly[Methyl MethAcrylate] (PMMA) Samples - A Null Result

NASA Astrophysics Data System (ADS)

Fajardo, Mario; Neel, Christopher; Lacina, David

2017-06-01

We report (null) results of experiments testing the hypothesis that mid-infrared (mid-IR) spectroscopy can be used to distinguish samples of poly[methyl methacrylate] (PMMA) obtained from different commercial suppliers. This work was motivated by the desire for a simple non-destructive and non-invasive test for pre-sorting PMMA samples prior to use in shock and high-strain-rate experiments, where PMMA is commonly used as a standard material. We discuss: our choice of mid-IR external reflectance spectroscopy, our approach to recording reflectance spectra at near-normal (θ = 0 + / - 5 degree) incidence and for extracting the wavelength-weighted absorption spectrum from the raw reflectance data via a Kramers-Krönig analysis. We employ extensive signal, which necessitates adopting a special experimental protocol to mitigate the effects of instrumental drift. Finally, we report spectra of three PMMA samples with different commercial pedigrees, and show that they are virtually identical (+ / - 1 % error, 95% confidence); obviating the use of mid-IR reflectance spectroscopy to tell the samples apart.

Mapping CTTS dynamics of Na- in tetrahydrofurane with ultrafast multichannel pump-probe spectroscopy.

PubMed

Shoshana, O; Pérez Lustres, J L; Ernsting, N P; Ruhman, S

2006-06-14

Using multichannel femtosecond spectroscopy we have followed Na- charge transfer to solvent (CTTS) dynamics in THF solution. Absorption of the primary photoproducts in the visible, resolved here for the first time, consists of an asymmetric triplet centered at 595 nm, which we assign to a metastable incompletely solvated neutral atomic sodium species. Decay of this feature within approximately 1 ps to a broad and structureless solvated neutral is accompanied by broadening and loss of spectral detail. Kinetic analysis shows that both the spectral structure and the decay of this band are independent of the excitation photon frequency in the range 400-800 nm. With different pump-probe polarizations the anisotropy in transient transmission has been charted and its variation with excitation wavelength surveyed. The anisotropies are assigned to the reactant bleach, indicating that due to solvent-induced symmetry breaking, the CTTS absorption band of Na- is made up of discreet orthogonally polarized sub bands. None of the anisotropy in transient absorption could be associated with the photoproduct triplet band even at the earliest measurable time delays. Along with the documented differences in the spatial distribution of ejected electrons across the tested excitation wavelength range, these results lead us to conclude that photoejection is extremely rapid, and that loss of correlations between the departing electron and its neutral core is faster than our time resolution of approximately 60 fs.

Binding of transducin and transducin-derived peptides to rhodopsin studies by attenuated total reflection-Fourier transform infrared difference spectroscopy.

PubMed Central

Fahmy, K

1998-01-01

Fourier transform infrared difference spectroscopy combined with the attenuated total reflection technique allows the monitoring of the association of transducin with bovine photoreceptor membranes in the dark. Illumination causes infrared absorption changes linked to formation of the light-activated rhodopsin-transducin complex. In addition to the spectral changes normally associated with meta II formation, prominent absorption increases occur at 1735 cm-1, 1640 cm-1, 1550 cm-1, and 1517 cm-1. The D2O sensitivity of the broad carbonyl stretching band around 1735 cm-1 indicates that a carboxylic acid group becomes protonated upon formation of the activated complex. Reconstitution of rhodopsin into phosphatidylcholine vesicles has little influence on the spectral properties of the rhodopsin-transducin complex, whereas pH affects the intensity of the carbonyl stretching band. AC-terminal peptide comprising amino acids 340-350 of the transducin alpha-subunit reproduces the frequencies and isotope sensitivities of several of the transducin-induced bands between 1500 and 1800 cm-1, whereas an N-terminal peptide (aa 8-23) does not. Therefore, the transducin-induced absorption changes can be ascribed mainly to an interaction between the transducin-alpha C-terminus and rhodopsin. The 1735 cm-1 vibration is also seen in the complex with C-terminal peptides devoid of free carboxylic acid groups, indicating that the corresponding carbonyl group is located on rhodopsin. PMID:9726932

Titanium-silicon oxide film structures for polarization-modulated infrared reflection absorption spectroscopy

PubMed Central

Dunlop, Iain E.; Zorn, Stefan; Richter, Gunther; Srot, Vesna; Kelsch, Marion; van Aken, Peter A.; Skoda, Maximilian; Gerlach, Alexander; Spatz, Joachim P.; Schreiber, Frank

2010-01-01

We present a titanium-silicon oxide film structure that permits polarization modulated infrared reflection absorption spectroscopy on silicon oxide surfaces. The structure consists of a ~6 nm sputtered silicon oxide film on a ~200 nm sputtered titanium film. Characterization using conventional and scanning transmission electron microscopy, electron energy loss spectroscopy, X-ray photoelectron spectroscopy and X-ray reflectometry is presented. We demonstrate the use of this structure to investigate a selectively protein-resistant self-assembled monolayer (SAM) consisting of silane-anchored, biotin-terminated poly(ethylene glycol) (PEG). PEG-associated IR bands were observed. Measurements of protein-characteristic band intensities showed that this SAM adsorbed streptavidin whereas it repelled bovine serum albumin, as had been expected from its structure. PMID:20418963

Fluorescent quantification of melanin.

PubMed

Fernandes, Bruno; Matamá, Teresa; Guimarães, Diana; Gomes, Andreia; Cavaco-Paulo, Artur

2016-11-01

Melanin quantification is reportedly performed by absorption spectroscopy, commonly at 405 nm. Here, we propose the implementation of fluorescence spectroscopy for melanin assessment. In a typical in vitro assay to assess melanin production in response to an external stimulus, absorption spectroscopy clearly overvalues melanin content. This method is also incapable of distinguishing non-melanotic/amelanotic control cells from those that are actually capable of performing melanogenesis. Therefore, fluorescence spectroscopy is the best method for melanin quantification as it proved to be highly specific and accurate, detecting even small variations in the synthesis of melanin. This method can also be applied to the quantification of melanin in more complex biological matrices like zebrafish embryos and human hair. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Light Absorption and Excitation-Emission Fluorescence of Urban Organic Aerosol Components and Their Relationship to Chemical Structure.

PubMed

Chen, Qingcai; Ikemori, Fumikazu; Mochida, Michihiro

2016-10-18

The present study used a combination of solvent and solid-phase extractions to fractionate organic compounds with different polarities from total suspended particulates in Nagoya, Japan, and their optical characteristics were obtained on the basis of their UV-visible absorption spectra and excitation-emission matrices (EEMs). The relationship between their optical characteristics and chemical structures was investigated based on high-resolution aerosol mass spectra (HR-AMS spectra), soft ionization mass spectra and Fourier transform infrared (FT-IR) spectra. The major light-absorption organics were less polar organic fractions, which tended to have higher mass absorption efficiencies (MAEs) and lower wavelength dependent Ångström exponents (Å) than the more polar organic fractions. Correlation analyses indicate that organic compounds with O and N atoms may contribute largely to the total light absorption and fluorescence of the organic aerosol components. The extracts from the aerosol samples were further characterized by a classification of the EEM profiles using a PARAFAC model. Different fluorescence components in the aerosol organic EEMs were associated with specific AMS ions and with different functional groups from the FT-IR analysis. These results may be useful to determine and further classify the chromophores in atmospheric organic aerosols using EEM spectroscopy.

Ultrafast carrier dynamics of titanic acid nanotubes investigated by transient absorption spectroscopy.

PubMed

Wang, Li; Zhao, Hui; Pan, Lin Yun; Weng, Yu Xiang; Nakato, Yoshihiro; Tamai, Naoto

2010-12-01

Carrier dynamics of titanic acid nanotubes (phase of H2Ti2O5.H2O) deposited on a quartz plate was examined by visible/near-IR transient absorption spectroscopy with an ultraviolet excitation. The carrier dynamics of titanic acid nanotubes follows the fast trapping process which attributed to the intrinsic tubular structure, the relaxation of shallow trapped carriers and the recombination as a second-order kinetic process. Transient absorption of titanic acid nanotubes was dominated by the absorption of surface-trapped holes in visible region around 500 nm, which was proved by the faster decay dynamics in the presence of polyvinyl alcohol as a hole-scavenger. However, the slow relaxation of free carriers was much more pronounced in the TiO2 single crystals, as compared with the transient absorption spectra of titanic acid nanotubes under the similar excitation.

Reflectance-mode interferometric near-infrared spectroscopy quantifies brain absorption, scattering, and blood flow index in vivo.

PubMed

Borycki, Dawid; Kholiqov, Oybek; Srinivasan, Vivek J

2017-02-01

Interferometric near-infrared spectroscopy (iNIRS) is a new technique that measures time-of-flight- (TOF-) resolved autocorrelations in turbid media, enabling simultaneous estimation of optical and dynamical properties. Here, we demonstrate reflectance-mode iNIRS for noninvasive monitoring of a mouse brain in vivo. A method for more precise quantification with less static interference from superficial layers, based on separating static and dynamic components of the optical field autocorrelation, is presented. Absolute values of absorption, reduced scattering, and blood flow index (BFI) are measured, and changes in BFI and absorption are monitored during a hypercapnic challenge. Absorption changes from TOF-resolved iNIRS agree with absorption changes from continuous wave NIRS analysis, based on TOF-integrated light intensity changes, an effective path length, and the modified Beer-Lambert Law. Thus, iNIRS is a promising approach for quantitative and noninvasive monitoring of perfusion and optical properties in vivo.

Diagnosis of a two wire X-pinch by X-ray absorption spectroscopy utilizing a doubly curved ellipsoidal crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cahill, A. D., E-mail: adc87@cornell.edu; Hoyt, C. L., E-mail: adc87@cornell.edu; Shelkovenko, T. A., E-mail: adc87@cornell.edu

2014-12-15

X-ray absorption spectroscopy is a powerful tool for the diagnosis of plasmas over a wide range of both temperature and density. However, such a measurement is often limited to probing plasmas with temperatures well below that of the x-ray source in order to avoid object plasma emission lines from obscuring important features of the absorption spectrum. This has excluded many plasmas from being investigated by this technique. We have developed an x-ray spectrometer that provides the ability to record absorption spectra from higher temperature plasmas than the usual approach allows without the risk of data contamination by line radiation emittedmore » by the plasma under study. This is accomplished using a doubly curved mica crystal which is bent both elliptically and cylindrically. We present here initial absorption spectra obtained from an aluminum x-pinch plasma.« less

Measurements of the Weak UV Absorptions of Isoprene and Acetone at 261–275 nm Using Cavity Ringdown Spectroscopy for Evaluation of a Potential Portable Ringdown Breath Analyzer

PubMed Central

Sahay, Peeyush; Scherrer, Susan T.; Wang, Chuji

2013-01-01

The weak absorption spectra of isoprene and acetone have been measured in the wavelength range of 261–275 nm using cavity ringdown spectroscopy. The measured absorption cross-sections of isoprene in the wavelength region of 261–266 nm range from 3.65 × 10−21 cm2·molecule−1 at 261 nm to 1.42 × 10−21 cm2·molecule−1 at 266 nm; these numbers are in good agreement with the values reported in the literature. In the longer wavelength range of 270–275 nm, however, where attractive applications using a single wavelength compact diode laser operating at 274 nm is located, isoprene has been reported in the literature to have no absorption (too weak to be detected). Small absorption cross-sections of isoprene in this longer wavelength region are measured using cavity ringdown spectroscopy for the first time in this work, i.e., 6.20 × 10−23 cm2·molecule−1 at 275 nm. With the same experimental system, wavelength-dependent absorption cross-sections of acetone have also been measured. Theoretical detection limits of isoprene and comparisons of absorbance of isoprene, acetone, and healthy breath gas in this wavelength region are also discussed. PMID:23803787

Incorporation of Trace Elements in Ancient and Modern Human Bone: An X-Ray Absorption Spectroscopy Study

NASA Astrophysics Data System (ADS)

Pingitore, N. E.; Cruz-Jimenez, G.; Price, T. D.

2001-12-01

X-ray absorption spectroscopy (XAS) affords the opportunity to probe the atomic environment of trace elements in human bone. We are using XAS to investigate the mode(s) of incorporation of Sr, Zn, Pb, and Ba in both modern and ancient (and thus possibly altered) human and animal bone. Because burial and diagenesis may add trace elements to bone, we performed XAS analysis on samples of pristine contemporary and ancient, buried human and animal bone. We assume that deposition of these elements during burial occurs by processes distinct from those in vivo, and this will be reflected in their atomic environments. Archaeologists measure strontium in human and animal bone as a guide to diet. Carnivores show lower Sr/Ca ratios than their herbivore prey due to discrimination against Sr relative to Ca up the food chain. In an initial sample suite no difference was observed between modern and buried bone. Analysis of additional buried samples, using a more sensitive detector, revealed significant differences in the distance to the second and third neighbors of the Sr in some of the buried samples. Distances to the first neighbor, oxygen, were similar in all samples. Zinc is also used in paleo-diet studies. Initial x-ray absorption spectroscopy of a limited suite of bones did not reveal any differences between modern and buried samples. This may reflect the limited number of samples examined or the low levels of Zn in typical aqueous solutions in soils. Signals from barium and lead were too low to record useful XAS spectra. Additional samples will be studied for Zn, Ba, and Pb. We conducted our XAS experiments on beam lines 4-1 and 4-3 at the Stanford Synchrotron Radiation Laboratory. Data were collected in the fluorescence mode, using a Lytle detector and appropriate filter, and a solid state, 13-element Ge-detector.

Full-Field Calcium K-Edge X-ray Absorption Near-Edge Structure Spectroscopy on Cortical Bone at the Micron-Scale: Polarization Effects Reveal Mineral Orientation.

PubMed

Hesse, Bernhard; Salome, Murielle; Castillo-Michel, Hiram; Cotte, Marine; Fayard, Barbara; Sahle, Christoph J; De Nolf, Wout; Hradilova, Jana; Masic, Admir; Kanngießer, Birgit; Bohner, Marc; Varga, Peter; Raum, Kay; Schrof, Susanne

2016-04-05

Here, we show results on X-ray absorption near edge structure spectroscopy in both transmission and X-ray fluorescence full-field mode (FF-XANES) at the calcium K-edge on human bone tissue in healthy and diseased conditions and for different tissue maturation stages. We observe that the dominating spectral differences originating from different tissue regions, which are well pronounced in the white line and postedge structures are associated with polarization effects. These polarization effects dominate the spectral variance and must be well understood and modeled before analyzing the very subtle spectral variations related to the bone tissue variations itself. However, these modulations in the fine structure of the spectra can potentially be of high interest to quantify orientations of the apatite crystals in highly structured tissue matrices such as bone. Due to the extremely short wavelengths of X-rays, FF-XANES overcomes the limited spatial resolution of other optical and spectroscopic techniques exploiting visible light. Since the field of view in FF-XANES is rather large the acquisition times for analyzing the same region are short compared to, for example, X-ray diffraction techniques. Our results on the angular absorption dependence were verified by both site-matched polarized Raman spectroscopy, which has been shown to be sensitive to the orientation of bone building blocks and by mathematical simulations of the angular absorbance dependence. As an outlook we further demonstrate the polarization based assessment of calcium-containing crystal orientation and specification of calcium in a beta-tricalcium phosphate (β-Ca3(PO4)2 scaffold implanted into ovine bone. Regarding the use of XANES to assess chemical properties of Ca in human bone tissue our data suggest that neither the anatomical site (tibia vs jaw) nor pathology (healthy vs necrotic jaw bone tissue) affected the averaged spectral shape of the XANES spectra.

Investigations of the functional states of dendritic cells under different conditioned microenvironments by Fourier transformed infrared spectroscopy.

PubMed

Dong, Rong; Long, Jinhua; Xu, Xiaoli; Zhang, Chunlin; Wen, Zongyao; Li, Long; Yao, Weijuan; Zeng, Zhu

2014-01-10

Dendritic cells are potent and specialized antigen presenting cells, which play a crucial role in initiating and amplifying both the innate and adaptive immune responses. The dendritic cell-based vaccination against cancer has been clinically achieved promising successes. But there are still many challenges in its clinical application, especially for how to identify the functional states. The CD14+ monocytes were isolated from human peripheral blood after plastic adherence and purified to approximately 98% with cocktail immunomagnetic beads. The immature dendritic cells and mature dendritic cells were induced by traditional protocols. The resulting dendritic cells were cocultured with normal cells and cancer cells. The functional state of dendritic cells including immature dendritic cells (imDCs) and mature dendritic cells (mDCs) under different conditioned microenvironments were investigated by Fourier transformed infrared spectroscopy (FTIR) and molecular biological methods. The results of Fourier transformed infrared spectroscopy showed that the gene transcription activity and energy states of dendritic cells were specifically suppressed by tumor cells (P < 0.05 or 0.01). The expression levels of NF-kappa B (NF-κB) in dendritic cells were also specifically inhibited by tumor-derived factors (P < 0.05 or 0.01). Moreover, the ratios of absorption intensities of Fourier transformed infrared spectroscopy at given wave numbers were closely correlated with the expression levels of NF-κB (R2:0.69 and R2:0.81, respectively). Our results confirmed that the ratios of absorption intensities of Fourier transformed infrared spectroscopy at given wave numbers were positively correlated with the expression levels of NF-κB, suggesting that Fourier transformed infrared spectroscopy technology could be clinically applied to identify the functional states of dendritic cell when performing dendritic cell-based vaccination. It's significant for the simplification and standardization of dendritic cell-based vaccination clinical preparation protocols.

Analysis of Chuanxiong Rhizoma and its active components by Fourier transform infrared spectroscopy combined with two-dimensional correlation infrared spectroscopy.

PubMed

Guo, Yizhen; Lv, Beiran; Wang, Jingjuan; Liu, Yang; Sun, Suqin; Xiao, Yao; Lu, Lina; Xiang, Li; Yang, Yanfang; Qu, Lei; Meng, Qinghong

2016-01-15

As complicated mixture systems, active components of Chuanxiong Rhizoma are very difficult to identify and discriminate. In this paper, the macroscopic IR fingerprint method including Fourier transform infrared spectroscopy (FT-IR), the second derivative infrared spectroscopy (SD-IR) and two-dimensional correlation infrared spectroscopy (2DCOS-IR), was applied to study and identify Chuanxiong raw materials and its different segmented production of HPD-100 macroporous resin. Chuanxiong Rhizoma is rich in sucrose. In the FT-IR spectra, water eluate is more similar to sucrose than the powder and the decoction. Their second derivative spectra amplified the differences and revealed the potentially characteristic IR absorption bands and combined with the correlation coefficient, concluding that 50% ethanol eluate had more ligustilide than other eluates. Finally, it can be found from 2DCOS-IR spectra that proteins were extracted by ethanol from Chuanxiong decoction by HPD-100 macroporous resin. It was demonstrated that the above three-step infrared spectroscopy could be applicable for quick, non-destructive and effective analysis and identification of very complicated and similar mixture systems of traditional Chinese medicines. Copyright © 2015 Elsevier B.V. All rights reserved.

Steady-State Linear and Non-linear Optical Spectroscopy of Organic Chromophores and Bio-macromolecules

NASA Astrophysics Data System (ADS)

Marazzi, Marco; Gattuso, Hugo; Monari, Antonio; Assfeld, Xavier

2018-04-01

Bio-macromolecules as DNA, lipid membranes and (poly)peptides are essential compounds at the core of biological systems. The development of techniques and methodologies for their characterization is therefore necessary and of utmost interest, even though difficulties can be experienced due to their intrinsic complex nature. Among these methods, spectroscopies, relying on optical properties are especially important to determine their macromolecular structures and behaviors, as well as the possible interactions and reactivity with external dyes – often drugs or pollutants – that can (photo)sensitize the bio-macromolecule leading to eventual chemical modifications, thus damages. In this review, we will focus on the theoretical simulation of electronic spectroscopies of bio-macromolecules, considering their secondary structure and including their interaction with different kind of (photo)sensitizers. Namely, absorption, emission and electronic circular dichroism (CD) spectra are calculated and compared with the available experimental data. Non-linear properties will be also taken into account by two-photon absorption, a highly promising technique (i) to enhance absorption in the red and infra-red windows and (ii) to enhance spatial resolution. Methodologically, the implications of using implicit and explicit solvent, coupled to quantum and thermal samplings of the phase space, will be addressed. Especially, hybrid quantum mechanics/ molecular mechanics (QM/MM) methods are explored for a comparison with solely QM methods, in order to address the necessity to consider an accurate description of environmental effects on spectroscopic properties of biological systems.

Non-destructive plant health sensing using absorption spectroscopy

NASA Technical Reports Server (NTRS)

Bledsoe, Jim; Manukian, Ara; Pearce, Michael; Weiss, Lee

1988-01-01

The sensor group of the 1988 EGM 4001 class, working on NASA's Controlled Ecological Life Support Systems (CELSS) project, investigated many different plant health indicators and the technologies used to test them. The project selected by the group was to measure chlorophyll levels using absorption spectroscopy. The spectrometer measures the amount of chlorophyll in a leaf by measuring the intensity of light of a specific wavelength that is passed through a leaf. The three wavelengths of light being used corresponded to the near-IR absorption peaks of chlorophyll a, chlorophyll b, and chlorophyll-free structures. Experimentation showed that the sensor is indeed measuring levels of chlorophyll a and b and their changes before the human eye can see any changes. The detector clamp causes little damage to the leaf and will give fairly accurate readings on similar locations on a leaf, freeing the clamp from having to remain on the same spot of a leaf for all measurements. External light affects the readings only slightly so that measurements may be taken in light or dark environments. Future designs and experimentation will concentrate on reducing the size of the sensor and adapting it to a wider range of plants.

Use of interfacial layers to prolong hole lifetimes in hematite probed by ultrafast transient absorption spectroscopy

NASA Astrophysics Data System (ADS)

Paradzah, Alexander T.; Diale, Mmantsae; Maabong, Kelebogile; Krüger, Tjaart P. J.

2018-04-01

Hematite is a widely investigated material for applications in solar water oxidation due primarily to its small bandgap. However, full realization of the material continues to be hampered by fast electron-hole recombination rates among other weaknesses such as low hole mobility, short hole diffusion length and low conductivity. To address the problem of fast electron-hole recombination, researchers have resorted to growth of nano-structured hematite, doping and use of under-layers. Under-layer materials enhance the photo-current by minimising electron-hole recombination through suppressing of back electron flow from the substrate, such as fluorine-doped tin oxide (FTO), to hematite. We have carried out ultrafast transient absorption spectroscopy on hematite in which Nb2O5 and SnO2 materials were used as interfacial layers to enhance hole lifetimes. The transient absorption data was fit with four different lifetimes ranging from a few hundred femtoseconds to a few nanoseconds. We show that the electron-hole recombination is slower in samples where interfacial layers are used than in pristine hematite. We also develop a model through target analysis to illustrate the effect of under-layers on electron-hole recombination rates in hematite thin films.

