Charge-induced equilibrium dynamics and structure at the Ag(001)–electrolyte interface

DOE PAGES

Karl Jr., Robert M.; Barbour, Andi; Komanicky, Vladimir; ...

2015-06-08

We have measured the applied potential dependent rate of atomic step motion of the Ag (001) surface in weak NaF electrolyte using a new extension of the technique of X-ray Photon Correlation Spectroscopy (XPCS). Furthermore, concurrent specular x-ray scattering measurements reveal how the ordering of the water layers at the interface correlates with the dynamics.

X-ray Photon Correlation Spectroscopy: A New Probe of Short Wavelength Dynamics

NASA Astrophysics Data System (ADS)

Dierker, S. B.

1996-03-01

The new field of x-ray photon correlation spectroscopy (XPCS) offers an unprecedented opportunity to extend the range of length scales over which a material's low frequency dynamics can be studied down to interatomic spacings. The critical development which has now made XPCS a feasible technique is the high brightness of insertion devices at second and third generation synchrotron sources. In this talk, I will describe the principles of the XPCS technique and how it is practiced, as well as its potential use for a variety of important problems in the low frequency dynamics of condensed matter systems, such as complex fluids, glasses, surfaces, and metallic alloys. Illustrations will be drawn from our(Research done in collaboration with R. Pindak, R. M. Fleming, I. K. Robinson, L. Berman, G. Grubel, and D. L. Abernathy. S.B.D. supported by NSF DMR92-17956. I.K.R. supported by NSF MDR 93-15691. The NSLS is supported by DOE DE-AC02-76CH00016.) results(S. B. Dierker, R. Pindak, R. M. Fleming, I. K. Robinson, L. Berman, Phys. Rev. Lett. 75), 449 (1995). on using XPCS to study the Brownian motion of a gold colloid. We made small angle x-ray scattering measurements of the static structure factor of an optically opaque gold colloid dispersed in the viscous liquid glycerol. We discovered a novel effect due to photoemission induced charging of the gold colloid which could be suppressed by the addition of salt. We determined the dynamic correlation functions for the Brownian motion of the colloid particles at wavevectors between 10-3 <= q <= 10-2 Åwhich extends well beyond the range of visible light scattering. The resulting diffusion coefficient is very q dependent, scaling approximately as D(q) = D_o/S(q). The results of recent progress in using the Prototype Small Gap Undulator (PSGU) at beam line X13 at the NSLS will also be described. We(Research done in collaboration with L. Berman, Z. Yin, and E. Dufresne.) have achieved a coherent flux of > 10^10 photons/second in a `pink' beam at 3 keV by using a mirror to filter out the harmonics. This should be an excellent source for small angle XPCS measurements. The results of initial experiments conducted with the PSGU will be presented. The experiments were conducted at the wiggler beam line X25 and the PSGU beamline X13 at the NSLS and at the undulator beamline 9/ID10 (Troika) at the ESRF.

Coherent X-ray Scattering from Liquid-Air Interfaces

NASA Astrophysics Data System (ADS)

Shpyrko, Oleg

Advances in synchrotron x-ray scattering techniques allow studies of structure and dynamics of liquid surfaces with unprecedented resolution. I will review x-ray scattering measurements of thermally excited capillary fluctuations in liquids, thin polymer liquid films and polymer surfaces in confined geometry. X-ray Diffuse scattering profile due to Debye-Waller like roughening of the surface allows to probe the distribution of capillary fluctuations over a wide range of length scales, while using X-ray Photon Correlation Spectroscopy (XPCS) one is able to directly couple to nanoscale dynamics of these surface fluctuations, over a wide range of temporal and spacial scales. I will also discuss recent XPCS measurements of lateral diffusion dynamics in Langmuir monolayers assembled at the liquid-air interface. This research was supported by NSF CAREER Grant 0956131.

Altered structural brain connectome in young adult fragile X premutation carriers.

PubMed

Leow, Alex; Harvey, Danielle; Goodrich-Hunsaker, Naomi J; Gadelkarim, Johnson; Kumar, Anand; Zhan, Liang; Rivera, Susan M; Simon, Tony J

2014-09-01

Fragile X premutation carriers (fXPC) are characterized by 55-200 CGG trinucleotide repeats in the 5' untranslated region on the Xq27.3 site of the X chromosome. Clinically, they are associated with the fragile X-Associated Tremor/Ataxia Syndrome, a late-onset neurodegenerative disorder with diffuse white matter neuropathology. Here, we conducted first-ever graph theoretical network analyses in fXPCs using 30-direction diffusion-weighted magnetic resonance images acquired from 42 healthy controls aged 18-44 years (HC; 22 male and 20 female) and 46 fXPCs (16 male and 30 female). Globally, we found no differences between the fXPCs and HCs within each gender for all global graph theoretical measures. In male fXPCs, global efficiency was significantly negatively associated with the number of CGG repeats. For nodal measures, significant group differences were found between male fXPCs and male HCs in the right fusiform and the right ventral diencephalon (for nodal efficiency), and in the left hippocampus [for nodal clustering coefficient (CC)]. In female fXPCs, CC in the left superior parietal cortex correlated with counting performance in an enumeration task. Copyright © 2014 Wiley Periodicals, Inc.

Exploring the relationship between nanoscale dynamics and macroscopic rheology in natural polymer gums

DOE PAGES

Grein-Iankovski, Aline; Riegel-Vidotti, Izabel C.; Simas-Tosin, Fernanda F.; ...