Simultaneous Speciation, Structure, and Equilibrium Constant Determination in the Ni2+-EDTA-CN- Ternary System via High-Resolution Laboratory X-ray Absorption Fine Structure Spectroscopy and Theoretical Calculations.

PubMed

Bajnóczi, Éva G; Németh, Zoltán; Vankó, György

2017-11-20

Even quite simple chemical systems can involve many components and chemical states, and sometimes it can be very difficult to differentiate them by their hardly separable physical-chemical properties. The Ni II -EDTA-CN - (EDTA = ethylenediaminetetraacetic acid) ternary system is a good example for this problem where, in spite of its fairly simple components and numerous investigations, several molecular combinations can exist, all of them not having been identified unambiguously yet. In order to achieve a detailed understanding of the reaction steps and chemical equilibria, methods are required in which the structural transitions in the different reaction steps can be followed via element-selective complex spectral feature sets. With the help of our recently developed von Hámos type high-resolution laboratory X-ray absorption spectrometer, both the structural variations and stability constants of the forming complexes were determined from the same measurement series, proving that X-ray absorption spectroscopy can be considered as a multifaced, table-top tool in coordination chemistry. Furthermore, with the help of theoretical calculations, independent structural evidence was also given for the formation of the [NiEDTA(CN)] 3- mixed complex.

Manganese L-edge X-ray absorption spectroscopy of manganese catalase from Lactobacillus plantarum and mixed valence manganese complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grush, M.M.; Chen, J.; George, S.J.

1996-01-10

The first Mn L-edge absorption spectra of a Mn metalloprotein are presented in this paper. Both reduced and superoxidized Mn catalase have been examined by fluorescence-detected soft X-ray absorption spectroscopy, and their Mn L-edge spectra are dramatically different. The spectrum of reduced Mn(II)Mn(II) catalase has been interpreted by ligand field atomic multiplet calculations and by comparison to model compound spectra. The analysis finds a 10 Dq value of nearly 1.1 eV, consistent with coordination by predominately nitrogen and oxygen donor ligands. For interpretation of mixed valence Mn spectra, an empirical simulation procedure based on the addition of homovalent model compoundmore » spectra has been developed and was tested on a variety of Mn complexes and superoxidized Mn catalase. This routine was also used to determine the oxidation state composition of the Mn in [Ba{sub 8}Na{sub 2}ClMn{sub 16}(OH){sub 8}(CO{sub 3}){sub 4}L{sub 8}] .53 H{sub 2}O (L=1,3-diamino-2-hydroxypropane-N,N,N`N`-tetraacetic acid). 27 refs., 6 figs.« less

Infrared reduction, an efficient method to control the non-linear optical property of graphene oxide in femtosecond regime

NASA Astrophysics Data System (ADS)

Bhattacharya, S.; Maiti, R.; Saha, S.; Das, A. C.; Mondal, S.; Ray, S. K.; Bhaktha, S. B. N.; Datta, P. K.

2016-04-01

Graphene Oxide (GO) has been prepared by modified Hummers method and it has been reduced using an IR bulb (800-2000 nm). Both as grown GO and reduced graphene oxide (RGO) have been characterized using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Raman spectra shows well documented Dband and G-band for both the samples while blue shift of G-band confirms chemical functionalization of graphene with different oxygen functional group. The XPS result shows that the as-prepared GO contains 52% of sp2 hybridized carbon due to the C=C bonds and 33% of carbon atoms due to the C-O bonds. As for RGO, increment of the atomic % of the sp2 hybridized carbon atom to 83% and rapid decrease in atomic % of C=O bonds confirm an efficient reduction with infrared radiation. UV-Visible absorption spectrum also confirms increment of conjugation with increased reduction. Non-linear optical properties of both GO and RGO are measured using single beam open aperture Z-Scan technique in femtosecond regime. Intensity dependent nonlinear phenomena are observed. Depending upon the intensity, both saturable absorption and two photon absorption contribute to the non-linearity of both the samples. Saturation dominates at low intensity (~ 127 GW/cm2) while two photon absorption become prominent at higher intensities (from 217 GW/cm2 to 302 GW/cm2). We have calculated the two-photon absorption co-efficient and saturation intensity for both the samples. The value of two photon absorption co-efficient (for GO~ 0.0022-0.0037 cm/GW and for RGO~ 0.0128-0.0143 cm/GW) and the saturation intensity (for GO~57 GW/cm2 and for RGO~ 194GW/cm2) is increased with reduction. Increase in two photon absorption coefficient with increasing intensity can also suggest that there may be multi-photon absorption is taking place.

An absorption spectral study of Nd (III) with glutathione (reduced), GSH in aqueous and aquated organic solvent in presence and absence of Zn (II)

NASA Astrophysics Data System (ADS)

Mehta, Jignasu P.; Bhatt, Prashant N.; Misra, Sudhindra N.

2003-02-01

The coordination chemistry of glutathione (reduced) GSH is of great importance as it acts as an excellent model system for the binding of metal ions. The GSH complexation with metal ions is involved in the toxicology of different metal ions. Its coordination behaviour for soft metal ions and hard metal ions is found different because of the structure of GSH and its different potential binding sites. We have studied two chemically dissimilar metal ions viz. Nd (III) being hard metal ion, which will prefer hard donor sites like carboxylic groups, and Zn (II) the soft metal ion more suited to peptide-NH and sulfhydryl groups. The absorption difference and comparative absorption spectroscopy involving 4f-4f transitions of the heterobimetallic complexation of GSH with Nd (III) and Zn (II) has been explored in aqueous and aquated organic solvents. The changes in the oscillator strengths of different 4f-4f bands and Judd-Ofelt intensity (Tλ) parameters determined experimentally is being used to investigate the complexation of GSH. The in vivo intracellular complexation of GSH with Ca (II) in presence of Zn (II) ion has been mimicked through Nd (III)-GSH-Zn (II) absorption spectral studies in vitro.

Fluorescence Spectroscopy Applied to Monitoring Biodiesel Degradation: Correlation with Acid Value and UV Absorption Analyses.

PubMed

Vasconcelos, Maydla Dos Santos; Passos, Wilson Espíndola; Lescanos, Caroline Honaiser; Pires de Oliveira, Ivan; Trindade, Magno Aparecido Gonçalves; Caires, Anderson Rodrigues Lima; Muzzi, Rozanna Marques

2018-01-01

The techniques used to monitor the quality of the biodiesel are intensely discussed in the literature, partly because of the different oil sources and their intrinsic physicochemical characteristics. This study aimed to monitor the thermal degradation of the fatty acid methyl esters of Sesamum indicum L. and Raphanus sativus L. biodiesels (SILB and RSLB, resp.). The results showed that both biodiesels present a high content of unsaturated fatty acids, ∼84% (SILB) and ∼90% (RSLB). The SILB had a high content of polyunsaturated linoleic fatty acid (18  :  2), about 49%, and the oleic monounsaturated (18  :  1), ∼34%. On the other hand, RSLB presented a considerable content of linolenic fatty acid (18  :  3), ∼11%. The biodiesel samples were thermal degraded at 110°C for 48 hours, and acid value, UV absorption, and fluorescence spectroscopy analysis were carried out. The results revealed that both absorption and fluorescence presented a correlation with acid value as a function of degradation time by monitoring absorptions at 232 and 270 nm as well as the emission at 424 nm. Although the obtained correlation is not completely linear, a direct correlation was observed in both cases, revealing that both properties can be potentially used for monitoring the biodiesel degradation.

Wavelength modulation diode laser absorption spectroscopy for high-pressure gas sensing

NASA Astrophysics Data System (ADS)

Sun, K.; Chao, X.; Sur, R.; Jeffries, J. B.; Hanson, R. K.

2013-03-01

A general model for 1 f-normalized wavelength modulation absorption spectroscopy with nf detection (i.e., WMS- nf) is presented that considers the performance of injection-current-tuned diode lasers and the reflective interference produced by other optical components on the line-of-sight (LOS) transmission intensity. This model explores the optimization of sensitive detection of optical absorption by species with structured spectra at elevated pressures. Predictions have been validated by comparison with measurements of the 1 f-normalized WMS- nf (for n = 2-6) lineshape of the R(11) transition in the 1st overtone band of CO near 2.3 μm at four different pressures ranging from 5 to 20 atm, all at room temperature. The CO mole fractions measured by 1 f-normalized WMS-2 f, 3 f, and 4 f techniques agree with calibrated mixtures within 2.0 %. At conditions where absorption features are significantly broadened and large modulation depths are required, uncertainties in the WMS background signals due to reflective interference in the optical path can produce significant error in gas mole fraction measurements by 1 f-normalized WMS-2 f. However, such potential errors can be greatly reduced by using the higher harmonics, i.e., 1 f-normalized WMS- nf with n > 2. In addition, less interference from pressure-broadened neighboring transitions has been observed for WMS with higher harmonics than for WMS-2 f.

Effects of Pulsed Electromagnetic Fields on Breast Cancer Cell Line MCF 7 Using Absorption Spectroscopy.

PubMed

Alcantara, Dominic Z; Soliman, Ian Jerry S; Pobre, Romeric F; Naguib, Raouf N G

2017-07-01

We present an analysis of the effects of pulsed electromagnetic fields (PEMF) with 3.3 MHz carrier frequency and modulated by audio resonant frequencies on the MCF-7 breast cancer cell line in vitro using absorption spectroscopy. This involves a fluorescence dye called PrestoBlue™ Cell Viability Reagent and a spectrophotometry to test the viability of MCF-7 breast cancer cells under different PEMF treatment conditions in terms of the cell absorption values. The DNA molecule of the MCF-7 breast cancer cells has an electric dipole property that renders it sensitive and reactive to applied electromagnetic fields. Resonant frequencies derived from four genes mutated in MCF-7 breast cancer cells [rapamycin-insensitive companion of mammalian target of rapamycin (RICTOR), peroxisome proliferator-activated receptor (PPARG), Nijmegen breakage syndrome 1 (NBN) and checkpoint kinase 2 (CHEK2)] were applied in generating square pulsed electromagnetic waves. Effects were monitored through measurement of absorption of the samples with PrestoBlue™, and the significance of the treatment was determined using the t-test. There was a significant effect on MCF-7 cells after treatment with PEMF at the resonant frequencies of the following genes for specific durations of exposure: RICTOR for 10 min, PPARG for 10 min, NBN for 15 min, and CHEK2 for 5 min. Copyright© 2017, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

Acceptor and Excitation Density Dependence of the Ultrafast Polaron Absorption Signal in Donor-Acceptor Organic Solar Cell Blends.

PubMed

Zarrabi, Nasim; Burn, Paul L; Meredith, Paul; Shaw, Paul E

2016-07-21

Transient absorption spectroscopy on organic semiconductor blends for solar cells typically shows efficient charge generation within ∼100 fs, accounting for the majority of the charge carriers. In this Letter, we show using transient absorption spectroscopy on blends containing a broad range of acceptor content (0.01-50% by weight) that the rise of the polaron signal is dependent on the acceptor concentration. For low acceptor content (<10% by weight), the polaron signal rises gradually over ∼1 ps with most polarons generated after 200 fs, while for higher acceptor concentrations (>10%) most polarons are generated within 200 fs. The rise time in blends with low acceptor content was also found to be sensitive to the pump fluence, decreasing with increasing excitation density. These results indicate that the sub-100 fs rise of the polaron signal is a natural consequence of both the high acceptor concentrations in many donor-acceptor blends and the high excitation densities needed for transient absorption spectroscopy, which results in a short average distance between the exciton and the donor-acceptor interface.

Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling

DOE PAGES

Riddle, Catherine; Czerwinski, Kenneth; Kim, Eunja; ...

2016-01-18

We studied the speciation of pentavalent and hexavalent americium (Am) complexes in nitric acidicby X-ray absorption fine structure spectroscopy (XAFS), UV-visible spectroscopy, and density functional theory (DFT). Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) results were consistent with the presence of a mixture of AmO 2 + and AmO 2 2+ with only a small amount AmO 2 present. The resulting average bond distances we found were 1.71 Å for Am=O and 2.44 Å for Am-O. All-electron scalar relativistic calculations were also carried out using DFT to predict the equilibrium geometries and properties ofmore » the AmO 2 + and AmO 2 2+ aquo complexes. Calculated bond distances for the Am(VI) complex are in reasonable agreement with EXAFS data and the computed energy gaps between frontier molecular orbitals suggest a slightly higher kinetic stability and chemical hardness of Am(VI) compared to Am(V).« less

Continuous Wave Ring-Down Spectroscopy for Velocity Distribution Measurements in Plasma

NASA Astrophysics Data System (ADS)

McCarren, Dustin W.

Cavity Ring-Down Spectroscopy CRDS is a proven, ultra-sensitive, cavity enhanced absorption spectroscopy technique. When combined with a continuous wavelength (CW) diode laser that has a sufficiently narrow line width, the Doppler broadened absorption line, i.e., the velocity distribution functions (VDFs) of the absorbing species, can be measured. Measurements of VDFs can be made using established techniques such as laser induced fluorescence (LIF). However, LIF suffers from the requirement that the initial state of the LIF sequence have a substantial density and that the excitation scheme fluoresces at an easily detectable wavelength. This usually limits LIF to ions and atoms with large metastable state densities for the given plasma conditions. CW-CRDS is considerably more sensitive than LIF and can potentially be applied to much lower density populations of ion and atom states. Also, as a direct absorption technique, CW-CRDS measurements only need to be concerned with the species' absorption wavelength and provide an absolute measure of the line integrated initial state density. Presented in this work are measurements of argon ion and neutral VDFs in a helicon plasma using CW-CRDS and LIF.

Near- and Extended-Edge X-Ray-Absorption Fine-Structure Spectroscopy Using Ultrafast Coherent High-Order Harmonic Supercontinua

NASA Astrophysics Data System (ADS)

Popmintchev, Dimitar; Galloway, Benjamin R.; Chen, Ming-Chang; Dollar, Franklin; Mancuso, Christopher A.; Hankla, Amelia; Miaja-Avila, Luis; O'Neil, Galen; Shaw, Justin M.; Fan, Guangyu; Ališauskas, Skirmantas; Andriukaitis, Giedrius; Balčiunas, Tadas; Mücke, Oliver D.; Pugzlys, Audrius; Baltuška, Andrius; Kapteyn, Henry C.; Popmintchev, Tenio; Murnane, Margaret M.

2018-03-01

Recent advances in high-order harmonic generation have made it possible to use a tabletop-scale setup to produce spatially and temporally coherent beams of light with bandwidth spanning 12 octaves, from the ultraviolet up to x-ray photon energies >1.6 keV . Here we demonstrate the use of this light for x-ray-absorption spectroscopy at the K - and L -absorption edges of solids at photon energies near 1 keV. We also report x-ray-absorption spectroscopy in the water window spectral region (284-543 eV) using a high flux high-order harmonic generation x-ray supercontinuum with 109 photons/s in 1% bandwidth, 3 orders of magnitude larger than has previously been possible using tabletop sources. Since this x-ray radiation emerges as a single attosecond-to-femtosecond pulse with peak brightness exceeding 1026 photons/s /mrad2/mm2/1 % bandwidth, these novel coherent x-ray sources are ideal for probing the fastest molecular and materials processes on femtosecond-to-attosecond time scales and picometer length scales.

Research on atmospheric CO2 remote sensing with open-path tunable diode laser absorption spectroscopy and comparison methods

NASA Astrophysics Data System (ADS)

Xin, Fengxin; Guo, Jinjia; Sun, Jiayun; Li, Jie; Zhao, Chaofang; Liu, Zhishen

2017-06-01

An open-path atmospheric CO2 measurement system was built based on tunable diode laser absorption spectroscopy (TDLAS). The CO2 absorption line near 2 μm was selected, measuring the atmospheric CO2 with direct absorption spectroscopy and carrying on the comparative experiment with multipoint measuring instruments of the open-path. The detection limit of the TDLAS system is 1.94×10-6. The calibration experiment of three AZ-7752 handheld CO2 measuring instruments was carried out with the Los Gatos Research gas analyzer. The consistency of the results was good, and the handheld instrument could be used in the TDLAS system after numerical calibration. With the contrast of three AZ-7752 and their averages, the correlation coefficients are 0.8828, 0.9004, 0.9079, and 0.9393 respectively, which shows that the open-path TDLAS has the best correlation with the average of three AZ-7752 and measures the concentration of atmospheric CO2 accurately. Multipoint measurement provides a convenient comparative method for open-path TDLAS.

Dynamic Optoelectronic Properties in Perovskite Oxide Thin Films Measured with Ultrafast Transient Absorption & Reflectance Spectroscopy

NASA Astrophysics Data System (ADS)

Smolin, Sergey Y.

Ultrafast transient absorption and reflectance spectroscopy are foundational techniques for studying photoexcited carrier recombination mechanisms, lifetimes, and charge transfer rates. Because quantifying photoexcited carrier dynamics is central to the intelligent design and improvement of many solid state devices, these transient optical techniques have been applied to a wide range of semiconductors. However, despite their promise, interpretation of transient absorption and reflectance data is not always straightforward and often relies on assumptions of physical processes, especially with respect to the influence of heating. Studying the material space of perovskite oxides, the careful collection, interpretation, and analysis of ultrafast data is presented here as a guide for future research into novel semiconductors. Perovskite oxides are a class of transition metal oxides with the chemical structure ABO3. Although traditionally studied for their diverse physical, electronic, and magnetic properties, perovskite oxides have gained recent research attention as novel candidates for light harvesting applications. Indeed, strong tunable absorption, unique interfacial properties, and vast chemical flexibility make perovskite oxides a promising photoactive material system. However, there is limited research characterizing dynamic optoelectronic properties, such as recombination lifetimes, which are critical to know in the design of any light-harvesting device. In this thesis, ultrafast transient absorption and reflectance spectroscopy was used to understand these dynamic optoelectronic properties in highquality, thin (<50 nm) perovskite oxide films grown by molecular beam epitaxy. Starting with epitaxial LaFeO3 (LFO) grown on (LaAlO 3)0.3(Sr2AlTaO6)0.7 (LSAT), transient absorption spectroscopy reveals two photoinduced absorption features at the band gap of LFO at 2.4 eV and at the higher energy absorption edge at 3.5 eV. Using a combination of temperature-dependent, variable-angle spectroscopic ellipsometry and time-resolved ultrafast optical spectroscopy on a type I heterostructure, we clarify thermal and electronic contributions to spectral transients in LaFeO3. Upon comparison to thermally-derived static spectra of LaFeO3, we find that thermal contributions dominate the transient absorption and reflectance spectra above the band gap. A transient photoinduced absorption feature below the band gap at 1.9 eV is not reproduced in the thermally derived spectra and has significantly longer decay kinetics from the thermallyinduced features; therefore, this long lived photoinduced absorption is likely derived, at least partially, from photoexcited carriers with lifetimes much longer than 3 nanoseconds. LaFeO3 has a wide band gap of 2.4 eV but its absorption can be decreased with chemical substitution of Sr for Fe to make it more suitable for various applications. This type of A-site substitution is a common route to change static optical absorption in perovskite oxides, but there are no systematic studies looking at how A-site substitution changes dynamic optoelectronic properties. To understand the relationship between composition and static and dynamic optical properties we worked with the model system of La1-xSrxFeO 3-delta epitaxial films grown on LSAT, uncovering the effects of A-site cation substitution and oxygen stoichiometry. Variable-angle spectroscopic ellipsometry was used to measure static optical properties, revealing a linear increase in absorption coefficient at 1.25 eV and a red-shifting of the optical absorption edge with increasing Sr fraction. The absorption spectra can be similarly tuned through the introduction of oxygen vacancies, indicating the critical role that nominal Fe valence plays in optical absorption. Dynamic optoelectronic properties were studied with ultrafast transient reflectance spectroscopy with broadband visible (1.6 eV to 4 eV) and near-infrared (0.9 eV to 1.5 eV) probes. The sign of the reflectance change in the near-infrared region in LSFO is indicative of carrier bandfilling of newly created electronic states by photoexcited carriers. Moreover, we find that similar transient spectral trends can be induced with A-site substitution or through oxygen vacancies, which is a surprising result. Probing the near-infrared region reveals similar nanosecond (1-3 ns) photoexcited carrier lifetimes for oxygen deficient and stoichiometric films. These results demonstrate that while the static optical absorption is strongly dependent on nominal Fe valence tuned through cation or anion stoichiometry, oxygen vacancies do not appear to play a significantly detrimental role in long lived recombination kinetics. Although this thesis represents one of the first comprehensive studies using broad band transient absorption and reflectance spectroscopy to study dynamic optoelectronic phenomena in perovskite oxides, it can also serve as a guide for the implementation and interpretation of ultrafast spectroscopy in other material systems. Moreover, the ultrafast work on perovskite oxides indicates that these materials have long nanosecond lifetimes required for light harvesting devices and should be investigated further.

New Developments of Broadband Cavity Enhanced Spectroscopic Techniques

NASA Astrophysics Data System (ADS)

Walsh, A.; Zhao, D.; Linnartz, H.; Ubachs, W.

2013-06-01

In recent years, cavity enhanced spectroscopic techniques, such as cavity ring-down spectroscopy (CRDS), cavity enhanced absorption spectroscopy (CEAS), and broadband cavity enhanced absorption spectroscopy (BBCEAS), have been widely employed as ultra-sensitive methods for the measurement of weak absorptions and in the real-time detection of trace species. In this contribution, we introduce two new cavity enhanced spectroscopic concepts: a) Optomechanical shutter modulated BBCEAS, a variant of BBCEAS capable of measuring optical absorption in pulsed systems with typically low duty cycles. In conventional BBCEAS applications, the latter substantially reduces the signal-to-noise ratio (S/N), consequently also reducing the detection sensitivity. To overcome this, we incorporate a fast optomechanical shutter as a time gate, modulating the detection scheme of BBCEAS and increasing the effective duty cycle reaches a value close to unity. This extends the applications of BBCEAS into pulsed samples and also in time-resolved studies. b) Cavity enhanced self-absorption spectroscopy (CESAS), a new spectroscopic concept capable of studying light emitting matter (plasma, flames, combustion samples) simultaneously in absorption and emission. In CESAS, a sample (plasma, flame or combustion source) is located in an optically stable cavity consisting of two high reflectivity mirrors, and here it acts both as light source and absorbing medium. A high detection sensitivity of weak absorption is reached without the need of an external light source, such as a laser or broadband lamp. The performance is illustrated by the first CESAS result on a supersonically expanding hydrocarbon plasma. We expect CESAS to become a generally applicable analytical tool for real time and in situ diagnostics. A. Walsh, D. Zhao, W. Ubachs, H. Linnartz, J. Phys. Chem. A, {dx.doi.org/10.1021/jp310392n}, in press, 2013. A. Walsh, D. Zhao, H. Linnartz Rev. Sci. Instrum. {84}(2), 021608 2013. A. Walsh, D. Zhao, H. Linnartz Appl. Phys. Lett. {101}(9), 091111 2012.

Arsenic and 17-β-estradiol bind to each other and neutralize each other’s signaling effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Sukhdeep; Mukherjee, Tapan K.; Guptasarma, Purnananda, E-mail: guptasarma@iisermohali.ac.in

We report that arsenic trioxide (ATO) and 17-beta-estradiol (E2) abolish each other’s independent cell signaling effects in respect of cell survival and proliferation/migration of breast cancer (MCF-7) cells. The possibility that this is due to binding of ATO to E2 was confirmed through difference absorption spectroscopy, chromatography-coupled voltammometry and 1-D {sup 1}H and {sup 13}C NMR spectroscopy. Binding leads to attenuation of E2’s hydroxyl {sup 1}H peaks at its C17 and C3 carbon positions. The results suggest that ATO and E2 can titrate each other’s levels, potentially explaining why sustained arsenic exposure tends to be associated with delays in agemore » of menarche, advanced age of menopause, poorer sperm quality, higher overall morbidity in men, and lower incidences of breast cancer in women in some arsenic-contaminated areas. - Highlights: • Difference absorption spectroscopy suggests that arsenic binds to estradiol. • Interaction with arsenic alters {sup 1}H and {sup 13}C NMR spectra of estradiol at positions C3 and C17. • Estradiol traps arsenic on C{sub 18} reverse-phase columns. • Estradiol and arsenic neutralize each other’s ability to stimulate scratch wound healing. • Arsenic appears to form pnictogen bonds with hydroxyls on estradiol.« less

Electronic structure of LiCoO2 thin films: A combined photoemission spectroscopy and density functional theory study

NASA Astrophysics Data System (ADS)

Ensling, David; Thissen, Andreas; Laubach, Stefan; Schmidt, Peter C.; Jaegermann, Wolfram

2010-11-01

The electronic properties of LiCoO2 have been studied by theoretical band-structure calculations (using density functional theory) and experimental methods (photoemission). Synchrotron-induced photoelectron spectroscopy, resonant photoemission spectroscopy (ResPES), and soft x-ray absorption (XAS) have been applied to investigate the electronic structure of both occupied and unoccupied states. High-quality PES spectra were obtained from stoichiometric and highly crystalline LiCoO2 thin films deposited “in situ” by rf magnetron sputtering. An experimental approach of separating oxygen- and cobalt-derived (final) states by ResPES in the valence-band region is presented. The procedure takes advantage of an antiresonant behavior of cobalt-derived states at the 3p-3d excitation threshold. Information about the unoccupied density of states has been obtained by OK XAS. The structure of the CoL absorption edge is compared to semiempirical charge-transfer multiplet calculations. The experimental results are furthermore compared with band-structure calculations considering three different exchange potentials [generalized gradient approximation (GGA), using a nonlocal Hubbard U (GGA+U) and using a hybrid functional (Becke, three-parameter, Lee-Yang-Parr [B3LYP])]. For these different approaches total density of states and partial valence-band density of states have been investigated. The best qualitative agreement with experimental results has been obtained by using a GGA+U functional with U=2.9eV .

Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering

NASA Astrophysics Data System (ADS)

Yang, Wanli; Devereaux, Thomas P.

2018-06-01

Recent advances in battery science and technology have triggered both the challenges and opportunities on studying the materials and interfaces in batteries. Here, we review the recent demonstrations of soft X-ray spectroscopy for studying the interfaces and electrode materials. The focus of this review is on the recently developed mapping of resonant inelastic X-ray scattering (mRIXS) as a powerful probe of battery chemistry with superior sensitivity. Six different channels of soft X-ray absorption spectroscopy (sXAS) are introduced for different experimental purposes. Although conventional sXAS channels remain effective tools for quantitative analysis of the transition-metal states and surface chemistry, we elaborate the limitations of sXAS in both cationic and anionic redox studies. Particularly, based on experimental findings in various electrodes, we show that sXAS is unreliable for studying oxygen redox. We then demonstrate the mRIXS as a reliable technique for fingerprinting oxygen redox and summarize several crucial observations. We conclude that mRIXS is the tool-of-choice to study both the practical issue on reversibility of oxygen redox and the fundamental nature of bulk oxygen states. We hope this review clarifies the popular misunderstanding on oxygen sXAS results of oxide electrodes, and establishes a reliable technique for detecting oxygen redox through mRIXS.

Monte Carlo analysis on probe performance for endoscopic diffuse optical spectroscopy of tubular organ

NASA Astrophysics Data System (ADS)

Zhang, Yunyao; Zhu, Jingping; Cui, Weiwen; Nie, Wei; Li, Jie; Xu, Zhenghong

2015-03-01

We investigated the performance of endoscopic diffuse optical spectroscopy probes with circular or linear fiber arrangements for tubular organ cancer detection. Probe performance was measured by penetration depth. A Monte Carlo model was employed to simulate light transport in the hollow cylinder that both emits and receives light from the inner boundary of the sample. The influence of fiber configurations and tissue optical properties on penetration depth was simulated. The results show that under the same condition, probes with circular fiber arrangement penetrate deeper than probes with linear fiber arrangement, and the difference between the two probes' penetration depth decreases with an increase in the 'distance between source and detector (SD)' and the radius of the probe. Other results show that the penetration depths and their differences both decrease with an increase in the absorption coefficient and the reduced scattering coefficient but remain constant with changes in the anisotropy factor. Moreover, the penetration depth was more affected by the absorption coefficient than the reduced scattering coefficient. It turns out that in NIR band, probes with linear fiber arrangements are more appropriate for diagnosing superficial cancers, whereas probes with circular fiber arrangements should be chosen for diagnosing adenocarcinoma. But in UV-VIS band, the two probe configurations exhibit nearly the same. These results are useful in guiding endoscopic diffuse optical spectroscopy-based diagnosis for esophageal, cervical, colorectal and other cancers.

Intracavity Laser Absorption Spectroscopy of Platinum Nitride in the Near Infrared

NASA Astrophysics Data System (ADS)

O'Brien, Leah C.; Womack, Kaitlin A.; O'Brien, James J.; Whittemore, Sean

2013-06-01

The (2,0) band of the A^{2}Σ^{-} - X^{2}Π_{1/2} electronic transition of PtN has been recorded using intracavity laser absorption spectroscopy. Transitions from ^{194}PtN, ^{195}PtN, and ^{196}PtN isotopologues are observed, as well as the nuclear hyperfine splitting due to ^{195}Pt with I=1/2. The results of the analysis will be presented and compared with ab initio calculations.

Birge-Sponer Estimation of the C-H Bond Dissociation Energy in Chloroform Using Infrared, Near-Infrared, and Visible Absorption Spectroscopy: An Experiment in Physical Chemistry

ERIC Educational Resources Information Center

Myrick, M. L.; Greer, A. E.; Nieuwland, A. A.; Priore, R. J.; Scaffidi, J.; Andreatta, Danielle; Colavita, Paula

2008-01-01

The fundamental and overtone vibrational absorption spectroscopy of the C-H unit in CHCl[subscript 3] is measured for transitions from the v = 0 energy level to v = 1 through v = 5 energy levels. The energies of the transitions exhibit a linearly-decreasing spacing between adjacent vibrational levels as the vibrational quantum number increases.…

Excitation energy dependence of excited states dynamics in all- trans-carotenes determined by femtosecond absorption and fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Kosumi, Daisuke; Yanagi, Kazuhiro; Nishio, Tomohiro; Hashimoto, Hideki; Yoshizawa, Masayuki

2005-06-01

Ultrafast relaxation kinetics in β-carotene and lycopene has been investigated by femtosecond absorption and fluorescence spectroscopies using tunable excitation pulses. The transient signals induced by the photoexcitation with larger excess energy have broader bands and longer lifetimes both in the 11Bu+and21Ag- excited states. The excess vibrational energy remains longer than several picoseconds and slows the relaxation kinetics in carotenoids.

Confocal depth-resolved fluorescence micro-X-ray absorption spectroscopy for the study of cultural heritage materials: a new mobile endstation at the Beijing Synchrotron Radiation Facility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Guang; Chu, Shengqi; Sun, Tianxi

A confocal fluorescence endstation for depth-resolved micro-X-ray absorption spectroscopy is described. A polycapillary half-lens defines the incident beam path and a second polycapillary half-lens at 90° defines the probe sample volume. An automatic alignment program based on an evolutionary algorithm is employed to make the alignment procedure efficient. This depth-resolved system was examined on a general X-ray absorption spectroscopy (XAS) beamline at the Beijing Synchrotron Radiation Facility. Sacrificial red glaze (AD 1368–1644) china was studied to show the capability of the instrument. As a mobile endstation to be applied on multiple beamlines, the confocal system can improve the function andmore » flexibility of general XAS beamlines, and extend their capabilities to a wider user community.« less

In Situ X-ray Absorption Near-Edge Structure Spectroscopy of ZnO Nanowire Growth During Chemical Bath Deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

McPeak, Kevin M.; Becker, Matthew A.; Britton, Nathan G.

2010-12-03

Chemical bath deposition (CBD) offers a simple and inexpensive route to deposit semiconductor nanostructures, but lack of fundamental understanding and control of the underlying chemistry has limited its versatility. Here we report the first use of in situ X-ray absorption spectroscopy during CBD, enabling detailed investigation of both reaction mechanisms and kinetics of ZnO nanowire growth from zinc nitrate and hexamethylenetetramine (HMTA) precursors. Time-resolved X-ray absorption near-edge structure (XANES) spectra were used to quantify Zn(II) speciation in both solution and solid phases. ZnO crystallizes directly from [Zn(H{sub 2}O){sub 6}]{sup 2+} without long-lived intermediates. Using ZnO nanowire deposition as an example,more » this study establishes in situ XANES spectroscopy as an excellent quantitative tool to understand CBD of nanomaterials.« less

Degradation of Beta-Cloth Covering for a Battery Orbital Replacement Unit in Low Earth Orbit

NASA Technical Reports Server (NTRS)

Gaier, James R.; Baldwin, Sammantha; Folz, Angela D.; Waters, Deborah L.; Loos, Alyssa

2016-01-01

Samples from the B-cloth cover for a battery orbit replaceable unit from the International Space Station were characterized using optical and electron microscopy, UV-vis-NIR spectrophotometry, and x-ray energy dispersive spectroscopy. Results showed that in areas where the fabric was exposed to solar radiation the absorptance increased by as much as 20 percent, and the peak difference was in the ultraviolet, indicating that the increased absorptance may have been due to radiation. The emissivity of the material over a temperature range of 300 - 700 K was essentially unchanged.

Degradation of Beta Cloth Covering for a Battery Orbital Replacement Unit in Low Earth Orbit

NASA Technical Reports Server (NTRS)

Gaier, James R.; Waters, Deborah L.; Baldwin, Sammantha; Folz, Angela D.; Loos, Alyssa

2016-01-01

Samples from the beta cloth cover for a battery orbit replaceable unit from the International Space Station (ISS) were characterized using optical and electron microscopy, UV-vis-NIR spectrophotometry, and x-ray energy dispersive spectroscopy. Results showed that in areas where the fabric was exposed to solar radiation the absorptance increased by as much as 20 percent, and the peak difference was in the ultraviolet, indicating that the increased absorptance may have been due to radiation. The emissivity of the material over a temperature range of 300 to 700 K was essentially unchanged.

Monitoring Temperature in High Enthalpy Arc-heated Plasma Flows using Tunable Diode Laser Absorption Spectroscopy

NASA Technical Reports Server (NTRS)

Martin, Marcel Nations; Chang, Leyen S.; Jeffries, Jay B.; Hanson, Ronald K.; Nawaz, Anuscheh; Taunk, Jaswinder S.; Driver, David M.; Raiche, George

2013-01-01

A tunable diode laser sensor was designed for in situ monitoring of temperature in the arc heater of the NASA Ames IHF arcjet facility (60 MW). An external cavity diode laser was used to generate light at 777.2 nm and laser absorption used to monitor the population of electronically excited oxygen atoms in an air plasma flow. Under the assumption of thermochemical equilibrium, time-resolved temperature measurements were obtained on four lines-of-sight, which enabled evaluation of the temperature uniformity in the plasma column for different arcjet operating conditions.

Gas trace detection with cavity enhanced absorption spectroscopy: a review of its process in the field

NASA Astrophysics Data System (ADS)

Liu, Siqi; Luo, Zhifu; Tan, Zhongqi; Long, Xingwu

2016-11-01

Cavity-enhanced absorption spectroscopy (CEAS) is a technology in which the intracavity absorption is deduced from the intensity of light transmitted by the high finesse optical cavity. Then the samples' parameters, such as their species, concentration and absorption cross section, would be detection. It was first proposed and demonstrated by Engeln R. [1] and O'Keefe[2] in 1998. This technology has extraordinary detection sensitivity, high resolution and good practicability, so it is used in many fields , such as clinical medicine, gas detection and basic physics research. In this paper, we focus on the use of gas trace detection, including the advance of CEAS over the past twenty years, the newest research progresses, and the prediction of this technology's development direction in the future.

The visible absorption spectrum of NO3 measured by high-resolution Fourier transform spectroscopy

NASA Astrophysics Data System (ADS)

Orphal, J.; Fellows, C. E.; Flaud, P.-M.

2003-02-01

The visible absorption spectrum of the nitrate radical NO3 has been measured using high-resolution Fourier transform spectroscopy. The spectrum was recorded at 294 K using a resolution of 0.6 cm-1 (corresponding to 0.026 nm at 662 nm) and covers the 12600-21500 cm-1 region (465-794 nm). Compared to absorption spectra of NO3 recorded previously, the new data show improvements concerning absolute wavelength calibration (uncertainty 0.02 cm-1), and spectral resolution. A new interpretation and model of the temperature dependence of the strong (0-0) band around 662 nm are proposed. The results are important for long-path tropospheric absorption measurements of NO3 and optical remote sensing of the Earth's atmosphere from space.

Use of X-Ray Absorption Spectroscopy (XAS) to Speciate Manganese in Airborne Particulate Matter from 5 Counties Across the US

PubMed Central

Datta, Saugata; Rule, Ana M; Mihalic, Jana N; Chillrud, Steve N; Bostick, Benjamin C.; Ramos-Bonilla, Juan P; Han, Inkyu; Polyak, Lisa M; Geyh, Alison S; Breysse, Patrick N

2012-01-01

The purpose of this study is to characterize manganese oxidation states and speciation in airborne particulate matter (PM), and describe how these potentially important determinants of PM toxicity vary by location. Ambient PM samples were collected from five counties across the US using a high volume sequential cyclone system that collects PM in dry bulk form segregated into “coarse” and “fine” size fractions. The fine fraction was analyzed for this study. Analyses included total Mn using ICP-MS, and characterization of oxidation states and speciation using X-ray Absorption Spectroscopy (XAS). XAS spectra of all samples and ten standard compounds of Mn were obtained at the National Synchrotron Light Source. XAS data was analyzed using Linear Combination Fitting (LCF). Results of the LCF analysis describe differences in composition between samples. Mn(II) acetate and Mn(II) oxide are present in all samples, while Mn(II) carbonate and Mn(IV) oxide are absent. To the best of our knowledge, this is the first paper to characterize Mn composition of ambient PM and examine differences between urban sites in the US. Differences in oxidation state and composition indicate regional variations in sources and atmospheric chemistry that may help explain differences in health effects identified in epidemiological studies. PMID:22309075

Practical Problems in the Cement Industry Solved by Modern Research Techniques

ERIC Educational Resources Information Center

Daugherty, Kenneth E.; Robertson, Les D.

1972-01-01

Practical chemical problems in the cement industry are being solved by such techniques as infrared spectroscopy, gas chromatography-mass spectrometry, X-ray diffraction, atomic absorption and arc spectroscopy, thermally evolved gas analysis, Mossbauer spectroscopy, transmission and scanning electron microscopy. (CP)

Breath Analysis Using Laser Spectroscopic Techniques: Breath Biomarkers, Spectral Fingerprints, and Detection Limits

PubMed Central

Wang, Chuji; Sahay, Peeyush

2009-01-01

Breath analysis, a promising new field of medicine and medical instrumentation, potentially offers noninvasive, real-time, and point-of-care (POC) disease diagnostics and metabolic status monitoring. Numerous breath biomarkers have been detected and quantified so far by using the GC-MS technique. Recent advances in laser spectroscopic techniques and laser sources have driven breath analysis to new heights, moving from laboratory research to commercial reality. Laser spectroscopic detection techniques not only have high-sensitivity and high-selectivity, as equivalently offered by the MS-based techniques, but also have the advantageous features of near real-time response, low instrument costs, and POC function. Of the approximately 35 established breath biomarkers, such as acetone, ammonia, carbon dioxide, ethane, methane, and nitric oxide, 14 species in exhaled human breath have been analyzed by high-sensitivity laser spectroscopic techniques, namely, tunable diode laser absorption spectroscopy (TDLAS), cavity ringdown spectroscopy (CRDS), integrated cavity output spectroscopy (ICOS), cavity enhanced absorption spectroscopy (CEAS), cavity leak-out spectroscopy (CALOS), photoacoustic spectroscopy (PAS), quartz-enhanced photoacoustic spectroscopy (QEPAS), and optical frequency comb cavity-enhanced absorption spectroscopy (OFC-CEAS). Spectral fingerprints of the measured biomarkers span from the UV to the mid-IR spectral regions and the detection limits achieved by the laser techniques range from parts per million to parts per billion levels. Sensors using the laser spectroscopic techniques for a few breath biomarkers, e.g., carbon dioxide, nitric oxide, etc. are commercially available. This review presents an update on the latest developments in laser-based breath analysis. PMID:22408503

Applications of synchrotron-based spectroscopic techniques in studying nucleic acids and nucleic acid-functionalized nanomaterials

PubMed Central

Wu, Peiwen; Yu, Yang; McGhee, Claire E.; Tan, Li Huey

2014-01-01

In this review, we summarize recent progresses in the application of synchrotron-based spectroscopic techniques for nucleic acid research that takes advantage of high-flux and high-brilliance electromagnetic radiation from synchrotron sources. The first section of the review focuses on the characterization of the structure and folding processes of nucleic acids using different types of synchrotron-based spectroscopies, such as X-ray absorption spectroscopy, X-ray emission spectroscopy, X-ray photoelectron spectroscopy, synchrotron radiation circular dichroism, X-ray footprinting and small-angle X-ray scattering. In the second section, the characterization of nucleic acid-based nanostructures, nucleic acid-functionalized nanomaterials and nucleic acid-lipid interactions using these spectroscopic techniques is summarized. Insights gained from these studies are described and future directions of this field are also discussed. PMID:25205057

Applications of synchrotron-based spectroscopic techniques in studying nucleic acids and nucleic acid-functionalized nanomaterials

DOE PAGES

Wu, Peiwen; Yu, Yang; McGhee, Claire E.; ...

2014-09-10

In this paper, we summarize recent progress in the application of synchrotron-based spectroscopic techniques for nucleic acid research that takes advantage of high-flux and high-brilliance electromagnetic radiation from synchrotron sources. The first section of the review focuses on the characterization of the structure and folding processes of nucleic acids using different types of synchrotron-based spectroscopies, such as X-ray absorption spectroscopy, X-ray emission spectroscopy, X-ray photoelectron spectroscopy, synchrotron radiation circular dichroism, X-ray footprinting and small-angle X-ray scattering. In the second section, the characterization of nucleic acid-based nanostructures, nucleic acid-functionalized nanomaterials and nucleic acid-lipid interactions using these spectroscopic techniques is summarized. Insightsmore » gained from these studies are described and future directions of this field are also discussed.« less

Tissue phantom-based breast cancer detection using continuous near-infrared sensor

PubMed Central

Liu, Dan; Liu, Xin; Zhang, Yan; Wang, Qisong; Lu, Jingyang

2016-01-01

ABSTRACT Women's health is seriously threatened by breast cancer. Taking advantage of efficient diagnostic instruments to identify the disease is very meaningful in prolonging life. As a cheap noninvasive radiation-free technology, Near-infrared Spectroscopy is suitable for general breast cancer examination. A discrimination method of breast cancer is presented using the deference between absorption coefficients and applied to construct a blood oxygen detection device based on Modified Lambert-Beer theory. Combined with multi-wavelength multi-path near-infrared sensing technology, the proposed method can quantitatively distinguish the normal breast from the abnormal one by measuring the absorption coefficients of breast tissue and the blood oxygen saturation. An objective judgment about the breast tumor is made according to its high absorption of near-infrared light. The phantom experiment is implemented to show the presented method is able to recognize the absorption differences between phantoms and demonstrates its feasibility in the breast tumor detection. PMID:27459672

Tissue phantom-based breast cancer detection using continuous near-infrared sensor.

PubMed

Liu, Dan; Liu, Xin; Zhang, Yan; Wang, Qisong; Lu, Jingyang

2016-09-02

Women's health is seriously threatened by breast cancer. Taking advantage of efficient diagnostic instruments to identify the disease is very meaningful in prolonging life. As a cheap noninvasive radiation-free technology, Near-infrared Spectroscopy is suitable for general breast cancer examination. A discrimination method of breast cancer is presented using the deference between absorption coefficients and applied to construct a blood oxygen detection device based on Modified Lambert-Beer theory. Combined with multi-wavelength multi-path near-infrared sensing technology, the proposed method can quantitatively distinguish the normal breast from the abnormal one by measuring the absorption coefficients of breast tissue and the blood oxygen saturation. An objective judgment about the breast tumor is made according to its high absorption of near-infrared light. The phantom experiment is implemented to show the presented method is able to recognize the absorption differences between phantoms and demonstrates its feasibility in the breast tumor detection.

Optical studies of native defects in π-conjugated donor-acceptor copolymers

NASA Astrophysics Data System (ADS)

Baniya, Sangita; Khanal, Dipak; Lafalce, Evan; You, Wei; Valy Vardeny, Z.