2016-11-02

Here, we report a study connecting the nanoscale and macroscale structure and dynamics of Acacia mearnsii gum as probed by small-angle x-ray scattering (SAXS), x-ray photon correlation spectroscopy (XPCS) and rheology. Acacia gum, in general, is a complex polysaccharide used extensively in industry. Over the analyzed concentration range (15 to 30 wt%) the A. mearnsii gum is found to have a gel-like linear rheology and to exhibit shear thinning flow behavior under steady shear. The gum exhibited a steadily increasing elastic modulus with increasing time after they were prepared and also the emergence of shear thickening events within the shearmore » thinning behavior, characteristic of associative polymers. XPCS measurements using gold nanoparticles as tracers were used to explore the microscopic dynamics within the biopolymer gels and revealed a two-step relaxation process with a partial decay at inaccessibly short times, suggesting caged motion of the nanoparticles, followed by a slow decay at later delay times. Non-diffusive motion evidenced by a compressed exponential line shape and an inverse relationship between relaxation time and wave vector characterizes the slow dynamics of A. mearnsii gum gels. Surprisingly, we have determined that the nanometer-scale mean square displacement of the nanoparticles showed a close relationship to the values predicted from the macroscopic elastic properties of the material, obtained through the rheology experiments. Our results demonstrate the potential applicability of the XPCS technique in the natural polymers field to connect their macroscale properties with their nanoscale structure and dynamics.« less

Exploring the relationship between nanoscale dynamics and macroscopic rheology in natural polymer gums

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

Grein-Iankovski, Aline; Riegel-Vidotti, Izabel C.; Simas-Tosin, Fernanda F.

Here, we report a study connecting the nanoscale and macroscale structure and dynamics of Acacia mearnsii gum as probed by small-angle x-ray scattering (SAXS), x-ray photon correlation spectroscopy (XPCS) and rheology. Acacia gum, in general, is a complex polysaccharide used extensively in industry. Over the analyzed concentration range (15 to 30 wt%) the A. mearnsii gum is found to have a gel-like linear rheology and to exhibit shear thinning flow behavior under steady shear. The gum exhibited a steadily increasing elastic modulus with increasing time after they were prepared and also the emergence of shear thickening events within the shearmore » thinning behavior, characteristic of associative polymers. XPCS measurements using gold nanoparticles as tracers were used to explore the microscopic dynamics within the biopolymer gels and revealed a two-step relaxation process with a partial decay at inaccessibly short times, suggesting caged motion of the nanoparticles, followed by a slow decay at later delay times. Non-diffusive motion evidenced by a compressed exponential line shape and an inverse relationship between relaxation time and wave vector characterizes the slow dynamics of A. mearnsii gum gels. Surprisingly, we have determined that the nanometer-scale mean square displacement of the nanoparticles showed a close relationship to the values predicted from the macroscopic elastic properties of the material, obtained through the rheology experiments. Our results demonstrate the potential applicability of the XPCS technique in the natural polymers field to connect their macroscale properties with their nanoscale structure and dynamics.« less

Dynamic and static structure studies of colloidal suspensions with XPCS, SAXS and XNFS

NASA Astrophysics Data System (ADS)

Lu, Xinhui

In the first project, I studied the onset of structural arrest and glass formation in a suspension of silica nanoparticles in a water-lutidine binary mixture near its consolute point using X-ray Photon Correlation Spectroscopy (XPCS) and Small Angle X-ray Scattering (SAXS). I obtained the temperature evolution of the static and dynamic structure, revealing that glass transitions occur both on cooling and on heating, and an unusual logarithmic relaxation within the intermediate liquid between the two glasses, as predicted by mode-coupling theory. In another project, I implemented and exploited the recently-introduced, coherence-based technique of X-ray Near-Field Speckle (XNFS) to characterize the structure and dynamics of micrometer-sized particles. In XNFS, the measured speckles originate from the interference between the incident and scattered beams, and enable truly ultra-small angle x-ray scattering measurements with a simple setup. We built a micrometer-resolution XNFS detector with a high numerical aperture microscope objective and demonstrated its capability of studying static structures and dynamics in longer length scale than traditional far field x-ray techniques by measuring dilute silica and polystyrene samples. We also discussed the limitation of this technique.

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

Johnson, Kyle J.; Glynos, Emmanouil; Maroulas, Serafeim-Dionysios

Incorporating nanoparticles (NPs) within a polymer host to create polymer nanocomposites (PNCs) while having the effect of increasing the functionality (e.g.: sensing, energy conversion) of these materials, introduces additional complications with regard to the processing-morphology-function behavior. A primary challenge is to understand and control the viscosity of a PNC with decreasing film thickness confinement for nanoscale applications. Using a combination of X-ray photon correlation spectroscopy (XPCS) and X-ray standing wave based resonance enhanced XPCS to study the dynamics of neat poly-2-vinyl pyridine (P2VP) chains and the nanoparticle dynamics, respectively, we identified a new mechanism that dictates the viscosity of PNCmore » films in the nanoscale regime. We show that while the viscosities of neat P2VP films as thin as 50 nm remained the same as the bulk, PNC films containing P2VP brush-coated gold NPs, spaced 50 nm apart, exhibited unprecedented increases in viscosities of over an order of magnitude. For thicker films or more widely separated NPs, the chain dynamics and viscosities were equal to the bulk values. These results -NP proximities and suppression of their dynamics -suggest a new mechanism by which the viscosities of polymeric liquids could be controlled for 2D and 3D nanoscale applications.« less

Xeroderma pigmentosum-Cockayne syndrome complex.

PubMed

Natale, Valerie; Raquer, Hayley

2017-04-04

Xeroderma pigmentosum-Cockayne syndrome complex is a very rare multisystem degenerative disorder (Orpha: 220295; OMIM: 278730, 278760, 278780, 610651). Published information on XP-CS is mostly scattered throughout the literature. We compiled statistics related to symptom prevalence in XP-CS and have written a clinical description of the syndrome. We also drew on clinical practices used in XP and in Cockayne syndrome without XP to aid management of XP-CS.Extensive searches of the literature identified 43 XP-CS patients. The diagnosis had been confirmed with molecular or biochemical methods in 42 of them. Clinical features of each patient were summarized in spreadsheets and summary statistics were generated from this data. XP patients are classified into complementation groups according to the gene that is mutated. There are four groups in XP-CS, and classification was available for 42 patients. Twenty-one were in the XP-G complementation group, 13 in XP-D, 5 in XP-B, and 3 in XP-F. Overall, the clinical features of XP-CS are very similar to those of CS without XP, with the exception of skin cancers in XP-CS. However, one intriguing finding was that cancer incidence was lower in XP-CS compared to XP alone or XP-neurological disorder. The cancer rate in XP-CS was higher than in CS without XP, an unsurprising finding. There is preliminary evidence for the existence of severity groups in XP-CS, as is the case in CS.Although health problems in XP-CS vary both in severity and in when they the first occur, there was overall homogeneity between all complementation groups and putative severity groups. Severely affected patients met fewer milestones and died at younger ages compared to more mildly affected patients.