2018-04-01

We used multiple spectroscopies such as photoinduced absorption (PIA), magneto photoinduced absorption, and doping induced absorption for studying native defects in π-conjugated donor-acceptor copolymer chains of benzodithio-phene fluorinated benzotriazole. The PIA spectrum contains characteristic photoinduced absorption bands that are due to polarons and triplet exciton species, whose strengths have different dependencies on the modulation frequency, temperature, and laser excitation, as well as magnetic field response. We found that the native defects in the copolymer chains serve as efficient traps that ionize the photoexcited excitons, thereby generating charge carriers whose characteristic optical properties are similar, but not equal to those of intrachain polarons formed by doping. The native defects density is of the order of 1017 cm-3 indicating that most of the copolymer chains contain native defects upon synthesis; however, this does not preclude their used-for photovoltaic applications.

Accurate predictions of iron redox state in silicate glasses: A multivariate approach using X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dyar, M. Darby; McCanta, Molly; Breves, Elly

2016-03-01

Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yield accurate resultsmore » from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 × 1 μm pixel sizes.« less

Accurate predictions of iron redox state in silicate glasses: A multivariate approach using X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dyar, M. Darby; McCanta, Molly; Breves, Elly

2016-03-01

Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe 3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe 3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yieldmore » accurate results from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 × 1 μm pixel sizes.« less

Underresolved absorption spectroscopy of OH radicals in flames using broadband UV LEDs

NASA Astrophysics Data System (ADS)

White, Logan; Gamba, Mirko

2018-04-01

A broadband absorption spectroscopy diagnostic based on underresolution of the spectral absorption lines is evaluated for the inference of species mole fraction and temperature in combustion systems from spectral fitting. The approach uses spectrally broadband UV light emitting diodes and leverages low resolution, small form factor spectrometers. Through this combination, the method can be used to develop high precision measurement sensors. The challenges of underresolved spectroscopy are explored and addressed using spectral derivative fitting, which is found to generate measurements with high precision and accuracy. The diagnostic is demonstrated with experimental measurements of gas temperature and OH mole fraction in atmospheric air/methane premixed laminar flat flames. Measurements exhibit high precision, good agreement with 1-D flame simulations, and high repeatability. A newly developed model of uncertainty in underresolved spectroscopy is applied to estimate two-dimensional confidence regions for the measurements. The results of the uncertainty analysis indicate that the errors in the outputs of the spectral fitting procedure are correlated. The implications of the correlation between uncertainties for measurement interpretation are discussed.

Temperature dependence of the hydrated electron's excited-state relaxation. II. Elucidating the relaxation mechanism through ultrafast transient absorption and stimulated emission spectroscopy

NASA Astrophysics Data System (ADS)

Farr, Erik P.; Zho, Chen-Chen; Challa, Jagannadha R.; Schwartz, Benjamin J.

2017-08-01

The structure of the hydrated electron, particularly whether it exists primarily within a cavity or encompasses interior water molecules, has been the subject of much recent debate. In Paper I [C.-C. Zho et al., J. Chem. Phys. 147, 074503 (2017)], we found that mixed quantum/classical simulations with cavity and non-cavity pseudopotentials gave different predictions for the temperature dependence of the rate of the photoexcited hydrated electron's relaxation back to the ground state. In this paper, we measure the ultrafast transient absorption spectroscopy of the photoexcited hydrated electron as a function of temperature to confront the predictions of our simulations. The ultrafast spectroscopy clearly shows faster relaxation dynamics at higher temperatures. In particular, the transient absorption data show a clear excess bleach beyond that of the equilibrium hydrated electron's ground-state absorption that can only be explained by stimulated emission. This stimulated emission component, which is consistent with the experimentally known fluorescence spectrum of the hydrated electron, decreases in both amplitude and lifetime as the temperature is increased. We use a kinetic model to globally fit the temperature-dependent transient absorption data at multiple temperatures ranging from 0 to 45 °C. We find the room-temperature lifetime of the excited-state hydrated electron to be 137 ±40 fs, in close agreement with recent time-resolved photoelectron spectroscopy (TRPES) experiments and in strong support of the "non-adiabatic" picture of the hydrated electron's excited-state relaxation. Moreover, we find that the excited-state lifetime is strongly temperature dependent, changing by slightly more than a factor of two over the 45 °C temperature range explored. This temperature dependence of the lifetime, along with a faster rate of ground-state cooling with increasing bulk temperature, should be directly observable by future TRPES experiments. Our data also suggest that the red side of the hydrated electron's fluorescence spectrum should significantly decrease with increasing temperature. Overall, our results are not consistent with the nearly complete lack of temperature dependence predicted by traditional cavity models of the hydrated electron but instead agree qualitatively and nearly quantitatively with the temperature-dependent structural changes predicted by the non-cavity hydrated electron model.

X-ray scattering and spectroscopy studies on diesel soot from oxygenated fuel under various engine load conditions

USGS Publications Warehouse

Braun, Andreas; Shah, N.; Huggins, Frank E.; Kelly, K.E.; Sarofim, A.; Jacobsen, C.; Wirick, S.; Francis, H.; Ilavsky, J.; Thomas, G.E.; Huffman, G.P.

2005-01-01

Diesel soot from reference diesel fuel and oxygenated fuel under idle and load engine conditions was investigated with X-ray scattering and X-ray carbon K-edge absorption spectroscopy. Up to five characteristic size ranges were found. Idle soot was generally found to have larger primary particles and aggregates but smaller crystallites, than load soot. Load soot has a higher degree of crystallinity than idle soot. Adding oxygenates to diesel fuel enhanced differences in the characteristics of diesel soot, or even reversed them. Aromaticity of idle soot from oxygenated diesel fuel was significantly larger than from the corresponding load soot. Carbon near-edge X-ray absorption fine structure (NEXAFS) spectroscopy was applied to gather information about the presence of relative amounts of carbon double bonds (CC, CO) and carbon single bonds (C-H, C-OH, COOH). Using scanning X-ray transmission microspectroscopy (STXM), the relative amounts of these carbon bond states were shown to vary spatially over distances approximately 50 to 100 nm. The results from the X-ray techniques are supported by thermo-gravimetry analysis and high-resolution transmission electron microscopy. ?? 2005 Elsevier Ltd. All rights reserved.

Green synthesis of Pt and Ag nanoparticles and their use towards nitric oxide abatement

NASA Astrophysics Data System (ADS)

Castegnaro, Marcus V.; Alexandre, Jéssica; Baibich, Ione M.; Alves, Maria C. M.; Morais, Jonder

2014-12-01

Pt and Ag nanoparticles (NPs) were synthesized by eco-friendly room-temperature chemical reduction routes based on trisodium citrate and L-ascorbic acid (for Pt NPs) and on gelatin and trisodium citrate (for Ag NPs). The as-prepared NPs were characterized by UV-visible absorption spectroscopy and transmission electron microscopy analyses, which confirmed the formation of sub-10 nm metal particles. Then, the colloidal solutions were used to obtain activated carbon-supported catalysts (metal/AC) for direct NO decomposition. X-ray photoelectron spectroscopy and x-ray diffraction measurements proved that the NPs hosted on the support surface were present in the metallic chemical state. In situ infrared absorption spectroscopy investigations during NO reduction catalytic reactions showed that the Pt/AC and Ag/AC catalysts were highly active at 373 K. At 573 K, we observed different behaviors for each catalyst. While Ag/AC performed similarly to the reaction at 373 K, Pt/AC was found to participate in a redox mechanism, where the catalyst’s active sites were oxidized by NO and reduced by carbon, thus emitting CO2 and enhancing its catalytic activity, an effect that we have also observed in carbon-supported Pd NPs.

Thin layered drawing media probed by THz time-domain spectroscopy.

PubMed

Tasseva, J; Taschin, A; Bartolini, P; Striova, J; Fontana, R; Torre, R

2016-12-19

Dry and wet drawing materials were investigated by THz time-domain spectroscopy in transmission mode. Carbon-based and iron-gall inks have been studied, some prepared following ancient recipes and others using current synthetic materials; a commercial ink was studied as well. We measured the THz signals on the thin films of liquid inks deposited on polyethylene pellicles, comparing the results with the thick pellets of dried inks blended with polyethylene powder. This study required the implementation of an accurate experimental method and data analysis procedure able to provide a reliable extraction of the material transmission parameters from a structured sample composed of thin layers, down to a thickness of a few tens of micrometers. THz measurements on thin ink layers enabled the determination of both the absorption and the refractive index in an absolute scale in the 0.1-3 THz range, as well as the layer thickness. THz spectroscopic features of a paper sheet dyed by using one of the iron-gall inks were also investigated. Our results showed that THz time-domain spectroscopy enables the discrimination of various inks on different supports, including the application on paper, together with the proper determination of the absorption coefficients and indices of refraction.

Potential of far-ultraviolet absorption spectroscopy as a highly sensitive qualitative and quantitative analysis method for polymer films, part I: classification of commercial food wrap films.

PubMed

Sato, Harumi; Higashi, Noboru; Ikehata, Akifumi; Koide, Noriko; Ozaki, Yukihiro

2007-07-01

The aim of the present study is to propose a totally new technique for the utilization of far-ultraviolet (UV) spectroscopy in polymer thin film analysis. Far-UV spectra in the 120-300 nm region have been measured in situ for six kinds of commercial polymer wrap films by use of a novel type of far-UV spectrometer that does not need vacuum evaporation. These films can be straightforwardly classified into three groups, polyethylene (PE) films, polyvinyl chloride (PVC) films, and polyvinylidene chloride (PVDC) films, by using the raw spectra. The differences in the wavelength of the absorption band due to the sigma-sigma* transition of the C-C bond have been used for the classification of the six kinds of films. Using this method, it was easy to distinguish the three kinds of PE films and to separate the two kinds of PVDC films. Compared with other spectroscopic methods, the advantages of this technique include nondestructive analysis, easy spectral measurement, high sensitivity, and simple spectral analysis. The present study has demonstrated that far-UV spectroscopy is a very promising technique for polymer film analysis.

Two-Photon Absorption Spectroscopy of Rubidium with a Dual-Comb Tequnique

NASA Astrophysics Data System (ADS)

Nishiyama, Akiko; Yoshida, Satoru; Hariki, Takuya; Nakajima, Yoshiaki; Minoshima, Kaoru

2017-06-01

Dual-comb spectroscopies have great potential for high-resolution molecular and atomic spectroscopies, thanks to the broadband comb spectrum consisting of dense narrow modes. In this study, we apply the dual-comb system to Doppler-free two-photon absorption spectroscopy. The outputs of two frequency combs excite several two-photon transitions of rubidium, and we obtained broadband Doppler-free spectra from dual-comb fluorescence signals. The fluorescence detection scheme circumvents the sensitivity limit which is effectively determined by the dynamic range of photodetectors in absorption-based dual-comb spectroscopies. Our system realized high-sensitive, Doppler-free high-resolution and broadband atomic spectroscopy. A part of observed spectra of 5S_{1/2} - 5D_{5/2} transition is shown in the figure. The hyperfine structures of the F" = 1 - F' = 3,2,1 transitions are fully-resolved and the spectral widths are approximately 5 MHz. The absolute frequency axis is precisely calibrated from comb mode frequencies which were stabilized to a GPS-disciplined clock. This work was supported by JST through the ERATO MINOSHIMA Intelligent Optical Synthesizer Project and Grant-in-Aid for JSPS Fellows (16J02345). A. Nishiyama, S. Yoshida, Y. Nakajima, H. Sasada, K. Nakagawa, A. Onae, K. and Minoshima, Opt. Express 24, 25894 (2016). A. Hipke, S. A. Meek, T. Ideguchi, T.W. Hänsch, and N. Picqué, Phys. Rev. A 90, 011805(R) (2014).

Single-ended retroreflection sensors for absorption spectroscopy in high-temperature environments

NASA Astrophysics Data System (ADS)

Melin, Scott T.; Wang, Ze; Neal, Nicholas J.; Rothamer, David A.; Sanders, Scott T.

2017-04-01

Novel single-ended sensor arrangements are demonstrated for in situ absorption spectroscopy in combustion and related test articles. A single-ended optical access technique based on back-reflection from a polished test article surface is presented. H2O vapor absorption spectra were measured at 10 kHz in a homogeneous-charge compression-ignition engine using a sensor of this design collecting back-reflection from a polished piston surface. The measured spectra show promise for high-repetition-rate measurements in practical combustion devices. A second sensor was demonstrated based on a modification to this optical access technique. The sensor incorporates a nickel retroreflective surface as back-reflector to reduce sensitivity to beam steering and misalignment. In a propane-fired furnace, H2O vapor absorption spectra were obtained over the range 7315-7550 cm- 1 at atmospheric pressure and temperatures up to 775 K at 20 Hz using an external-cavity diode laser spectrometer. Gas properties of temperature and mole fraction were obtained from this furnace data using a band-shape spectral fitting technique. The temperature accuracy of the band-shape fitting was demonstrated to be ±1.3 K for furnace measurements at atmospheric pressure. These results should extend the range of applications in which absorption spectroscopy sensors are attractive candidates.

Study of the laser-induced decomposition of energetic materials at static high-pressure by time-resolved absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hebert, Philippe; Saint-Amans, Charles

2013-06-01

A detailed description of the reaction rates and mechanisms occurring in shock-induced decomposition of condensed explosives is very important to improve the predictive capabilities of shock-to-detonation transition models. However, direct measurements of such experimental data are difficult to perform during detonation experiments. By coupling pulsed laser ignition of an explosive in a diamond anvil cell (DAC) with time-resolved streak camera recording of transmitted light, it is possible to make direct observations of deflagration phenomena at detonation pressure. We have developed an experimental set-up that allows combustion front propagation rates and time-resolved absorption spectroscopy measurements. The decomposition reactions are initiated using a nanosecond YAG laser and their kinetics is followed by time-resolved absorption spectroscopy. The results obtained for two explosives, nitromethane (NM) and HMX are presented in this paper. For NM, a change in reactivity is clearly seen around 25 GPa. Below this pressure, the reaction products are essentially carbon residues whereas at higher pressure, a transient absorption feature is first observed and is followed by the formation of a white amorphous product. For HMX, the evolution of the absorption as a function of time indicates a multi-step reaction mechanism which is found to depend on both the initial pressure and the laser fluence.

Photoacoustic spectroscopy of condensed matter

NASA Technical Reports Server (NTRS)

Somoano, R. B.

1978-01-01

Photoacoustic spectroscopy is a new analytical tool that provides a simple nondestructive technique for obtaining information about the electronic absorption spectrum of samples such as powders, semisolids, gels, and liquids. It can also be applied to samples which cannot be examined by conventional optical methods. Numerous applications of this technique in the field of inorganic and organic semiconductors, biology, and catalysis have been described. Among the advantages of photoacoustic spectroscopy, the signal is almost insensitive to light scattering by the sample and information can be obtained about nonradiative deactivation processes. Signal saturation, which can modify the intensity of individual absorption bands in special cases, is a drawback of the method.

[Acoustic detection of absorption of millimeter-band electromagnetic waves in biological objects].

PubMed

Polnikov, I G; Putvinskiĭ, A V

1988-01-01

Principles of photoacoustic spectroscopy were applied to elaborate a new method for controlling millimeter electromagnetic waves absorption in biological objects. The method was used in investigations of frequency dependence of millimeter wave power absorption in vitro and in vivo in the commonly used experimental irradiation systems.

Direct and Quantitative Photothermal Absorption Spectroscopy of Individual Particulates

DTIC Science & Technology

2013-01-01

1(a). By taking the ratio of the spectral absorption efficiency of the microwire to the corresponding volumetri - cally equivalent thin film, an...of D¼ 983 nm. For further comparison, the theoretical spectral absorption efficiency for a volumetri - cally equivalent (t¼ 983p/4 nm) thin film, Qabs

Arsenic speciation in solids using X-ray absorption spectroscopy

USGS Publications Warehouse

Foster, Andrea L.; Kim, Chris S.

2014-01-01

One of the most important aims of this review is to clarify the different types of analysis that are performed on As-XAS spectra, and to describe the benefits, drawbacks, and limitations of each. Arsenic XAS spectra are analyzed to obtain one or more of the following types of information (in increasing order of sophistication):

40 CFR Appendix D to Part 136 - Precision and Recovery Statements for Methods for Measuring Metals

Code of Federal Regulations, 2010 CFR

2010-07-01

... Spectroscopy (Direction Aspiration) and Colorimetry”, National Technical Information Service, 5285 Port Royal... Spectroscopy (Direct Aspiration) and Colorimetry”, National Technical Information Service, 5285 Port Royal Road... Absorption Spectroscopy (Direct Aspiration) and Colorimetry”, National Technical Information Service, 5285...

Laser techniques for spectroscopy of core-excited atomic levels

NASA Technical Reports Server (NTRS)

Harris, S. E.; Young, J. F.; Falcone, R. W.; Rothenberg, J. E.; Willison, J. R.

1982-01-01

We discuss three techniques which allow the use of tunable lasers for high resolution and picosecond time scale spectroscopy of core-excited atomic levels. These are: anti-Stokes absorption spectroscopy, laser induced emission from metastable levels, and laser designation of selected core-excited levels.

Facile and fast synthesis of SnS2 nanoparticles by pulsed laser ablation in liquid

NASA Astrophysics Data System (ADS)

Johny, J.; Sepulveda-Guzman, S.; Krishnan, B.; Avellaneda, D.; Shaji, S.

2018-03-01

Nanoparticles (NPs) of tin disulfide (SnS2) were synthesized using pulsed laser ablation in liquid (PLAL) technique. Effects of different liquid media and ablation wavelengths on the morphology and optical properties of the nanoparticles were studied. Nd: YAG laser wavelengths of 532 nm and 1064 nm (frequency 10 Hz and pulse width 10 ns) were used to irradiate SnS2 target immersed in liquid for the synthesis of SnS2 nanoparticles. Here PLAL was a fast synthesis technique, the ablation was only for 30 s. Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, UV-vis absorption spectroscopy and photoluminescence spectroscopy were used to characterize the SnS2 NPs. TEM images showed that the liquid medium and laser wavelength influence the morphology of the NPs. SAED patterns and high resolution TEM (HRTEM) images confirmed the crystallinity of the particles. XRD and XPS analyses confirmed that SnS2 NPs were having exact crystalline structure and chemical states as that of the target. Raman analysis also supported the results obtained by XRD and XPS. Optical band gaps of the nanocolloids evaluated from their UV-vis absorption spectra were 2.4-3.05 eV. SnS2 NPs were having luminescence spectra in the blue-green region irrespective of the liquid media and ablation wavelength.

Time- and Space-Resolved Spectroscopic Investigation on Pi-Conjugated Nanostructures - 2

DTIC Science & Technology

2016-01-12

15. SUBJECT TERMS Materials Characterization, Materials Chemistry, Nonlinear Optical Materials, Spectroscopy 16. SECURITY CLASSIFICATION...nanostructures will translate into new ground-breaking developments that not only allow the structure-property relationships to be probed in greater detail... spectroscopy . I. Experimental method 1. Steady-state Spectroscopy - UV-Vis-NIR Absorption & Emission Steady-state Spectroscopy - NIR

Substitution effects on the absorption spectra of nitrophenolate isomers.

PubMed

Wanko, Marius; Houmøller, Jørgen; Støchkel, Kristian; Suhr Kirketerp, Maj-Britt; Petersen, Michael Åxman; Nielsen, Mogens Brøndsted; Nielsen, Steen Brøndsted; Rubio, Angel

2012-10-05

Charge-transfer excitations highly depend on the electronic coupling between the donor and acceptor groups. Nitrophenolates are simple examples of charge-transfer systems where the degree of coupling differs between ortho, meta and para isomers. Here we report the absorption spectra of the isolated anions in vacuo to avoid the complications of solvent effects. Gas-phase action spectroscopy was done with two different setups, an electrostatic ion storage ring and an accelerator mass spectrometer. The results are interpreted on the basis of CC2 quantum chemical calculations. We identified absorption maxima at 393, 532, and 399 nm for the para, meta, and ortho isomer, respectively, with the charge-transfer transition into the lowest excited singlet state. In the meta isomer, this π-π* transition is strongly redshifted and its oscillator strength reduced, which is related to the pronounced charge-transfer character, as a consequence of the topology of the conjugated π-system. Each isomer's different charge distribution in the ground state leads to a very different solvent shift, which in acetonitrile is bathochromic for the para and ortho, but hypsochromic for the meta isomer.

Improving the accuracy of S02 column densities and emission rates obtained from upward-looking UV-spectroscopic measurements of volcanic plumes by taking realistic radiative transfer into account

USGS Publications Warehouse

Kern, Christoph; Deutschmann, Tim; Werner, Cynthia; Sutton, A. Jeff; Elias, Tamar; Kelly, Peter J.

2012-01-01

Sulfur dioxide (SO2) is monitored using ultraviolet (UV) absorption spectroscopy at numerous volcanoes around the world due to its importance as a measure of volcanic activity and a tracer for other gaseous species. Recent studies have shown that failure to take realistic radiative transfer into account during the spectral retrieval of the collected data often leads to large errors in the calculated emission rates. Here, the framework for a new evaluation method which couples a radiative transfer model to the spectral retrieval is described. In it, absorption spectra are simulated, and atmospheric parameters are iteratively updated in the model until a best match to the measurement data is achieved. The evaluation algorithm is applied to two example Differential Optical Absorption Spectroscopy (DOAS) measurements conducted at Kilauea volcano (Hawaii). The resulting emission rates were 20 and 90% higher than those obtained with a conventional DOAS retrieval performed between 305 and 315 nm, respectively, depending on the different SO2 and aerosol loads present in the volcanic plume. The internal consistency of the method was validated by measuring and modeling SO2 absorption features in a separate wavelength region around 375 nm and comparing the results. Although additional information about the measurement geometry and atmospheric conditions is needed in addition to the acquired spectral data, this method for the first time provides a means of taking realistic three-dimensional radiative transfer into account when analyzing UV-spectral absorption measurements of volcanic SO2 plumes.

Design and implementation of a laser-based absorption spectroscopy sensor for in situ monitoring of biomass gasification

NASA Astrophysics Data System (ADS)

Viveros Salazar, David; Goldenstein, Christopher S.; Jeffries, Jay B.; Seiser, Reinhard; Cattolica, Robert J.; Hanson, Ronald K.

2017-12-01

Research to demonstrate in situ laser-absorption-based sensing of H2O, CH4, CO2, and CO mole fraction is reported for the product gas line of a biomass gasifier. Spectral simulations were used to select candidate sensor wavelengths that optimize sensitive monitoring of the target species while minimizing interference from other species in the gas stream. A prototype sensor was constructed and measurements performed in the laboratory at Stanford to validate performance. Field measurements then were demonstrated in a pilot scale biomass gasifier at West Biofuels in Woodland, CA. The performance of a prototype sensor was compared for two sensor strategies: wavelength-scanned direct absorption (DA) and wavelength-scanned wavelength modulation spectroscopy (WMS). The lasers used had markedly different wavelength tuning response to injection current, and modern distributed feedback lasers (DFB) with nearly linear tuning response to injection current were shown to be superior, leading to guidelines for laser selection for sensor fabrication. Non-absorption loss in the transmitted laser intensity from particulate scattering and window fouling encouraged the use of normalized WMS measurement schemes. The complications of using normalized WMS for relatively large values of absorbance and its mitigation are discussed. A method for reducing adverse sensor performance effects of a time-varying WMS background signal is also presented. The laser absorption sensor provided measurements with the sub-second time resolution needed for gasifier control and more importantly provided precise measurements of H2O in the gasification products, which can be problematic for the typical gas chromatography sensors used by industry.

Algorithm for removing scalp signals from functional near-infrared spectroscopy signals in real time using multidistance optodes.

PubMed

Kiguchi, Masashi; Funane, Tsukasa

2014-11-01

A real-time algorithm for removing scalp-blood signals from functional near-infrared spectroscopy signals is proposed. Scalp and deep signals have different dependencies on the source-detector distance. These signals were separated using this characteristic. The algorithm was validated through an experiment using a dynamic phantom in which shallow and deep absorptions were independently changed. The algorithm for measurement of oxygenated and deoxygenated hemoglobins using two wavelengths was explicitly obtained. This algorithm is potentially useful for real-time systems, e.g., brain-computer interfaces and neuro-feedback systems.

Biological synthesis of metallic nanoparticles using algae.

PubMed

Castro, Laura; Blázquez, María Luisa; Muñoz, Jesus Angel; González, Felisa; Ballester, Antonio

2013-09-01

The increasing demand and limited natural resources of noble metals make its recovery from dilute industrial wastes attractive, especially when using environmentally friendly methods. Nowadays, the high impact that nanotechnology is having in both science and society offers new research possibilities. Gold and silver nanoparticles were biosynthesised by a simple method using different algae as reducing agent. The authors explored the application of dead algae in an eco-friendly procedure. The nanoparticle formation was followed by UV-vis absorption spectroscopy and transmission electron microscopy. The functional groups involved in the bioreduction were studied by Fourier transform infrared spectroscopy.

Modification of Aspergillus niger by conducting polymer, Polypyrrole, and the evaluation of electrochemical properties of modified cells.

PubMed

Apetrei, Roxana-Mihaela; Carac, Geta; Bahrim, Gabriela; Ramanaviciene, Almira; Ramanavicius, Arunas

2018-06-01

The enhancement of bioelectrochemical properties of microorganism by in situ formation of conducting polymer within the cell structures (e.g. cell wall) was performed. The synthesis of polypyrrole (Ppy) within fungi (Aspergillus niger) cells was achieved. Two different Aspergillus niger strains were selected due to their ability to produce glucose oxidase, which initiated the Ppy formation through products of enzymatic reaction. The evolution of Ppy structural features was investigated by absorption spectroscopy, cyclic voltammetry and Fourier transform infrared spectroscopy. Copyright © 2018 Elsevier B.V. All rights reserved.

Label-free pathological evaluation of grade 3 cancer using Stokes shift spectroscopy

NASA Astrophysics Data System (ADS)

Sordillo, Laura A.; Sordillo, Peter P.; Alfano, R. R.

2016-03-01

In this study, Stokes shift spectroscopy (S3) is used for measuring the aggressiveness of malignant tumors. S3 is an optical tool which utilizes the difference between the emission wavelength (λem) and the absorption wavelength (λabs) (the Stokes shift) to give a fixed wavelength shift (Δλs).Our analysis of tumor samples using S3 shows grade 3 (high grade) cancers consistently have increased relative tryptophan content compared to grade 1 or 2 tumors. This technique may be a useful tool in the evaluation of a patient's cancer.

Investigation of Industrial Polyurethane Foams Modified with Antimicrobial Copper Nanoparticles

PubMed Central

Sportelli, Maria Chiara; Picca, Rosaria Anna; Ronco, Roberto; Bonerba, Elisabetta; Tantillo, Giuseppina; Pollini, Mauro; Sannino, Alessandro; Valentini, Antonio; Cataldi, Tommaso R.I.; Cioffi, Nicola

2016-01-01

Antimicrobial copper nanoparticles (CuNPs) were electrosynthetized and applied to the controlled impregnation of industrial polyurethane foams used as padding in the textile production or as filters for air conditioning systems. CuNP-modified materials were investigated and characterized morphologically and spectroscopically, by means of Transmission Electron Microscopy (TEM), and X-ray Photoelectron Spectroscopy (XPS). The release of copper ions in solution was studied by Electro-Thermal Atomic Absorption Spectroscopy (ETAAS). Finally, the antimicrobial activity of freshly prepared, as well as aged samples—stored for two months—was demonstrated towards different target microorganisms. PMID:28773665

Elucidating light-induced charge accumulation in an artificial analogue of methane monooxygenase enzymes using time-resolved X-ray absorption spectroscopy

DOE PAGES

Moonshiram, Dooshaye; Picon, Antonio; Vazquez-Mayagoitia, Alvaro; ...

2017-02-08

Here, we report the use of time-resolved X-ray absorption spectroscopy in the ns–μs time scale to track the light induced two electron transfer processes in a multi-component photocatalytic system, consisting of [Ru(bpy) 3] 2+/ a diiron(III,III) model/triethylamine. EXAFS analysis with DFT calculations confirms the structural configurations of the diiron(III,III) and reduced diiron(II,II) states.

Elucidating light-induced charge accumulation in an artificial analogue of methane monooxygenase enzymes using time-resolved X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moonshiram, Dooshaye; Picon, Antonio; Vazquez-Mayagoitia, Alvaro

Here, we report the use of time-resolved X-ray absorption spectroscopy in the ns–μs time scale to track the light induced two electron transfer processes in a multi-component photocatalytic system, consisting of [Ru(bpy) 3] 2+/ a diiron(III,III) model/triethylamine. EXAFS analysis with DFT calculations confirms the structural configurations of the diiron(III,III) and reduced diiron(II,II) states.

Diiodobodipy-styrylbodipy Dyads: Preparation and Study of the Intersystem Crossing and Fluorescence Resonance Energy Transfer.

PubMed

Wang, Zhijia; Xie, Yun; Xu, Kejing; Zhao, Jianzhang; Glusac, Ksenija D

2015-07-02

2,6-Diiodobodipy-styrylbodipy dyads were prepared to study the competing intersystem crossing (ISC) and the fluorescence-resonance-energy-transfer (FRET), and its effect on the photophysical property of the dyads. In the dyads, 2,6-diiodobodipy moiety was used as singlet energy donor and the spin converter for triplet state formation, whereas the styrylbodipy was used as singlet and triplet energy acceptors, thus the competition between the ISC and FRET processes is established. The photophysical properties were studied with steady-state UV-vis absorption and fluorescence spectroscopy, electrochemical characterization, and femto/nanosecond time-resolved transient absorption spectroscopies. FRET was confirmed with steady state fluorescence quenching and fluorescence excitation spectra and ultrafast transient absorption spectroscopy (kFRET = 5.0 × 10(10) s(-1)). The singlet oxygen quantum yield (ΦΔ = 0.19) of the dyad was reduced as compared with that of the reference spin converter (2,6-diiodobodipy, ΦΔ = 0.85), thus the ISC was substantially inhibited by FRET. Photoinduced intramolecular electron transfer (ET) was studied by electrochemical data and fluorescence quenching. Intermolecular triplet energy transfer was studied with nanosecond transient absorption spectroscopy as an efficient (ΦTTET = 92%) and fast process (kTTET = 5.2 × 10(4) s(-1)). These results are useful for designing organic triplet photosensitizers and for the study of the photophysical properties.

Evaluation of biodegradable plastics for rubber seedling applications

NASA Astrophysics Data System (ADS)

Mansor, Mohd Khairulniza; Dayang Habibah A. I., H.; Kamal, Mazlina Mustafa

2015-08-01

The main negative consequence of conventional plastics in agriculture is related to handling the wastes plasticand the associated environmental impact. Hence, a study of different types of potentially biodegradable plastics used for nursery applications have been evaluated on its mechanical,water absorption propertiesand Fourier transform infra-red (FTIR) spectroscopy. Supplied samples from different companies were designated as SF, CF and CO. Most of the polybags exhibited mechanical properties quite similar to the conventional plastics (polybag LDPE). CO polybag which is based on PVA however had extensively higher tensile strength and water absorption properties. FTIR study revealed a characteristics absorbance of conventional plastic, SF, CF and CO biodegradable polybag are associated with polyethylene, poly(butylene adipate-co-terephthalate) (PBAT), polyethylene and polyvinyl alcohol (PVA) structures respectively.

Charge transfer in photorefractive CdTe:Ge at different wavelengths

NASA Astrophysics Data System (ADS)

Shcherbin, K.; Odoulov, S.; Ramaz, F.; Farid, B.; Briat, B.; von Bardeleben, H. J.; Delaye, P.; Roosen, G.

2001-10-01

The charge transfer processes in photorefractive CdTe:Ge were modeled using the data of optical absorption, magnetic circular dichroism (MCD) and electron paramagnetic resonance (EPR) spectroscopies. Within the developed model the variations in the photorefractive properties of different CdTe:Ge samples are explained by differences in the relative concentrations of donor and trap centers. The existence of two different centers of comparable concentrations, each in two charge states, allows charge redistribution between them and gives rise to optical sensitization of some CdTe:Ge samples for photorefractive recording under an auxiliary illumination. In the present article we follow the proposal of pseudo-3D presentation of light-induced absorption to distinguish the main charge transfer processes at different excitation energies and explain the sensitization of CdTe:Ge for photorefractive recording at 1.06, 1.32 and 1.55 μm by light with appropriate wavelength.

New High-Resolution Absorption Cross-Section Measurements of HCFC-142B in the Mid-Ir

NASA Astrophysics Data System (ADS)

Le Bris, Karine; Strong, Kimberly; Melo, Stella

2009-06-01

HCFC-142b (1-chloro-1,1-difluoroethane) is a temporary substitute for ozone-depleting chlorofluorocarbons (CFCs). However, due to its high absorption cross-sections in the mid-IR, HCFC-142b is also a highly potent greenhouse gas, now detectable from space by satellite missions. So far, the accuracy of the retrieval has been limited by the lack of reference data in a range of temperatures compatible with atmospheric observations. We present new absorption cross section measurements of HCFC-142b at high-resolution (0.02 cm^{-1}) from 223 K to 283 K in the 600 cm^{-1}- 4000 cm^{-1} spectral window. The composite spectra are calculated for each temperature from a set of acquisitions at different pressures by Fourier transform spectroscopy.

LED-Absorption-QEPAS Sensor for Biogas Plants

PubMed Central

Köhring, Michael; Böttger, Stefan; Willer, Ulrike; Schade, Wolfgang

2015-01-01

A new sensor for methane and carbon dioxide concentration measurements in biogas plants is presented. LEDs in the mid infrared spectral region are implemented as low cost light source. The combination of quartz-enhanced photoacoustic spectroscopy with an absorption path leads to a sensor setup suitable for the harsh application environment. The sensor system contains an electronics unit and the two gas sensors; it was designed to work as standalone device and was tested in a biogas plant for several weeks. Gas concentration dependent measurements show a precision better than 1% in a range between 40% and 60% target gas concentration for both sensors. Concentration dependent measurements with different background gases show a considerable decrease in cross sensitivity against the major components of biogas in direct comparison to common absorption based sensors. PMID:26007746

Spectroscopic identification of rare earth elements in phosphate glass

NASA Astrophysics Data System (ADS)

Devangad, Praveen; Tamboli, Maktum; Muhammed Shameem, K. M.; Nayak, Rajesh; Patil, Ajeetkumar; Unnikrishnan, V. K.; Santhosh, C.; Kumar, G. A.

2018-01-01

In this work, rare earth-doped phosphate glasses were synthesized and characterized using three different spectroscopic techniques. The absorption spectra of the prepared praseodymium (Pr) and samarium (Sm) doped glasses, recorded by a UV-VIS-NIR spectrophotometer, show the characteristic absorption bands of these elements. To confirm this inference, laser-induced fluorescence spectra of Pr and Sm were obtained at a laser excitation of 442 nm. Their emission bands are reported here. The elemental analysis of these samples was carried out using a laser-induced breakdown spectroscopy (LIBS) system. Characteristic emission lines of Pr and Sm have been identified and reported by the recorded LIBS spectra of glass samples. Results prove that using these three complimentary spectroscopic techniques (absorption, fluorescence and LIBS), we can meaningfully characterize rare earth-doped glass samples.

Analyzing silver concentration in soil using laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Prasetyo, S.; Isnaeni; Zaitun; Mitchell, K.; Suliyanti, M. M.; Herbani, Y.

2018-03-01

Determination of concentration of heavy metal ions in soil, such as silver, is very important to study soil pollution levels. Several techniques have been developed to determine silver ion concentration in soil. In this paper, we utilized laser-induced breakdown spectroscopy (LIBS) to study silver concentration in soil. We used four different data analysis methods to calculate silver concentration. In this case, we prepared soil samples with different silver ion concentrations from 400 ppm to 1000 ppm. Our analysis was focused on the 843.15 nm silver atomic absorption line. We found that plasma intensity increased as silver concentration increased. Our findings were based on our analysis using four different analysis methods. We believe that these analysis methods are able to calculate silver concentration in soil using LIBS.

Miniaturized King furnace permits absorption spectroscopy of small samples

NASA Technical Reports Server (NTRS)

Ercoli, B.; Tompkins, F. S.

1968-01-01

Miniature King-type furnace, consisting of an inductively heated, small diameter tantalum tube supported in a radiation shield eliminates the disadvantages of the conventional furnace in obtaining absorption spectra of metal vapors.

NIR remission spectroscopy of turbid media

NASA Astrophysics Data System (ADS)

Krauter, P.; Foschum, F.; Kienle, A.

2013-06-01

We present a method for the determination of absorption spectra in VIS and NIR spectra of turbid media without the need for calibration. Measurements of the absorption spectra of a phantom and butter are presented.

Absorption spectroscopy setup for determination of whole human blood and blood-derived materials spectral characteristics

NASA Astrophysics Data System (ADS)

Wróbel, M. S.; Gnyba, M.; Milewska, D.; Mitura, K.; Karpienko, K.

2015-09-01

A dedicated absorption spectroscopy system was set up using tungsten-halogen broadband source, optical fibers, sample holder, and a commercial spectrometer with CCD array. Analysis of noise present in the setup was carried out. Data processing was applied to the absorption spectra to reduce spectral noise, and improve the quality of the spectra and to remove the baseline level. The absorption spectra were measured for whole blood samples, separated components: plasma, saline, washed erythrocytes in saline and human whole blood with biomarkers - biocompatible nanodiamonds (ND). Blood samples had been derived from a number of healthy donors. The results prove a correct setup arrangement, with adequate preprocessing of the data. The results of blood-ND mixtures measurements show no toxic effect on blood cells, which proves the NDs as a potential biocompatible biomarkers.

A broadband Tm/Ho-doped fiber laser tunable from 1.8 to 2.09 µm for intracavity absorption spectroscopy

NASA Astrophysics Data System (ADS)

Fjodorow, Peter; Hellmig, Ortwin; Baev, Valery M.

2018-04-01

A broadband tunable Tm/Ho-doped fiber laser is developed for sensitive in situ measurements of intracavity absorption spectra in the spectral range of 4780-5560 cm-1. This spectral range includes an atmospheric transmission window enabling sensitive measurements of various species. The spectral bandwidth of laser emission varies from 20 to 60 cm-1 and is well suitable for multicomponent spectroscopy. The sensitivity achieved in cw operation corresponds to an effective absorption path length of L eff = 20 km, with a spectral noise of less than 1%. The spectroscopic system is applied for measurements of absorption spectra of H2O, NH3 and for simultaneous in situ detection of three isotopes of CO2 in human breath, which is important for medical diagnostics procedures.

Vibrational Stark effect spectroscopy at the interface of Ras and Rap1A bound to the Ras binding domain of RalGDS reveals an electrostatic mechanism for protein-protein interaction.

PubMed

Stafford, Amy J; Ensign, Daniel L; Webb, Lauren J

2010-11-25

Electrostatic fields at the interface of the Ras binding domain of the protein Ral guanine nucleotide dissociation stimulator (RalGDS) with the structurally analogous GTPases Ras and Rap1A were measured with vibrational Stark effect (VSE) spectroscopy. Eleven residues on the surface of RalGDS that participate in this protein-protein interaction were systematically mutated to cysteine and subsequently converted to cyanocysteine in order to introduce a nitrile VSE probe in the form of the thiocyanate (SCN) functional group. The measured SCN absorption energy on the monomeric protein was compared with solvent-accessible surface area (SASA) calculations and solutions to the Poisson-Boltzmann equation using Boltzmann-weighted structural snapshots from molecular dynamics simulations. We found a weak negative correlation between SASA and measured absorption energy, indicating that water exposure of protein surface amino acids can be estimated from experimental measurement of the magnitude of the thiocyanate absorption energy. We found no correlation between calculated field and measured absorption energy. These results highlight the complex structural and electrostatic nature of the protein-water interface. The SCN-labeled RalGDS was incubated with either wild-type Ras or wild-type Rap1A, and the formation of the docked complex was confirmed by measurement of the dissociation constant of the interaction. The change in absorption energy of the thiocyanate functional group due to complex formation was related to the change in electrostatic field experienced by the nitrile functional group when the protein-protein interface forms. At some locations, the nitrile experiences the same shift in field when bound to Ras and Rap1A, but at others, the change in field is dramatically different. These differences identify residues on the surface of RalGDS that direct the specificity of RalGDS binding to its in vivo binding partner, Rap1A, through an electrostatic mechanism.

LED-CE-DOAS measurements of NO2: intercomparison with CaRDS

NASA Astrophysics Data System (ADS)

Thalman, R. M.; Washenfelder, R.; Brown, S. S.; Volkamer, R.

2009-04-01

The combination of cavity enhanced absorption spectroscopy (CEAS) with Light Emitting Diode (LED) light sources lends itself to the application of the well established Differential Optical Absorption Spectroscopy (DOAS) technique (LED-CE-DOAS). In contrast to other broad band CEAS (BB-CEAS) techniques, CE-DOAS relies only on the measurement of relative intensity changes, i.e., does not require knowledge of the light intensity in the absence of trace gases (I0). With CE-DOAS there is no necessity for sampling lines to supply air samples into a cavity, or filters to remove aerosols from the airstream, as measurements are possible in a cavity that can be open to the atmosphere. A novel LED-CE-DOAS instrument was built at CU Boulder for the sensitive and selective detection of nitrogen dioxide (NO2), glyoxal (CHOCHO), iodine oxide (IO), water, and oxygen dimers (O4). CU Boulder's LED-CE-DOAS instrument was collocated to NOAA's NO2 Cavity Ring Down (CaRDS) instrument to test different CE-DOAS data retrieval algorithms for NO2 and O4. Both instruments were collocated to sample known NO2 concentrations from the same gas manifold, and to sample atmospheric air in a parking lot. This contribution focuses on the instrument components, challenges and means to retrieve quantitative concentrations of NO2 by LED-CE-DOAS, i.e., the distortion of NO2 and O4 absorption features due to different effective path lengths induced by (1) changes in the mirror reflectivity with wavelength, and (2) changes in light extinction across the absorption bands due to differential trace gas absorption features. We demonstrate that simultaneous measurements of O4 and NO2 enable to characterize the effective pathlength in the absence and presence of NO2 and perform absolute measurements based only on relative intensity measurements. To our knowledge these are the first CEAS measurements that rely solely on relative intensity measurements.

Collision-Induced Infrared Absorption by Hydrogen-Helium gas mixtures at Thousands of Kelvin

NASA Astrophysics Data System (ADS)

Abel, Martin; Frommhold, Lothar; Li, Xiaoping; Hunt, Katharine L. C.

2010-10-01

The interaction-induced absorption by collisional pairs of H2 molecules is an important opacity source in the atmospheres of the outer planets and cool stars ^[1]. The emission spectra of cool white dwarf stars differ significantly in the infrared from the expected blackbody spectra of their cores, which is largely due to absorption by collisional H2--H2, H2--He, and H2--H complexes in the stellar atmospheres. Using quantum-chemical methods we compute the atmospheric absorption from hundreds to thousands of kelvin ^[2]. Laboratory measurements of interaction-induced absorption spectra by H2 pairs exist only at room temperature and below. We show that our results reproduce these measurements closely ^[2], so that our computational data permit reliable modeling of stellar atmosphere opacities even for the higher temperatures ^[2]. [1] L. Frommhold, Collision-Induced Absorption in Gases, Cambridge University Press, Cambridge, New York, 1993 and 2006 [2] Xiaoping Li, Katharine L. C. Hunt, Fei Wang, Martin Abel, and Lothar Frommhold, ``Collision-Induced Infrared Absorption by Molecular Hydrogen Pairs at Thousands of Kelvin'', International Journal of Spectroscopy, vol. 2010, Article ID 371201, 11 pages, 2010. doi: 10.1155/2010/371201

Tunable Nanoantennas for Surface Enhanced Infrared Absorption Spectroscopy by Colloidal Lithography and Post-Fabrication Etching

NASA Astrophysics Data System (ADS)

Chen, Kai; Duy Dao, Thang; Nagao, Tadaaki

2017-03-01

We fabricated large-area metallic (Al and Au) nanoantenna arrays on Si substrates using cost-effective colloidal lithography with different micrometer-sized polystyrene spheres. Variation of the sphere size leads to tunable plasmon resonances in the middle infrared (MIR) range. The enhanced near-fields allow us to detect the surface phonon polaritons in the natural SiO2 thin layers. We demonstrated further tuning capability of the resonances by employing dry etching of the Si substrates with the nanoantennas acting as the etching masks. The effective refractive index of the nanoantenna surroundings is efficiently decreased giving rise to blueshifts of the resonances. In addition, partial removal of the Si substrates elevates the nanoantennas from the high-refractive-index substrates making more enhanced near-fields accessible for molecular sensing applications as demonstrated here with surface-enhanced infrared absorption (SEIRA) spectroscopy for a thin polymer film. We also directly compared the plasmonic enhancement from the Al and Au nanoantenna arrays.

Polarization-modulated FTIR spectroscopy of lipid/gramicidin monolayers at the air/water interface.