Diffusive dynamics during the high-to-low density transition in amorphous ice

DOE PAGES

Perakis, Fivos; Amann-Winkel, Katrin; Lehmkuhler, Felix; ...

2017-06-26

Water exists in high- and low-density amorphous ice forms (HDA and LDA), which could correspond to the glassy states of high- (HDL) and low-density liquid (LDL) in the metastable part of the phase diagram. However, the nature of both the glass transition and the high-to-low-density transition are debated and new experimental evidence is needed. Here we combine wide-angle X-ray scattering (WAXS) with X-ray photon-correlation spectroscopy (XPCS) in the small-angle X-ray scattering (SAXS) geometry to probe both the structural and dynamical properties during the high-to-low-density transition in amorphous ice at 1 bar. By analyzing the structure factor and the radial distributionmore » function, the coexistence of two structurally distinct domains is observed at T = 125 K. XPCS probes the dynamics in momentum space, which in the SAXS geometry reflects structural relaxation on the nanometer length scale. The dynamics of HDA are characterized by a slow component with a large time constant, arising from viscoelastic relaxation and stress release from nanometer-sized heterogeneities. Above 110 K a faster, strongly temperature-dependent component appears, with momentum transfer dependence pointing toward nanoscale diffusion. This dynamical component slows down after transition into the low-density form at 130 K, but remains diffusive. In conclusion, the diffusive character of both the high- and low-density forms is discussed among different interpretations and the results are most consistent with the hypothesis of a liquid–liquid transition in the ultraviscous regime.« less

Diffusive dynamics during the high-to-low density transition in amorphous ice

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

Perakis, Fivos; Amann-Winkel, Katrin; Lehmkuhler, Felix

Water exists in high- and low-density amorphous ice forms (HDA and LDA), which could correspond to the glassy states of high- (HDL) and low-density liquid (LDL) in the metastable part of the phase diagram. However, the nature of both the glass transition and the high-to-low-density transition are debated and new experimental evidence is needed. Here we combine wide-angle X-ray scattering (WAXS) with X-ray photon-correlation spectroscopy (XPCS) in the small-angle X-ray scattering (SAXS) geometry to probe both the structural and dynamical properties during the high-to-low-density transition in amorphous ice at 1 bar. By analyzing the structure factor and the radial distributionmore » function, the coexistence of two structurally distinct domains is observed at T = 125 K. XPCS probes the dynamics in momentum space, which in the SAXS geometry reflects structural relaxation on the nanometer length scale. The dynamics of HDA are characterized by a slow component with a large time constant, arising from viscoelastic relaxation and stress release from nanometer-sized heterogeneities. Above 110 K a faster, strongly temperature-dependent component appears, with momentum transfer dependence pointing toward nanoscale diffusion. This dynamical component slows down after transition into the low-density form at 130 K, but remains diffusive. In conclusion, the diffusive character of both the high- and low-density forms is discussed among different interpretations and the results are most consistent with the hypothesis of a liquid–liquid transition in the ultraviscous regime.« less

Diffusive dynamics during the high-to-low density transition in amorphous ice

NASA Astrophysics Data System (ADS)

Perakis, Fivos; Amann-Winkel, Katrin; Lehmkühler, Felix; Sprung, Michael; Mariedahl, Daniel; Sellberg, Jonas A.; Pathak, Harshad; Späh, Alexander; Cavalca, Filippo; Schlesinger, Daniel; Ricci, Alessandro; Jain, Avni; Massani, Bernhard; Aubree, Flora; Benmore, Chris J.; Loerting, Thomas; Grübel, Gerhard; Pettersson, Lars G. M.; Nilsson, Anders

2017-08-01

Water exists in high- and low-density amorphous ice forms (HDA and LDA), which could correspond to the glassy states of high- (HDL) and low-density liquid (LDL) in the metastable part of the phase diagram. However, the nature of both the glass transition and the high-to-low-density transition are debated and new experimental evidence is needed. Here we combine wide-angle X-ray scattering (WAXS) with X-ray photon-correlation spectroscopy (XPCS) in the small-angle X-ray scattering (SAXS) geometry to probe both the structural and dynamical properties during the high-to-low-density transition in amorphous ice at 1 bar. By analyzing the structure factor and the radial distribution function, the coexistence of two structurally distinct domains is observed at T = 125 K. XPCS probes the dynamics in momentum space, which in the SAXS geometry reflects structural relaxation on the nanometer length scale. The dynamics of HDA are characterized by a slow component with a large time constant, arising from viscoelastic relaxation and stress release from nanometer-sized heterogeneities. Above 110 K a faster, strongly temperature-dependent component appears, with momentum transfer dependence pointing toward nanoscale diffusion. This dynamical component slows down after transition into the low-density form at 130 K, but remains diffusive. The diffusive character of both the high- and low-density forms is discussed among different interpretations and the results are most consistent with the hypothesis of a liquid-liquid transition in the ultraviscous regime.

Shear banding leads to accelerated aging dynamics in a metallic glass

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

Küchemann, Stefan; Liu, Chaoyang; Dufresne, Eric M.

Traditionally, strain localization in metallic glasses is related to the thickness of the shear defect, which is confined to the nanometer scale. In this study, using site-specific x-ray photon correlation spectroscopy (XPCS), we reveal significantly accelerated relaxation dynamics around a shear band in a metallic glass at a length scale that is orders of magnitude larger than the defect itself. The relaxation time in the shear-band vicinity is up to ten-times smaller compared to the as-cast matrix, and the relaxation dynamics occurs in a characteristic three-stage aging response that manifests itself in the temperature-dependent shape parameter known from classical stretchedmore » exponential relaxation dynamics of disordered materials. We demonstrate that the time-dependent correlation functions describing the aging at different temperatures can be captured and collapsed using simple scaling functions. Finally, these insights highlight how an ubiquitous nano-scale strain-localization mechanism in metallic glasses leads to a fundamental change of the relaxation dynamics at the mesoscale.« less

Shear banding leads to accelerated aging dynamics in a metallic glass

DOE PAGES

Küchemann, Stefan; Liu, Chaoyang; Dufresne, Eric M.; ...