PubMed Central

Ulrich, W P; Vogel, H

1999-01-01

Monolayers of gramicidin A, pure and in mixtures with dimyristoylphosphatidylcholine (DMPC), were studied in situ at the air/H2O and air/D2O interfaces by polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS). Simulations of the entire set of amide I absorption modes were also performed, using complete parameter sets for different conformations based on published normal mode calculations. The structure of gramicidin A in the DMPC monolayer could clearly be assigned to a beta6.3 helix. Quantitative analysis of the amide I bands revealed that film pressures of up to 25-30 mN/m the helix tilt angle from the vertical in the pure gramicidin A layer exceeded 60 degrees. A marked dependence of the peptide orientation on the applied surface pressure was observed for the mixed lipid-peptide monolayers. At low pressure the helix lay flat on the surface, whereas at high pressures the helix was oriented almost parallel to the surface normal. PMID:10049344

Assessment of morphology and property of graphene oxide-hydroxypropylmethylcellulose nanocomposite films.

PubMed

Ghosh, Tapas Kumar; Gope, Shirshendu; Mondal, Dibyendu; Bhowmik, Biplab; Mollick, Md Masud Rahaman; Maity, Dipanwita; Roy, Indranil; Sarkar, Gunjan; Sadhukhan, Sourav; Rana, Dipak; Chakraborty, Mukut; Chattopadhyay, Dipankar

2014-05-01

Graphene oxide (GO) was synthesized by Hummer's method and characterized by using Fourier transform infrared spectroscopy and Raman spectroscopy. The as synthesized GO was used to make GO/hydroxypropylmethylcellulose (HPMC) nanocomposite films by the solution mixing method using different concentrations of GO. The nanocomposite films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and thermo-gravimetric analysis. Mechanical properties, water absorption property and water vapor transmission rate were also measured. XRD analysis showed the formation of exfoliated HPMC/GO nanocomposites films. The FESEM results revealed high interfacial adhesion between the GO and HPMC matrix. The tensile strength and Young's modulus of the nanocomposite films containing the highest weight percentage of GO increased sharply. The thermal stability of HPMC/GO nanocomposites was slightly better than pure HPMC. The water absorption and water vapor transmission rate of HPMC film was reduced with the addition of up to 1 wt% GO. Copyright © 2014 Elsevier B.V. All rights reserved.

Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons under Interstellar Conditions

NASA Technical Reports Server (NTRS)

Stone, Bradley M.

1996-01-01

The presence and importance of polycyclic aromatic hydrocarbons (PAHs, a large family of organic compounds containing carbon and hydrogen) in the interstellar medium has already been well established. The Astrochemistry Laboratory at NASA Ames Research Center (under the direction of Louis Allamandola and Scott Sandford) has been the center of pioneering work in performing spectroscopy on these molecules under simulated interstellar conditions, and consequently in the identification of these species in the interstellar medium by comparison to astronomically obtained spectra. My project this summer was twofold: (1) We planned on obtaining absorption spectra of a number of PAHs and their cations in cold (4K) Ne matrices. The purpose of these experiments was to increase the number of different PAHs for which laboratory spectra have been obtained under these simulated interstellar conditions; and (2) I was to continue the planning and design of a new laser facility that is being established in the Astrochemistry laboratory. The laser-based experimental set-up will greatly enhance our capability in examining this astrophysically important class of compounds.

Sol-to-Gel Transition in Fast Evaporating Systems Observed by in Situ Time-Resolved Infrared Spectroscopy.

PubMed

Innocenzi, Plinio; Malfatti, Luca; Carboni, Davide; Takahashi, Masahide

2015-06-22

The in situ observation of a sol-to-gel transition in fast evaporating systems is a challenging task and the lack of a suitable experimental design, which includes the chemistry and the analytical method, has limited the observations. We synthesise an acidic sol, employing only tetraethylorthosilicate, SiCl4 as catalyst and deuterated water; the absence of water added to the sol allows us to follow the absorption from the external environment and the evaporation of deuterated water. The time-resolved data, obtained by attenuated total reflection infrared spectroscopy on an evaporating droplet, enables us to identify four different stages during evaporation. They are linked to specific hydrolysis and condensation rates that affect the uptake of water from external environment. The second stage is characterized by a decrease in hydroxyl content, a fast rise of condensation rate and an almost stationary absorption of water. This stage has been associated with the sol-to-gel transition. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and Study of Optical Properties of Graphene/TiO2 Composites Using UV-VIS Spectroscopy

NASA Astrophysics Data System (ADS)

Rathod, P. B.; Waghuley, S. A.

2016-09-01

Graphene and TiO2 were synthesized using electrochemical exfoliation and co-precipitation methods, respectively. An ex situ approach was adopted for the graphene/TiO2 composites. The conformation of graphene in the TiO2 samples was examined through X-ray diffraction. Optical properties of the as-synthesised composites such as optical absorption, extinction coefficient, refractive index, real dielectric constant, imaginary dielectric constant, dissipation factor, and optical conductivity were measured using UV-Vis spectroscopy. The varying concentration of graphene in TiO2 affects the optical properties which appear different for 10 wt.% as compared to 5 wt.% graphene/ TiO2 composite. The composites exhibit an absorption peak at 300 nm with a decrease in band gap for 10 wt.% as compared to 5 wt.% graphene/TiO2 composite. The maximum optical conductivity for the graphene/TiO2 composite of 10 wt.% was found to be 1.86·10-2 Ω-1·m-1 at 300 nm.

Measurement of temperature profiles in flames by emission-absorption spectroscopy

NASA Technical Reports Server (NTRS)

Simmons, F. S.; Arnold, C. B.; Lindquist, G. H.

1972-01-01

An investigation was conducted to explore the use of infrared and ultraviolet emission-absorption spectroscopy for determination of temperature profiles in flames. Spectral radiances and absorptances were measured in the 2.7-micron H2O band and the 3064-A OH band in H2/O2 flames for several temperature profiles which were directly measured by a sodium line-reversal technique. The temperature profiles, determined by inversion of the infrared and ultraviolet spectra, showed an average disagreement with line-reversal measurements of 50 K for the infrared and 200 K for the ultraviolet at a temperature of 2600 K. The reasons for these discrepancies are discussed in some detail.

Quantum state-resolved probing of strong-field-ionized xenon atoms using femtosecond high-order harmonic transient absorption spectroscopy.

PubMed

Loh, Zhi-Heng; Khalil, Munira; Correa, Raoul E; Santra, Robin; Buth, Christian; Leone, Stephen R

2007-04-06

Femtosecond high-order harmonic transient absorption spectroscopy is used to resolve the complete |j,m quantum state distribution of Xe+ produced by optical strong-field ionization of Xe atoms at 800 nm. Probing at the Xe N4/5 edge yields a population distribution rhoj,|m| of rho3/2,1/2ratiorho1/2,1/2ratiorho3/2,3/2=75+/-6 :12+/-3 :13+/-6%. The result is compared to a tunnel ionization calculation with the inclusion of spin-orbit coupling, revealing nonadiabatic ionization behavior. The sub-50-fs time resolution paves the way for tabletop extreme ultraviolet absorption probing of ultrafast dynamics.

Differential Optical Absorption Spectroscopy (DOAS) using Targets: SO2 and NO2 Measurements in Montevideo City

NASA Astrophysics Data System (ADS)

Louban, Ilia; Píriz, Gustavo; Platt, Ulrich; Frins, Erna

2008-04-01

SO2 and NO2 were remotely measured in a main street of Montevideo city using Multiaxis-Differential Optical Absorption Spectroscopy (MAX-DOAS) combined with on-field selected targets. Target-based measurements are the basis of a new experimental procedure called Topographic Target Light scattering-DOAS (TOTAL-DOAS) that provides a well define absorption path to measure the near surface distribution of trace gases in the boundary layer. It combines the measurement principles of the long-path DOAS and zenith-scattered sunlight DOAS, within the near UV and VIS spectral range. We give a general description of the procedure and present first results of the 2006 campaign at Montevideo.

Spectroscopy of Reaction Intermediates in Nitramine Decomposition and Combustion

DTIC Science & Technology

1991-06-20

Dakhis and co-workers, s the very strong absorption of MMN near 1332 cm - 1 did not appear. Unassigned absorptions appeared near 930, 1240, 1460, 2990, and...sharp NO2 absorption. In Table I, the positions of these absorptions are compared with the infrared absorptions of MMN reported by Dakhis and co-workers...Chemistry and Physics of Energetic Materials, S. N. Bulusu, Ed., pp. 51-78 (Kluwer Academic Publishers, Dordrecht, 1990). 56. M. I. Dakhis , V. G. Dashevsky

Spectroscopy of Reaction Intermediates in Nitramine Decomposition and Combustion

DTIC Science & Technology

1991-06-20

absorptions of gas-phase MMN reported by Dakhis and co-workers,5 6 the very strong absorption of MMN near 1332 cm - ’ did not appear. Unassigned...sharp NO 2 absorption. In Table I, the positions of these absorptions are compared with the infrared absorptions of MMN reported by Dakhis and co-workers...Chemistry and Physics of Energetic Materials, S. N. Bulusu, Ed., pp. 51-78 (Kluwer Academic Publishers, Dordrecht, 1990). 56. M. I. Dakhis , V. G

A variable-density absorption event in NGC 3227 mapped with Suzaku and Swift

NASA Astrophysics Data System (ADS)

Beuchert, T.; Markowitz, A. G.; Krauß, F.; Miniutti, G.; Longinotti, A. L.; Guainazzi, M.; de La Calle Pérez, I.; Malkan, M.; Elvis, M.; Miyaji, T.; Hiriart, D.; López, J. M.; Agudo, I.; Dauser, T.; Garcia, J.; Kreikenbohm, A.; Kadler, M.; Wilms, J.

2015-12-01

Context. The morphology of the circumnuclear gas accreting onto supermassive black holes in Seyfert galaxies remains a topic of much debate. As the innermost regions of active galactic nuclei (AGN) are spatially unresolved, X-ray spectroscopy, and in particular line-of-sight absorption variability, is a key diagnostic to map out the distribution of gas. Aims: Observations of variable X-ray absorption in multiple Seyferts and over a wide range of timescales indicate the presence of clumps/clouds of gas within the circumnuclear material. Eclipse events by clumps transiting the line of sight allow us to explore the properties of the clumps over a wide range of radial distances from the optical/UV broad line region (BLR) to beyond the dust sublimation radius. Time-resolved absorption events have been extremely rare so far, but suggest a range of density profiles across Seyferts. We resolve a weeks-long absorption event in the Seyfert NGC 3227. Methods: We examine six Suzaku and 12 Swift observations from a 2008 campaign spanning five weeks. We use a model accounting for the complex spectral interplay of three absorbers with different levels of ionization. We perform time-resolved spectroscopy to discern the absorption variability behavior. We also examine the IR to X-ray spectral energy distribution (SED) to test for reddening by dust. Results: The 2008 absorption event is due to moderately-ionized (log ξ ~ 1.2-1.4) gas covering 90% of the line of sight. We resolve the density profile to be highly irregular, in contrast to a previous symmetric and centrally-peaked event mapped with RXTE in the same object. The UV data do not show significant reddening, suggesting that the cloud is dust-free. Conclusions: The 2008 campaign has revealed a transit by a filamentary, moderately-ionized cloud of variable density that is likely located in the BLR, and possibly part of a disk wind.

One body, many heads; the Cerberus of catalysis. A new multipurpose in-situ cell for XAS at ALBA

NASA Astrophysics Data System (ADS)

Guilera, G.; Rey, F.; Hernández-Fenollosa, J.; Cortés-Vergaz, J. J.

2013-04-01

A new multi-purpose in-situ cell and its control system have been developed for synchrotron-based techniques as are X-Ray Absorption spectroscopy (XAS) and X-Ray Diffraction (XRD). The cell is made of a stainless steel 'body' and three different exchangeable 'heads' to tackle different scientific areas that include solid-gas catalysis, solid-liquid catalysis and electrocatalysis. The different versions of the cell are herein described and their functionality is exemplified by some case studies.

FEASIBILITY STUDY TO DEMONSTRATE APPLICABILITY OF TUNABLE INFRARED LASER EMISSION SPECTROSCOPY TECHNOLOGY TO MEASURE AIR POLLUTION

EPA Science Inventory

This project involves the real-time measurement of air quality using open-path IR spectroscopy. A prototype open-path tunable laser absorption spectroscopy instrument was designed, built, and successfully operated for several hundred hours between October and December 2000. The...

A promising diagnostic method: Terahertz pulsed imaging and spectroscopy

PubMed Central

Sun, Yiwen; Sy, Ming Yiu; Wang, Yi-Xiang J; Ahuja, Anil T; Zhang, Yuan-Ting; Pickwell-MacPherson, Emma

2011-01-01

The terahertz band lies between the microwave and infrared regions of the electromagnetic spectrum. This radiation has very low photon energy and thus it does not pose any ionization hazard for biological tissues. It is strongly attenuated by water and very sensitive to water content. Unique absorption spectra due to intermolecular vibrations in this region have been found in different biological materials. These unique features make terahertz imaging very attractive for medical applications in order to provide complimentary information to existing imaging techniques. There has been an increasing interest in terahertz imaging and spectroscopy of biologically related applications within the last few years and more and more terahertz spectra are being reported. This paper introduces terahertz technology and provides a short review of recent advances in terahertz imaging and spectroscopy techniques, and a number of applications such as molecular spectroscopy, tissue characterization and skin imaging are discussed. PMID:21512652

Single and double core-hole ion emission spectroscopy of transient neon plasmas produced by ultraintense x-ray laser pulses

NASA Astrophysics Data System (ADS)

Gao, Cheng; Zeng, Jiaolong; Yuan, Jianmin

2016-05-01

Single core-hole (SCH) and double core-hole (DCH) spectroscopy is investigated systematically for neon gas in the interaction with ultraintense x-ray pulses with photon energy from 937 eV to 2000 eV. A time-dependent rate equation, implemented in the detailed level accounting approximation, is utilized to study the dynamical evolution of the level population and emission properties of the laser-produced highly transient plasmas. The plasma density effects on level populations are demonstrated with an x-ray photon energy of 2000 eV. For laser photon energy in the range of 937 - 1360 eV, resonant absorptions (RA) of 1s-np (n> = 2) transitions play important roles in time evolution of the population and DCH emission spectroscopy. For x-ray photon energy larger than 1360 eV, no RA exist and transient plasmas show different features in the DCH spectroscopy.

Synthesis and characterization of blue fluorescent surface modified nano-graphene oxide flakes as a pH-sensitive drug delivery system

NASA Astrophysics Data System (ADS)

Hashemi, Hamed; Namazi, Hassan

2018-07-01

A new blue fluorescent surface modified graphene oxide (GO) by 6-(5-bromothiophen-2-yl) benzo[c][1,2,5]selenadiazole-5-carboxylic acid (TB) denoted as (GO-TB) was synthesized. The obtained hybrid was characterized by Scanning Electron Microscope (SEM/EDS); Brunauer-Emmett-Teller (BET); X-Ray Diffraction Spectroscopy (XRD); X-Ray Photoelectron Spectroscopy (XPS); UV-Vis Absorption Spectroscopy, and Fourier Transformed Infrared Spectroscopy (FTIR). The synthesized TB moiety displayed orange emission around 590 nm, while GO-TB exhibited a blue photoluminescence around 431 and 159 nm blue shift of photoluminescence. Doxorubicin immobilized on the hybrid surface up to 93%, and the release behavior in three different pHs was investigated. The release profile indicated a pH-dependent liberation with Fickian diffusion mechanism. The cytotoxicity of the hybrid was studied and the IC50 value for the hybrid was 5.16 µg/ml.

Enhancement of room temperature ferromagnetism in tin oxide nanocrystal using organic solvents

NASA Astrophysics Data System (ADS)

Sakthiraj, K.; Hema, M.; Balachandra Kumar, K.

2017-10-01

The effect of organic solvents (ethanol & ethylene glycol) on the room temperature ferromagnetism in nanocrystalline tin oxide has been studied. The samples were synthesized using sol-gel method with the mixture of water & organic liquid as solvent. It is found that pristine SnO2 nanocrystal contain two different types of paramagnetic centres over their surface:(i) surface chemisorbed oxygen species and (ii) Sn interstitial & oxygen vacancy defect pair. The magnetic moment induced in the as-prepared samples is mainly contributed by the alignment of local spin moments resulting from these defects. These surface defect states are highly activated by the usage of ethylene glycol solvent rather than ethylene in tin oxide nanostructure synthesis. Powder X-ray diffraction, transmission electron microscope imaging, energy dispersive spectrometry, Fourier transformed infrared spectroscopy, UV-vis absorption spectroscopy, photoluminescence spectroscopy, vibrating sample magnetometer measurement and electron spin resonance spectroscopy were employed to characterize the nanostructured tin oxide materials.

Oxidation and crystal field effects in uranium

NASA Astrophysics Data System (ADS)

Tobin, J. G.; Yu, S.-W.; Booth, C. H.; Tyliszczak, T.; Shuh, D. K.; van der Laan, G.; Sokaras, D.; Nordlund, D.; Weng, T.-C.; Bagus, P. S.

2015-07-01

An extensive investigation of oxidation in uranium has been pursued. This includes the utilization of soft x-ray absorption spectroscopy, hard x-ray absorption near-edge structure, resonant (hard) x-ray emission spectroscopy, cluster calculations, and a branching ratio analysis founded on atomic theory. The samples utilized were uranium dioxide (U O2) , uranium trioxide (U O3) , and uranium tetrafluoride (U F4) . A discussion of the role of nonspherical perturbations, i.e., crystal or ligand field effects, will be presented.

Theory of fiber-optic, evanescent-wave spectroscopy and sensors

NASA Astrophysics Data System (ADS)

Messica, A.; Greenstein, A.; Katzir, A.

1996-05-01

A general theory for fiber-optic, evanescent-wave spectroscopy and sensors is presented for straight, uncladded, step-index, multimode fibers. A three-dimensional model is formulated within the framework of geometric optics. The model includes various launching conditions, input and output end-face Fresnel transmission losses, multiple Fresnel reflections, bulk absorption, and evanescent-wave absorption. An evanescent-wave sensor response is analyzed as a function of externally controlled parameters such as coupling angle, f number, fiber length, and diameter. Conclusions are drawn for several experimental apparatuses.

Characterization of Infrared Properties of Layered Semiconductors.

DTIC Science & Technology

1987-02-20

candidate -10- V. PUBLICATIONS INCLUDED WITH REPORT 1) R. Braunstein, R. K . Kim, D. Matthews, and M. Braunstein: "Derivative Absorption Spectroscopy of...34Wavelength Modulation Spectra of a-Ag0.7Zn0 .3 Near the Optical Absorption Edge," Phys. Stat. Sol.(b) 131, 659 (1983). 5) R. K . Kim and R. Braunstein...34Infrared Wavelength Modulation Spectroscopy of Some Optical Material," Appl. Optics 23(8), 1166 (1984). 6) C.E. Jones, K . James, J. Merz, R. Braunstein, M

Isothermal crystallization of poly(3-hydroxybutyrate) studied by terahertz two-dimensional correlation spectroscopy

NASA Astrophysics Data System (ADS)

Hoshina, Hiromichi; Ishii, Shinya; Morisawa, Yusuke; Sato, Harumi; Noda, Isao; Ozaki, Yukihiro; Otani, Chiko

2012-01-01

The isothermal crystallization of poly(3-hydroxybutylate) (PHB) was studied by monitoring the temporal evolution of terahertz absorption spectra in conjunction with spectral analysis using two-dimensional correlation spectroscopy. Correlation between the absorption peaks and the sequential order of the changes in spectral intensity extracted from synchronous and asynchronous plots indicated that crystallization of PHB at 90 °C is a two step process, in which C-H...O=C hydrogen bonds are initially formed before well-defined crystal structures are established.

Determination of traces of silicone defoamer in fruit juices by solvent extraction/atomic absorption spectroscopy.

PubMed

Gooch, E G

1993-01-01

Silicone defoamers are used to control foam during the processing of fruit juices. Residual silicones in fruit juices can be separated from the naturally occurring siliceous materials in fruit products and selectively recovered by solvent extraction, after suitable pretreatment. The recovered silicone is measured by atomic absorption spectroscopy. Silicone concentrations as low as about 1 ppm can be measured. The juices are accurately spiked for recovery studies by the addition of silicone dispersed in D-sorbitol.

Concentration measurement of NO using self-absorption spectroscopy of the γ band system in a pulsed corona discharge.

PubMed

Zhai, Xiaodong; Ding, Yanjun; Peng, Zhimin; Luo, Rui

2012-07-10

Nitric oxide (NO) concentrations were measured using the γ band system spectrum based on the strong self-absorption effect of NO in pulsed corona discharges. The radiative transitional intensities of the NO γ band were simulated based on the theory of molecular spectroscopy. The intensities of some bands, especially γ(0,0) and γ(1,0), are weakened by the self-absorption. The correlations between the spectral self-absorption intensities and NO concentration were validated using a modified Beer-Lambert law with a combined factor K relating the branching ratio and the NO concentration, and a nonlinear index α that is applicable to the broadband system. Optical emissive spectra in pulsed corona discharges in NO and N2/He mixtures were used to evaluate the two parameters for various conditions. Good agreement between the experimental and theoretical results verifies the self-absorption behavior seen in the UV spectra of the NO γ bands.

Reflectance-mode interferometric near-infrared spectroscopy quantifies brain absorption, scattering, and blood flow index in vivo

PubMed Central

Borycki, Dawid; Kholiqov, Oybek; Srinivasan, Vivek J.

2017-01-01

Interferometric near-infrared spectroscopy (iNIRS) is a new technique that measures time-of-flight- (TOF-) resolved autocorrelations in turbid media, enabling simultaneous estimation of optical and dynamical properties. Here, we demonstrate reflectance-mode iNIRS for noninvasive monitoring of a mouse brain in vivo. A method for more precise quantification with less static interference from superficial layers, based on separating static and dynamic components of the optical field autocorrelation, is presented. Absolute values of absorption, reduced scattering, and blood flow index (BFI) are measured, and changes in BFI and absorption are monitored during a hypercapnic challenge. Absorption changes from TOF-resolved iNIRS agree with absorption changes from continuous wave NIRS analysis, based on TOF-integrated light intensity changes, an effective path length, and the modified Beer–Lambert Law. Thus, iNIRS is a promising approach for quantitative and non-invasive monitoring of perfusion and optical properties in vivo. PMID:28146535

Absorption Spectroscopy of Mercury's Exosphere During the 2016 Solar Transit

NASA Astrophysics Data System (ADS)

Schmidt, C. A.; Leblanc, F.; Reardon, K.; Killen, R. M.; Gary, D. E.; Ahn, K.

2018-05-01

Solar transits of Mercury provide a rare opportunity to study the exosphere in absorption and a valuable analog to transiting exoplanet studies. This presentation will characterize the sodium exosphere during the 2016 transit.

Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics

NASA Astrophysics Data System (ADS)

Neville, Simon P.; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

2016-10-01

We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L 2 method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

Diagnosing the plasma nonuniformity in an iron opacity experiment by spatially resolved Al 1s-2p absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang Xiaoding; Research Center of Laser Fusion, P. O. Box 919-986, Mianyang 621900; Zhang Jiyan

Generating a well-characterized hot-dense sample is of great importance to high quality opacity measurements. In this paper, we report on an experimental investigation of the plasma nonuniformity in a radiatively heated iron opacity sample by spatially resolved Al 1s-2p absorption spectroscopy. The iron sample was tamped by plastic at both sides and was heated by thermal x-ray radiation generated in a gold Hohlraum, and an Al layer attached to it was used as a tracer for temperature diagnosis. Spatially resolved 1s-2p transition absorption spectra of the Al tracer were measured by the technique of point-projection-spectroscopy, and temperatures in the samplemore » were obtained by comparing the measured spectra with detailed-term-accounting model calculations, with the density of the sample deduced using a combination of side-on radiography and radiative hydrodynamic simulation. The results showed the existence of axial temperature nonuniformity in the sample, and these temperature variations have been used to explain the shift of iron 2p-3d transition absorption feature along the axial direction of the Hohlraum used to heat the sample successfully.« less

Simultaneous Chemical and Refractive Index Sensing in the 1-2.5 μm Near-Infrared Wavelength Range on Nanoporous Gold Disks.

PubMed

Shih, Wei-Chuan; Santos, Greggy M; Zhao, Fusheng; Zenasni, Oussama; Arnob, Md Masud Parvez

2016-07-13

Near-infrared (NIR) absorption spectroscopy provides molecular and chemical information based on overtones and combination bands of the fundamental vibrational modes in the infrared wavelengths. However, the sensitivity of NIR absorption measurement is limited by the generally weak absorption and the relatively poor detector performance compared to other wavelength ranges. To overcome these barriers, we have developed a novel technique to simultaneously obtain chemical and refractive index sensing in 1-2.5 μm NIR wavelength range on nanoporous gold (NPG) disks, which feature high-density plasmonic hot-spots of localized electric field enhancement. For the first time, surface-enhanced near-infrared absorption (SENIRA) spectroscopy has been demonstrated for high sensitivity chemical detection. With a self-assembled monolayer (SAM) of octadecanethiol (ODT), an enhancement factor (EF) of up to ∼10(4) has been demonstrated for the first C-H combination band at 2400 nm using NPG disk with 600 nm diameter. Together with localized surface plasmon resonance (LSPR) extinction spectroscopy, simultaneous sensing of sample refractive index has been achieved for the first time. The performance of this technique has been evaluated using various hydrocarbon compounds and crude oil samples.

Highly vibrationally excited O2 molecules in low-pressure inductively-coupled plasmas detected by high sensitivity ultra-broad-band optical absorption spectroscopy

NASA Astrophysics Data System (ADS)

Foucher, Mickaël; Marinov, Daniil; Carbone, Emile; Chabert, Pascal; Booth, Jean-Paul

2015-08-01

Inductively-coupled plasmas in pure O2 (at pressures of 5-80 mTorr and radiofrequency power up to 500 W) were studied by optical absorption spectroscopy over the spectral range 200-450 nm, showing the presence of highly vibrationally excited O2 molecules (up to vʺ = 18) by Schumann-Runge band absorption. Analysis of the relative band intensities indicates a vibrational temperature up to 10,000 K, but these hot molecules only represent a fraction of the total O2 density. By analysing the (11-0) band at higher spectral resolution the O2 rotational temperature was also determined, and was found to increase with both pressure and power, reaching 900 K at 80 mTorr 500 W. These measurements were achieved using a new high-sensitivity ultra-broad-band absorption spectroscopy setup, based on a laser-plasma light source, achromatic optics and an aberration-corrected spectrograph. This setup allows the measurement of weak broadband absorbances due to a baseline variability lower than 2   ×   10-5 across a spectral range of 250 nm.

A new high temperature reactor for operando XAS: Application for the dry reforming of methane over Ni/ZrO2 catalyst.

PubMed

Aguilar-Tapia, Antonio; Ould-Chikh, Samy; Lahera, Eric; Prat, Alain; Delnet, William; Proux, Olivier; Kieffer, Isabelle; Basset, Jean-Marie; Takanabe, Kazuhiro; Hazemann, Jean-Louis

2018-03-01

The construction of a high-temperature reaction cell for operando X-ray absorption spectroscopy characterization is reported. A dedicated cell was designed to operate as a plug-flow reactor using powder samples requiring gas flow and thermal treatment at high temperatures. The cell was successfully used in the reaction of dry reforming of methane (DRM). We present X-ray absorption results in the fluorescence detection mode on a 0.4 wt. % Ni/ZrO 2 catalyst under realistic conditions at 750 °C, reproducing the conditions used for a conventional dynamic microreactor for the DRM reaction. The setup includes a gas distribution system that can be fully remotely operated. The reaction cell offers the possibility of transmission and fluorescence detection modes. The complete setup dedicated to the study of catalysts is permanently installed on the Collaborating Research Groups French Absorption spectroscopy beamline in Material and Environmental sciences (CRG-FAME) and French Absorption spectroscopy beamline in Material and Environmental sciences at Ultra-High Dilution (FAME-UHD) beamlines (BM30B and BM16) at the European Synchrotron Radiation Facility in Grenoble, France.

A new high temperature reactor for operando XAS: Application for the dry reforming of methane over Ni/ZrO2 catalyst

NASA Astrophysics Data System (ADS)

Aguilar-Tapia, Antonio; Ould-Chikh, Samy; Lahera, Eric; Prat, Alain; Delnet, William; Proux, Olivier; Kieffer, Isabelle; Basset, Jean-Marie; Takanabe, Kazuhiro; Hazemann, Jean-Louis

2018-03-01

The construction of a high-temperature reaction cell for operando X-ray absorption spectroscopy characterization is reported. A dedicated cell was designed to operate as a plug-flow reactor using powder samples requiring gas flow and thermal treatment at high temperatures. The cell was successfully used in the reaction of dry reforming of methane (DRM). We present X-ray absorption results in the fluorescence detection mode on a 0.4 wt. % Ni/ZrO2 catalyst under realistic conditions at 750 °C, reproducing the conditions used for a conventional dynamic microreactor for the DRM reaction. The setup includes a gas distribution system that can be fully remotely operated. The reaction cell offers the possibility of transmission and fluorescence detection modes. The complete setup dedicated to the study of catalysts is permanently installed on the Collaborating Research Groups French Absorption spectroscopy beamline in Material and Environmental sciences (CRG-FAME) and French Absorption spectroscopy beamline in Material and Environmental sciences at Ultra-High Dilution (FAME-UHD) beamlines (BM30B and BM16) at the European Synchrotron Radiation Facility in Grenoble, France.

Gas in scattering media absorption spectroscopy - GASMAS

NASA Astrophysics Data System (ADS)

Svanberg, Sune

2008-09-01

An overview of the new field of Gas in Scattering Media Absorption Spectroscopy (GASMAS) is presented. GASMAS combines narrow-band diode-laser spectroscopy with diffuse media optical propagation. While solids and liquids have broad absorption features, free gas in pores and cavities in the material is characterized by sharp spectral signatures, typically 10,000 times sharper than those of the host material. Many applications in materials science, food packaging, pharmaceutics and medicine have been demonstrated. So far molecular oxygen and water vapour have been studied around 760 and 935 nm, respectively. Liquid water, an important constituent in many natural materials, such as tissue, has a low absorption at such wavelengths, allowing propagation. Polystyrene foam, wood, fruits, food-stuffs, pharmaceutical tablets, and human sinus cavities have been studied. Transport of gas in porous media can readily be studied by first immersing the material in, e.g., pure nitrogen, and then observing the rate at which normal air, containing oxygen, reinvades the material. The conductance of the sinus connective passages can be measured in this way by flushing the nasal cavity with nitrogen. Also other dynamic processes such as drying of materials can be studied. The techniques have also been extended to remote-sensing applications (LIDAR-GASMAS).

High-Sensitivity Optical Techniques for Atmospheric Spectroscopy, Kinetics and Remote Sensing

NASA Technical Reports Server (NTRS)

2005-01-01

A principal objective of the work supported by this Grant has been to use IntraCavity Laser Absorption Spectroscopy (ICLAS) to acquire data on weakly absorbing species of atmospheric interest that are not accessible, or cannot be determined with sufficient precision, using conventional spectroscopic instrumentation. The principal focus has been to adapt the existing instrument to carry out Kinetic studies using IntraCavity Absorption Spectroscopy (KICAS) in order to measure rate parameters for weakly absorbing, environmentally significant species. Additional related work has been carried out in collaboration with Prof. M.J. Molina's program on air pollution in the Mexico City Metropolitan Area on modeling the role of these species in atmospheric chemistry.

Oxygen measurement by multimode diode lasers employing gas correlation spectroscopy.

PubMed

Lou, Xiutao; Somesfalean, Gabriel; Chen, Bin; Zhang, Zhiguo

2009-02-10

Multimode diode laser (MDL)-based correlation spectroscopy (COSPEC) was used to measure oxygen in ambient air, thereby employing a diode laser (DL) having an emission spectrum that overlaps the oxygen absorption lines of the A band. A sensitivity of 700 ppm m was achieved with good accuracy (2%) and linearity (R(2)=0.999). For comparison, measurements of ambient oxygen were also performed by tunable DL absorption spectroscopy (TDLAS) technique employing a vertical cavity surface emitting laser. We demonstrate that, despite slightly degraded sensitivity, the MDL-based COSPEC-based oxygen sensor has the advantages of high stability, low cost, ease-of-use, and relaxed requirements in component selection and instrument buildup compared with the TDLAS-based instrument.

Binding of a cyclic organoselenium compound with gold nanoparticles (GNP) and its effect on electron transfer properties.

PubMed

Kumar, Pavitra V; Singh, Beena G; Maiti, Nandita; Iwaoka, Michio; Priyadarsini, K Indira

2014-12-15

Binding of a cyclic organoselenium compound, DL-trans-3,4-dihydroxy-1-selenolane (DHSred) with gold nanoparticles (GNP) of different sizes was studied by absorption spectroscopy, dynamic light scattering (DLS), transmission electron microscope (TEM), surface enhanced Raman spectroscopy (SERS) and zeta-potential (ζ) measurements. GNP of different size were synthesized by varying the reaction conditions and their size was determined by DLS and TEM techniques. The absorption spectral data showed red shift in the surface plasmon resonance (SPR) band indicating increase in the size of GNP on binding to DHSred. SERS studies confirmed that the binding of DHSred with GNP is through selenium center with planar orientation of DHSred on the GNP surface. The product of the number of binding sites (n) in GNP and the binding constant (K) was estimated for GNP of different particle size. The zeta potential (ζ) value of GNP decreased marginally in the presence of DHSred. Further, the binding of DHSred with GNP was found to enhance its reactivity with 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) radicals (ABTS(·-)) and the reactivity increased with decrease in the GNP size. Such enhancement in the reducing ability may have a greater impact on the antioxidant activity of DHSred. Copyright © 2014 Elsevier Inc. All rights reserved.

Improved Optical and Morphological Properties of Vinyl-Substituted Hybrid Silica Materials Incorporating a Zn-Metalloporphyrin.

PubMed

Dudás, Zoltán; Fagadar-Cosma, Eugenia; Len, Adél; Románszki, Loránd; Almásy, László; Vlad-Oros, Beatrice; Dascălu, Daniela; Krajnc, Andraž; Kriechbaum, Manfred; Kuncser, Andrei

2018-04-06

This work is focused on a novel class of hybrid materials exhibiting enhanced optical properties and high surface areas that combine the morphology offered by the vinyl substituted silica host, and the excellent absorption and emission properties of 5,10,15,20-tetrakis( N -methyl-4-pyridyl)porphyrin-Zn(II) tetrachloride as a water soluble guest molecule. In order to optimize the synthesis procedure and the performance of the immobilized porphyrin, silica precursor mixtures of different compositions were used. To achieve the requirements regarding the hydrophobicity and the porous structure of the gels for the successful incorporation of porphyrin, the content of vinyltriacetoxysilane was systematically changed and thoroughly investigated. Substitution of the silica gels with organic groups is a viable way to provide new properties to the support. An exhaustive characterization of the synthesized silica samples was realised by complementary physicochemical methods, such as infrared spectroscopy (FT-IR), absorption spectroscopy (UV-Vis) and photoluminescence, nuclear magnetic resonance spectroscopy ( 29 Si-MAS-NMR) transmission and scanning electron microscopy (TEM and SEM), nitrogen absorption (BET), contact angle (CA), small angle X ray and neutron scattering (SAXS and SANS). All hybrids showed an increase in emission intensity in the wide region from 575 to 725 nm (Q bands) in comparison with bare porphyrin. By simply tuning the vinyltriacetoxysilane content, the hydrophilic/hydrophobic profile of the hybrid materials was changed, while maintaining a high surface area. Good control of hydrophobicity is important to enhance properties such as dispersion, stability behaviour, and resistance to water, in order to achieve highly dispersible systems in water for biomedical applications.

The electronic characterization of biphenylene—Experimental and theoretical insights from core and valence level spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lüder, Johann; Sanyal, Biplab; Eriksson, Olle

In this paper, we provide detailed insights into the electronic structure of the gas phase biphenylene molecule through core and valence spectroscopy. By comparing results of X-ray Photoelectron Spectroscopy (XPS) measurements with ΔSCF core-hole calculations in the framework of Density Functional Theory (DFT), we could decompose the characteristic contributions to the total spectra and assign them to non-equivalent carbon atoms. As a difference with similar molecules like biphenyl and naphthalene, an influence of the localized orbitals on the relative XPS shifts was found. The valence spectrum probed by photoelectron spectroscopy at a photon energy of 50 eV in conjunction withmore » hybrid DFT calculations revealed the effects of the localization on the electronic states. Using the transition potential approach to simulate the X-ray absorption spectroscopy measurements, similar contributions from the non-equivalent carbon atoms were determined from the total spectrum, for which the slightly shifted individual components can explain the observed asymmetric features.« less

Real-time dual-comb spectroscopy with a free-running bidirectionally mode-locked fiber laser

NASA Astrophysics Data System (ADS)

Mehravar, S.; Norwood, R. A.; Peyghambarian, N.; Kieu, K.

2016-06-01

Dual-comb technique has enabled exciting applications in high resolution spectroscopy, precision distance measurements, and 3D imaging. Major advantages over traditional methods can be achieved with dual-comb technique. For example, dual-comb spectroscopy provides orders of magnitude improvement in acquisition speed over standard Fourier-transform spectroscopy while still preserving the high resolution capability. Wider adoption of the technique has, however, been hindered by the need for complex and expensive ultrafast laser systems. Here, we present a simple and robust dual-comb system that employs a free-running bidirectionally mode-locked fiber laser operating at telecommunication wavelength. Two femtosecond frequency combs (with a small difference in repetition rates) are generated from a single laser cavity to ensure mutual coherent properties and common noise cancellation. As the result, we have achieved real-time absorption spectroscopy measurements without the need for complex servo locking with accurate frequency referencing, and relatively high signal-to-noise ratio.

Enhanced Vibrational Spectroscopies as Tools for Small Molecule Biosensing

PubMed Central

Boujday, Souhir; Lamy de la Chapelle, Marc; Srajer, Johannes; Knoll, Wolfgang

2015-01-01

In this short summary we summarize some of the latest developments in vibrational spectroscopic tools applied for the sensing of (small) molecules and biomolecules in a label-free mode of operation. We first introduce various concepts for the enhancement of InfraRed spectroscopic techniques, including the principles of Attenuated Total Reflection InfraRed (ATR-IR), (phase-modulated) InfraRed Reflection Absorption Spectroscopy (IRRAS/PM-IRRAS), and Surface Enhanced Infrared Reflection Absorption Spectroscopy (SEIRAS). Particular attention is put on the use of novel nanostructured substrates that allow for the excitation of propagating and localized surface plasmon modes aimed at operating additional enhancement mechanisms. This is then be complemented by the description of the latest development in Surface- and Tip-Enhanced Raman Spectroscopies, again with an emphasis on the detection of small molecules or bioanalytes. PMID:26343666

Sensitivity and resolution in frequency comb spectroscopy of buffer gas cooled polyatomic molecules

NASA Astrophysics Data System (ADS)

Changala, P. Bryan; Spaun, Ben; Patterson, David; Doyle, John M.; Ye, Jun

2016-12-01

We discuss the use of cavity-enhanced direct frequency comb spectroscopy in the mid-infrared region with buffer gas cooling of polyatomic molecules for high-precision rovibrational absorption spectroscopy. A frequency comb coupled to an optical enhancement cavity allows us to collect high-resolution, broad-bandwidth infrared spectra of translationally and rotationally cold (10-20 K) gas-phase molecules with high absorption sensitivity and fast acquisition times. The design and performance of the combined apparatus are discussed in detail. Recorded rovibrational spectra in the CH stretching region of several organic molecules, including vinyl bromide (CH_2CHBr), adamantane (C_{10}H_{16}), and diamantane (C_{14}H_{20}) demonstrate the resolution and sensitivity of this technique, as well as the intrinsic challenges faced in extending the frontier of high-resolution spectroscopy to large complex molecules.

Screening Technique for Lead and Cadmium in Toys and Other Materials Using Atomic Absorption Spectroscopy

ERIC Educational Resources Information Center

Brouwer, Henry

2005-01-01

A simple procedure to quickly screen different consumer products for the presence of lead, cadmium, and other metals is described. This screening technique avoids expending a lot of preparation time on samples known to contain low levels of hazardous metals where only samples testing positive for the desired elements need to be analyzed…

Qualitative and quantitative analysis of an additive element in metal oxide nanometer film using laser induced breakdown spectroscopy.

PubMed

Xiu, Junshan; Liu, Shiming; Sun, Meiling; Dong, Lili

2018-01-20

The photoelectric performance of metal ion-doped TiO 2 film will be improved with the changing of the compositions and concentrations of additive elements. In this work, the TiO 2 films doped with different Sn concentrations were obtained with the hydrothermal method. Qualitative and quantitative analysis of the Sn element in TiO 2 film was achieved with laser induced breakdown spectroscopy (LIBS) with the calibration curves plotted accordingly. The photoelectric characteristics of TiO 2 films doped with different Sn content were observed with UV visible absorption spectra and J-V curves. All results showed that Sn doping could improve the optical absorption to be red-shifted and advance the photoelectric properties of the TiO 2 films. We had obtained that when the concentration of Sn doping in TiO 2 films was 11.89  mmol/L, which was calculated by the LIBS calibration curves, the current density of the film was the largest, which indicated the best photoelectric performance. It indicated that LIBS was a potential and feasible measured method, which was applied to qualitative and quantitative analysis of the additive element in metal oxide nanometer film.

Structural investigation of the cocrystal formed between 5-fluorocytosine and fumaric acid based on vibrational spectroscopic technique

NASA Astrophysics Data System (ADS)

Du, Yong; Cai, Qiang; Xue, Jiadan; Zhang, Qi; Qin, Dan

2017-05-01

The vibrational spectra of 5-fluorocytosine, fumaric acid and their cocrystal were measured using terahertz time-domain spectroscopy (THz-TDS) and Raman spectroscopy at room temperature. Experimental THz results show that the cocrystal has distinct fingerprint spectra in terahertz region. The absorption peaks observed in the terahertz spectra of the cocrystal were at 0.61 and 0.91 THz. These are quite different from corresponding raw starting materials. Raman spectra also show similar results about differences between the cocrystal and corresponding raw starting materials. Density functional theory (DFT) was used to simulate the structure of the possible salt form and the cocrystal form between 5-fluorocytosine and fumaric acid. The theoretical terahertz result shows that the cocrystal form has absorption at 0.62 and 0.87 THz, which is in agreement with the experimental result. The theoretical Raman result also indicates that the cocrystal form has more possibilities than the salt form. So, it is more reasonable that the structure between 5-fluorocytosine and fumaric acid could be the corresponding cocrystal form. The characteristic bands of the cocrystal between 5-fluorocytosine and fumaric acid are also assigned based on the simulation results from the DFT calculation.

Mercury Speciation by X-ray Absorption Fine Structure Spectroscopy and Sequential Chemical Extractions: A Comparison of Speciation Methods

USGS Publications Warehouse

Kim, C.S.; Bloom, N.S.; Rytuba, J.J.; Brown, Gordon E.

2003-01-01

Determining the chemical speciation of mercury in contaminated mining and industrial environments is essential for predicting its solubility, transport behavior, and potential bioavailability as well as for designing effective remediation strategies. In this study, two techniques for determining Hg speciation-X-ray absorption fine structure (XAFS) spectroscopy and sequential chemical extractions (SCE)-are independently applied to a set of samples with Hg concentrations ranging from 132 to 7539 mg/kg to determine if the two techniques provide comparable Hg speciation results. Generally, the proportions of insoluble HgS (cinnabar, metacinnabar) and HgSe identified by XAFS correlate well with the proportion of Hg removed in the aqua regia extraction demonstrated to remove HgS and HgSe. Statistically significant (> 10%) differences are observed however in samples containing more soluble Hg-containing phases (HgCl2, HgO, Hg3S2O 4). Such differences may be related to matrix, particle size, or crystallinity effects, which could affect the apparent solubility of Hg phases present. In more highly concentrated samples, microscopy techniques can help characterize the Hg-bearing species in complex multiphase natural samples.

Chemical Form and Distribution of Selenium and Sulfur in the Selenium Hyperaccumulator Astragalus bisulcatus1

PubMed Central

Pickering, Ingrid J.; Wright, Carrie; Bubner, Ben; Ellis, Danielle; Persans, Michael W.; Yu, Eileen Y.; George, Graham N.; Prince, Roger C.; Salt, David E.

2003-01-01

In its natural habitat, Astragalus bisulcatus can accumulate up to 0.65% (w/w) selenium (Se) in its shoot dry weight. X-ray absorption spectroscopy has been used to examine the selenium biochemistry of A. bisulcatus. High concentrations of the nonprotein amino acid Se-methylseleno-cysteine (Cys) are present in young leaves of A. bisulcatus, but in more mature leaves, the Se-methylseleno-Cys concentration is lower, and selenate predominates. Seleno-Cys methyltransferase is the enzyme responsible for the biosynthesis of Se-methylseleno-Cys from seleno-Cys and S-methyl-methionine. Seleno-Cys methyltransferase is found to be expressed in A. bisulcatus leaves of all ages, and thus the biosynthesis of Se-methylseleno-Cys in older leaves is limited earlier in the metabolic pathway, probably by an inability to chemically reduce selenate. A comparative study of sulfur (S) and Se in A. bisulcatus using x-ray absorption spectroscopy indicates similar trends for oxidized and reduced Se and S species, but also indicates that the proportions of these differ significantly. These results also indicate that sulfate and selenate reduction are developmentally correlated, and they suggest important differences between S and Se biochemistries. PMID:12644695

Characterization of Maize Grains with Different Pigmentation Investigated by Photoacoustic Spectroscopy

NASA Astrophysics Data System (ADS)

Rico Molina, R.; Hernández Aguilar, C.; Dominguez Pacheco, A.; Cruz-Orea, A.; López Bonilla, J. L.