2018-01-11

Traditionally, strain localization in metallic glasses is related to the thickness of the shear defect, which is confined to the nanometer scale. In this study, using site-specific x-ray photon correlation spectroscopy (XPCS), we reveal significantly accelerated relaxation dynamics around a shear band in a metallic glass at a length scale that is orders of magnitude larger than the defect itself. The relaxation time in the shear-band vicinity is up to ten-times smaller compared to the as-cast matrix, and the relaxation dynamics occurs in a characteristic three-stage aging response that manifests itself in the temperature-dependent shape parameter known from classical stretchedmore » exponential relaxation dynamics of disordered materials. We demonstrate that the time-dependent correlation functions describing the aging at different temperatures can be captured and collapsed using simple scaling functions. Finally, these insights highlight how an ubiquitous nano-scale strain-localization mechanism in metallic glasses leads to a fundamental change of the relaxation dynamics at the mesoscale.« less

Presence of supercooling-facilitating (anti-ice nucleation) hydrolyzable tannins in deep supercooling xylem parenchyma cells in Cercidiphyllum japonicum.

PubMed

Wang, Donghui; Kasuga, Jun; Kuwabara, Chikako; Endoh, Keita; Fukushi, Yukiharu; Fujikawa, Seizo; Arakawa, Keita

2012-04-01

Xylem parenchyma cells (XPCs) in trees adapt to subzero temperatures by deep supercooling. Our previous study indicated the possibility of the presence of diverse kinds of supercooling-facilitating (SCF; anti-ice nucleation) substances in XPCs of katsura tree (Cercidiphyllum japonicum), all of which might have an important role in deep supercooling of XPCs. In the previous study, a few kinds of SCF flavonol glycosides were identified. Thus, in the present study, we tried to identify other kinds of SCF substances in XPCs of katsura tree. SCF substances were purified from xylem extracts by silica gel column chromatography and Sephadex LH-20 column chromatography. Then, four SCF substances isolated were identified by UV, mass and nuclear magnetic resonance analyses. The results showed that the four kinds of hydrolyzable gallotannins, 2,2',5-tri-O-galloyl-α,β-D-hamamelose (trigalloyl Ham or kurigalin), 1,2,6-tri-O-galloyl-β-D-glucopyranoside (trigalloyl Glc), 1,2,3,6-tetra-O-galloyl-β-D-glucopyranoside (tetragalloyl Glc) and 1,2,3,4,6-penta-O-galloyl-β-D-glucopyranoside (pentagalloyl Glc), in XPCs exhibited supercooling capabilities in the range of 1.5-4.5°C, at a concentration of 1 mg mL⁻¹. These SCF substances, including flavonol glycosides and hydrolyzable gallotannins, may contribute to the supercooling in XPCs of katsura tree.

Simultaneous multiplexed materials characterization using a high-precision hard X-ray micro-slit array.

PubMed

Zhang, Fan; Allen, Andrew J; Levine, Lyle E; Mancini, Derrick C; Ilavsky, Jan

2015-05-01

The needs both for increased experimental throughput and for in operando characterization of functional materials under increasingly realistic experimental conditions have emerged as major challenges across the whole of crystallography. A novel measurement scheme that allows multiplexed simultaneous measurements from multiple nearby sample volumes is presented. This new approach enables better measurement statistics or direct probing of heterogeneous structure, dynamics or elemental composition. To illustrate, the submicrometer precision that optical lithography provides has been exploited to create a multiplexed form of ultra-small-angle scattering based X-ray photon correlation spectroscopy (USAXS-XPCS) using micro-slit arrays fabricated by photolithography. Multiplexed USAXS-XPCS is applied to follow the equilibrium dynamics of a simple colloidal suspension. While the dependence of the relaxation time on momentum transfer, and its relationship with the diffusion constant and the static structure factor, follow previous findings, this measurements-in-parallel approach reduces the statistical uncertainties of this photon-starved technique to below those associated with the instrument resolution. More importantly, we note the potential of the multiplexed scheme to elucidate the response of different components of a heterogeneous sample under identical experimental conditions in simultaneous measurements. In the context of the X-ray synchrotron community, this scheme is, in principle, applicable to all in-line synchrotron techniques. Indeed, it has the potential to open a new paradigm for in operando characterization of heterogeneous functional materials, a situation that will be even further enhanced by the ongoing development of multi-bend achromat storage ring designs as the next evolution of large-scale X-ray synchrotron facilities around the world.

Simultaneous multiplexed materials characterization using a high-precision hard X-ray micro-slit array

DOE PAGES

Zhang, Fan; Allen, Andrew J.; Levine, Lyle E.; ...

2015-01-01

Here, the needs both for increased experimental throughput and forin operandocharacterization of functional materials under increasingly realistic experimental conditions have emerged as major challenges across the whole of crystallography. A novel measurement scheme that allows multiplexed simultaneous measurements from multiple nearby sample volumes is presented. This new approach enables better measurement statistics or direct probing of heterogeneous structure, dynamics or elemental composition. To illustrate, the submicrometer precision that optical lithography provides has been exploited to create a multiplexed form of ultra-small-angle scattering based X-ray photon correlation spectroscopy (USAXS-XPCS) using micro-slit arrays fabricated by photolithography. Multiplexed USAXS-XPCS is applied to followmore » the equilibrium dynamics of a simple colloidal suspension. While the dependence of the relaxation time on momentum transfer, and its relationship with the diffusion constant and the static structure factor, follow previous findings, this measurements-in-parallel approach reduces the statistical uncertainties of this photon-starved technique to below those associated with the instrument resolution. More importantly, we note the potential of the multiplexed scheme to elucidate the response of different components of a heterogeneous sample underidenticalexperimental conditions in simultaneous measurements. Lastly, in the context of the X-ray synchrotron community, this scheme is, in principle, applicable to all in-line synchrotron techniques. Indeed, it has the potential to open a new paradigm for in operando characterization of heterogeneous functional materials, a situation that will be even further enhanced by the ongoing development of multi-bend achromat storage ring designs as the next evolution of large-scale X-ray synchrotron facilities around the world.« less

Remarkable Stability of Charge Density Wave Order in La 1.875Ba 0.125CuO 4

DOE PAGES

Chen, X. M.; Thampy, V.; Mazzoli, C.; ...