2014-10-01

A knowledge of grains' optical parameters is of great relevance in the maize grain technology practice. Such parameters provide information about its absorption and reflectance, which in turn is related to its color. In the dough and tortilla industries, it is important to characterize this attribute of the corn kernel, as it is one of the attributes that directly affects the quality of the food product. Thus, it is important to have techniques that contribute to the characterization of this raw material. It is traditionally characterized by conventional methods, which usually destroy the grain and involve a laborious preparation of material plus they are expensive. The objective of this study was to determine the optical absorption coefficient for maize grains ( Zea mays L.) with different pigmentations by means of photoacoustic spectroscopy (PAS). The genotype A had bluish coloration and genotype B had yellowish coloration. In addition, the photoacoustic signal obtained by two methods was analyzed mathematically: the standard deviation and the first derivative; both results were compared (Fig. 1). In combination with mathematical analysis, PAS may be considered as a potential diagnostic tool for the characterization of the grains. [Figure not available: see fulltext.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ngu, Thanh T.; Sturzenbaum, Stephen R.; Stillman, Martin J.

The earthworm Lumbricus rubellus has been found to inhabit cadmium-rich soils and accumulate cadmium within its tissues. Two metallothionein (MT) isoforms (1 and 2) have been identified and cloned from L. rubellus. In this study, we address the metalation status, metal coordination, and structure of recombinant MT-2 from L. rubellus using electrospray ionization mass spectrometry (ESI-MS), UV absorption, and circular dichroism (CD) spectroscopy. This is the first study to show the detailed mass and CD spectral properties for the important cadmium-containing earthworm MT. We report that the 20-cysteine L. rubellus MT-2 binds seven Cd{sup 2+} ions. UV absorption and CDmore » spectroscopy and ESI-MS pH titrations show a distinct biphasic demetalation reaction, which we propose results from the presence of two metal-thiolate binding domains. We propose stoichiometries of Cd{sub 3}Cys{sub 9} and Cd{sub 4}Cys{sub 11} based on the presence of 20 cysteines split into two isolated regions of the sequence with 11 cysteines in the N-terminal and 9 cysteines in the C-terminal. The CD spectrum reported is distinctly different from any other metallothionein known suggesting quite different binding site structure for the peptide.« less

Gas monitoring in human sinuses using tunable diode laser spectroscopy.

PubMed

Persson, Linda; Andersson, Mats; Cassel-Engquist, Märta; Svanberg, Katarina; Svanberg, Sune

2007-01-01

We demonstrate a novel nonintrusive technique based on tunable diode laser absorption spectroscopy to investigate human sinuses in vivo. The technique relies on the fact that free gases have spectral imprints that are about 10.000 times sharper than spectral structures of the surrounding tissue. Two gases are detected; molecular oxygen at 760 nm and water vapor at 935 nm. Light is launched fiber optically into the tissue in close proximity to the particular maxillary sinus under study. When investigating the frontal sinuses, the fiber is positioned onto the caudal part of the frontal bone. Multiply scattered light in both cases is detected externally by a handheld probe. Molecular oxygen is detected in the maxillary sinuses on 11 volunteers, of which one had constantly recurring sinus problems. Significant oxygen absorption imprint differences can be observed between different volunteers and also left-right asymmetries. Water vapor can also be detected, and by normalizing the oxygen signal on the water vapor signal, the sinus oxygen concentration can be assessed. Gas exchange between the sinuses and the nasal cavity is also successfully demonstrated by flushing nitrogen through the nostril. Advantages over current ventilation assessment methods using ionizing radiation are pointed out.

A prototype stationary Fourier transform spectrometer for near-infrared absorption spectroscopy.

PubMed

Li, Jinyang; Lu, Dan-feng; Qi, Zhi-mei

2015-09-01

A prototype stationary Fourier transform spectrometer (FTS) was constructed with a fiber-coupled lithium niobate (LiNbO3) waveguide Mach-Zehnder interferometer (MZI) for the purpose of rapid on-site spectroscopy of biological and chemical measurands. The MZI contains push-pull electrodes for electro-optic modulation, and its interferogram as a plot of intensity against voltage was obtained by scanning the modulating voltage from -60 to +60 V in 50 ms. The power spectrum of input signal was retrieved by Fourier transform processing of the interferogram combined with the wavelength dispersion of half-wave voltage determined for the MZI used. The prototype FTS operates in the single-mode wavelength range from 1200 to 1700 nm and allows for reproducible spectroscopy. A linear concentration dependence of the absorbance at λmax = 1451 nm for water in ethanolic solution was obtained using the prototype FTS. The near-infrared spectroscopy of solid samples was also implemented, and the different spectra obtained with different materials evidenced the chemical recognition capability of the prototype FTS. To make this prototype FTS practically applicable, work on improving its spectral resolution by increasing the maximum optical path length difference is in progress.

Voxel-based measurement sensitivity of spatially resolved near-infrared spectroscopy in layered tissues

NASA Astrophysics Data System (ADS)

Niwayama, Masatsugu

2018-03-01

We quantitatively investigated the measurement sensitivity of spatially resolved spectroscopy (SRS) across six tissue models: cerebral tissue, a small animal brain, the forehead of a fetus, an adult brain, forearm muscle, and thigh muscle. The optical path length in the voxel of the model was analyzed using Monte Carlo simulations. It was found that the measurement sensitivity can be represented as the product of the change in the absorption coefficient and the difference in optical path length in two states with different source-detector distances. The results clarified the sensitivity ratio between the surface layer and the deep layer at each source-detector distance for each model and identified changes in the deep measurement area when one of the detectors was close to the light source. A comparison was made with the results from continuous-wave spectroscopy. The study also identified measurement challenges that arise when the surface layer is inhomogeneous. Findings on the measurement sensitivity of SRS at each voxel and in each layer can support the correct interpretation of measured values when near-infrared oximetry or functional near-infrared spectroscopy is used to investigate different tissue structures.

Group 6 metal pentacarbonyl complexes of air-stable primary, secondary, and tertiary ferrocenylethylphosphines.

PubMed

Rabiee Kenaree, Amir; Sauvé, Ethan R; Ragogna, Paul J; Gilroy, Joe B

2016-02-21

The synthesis and characterization of a series of Group 6 metal pentacarbonyl complexes of air stable primary, secondary, and tertiary phosphines containing ferrocenylethyl substituents are reported [M(CO)5L: M = Cr, Mo, W; L = PH2(CH2CH2Fc), PH(CH2CH2Fc)2, P(CH2CH2Fc)3]. The structure and composition of the complexes were confirmed by multinuclear NMR spectroscopy, IR and UV-Vis absorption spectroscopy, mass spectrometry, X-ray crystallography, and elemental analysis. The solid-state structural data reported revealed trends in M-C and M-P bond lengths that mirrored those of the atomic radii of the Group 6 metals involved. UV-Vis absorption spectroscopy and cyclic voltammetry highlighted characteristics consistent with electronically isolated ferrocene units including wavelengths of maximum absorption between 435 and 441 nm and reversible one-electron (per ferrocene unit) oxidation waves between 10 and -5 mV relative to the ferrocene/ferrocenium redox couple. IR spectroscopy confirmed that the σ donating ability of the phosphines increased as ferrocenylethyl substituents were introduced and that the tertiary phosphine ligand described is a stronger σ donor than PPh3 and a weaker σ donor than PEt3, respectively.

Novel Semi-Parametric Algorithm for Interference-Immune Tunable Absorption Spectroscopy Gas Sensing

PubMed Central

Michelucci, Umberto; Venturini, Francesca

2017-01-01

One of the most common limits to gas sensor performance is the presence of unwanted interference fringes arising, for example, from multiple reflections between surfaces in the optical path. Additionally, since the amplitude and the frequency of these interferences depend on the distance and alignment of the optical elements, they are affected by temperature changes and mechanical disturbances, giving rise to a drift of the signal. In this work, we present a novel semi-parametric algorithm that allows the extraction of a signal, like the spectroscopic absorption line of a gas molecule, from a background containing arbitrary disturbances, without having to make any assumption on the functional form of these disturbances. The algorithm is applied first to simulated data and then to oxygen absorption measurements in the presence of strong fringes.To the best of the authors’ knowledge, the algorithm enables an unprecedented accuracy particularly if the fringes have a free spectral range and amplitude comparable to those of the signal to be detected. The described method presents the advantage of being based purely on post processing, and to be of extremely straightforward implementation if the functional form of the Fourier transform of the signal is known. Therefore, it has the potential to enable interference-immune absorption spectroscopy. Finally, its relevance goes beyond absorption spectroscopy for gas sensing, since it can be applied to any kind of spectroscopic data. PMID:28991161

Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals. Final Performance Report, August 1, 1985--July 31, 1994

DOE R&D Accomplishments Database

Curl, R. F.; Glass, G. P.

1995-06-01

This research was directed at the detection, monitoring, and study (by infrared absorption spectroscopy) of the chemical kinetic behavior of small free radical species thought to be important intermediates in combustion. The work typically progressed from the detection and analysis of the infrared spectrum of combustion radical to the utilization of the infrared spectrum thus obtained in the investigation of chemical kinetics of the radical species. The methodology employed was infrared kinetic spectroscopy. In this technique the radical is produced by UV flash photolysis using an excimer laser and then its transient infrared absorption is observed using a single frequency cw laser as the source of the infrared probe light. When the probe laser frequency is near the center of an absorption line of the radical produced by the flash, the transient infrared absorption rises rapidly and then decays as the radical reacts with the precursor or with substances introduced for the purpose of studying the reaction kinetics or with itself. The decay times observed in these studies varied from less than one microsecond to more than one millisecond. By choosing appropriate time windows after the flash and the average infrared detector signal in a window as data channels, the infrared spectrum of the radical may be obtained. By locking the infrared probe laser to the center of the absorption line and measuring the rate of decay of the transient infrared absorption signal as the chemical composition of the gas mixture is varied, the chemical kinetics of the radical may be investigated. In what follows the systems investigated and the results obtained are outlined.

Determination of blood oxygenation in the brain by time-resolved reflectance spectroscopy: influence of the skin, skull, and meninges

NASA Astrophysics Data System (ADS)

Hielscher, Andreas H.; Liu, Hanli; Wang, Lihong V.; Tittel, Frank K.; Chance, Britton; Jacques, Steven L.

1994-07-01

Near infrared light has been used for the determination of blood oxygenation in the brain but little attention has been paid to the fact that the states of blood oxygenation in arteries, veins, and capillaries differ substantially. In this study, Monte Carlo simulations for a heterogeneous system were conducted, and near infrared time-resolved reflectance measurements were performed on a heterogeneous tissue phantom model. The model was made of a solid polyester resin, which simulates the tissue background. A network of tubes was distributed uniformly through the resin to simulate the blood vessels. The time-resolved reflectance spectra were taken with different absorbing solutions filled in the network. Based on the simulation and experimental results, we investigated the dependence of the absorption coefficient obtained from the heterogeneous system on the absorption of the actual absorbing solution filled in the tubes. We show that light absorption by the brain should result from the combination of blood and blood-free tissue background.

Mid-infrared absorption spectroscopy using quantum cascade lasers

NASA Astrophysics Data System (ADS)

Haibach, Fred; Erlich, Adam; Deutsch, Erik

2011-06-01

Block Engineering has developed an absorption spectroscopy system based on widely tunable Quantum Cascade Lasers (QCL). The QCL spectrometer rapidly cycles through a user-selected range in the mid-infrared spectrum, between 6 to 12 μm (1667 to 833 cm-1), to detect and identify substances on surfaces based on their absorption characteristics from a standoff distance of up to 2 feet with an eye-safe laser. It can also analyze vapors and liquids in a single device. For military applications, the QCL spectrometer has demonstrated trace explosive, chemical warfare agent (CWA), and toxic industrial chemical (TIC) detection and analysis. The QCL's higher power density enables measurements from diffuse and highly absorbing materials and substrates. Other advantages over Fourier Transform Infrared (FTIR) spectroscopy include portability, ruggedness, rapid analysis, and the ability to function from a distance through free space or a fiber optic probe. This paper will discuss the basic technology behind the system and the empirical data on various safety and security applications.

A new on-axis micro-spectrophotometer for combining Raman, fluorescence and UV/Vis absorption spectroscopy with macromolecular crystallography at the Swiss Light Source

PubMed Central

Pompidor, Guillaume; Dworkowski, Florian S. N.; Thominet, Vincent; Schulze-Briese, Clemens; Fuchs, Martin R.

2013-01-01

The combination of X-ray diffraction experiments with optical methods such as Raman, UV/Vis absorption and fluorescence spectroscopy greatly enhances and complements the specificity of the obtained information. The upgraded version of the in situ on-axis micro-spectrophotometer, MS2, at the macromolecular crystallography beamline X10SA of the Swiss Light Source is presented. The instrument newly supports Raman and resonance Raman spectroscopy, in addition to the previously available UV/Vis absorption and fluorescence modes. With the recent upgrades of the spectral bandwidth, instrument stability, detection efficiency and control software, the application range of the instrument and its ease of operation were greatly improved. Its on-axis geometry with collinear X-ray and optical axes to ensure optimal control of the overlap of sample volumes probed by each technique is still unique amongst comparable facilities worldwide and the instrument has now been in general user operation for over two years. PMID:23955041

Multiphoton-gated cycloreversion reaction of a fluorescent diarylethene derivative as revealed by transient absorption spectroscopy.

PubMed

Nagasaka, Tatsuhiro; Kunishi, Tomohiro; Sotome, Hikaru; Koga, Masafumi; Morimoto, Masakazu; Irie, Masahiro; Miyasaka, Hiroshi

2018-06-07

The one- and two-photon cycloreversion reactions of a fluorescent diarylethene derivative with oxidized benzothiophene moieties were investigated by means of ultrafast laser spectroscopy. Femtosecond transient absorption spectroscopy under the one-photon excitation condition revealed that the excited closed-ring isomer is simply deactivated into the initial ground state with a time constant of 2.6 ns without remarkable cycloreversion, the results of which are consistent with the very low cycloreversion reaction yield (<10-5) under steady-state light irradiation. On the other hand, an efficient cycloreversion reaction was observed under irradiation with a picosecond laser pulse at 532 nm. The excitation intensity dependence of the cycloreversion reaction indicates that a highly excited state attained by the stepwise two-photon absorption is responsible for the marked increase of the cycloreversion reaction, and the quantum yield at the highly excited state was estimated to be 0.018 from quantitative analysis, indicating that the reaction is enhanced by a factor of >1800.

Fringes in FTIR spectroscopy revisited: understanding and modelling fringes in infrared spectroscopy of thin films.

PubMed

Konevskikh, Tatiana; Ponossov, Arkadi; Blümel, Reinhold; Lukacs, Rozalia; Kohler, Achim

2015-06-21

The appearance of fringes in the infrared spectroscopy of thin films seriously hinders the interpretation of chemical bands because fringes change the relative peak heights of chemical spectral bands. Thus, for the correct interpretation of chemical absorption bands, physical properties need to be separated from chemical characteristics. In the paper at hand we revisit the theory of the scattering of infrared radiation at thin absorbing films. Although, in general, scattering and absorption are connected by a complex refractive index, we show that for the scattering of infrared radiation at thin biological films, fringes and chemical absorbance can in good approximation be treated as additive. We further introduce a model-based pre-processing technique for separating fringes from chemical absorbance by extended multiplicative signal correction (EMSC). The technique is validated by simulated and experimental FTIR spectra. It is further shown that EMSC, as opposed to other suggested filtering methods for the removal of fringes, does not remove information related to chemical absorption.

Cobalt Oxide Nanoclusters on Rutile Titania as Bifunctional Units for Water Oxidation Catalysis and Visible Light Absorption: Understanding the Structure-Activity Relationship.

PubMed

Maeda, Kazuhiko; Ishimaki, Koki; Okazaki, Megumi; Kanazawa, Tomoki; Lu, Daling; Nozawa, Shunsuke; Kato, Hideki; Kakihana, Masato

2017-02-22

The structure of cobalt oxide (CoO x ) nanoparticles dispersed on rutile TiO 2 (R-TiO 2 ) was characterized by X-ray diffraction, UV-vis-NIR diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray absorption fine-structure spectroscopy, and X-ray photoelectron spectroscopy. The CoO x nanoparticles were loaded onto R-TiO 2 by an impregnation method from an aqueous solution containing Co(NO 3 ) 2 ·6H 2 O followed by heating in air. Modification of the R-TiO 2 with 2.0 wt % Co followed by heating at 423 K for 1 h resulted in the highest photocatalytic activity with good reproducibility. Structural analyses revealed that the activity of this photocatalyst depended strongly on the generation of Co 3 O 4 nanoclusters with an optimal distribution. These nanoclusters are thought to interact with the R-TiO 2 surface, resulting in visible light absorption and active sites for water oxidation.

A new on-axis micro-spectrophotometer for combining Raman, fluorescence and UV/Vis absorption spectroscopy with macromolecular crystallography at the Swiss Light Source.

PubMed

Pompidor, Guillaume; Dworkowski, Florian S N; Thominet, Vincent; Schulze-Briese, Clemens; Fuchs, Martin R

2013-09-01

The combination of X-ray diffraction experiments with optical methods such as Raman, UV/Vis absorption and fluorescence spectroscopy greatly enhances and complements the specificity of the obtained information. The upgraded version of the in situ on-axis micro-spectrophotometer, MS2, at the macromolecular crystallography beamline X10SA of the Swiss Light Source is presented. The instrument newly supports Raman and resonance Raman spectroscopy, in addition to the previously available UV/Vis absorption and fluorescence modes. With the recent upgrades of the spectral bandwidth, instrument stability, detection efficiency and control software, the application range of the instrument and its ease of operation were greatly improved. Its on-axis geometry with collinear X-ray and optical axes to ensure optimal control of the overlap of sample volumes probed by each technique is still unique amongst comparable facilities worldwide and the instrument has now been in general user operation for over two years.

OH detection by Ford Motor Company

NASA Technical Reports Server (NTRS)

Wang, Charles C.

1986-01-01

Two different methods for detection of OH are presented: a low pressure flow cell system and a frequency modulation absorption measurement. Using conventional absorption spectroscopy, detection limits were quoted of 1,000,000 OH molecules per cu cm using a 30-minute averaging time on the ground, and a 3-hour averaging time in the air for present apparatus in use. With the addition of FM spectroscopy at 1 GHz, a double-beam machine should permit detectable absorption of and an OH limit of 100,000 per cu cm in a 30-minute averaging time. In the low pressure system on which experiments are ongoing nonexponential time behavior was observed after the decay had progressed to about 0.3 of its original level; this was attributed to ion emission in the photomultiplier. A flame source with OH present at high concentration levels was used as a calibration. It was estimated that within the sampling chamber, 400,000 OH could be measured. With a factor-of-2 loss at the sampling orifice, this means detectability of 5 to 8 x 100,000 cu cm at the present time. This could be reduced by a factor of 2 in one hour averaging time; improvements in laser bandwidth and energy should provide another factor of 2 in sensitivity.

Probing photochromic properties by correlation of UV-visible and infra-red absorption spectroscopy: a case study with cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethene.

PubMed

Spangenberg, Arnaud; Piedras Perez, Jose Alejandro; Patra, Abhijit; Piard, Jonathan; Brosseau, Arnaud; Métivier, Rémi; Nakatani, Keitaro

2010-02-01

Quantification of the relative composition of the isomers in a photochromic system at any irradiation time interval is a critical issue in determining absolute quantum yields. For this purpose, we have developed a simple and convenient protocol involving combination of UV-visible and infra-red absorption spectroscopy. Photochromic cyclization reaction of cis-l,2-dicyano-l,2-bis(2,4,5-trimethyl-3-thieny1)ethene (CMTE) is analyzed to demonstrate the efficiency of the proposed methodology. This approach is based on the fact that the two isomers show distinctive infra-red bands. Detailed investigations of the UV-visible and infra-red spectra of the mixture obtained at different irradiation times in CCl(4) supported by quantum chemical computations lead to the unambiguous estimation of molar absorption coefficients of the closed isomer (epsilon(CF) = 4650 L mol(-1) cm(-1) at 512 nm). It facilitates the first determination of absolute quantum yields of this reversible photochromic reaction in CCl(4) by fitting the UV-visible spectral data (Phi(OF-->CF) = 0.41 +/- 0.05 and Phi(CF-->OF) = 0.12 +/- 0.02 at 405 nm and 546 nm, respectively).

Synthesis, characterization, redox behavior, DNA and protein binding and antibacterial activity studies of ruthenium(II) complexes of bidentate schiff bases.

PubMed

Paul, Hena; Sen, Buddhadeb; Mondal, Tapan Kumar; Chattopadhyay, Pabitra

2017-08-03

Two new ruthenium(II) complexes of Schiff base ligands (L) derived from cinnamaldehyde and ethylenediamine formulated as [Ru(L)(bpy) 2 ](ClO 4 ) 2 , where L 1 = N,N'-bis(4-nitrocinnamald-ehyde)ethylenediamine and L 2 = N,N'-bis(2-nitrocinnamaldehyde)-ethylenediamine for complex 1 and 2, respectively, were isolated in pure form. The complexes were characterized by physicochemical and spectroscopic methods. The electrochemical behavior of the complexes showed the Ru(III)/Ru(II) couple at different potentials with quasi-reversible voltammograms. The interaction of the complexes with calf thymus DNA (CT-DNA) using absorption, emission spectral studies and electrochemical techniques have been used to determine the binding constant, K b and the linear Stern-Volmer quenching constant, K SV . The results indicate that the ruthenium(II) complexes interact with CT-DNA strongly in a groove binding mode. The interactions of bovine serum albumin (BSA) with the complexes were also investigated with the help of absorption and fluorescence spectroscopy tools. Absorption spectroscopy proved the formation of a ground state BSA-[Ru(L)(bpy) 2 ](ClO 4 ) 2 complex. The antibacterial study showed that the Ru(II) complexes (1 and 2) have better activity than the standard antibiotics but weak activity than the ligands.