2016-10-11

The occurrence of charge-density-wave (CDW) order in underdoped cuprates is now well established, although the precise nature of the CDW and its relationship with superconductivity is not. Theoretical proposals include contrasting ideas such as that pairing may be driven by CDW uctuations or that static CDWs may intertwine with a spatially-modulated superconducting wave function. We test the dynamics of CDW order in La 1.875Ba 0.125CuO 4 by using x-ray photon correlation spectroscopy (XPCS) at the CDW wave vector, detected resonantly at the Cu L 3-edge. We nd that the CDW domains are strikingly static, with no evidence of signi cantmore » uctuations up to 2 3/4 hours. We discuss the implications of these results for some of the competing theories.« less

Multiple dynamic regimes in colloid-polymer dispersions: New insight using X-ray photon correlation spectroscopy

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

Srivastava, Sunita; Kishore, Suhasini; Narayanan, Suresh

We present an X-ray photon correlation spectros- copy (XPCS) study of dynamic transitions in an anisotropic colloid-polymer dispersion with multiple arrested states. The results provide insight into the mechanism for formation of repulsive glasses, attractive glasses, and networked gels of col- loids with weakly adsorbing polymer chains. In the presence of adsorbing polymer chains, we observe three distinct regimes: a state with slow dynamics consisting of finite particles and clusters, for which interparticle interactions are predominantly repulsive; a second dynamic regime occurring above the satu- ration concentration of added polymer, in which small clusters of nanoparticles form via a short-rangemore » depletion attraction; and a third regime above the overlap concentration in which dynamics of clusters are independent of polymer chain length. The observed complex dynamic state diagram is primarily gov- erned by the structural reorganization of a nanoparticle cluster and polymer chains at the nanoparticle-polymer surface and in the concentrated medium, which in turn controls the dynamics of the dispersion« less

Effect of Molecular Architecture on Polymer Melt Surface Dynamics

NASA Astrophysics Data System (ADS)

Foster, Mark

The dynamics of the thermally stimulated surface height fluctuations in a polymer melt dictate wetting, adhesion, and tribology at that surface. These surface fluctuations can be profoundly altered by tethering of the chains. One type of tethering is the tethering of one part of a molecule to another part of the same molecule. This tethering is found in both long chain branched polymers and in macrocycles. We have studied the surface fluctuations with X-ray Photon Correlation Spectroscopy for melts of well-defined, anionically polymerized polystyrenes of various architectures, including linear, 6 arm star, pom-pom, comb and cyclic architectures. For linear chains, the variation of surface relaxation time with in-plane scattering vector can be fit using a hydrodynamic continuum theory (HCT) of thermally stimulated capillary waves that knows nothing of the chain architecture. Assuming the theory is applicable, apparent viscosities of the films may then be inferred from the XPCS data. For unentangled linear chains, the viscosity inferred from XPCS data in this manner is the same as that measured by conventional bulk rheometry. The HCT does a reasonable job of describing the variation of relaxation time with scattering vector for long branched chains also, but only if a viscosity much larger than that of the bulk is assumed. The discrepancy between the viscosity inferred from surface relaxation times using the HCT and that derived from conventional rheometry grows larger as the bulk Tg is approached and is different for each long chain branched architecture. However, for densely branched combs and cyclic chains different behaviors are found. Acknowledgement: Thanks to NSF (CBET 0730692) and the Advanced Photon Source, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Science, under Contract No. W-31-109-ENG-38.

A unified model for the molecular basis of Xeroderma pigmentosum-Cockayne Syndrome

PubMed Central

Moriel-Carretero, María; Herrera-Moyano, Emilia; Aguilera, Andrés

2015-01-01

Nucleotide Excision Repair (NER) is a pathway that removes lesions distorting the DNA helix. The molecular basis of the rare diseases Xeroderma pigmentosum (XP) and Cockayne Syndrome (CS) are explained based on the defects happening in 2 NER branches: Global-Genome Repair and Transcription-Coupled Repair, respectively. Nevertheless, both afflictions sporadically occur together, giving rise to XP/CS; however, the molecular basis of XP/CS is not understood very well. Many efforts have been made to clarify why mutations in only 4 NER genes, namely XPB, XPD, XPF and XPG, are the basis of this disease. Effort has also been made to unravel why mutations within these genes lead to XP, XP/CS, or other pathologies. We have recently contributed to the disclosure of this puzzle by characterizing Rad3/XPD mutations in Saccharomyces cerevisiae and human cells. Based on our, and others', observations, we propose a model compatible with all XP/CS cases and the current bibliography. PMID:26460500

Modifying Surface Fluctuations of Polymer Melt Films with Substrate Modification

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

Zhou, Yang; He, Qiming; Zhang, Fan

Deposition of a plasma polymerized film on a silicon substrate substantially changes the fluctuations on the surface of a sufficiently thin, melt polystyrene (PS) film atop the substrate. Surface fluctuation relaxation times measured with X-ray photon correlation spectroscopy (XPCS) for ca. 4R g thick melt films of 131 kg/mol linear PS on silicon and on a plasma polymer modified silicon wafer can both be described using a hydrodynamic continuum theory (HCT) that assumes the film is characterized throughout its depth by the bulk viscosity. However, when the film thickness is reduced to ~3R g, confinement effects are evident. The surfacemore » fluctuations are slower than predicted using the HCT, and the confinement effect for the PS on silicon is larger than that for the PS on the plasma polymerized film. This deviation is thus due to a difference in the thicknesses of the strongly adsorbed layers at the substrate which are impacted by the substrate surface energy.« less

ePix100 camera: Use and applications at LCLS

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

Carini, G. A., E-mail: carini@slac.stanford.edu; Alonso-Mori, R.; Blaj, G.

2016-07-27

The ePix100 x-ray camera is a new system designed and built at SLAC for experiments at the Linac Coherent Light Source (LCLS). The camera is the first member of a family of detectors built around a single hardware and software platform, supporting a variety of front-end chips. With a readout speed of 120 Hz, matching the LCLS repetition rate, a noise lower than 80 e-rms and pixels of 50 µm × 50 µm, this camera offers a viable alternative to fast readout, direct conversion, scientific CCDs in imaging mode. The detector, designed for applications such as X-ray Photon Correlation Spectroscopymore » (XPCS) and wavelength dispersive X-ray Emission Spectroscopy (XES) in the energy range from 2 to 10 keV and above, comprises up to 0.5 Mpixels in a very compact form factor. In this paper, we report the performance of the camera during its first use at LCLS.« less

Modifying Surface Fluctuations of Polymer Melt Films with Substrate Modification

DOE PAGES

Zhou, Yang; He, Qiming; Zhang, Fan; ...

2017-08-14

Deposition of a plasma polymerized film on a silicon substrate substantially changes the fluctuations on the surface of a sufficiently thin, melt polystyrene (PS) film atop the substrate. Surface fluctuation relaxation times measured with X-ray photon correlation spectroscopy (XPCS) for ca. 4R g thick melt films of 131 kg/mol linear PS on silicon and on a plasma polymer modified silicon wafer can both be described using a hydrodynamic continuum theory (HCT) that assumes the film is characterized throughout its depth by the bulk viscosity. However, when the film thickness is reduced to ~3R g, confinement effects are evident. The surfacemore » fluctuations are slower than predicted using the HCT, and the confinement effect for the PS on silicon is larger than that for the PS on the plasma polymerized film. This deviation is thus due to a difference in the thicknesses of the strongly adsorbed layers at the substrate which are impacted by the substrate surface energy.« less

Interplay of Structure and Dynamics in Biomaterials

NASA Astrophysics Data System (ADS)

Vodnala, Preeti

Study of structure and dynamic behavior is essential to understand molecular motions in biological systems. In this work, two biomaterials were studied to address membrane properties and protein diffusion. For the first project, we studied the structure of liposomes, artificial vesicles that are used for drug encapsulation and administration of pharmaceuticals or cellular nutrients. Small-angle x-ray scattering (SAXS) was used to determine the structural properties of different liposomes composed of egg-PC and cholesterol bilayer. We examined the location of cholesterol by labelling cholesterol with bromine molecule and reveal that cholesterol is located one side of the leaflet adjusting itself to the curvature of a liposome. In my second project, we studied the dynamics of concentrated suspensions of alpha crystallin, one of the most abundant proteins in the human eye lens using X-ray photon correlation spectroscopy (XPCS). An improved understanding of dynamics could point the way towards treatments presbyopia and cataract. The dynamics were measured at volume fraction close to the critical volume fraction for the glass transition, where the intermediate scattering function, ƒ(q,T) could be well fit using a double exponential decay. The measured relaxation is in reasonable agreement with published molecular dynamics simulations for the relaxation times of hard-sphere colloids.

Cockayne syndrome and xeroderma pigmentosum

PubMed Central

Rapin, I.; Lindenbaum, Y.; Dickson, D.W.; Kraemer, K.H.; Robbins, J.H.

2015-01-01

Objectives To review genetic variants of Cockayne syndrome (CS) and xeroderma pigmentosum (XP), autosomal recessive disorders of DNA repair that affect the nervous system, and to illustrate them by the first case of xeroderma pigmentosum–Cockayne syndrome (XP-CS) complex to undergo neuropathologic examination. Methods Published reports of clinical, pathologic, and molecular studies of CS, XP neurologic disease, and the XP-CS complex were reviewed, and a ninth case of XP-CS is summarized. Results CS is a multisystem disorder that causes both profound growth failure of the soma and brain and progressive cachexia, retinal, cochlear, and neurologic degeneration, with a leukodystrophy and demyelinating neuropathy without an increase in cancer. XP presents as extreme photosensitivity of the skin and eyes with a 1000-fold increased frequency of cutaneous basal and squamous cell carcinomas and melanomas and a small increase in nervous system neoplasms. Some 20% of patients with XP incur progressive degeneration of previously normally developed neurons resulting in cortical, basal ganglia, cerebellar, and spinal atrophy, cochlear degeneration, and a mixed distal axonal neuropathy. Cultured cells from patients with CS or XP are hypersensitive to killing by ultraviolet (UV) radiation. Both CS and most XP cells have defective DNA nucleotide excision repair of actively transcribing genes; in addition, XP cells have defective repair of the global genome. There are two complementation groups in CS and seven in XP. Patients with the XP-CS complex fall into three XP complementation groups. Despite their XP genotype, six of nine individuals with the XP-CS complex, including the boy we followed up to his death at age 6, had the typical clinically and pathologically severe CS phenotype. Cultured skin and blood cells had extreme sensitivity to killing by UV radiation, DNA repair was severely deficient, post-UV unscheduled DNA synthesis was reduced to less than 5%, and post-UV plasmid mutation frequency was increased. Conclusions The paradoxical lack of parallelism of phenotype to genotype is unexplained in these disorders. Perhaps diverse mutations responsible for UV sensitivity and deficient DNA repair may also produce profound failure of brain and somatic growth, progressive cachexia and premature aging, and tissue-selective neurologic deterioration by their roles in regulation of transcription and repair of endogenous oxidative DNA damage. PMID:11185579

X-Ray Studies of Diffusion Dynamics in Nano-Confined Geometries

NASA Astrophysics Data System (ADS)

Boucheron, Leandra

Since their discovery in the late 1800s, x-rays have taken the stage as one of the most powerful research techniques for materials science. Their element-specific absorption has allowed for everyday applications in security and medical imaging, while their short wavelength has a tremendous ability to resolve materials on a molecular or even atomic level. In this dissertation, I will discuss basic properties of x-rays as well as how they are produced and detected. I will also present x-ray scattering and analysis techniques before moving onto a discussion of my research on diffusion in soft-matter systems. I provide a full alignment guide for a lab-based dynamic light scattering (DLS) goniometer system, which I used for some preliminary studies of systems. I proceed to discuss diffusion on the nanoscale in quasi-1D (nanopores) and quasi-2D (liquid surface) systems. The latter of these systems was the main focus of my dissertation research. I utilized x-ray photon correlation spectroscopy (XPCS) to study the diffusion and interparticle dynamics of iron oxide nanoparticles at the air-water interface. Autocorrelation analysis revealed that these particles show signatures of a jammed system under lateral compression. I present these results as well as a description of their interpretation and importance in the main text.

Dynamic Scaling of Colloidal Gel Formation at Intermediate Concentrations

DOE PAGES

Zhang, Qingteng; Bahadur, Divya; Dufresne, Eric M.; ...

2017-10-25

Here, we have examined the formation and dissolution of gels composed of intermediate volume-fraction nanoparticles with temperature-dependent short-range attractions using small-angle x-ray scatter- ing (SAXS), x-ray photon correlation spectroscopy (XPCS), and rheology to obtain nanoscale and macroscale sensitivity to structure and dynamics. Gel formation after temperature quenches to the vicinity of the rheologically-determined gel temperature, T gel, was characterized via the slow-down of dynamics and changes in microstructure observed in the intensity autocorrelation functions and structure factor, respectively, as a function of quench depth (ΔT = T quench - T gel), wave vector, and formation time (t f). We findmore » similar patterns in the slow-down of dynamics that maps the wave-vector-dependent dynamics at a particular ΔT and t f to that at other ΔTs and t fs via an effective scaling temperature, Ts. A single Ts applies to a broad range of ΔT and tf but does depend on the particle size. The rate of formation implied by the scaling is a far stronger function of ΔT than that of the attraction strength between colloids. Finally, we interpret this strong temperature de- pendence in terms of changes in cooperative bonding required to form stable, energetically favored, local structures.« less

Dynamic Scaling of Colloidal Gel Formation at Intermediate Concentrations

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

Zhang, Qingteng; Bahadur, Divya; Dufresne, Eric M.

Here, we have examined the formation and dissolution of gels composed of intermediate volume-fraction nanoparticles with temperature-dependent short-range attractions using small-angle x-ray scatter- ing (SAXS), x-ray photon correlation spectroscopy (XPCS), and rheology to obtain nanoscale and macroscale sensitivity to structure and dynamics. Gel formation after temperature quenches to the vicinity of the rheologically-determined gel temperature, T gel, was characterized via the slow-down of dynamics and changes in microstructure observed in the intensity autocorrelation functions and structure factor, respectively, as a function of quench depth (ΔT = T quench - T gel), wave vector, and formation time (t f). We findmore » similar patterns in the slow-down of dynamics that maps the wave-vector-dependent dynamics at a particular ΔT and t f to that at other ΔTs and t fs via an effective scaling temperature, Ts. A single Ts applies to a broad range of ΔT and tf but does depend on the particle size. The rate of formation implied by the scaling is a far stronger function of ΔT than that of the attraction strength between colloids. Finally, we interpret this strong temperature de- pendence in terms of changes in cooperative bonding required to form stable, energetically favored, local structures.« less

Change of supercooling capability in solutions containing different kinds of ice nucleators by flavonol glycosides from deep supercooling xylem parenchyma cells in trees.

PubMed

Kuwabara, Chikako; Kasuga, Jun; Wang, Donghui; Fukushi, Yukiharu; Arakawa, Keita; Koyama, Toshie; Inada, Takaaki; Fujikawa, Seizo

2011-12-01

Deep supercooling xylem parenchyma cells (XPCs) in Katsura tree contain flavonol glycosides with high supercooling-facilitating capability in solutions containing the ice nucleation bacterium (INB) Erwinia ananas, which is thought to have an important role in deep supercooling of XPCs. The present study, in order to further clarify the roles of these flavonol glycosides in deep supercooling of XPCs, the effects of these supercooling-facilitating (anti-ice nucleating) flavonol glycosides, kaempferol 3-O-β-D-glucopyranoside (K3Glc), kaempferol 7-O-β-D-glucopyranoside (K7Glc) and quercetin 3-O-β-D-glucopyranoside (Q3Glc), in buffered Milli-Q water (BMQW) containing different kinds of ice nucleators, including INB Xanthomonas campestris, silver iodide and phloroglucinol, were examined by a droplet freezing assay. The results showed that all of the flavonol glycosides promoted supercooling in all solutions containing different kinds of ice nucleators, although the magnitudes of supercooling capability of each flavonol glycoside changed in solutions containing different kinds of ice nucleators. On the other hand, these flavonol glycosides exhibited complicated nucleating reactions in BMQW, which did not contain identified ice nucleators but contained only unidentified airborne impurities. Q3Glc exhibited both supercooling-facilitating and ice nucleating capabilities depending on the concentrations in such water. Both K3Glc and K7Glc exhibited only ice nucleation capability in such water. It was also shown by an emulsion freezing assay in BMQW that K3Glc and Q3Glc had no effect on homogeneous ice nucleation temperature, whereas K7Glc increased ice nucleation temperature. The results indicated that each flavonol glycoside affected ice nucleation by very complicated and varied reactions. More studies are necessary to determine the exact roles of these flavonol glycosides in deep supercooling of XPCs in which unidentified heterogeneous ice nucleators may exist. Copyright © 2011 Elsevier Inc. All rights reserved.

Nanorod Mobility within Entangled Wormlike Micelle Solutions

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

Lee, Jonghun; Grein-Iankovski, Aline; Narayanan, Suresh

In the semi-dilute regime, wormlike micelles form an isotropic entangled microstructure that is similar to that of an entangled polymer solution with a characteristic, nanometer-scale entanglement mesh size. We report a combined x-ray photon correlation spectroscopy (XPCS) and rheology study to investigate the translational dynamics of gold nanorods in semi-dilute solutions of entangled wormlike micelles formed by the surfactant cetylpyridinium chloride (CPyCl) and the counter-ion sodium salicylate (NaSal). The CPyCl concentration is varied to tune the entanglement mesh size over a range that spans from approximately equal to the nanorod diameter to larger than the nanorod length. The NaSal concentrationmore » is varied along with the CPyCl concentration so that the solutions have the maximum viscosity for given CPyCl concentration. On short time scales the nanorods are localized on a length scale matching that expected from the high-frequency elastic modulus of the solutions as long as the mesh size is smaller than the rod length. On longer time scales, the nanorods undergo free diffusion. At the highest CPyCl concentrations, the nanorod diffusivity approaches the value expected based on the macroscopic viscosity of the solutions, but it increases with decreasing CPyCl concentration more rapidly than expected from the macroscopic viscosity. A recent model by Cai et al. [Cai, L.-H.; Panyukov, S.; Rubinstein, M. Macromolecules 2015, 48, 847-862.] for nanoparticle “hopping” diffusion in entangled polymer solutions accounts quantitatively for this enhanced diffusivity.« less

Nanorod Mobility within Entangled Wormlike Micelle Solutions

DOE PAGES

Lee, Jonghun; Grein-Iankovski, Aline; Narayanan, Suresh; ...

2016-12-20

In the semi-dilute regime, wormlike micelles form an isotropic entangled microstructure that is similar to that of an entangled polymer solution with a characteristic, nanometer-scale entanglement mesh size. We report a combined x-ray photon correlation spectroscopy (XPCS) and rheology study to investigate the translational dynamics of gold nanorods in semi-dilute solutions of entangled wormlike micelles formed by the surfactant cetylpyridinium chloride (CPyCl) and the counter-ion sodium salicylate (NaSal). The CPyCl concentration is varied to tune the entanglement mesh size over a range that spans from approximately equal to the nanorod diameter to larger than the nanorod length. The NaSal concentrationmore » is varied along with the CPyCl concentration so that the solutions have the maximum viscosity for given CPyCl concentration. On short time scales the nanorods are localized on a length scale matching that expected from the high-frequency elastic modulus of the solutions as long as the mesh size is smaller than the rod length. On longer time scales, the nanorods undergo free diffusion. At the highest CPyCl concentrations, the nanorod diffusivity approaches the value expected based on the macroscopic viscosity of the solutions, but it increases with decreasing CPyCl concentration more rapidly than expected from the macroscopic viscosity. A recent model by Cai et al. [Cai, L.-H.; Panyukov, S.; Rubinstein, M. Macromolecules 2015, 48, 847-862.] for nanoparticle “hopping” diffusion in entangled polymer solutions accounts quantitatively for this enhanced diffusivity.« less

Young Adult Female Fragile X Premutation Carriers Show Age- and Genetically-Modulated Cognitive Impairments

ERIC Educational Resources Information Center

Goodrich-Hunsaker, Naomi J.; Wong, Ling M.; McLennan, Yingratana; Srivastava, Siddharth; Tassone, Flora; Harvey, Danielle; Rivera, Susan M.; Simon, Tony J.

2011-01-01

The high frequency of the fragile X premutation in the general population and its emerging neurocognitive implications highlight the need to investigate the effects of the premutation on lifespan cognitive development. Until recently, cognitive function in fragile X premutation carriers (fXPCs) was presumed to be unaffected by the mutation. Here…

Pellagra-like condition is xeroderma pigmentosum/Cockayne syndrome complex and niacin confers clinical benefit.

PubMed

Hijazi, H; Salih, M A; Hamad, M H A; Hassan, H H; Salih, S B M; Mohamed, K A; Mukhtar, M M; Karrar, Z A; Ansari, S; Ibrahim, N; Alkuraya, F S

2015-01-01

An extremely rare pellagra-like condition has been described, which was partially responsive to niacin and associated with a multisystem involvement. The condition was proposed to represent a novel autosomal recessive entity but the underlying mutation remained unknown for almost three decades. The objective of this study was to identify the causal mutation in the pellagra-like condition and investigate the mechanism by which niacin confers clinical benefit. Autozygosity mapping and exome sequencing were used to identify the causal mutation, and comet assay on patient fibroblasts before and after niacin treatment to assess its effect on DNA damage. We identified a single disease locus that harbors a novel mutation in ERCC5, thus confirming that the condition is in fact xeroderma pigmentosum/Cockayne syndrome (XP/CS) complex. Importantly, we also show that the previously described dermatological response to niacin is consistent with a dramatic protective effect against ultraviolet-induced DNA damage in patient fibroblasts conferred by niacin treatment. Our findings show the power of exome sequencing in reassigning previously described novel clinical entities, and suggest a mechanism for the dermatological response to niacin in patients with XP/CS complex. This raises interesting possibilities about the potential therapeutic use of niacin in XP. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

TFIIH Subunit Alterations Causing Xeroderma Pigmentosum and Trichothiodystrophy Specifically Disturb Several Steps during Transcription

PubMed Central

Singh, Amita; Compe, Emanuel; Le May, Nicolas; Egly, Jean-Marc

2015-01-01

Mutations in genes encoding the ERCC3 (XPB), ERCC2 (XPD), and GTF2H5 (p8 or TTD-A) subunits of the transcription and DNA-repair factor TFIIH lead to three autosomal-recessive disorders: xeroderma pigmentosum (XP), XP associated with Cockayne syndrome (XP/CS), and trichothiodystrophy (TTD). Although these diseases were originally associated with defects in DNA repair, transcription deficiencies might be also implicated. By using retinoic acid receptor beta isoform 2 (RARB2) as a model in several cells bearing mutations in genes encoding TFIIH subunits, we observed that (1) the recruitment of the TFIIH complex was altered at the activated RARB2 promoter, (2) TFIIH participated in the recruitment of nucleotide excision repair (NER) factors during transcription in a manner different from that observed during NER, and (3) the different TFIIH variants disturbed transcription by having distinct consequences on post-translational modifications of histones, DNA-break induction, DNA demethylation, and gene-loop formation. The transition from heterochromatin to euchromatin was disrupted depending on the variant, illustrating the fact that TFIIH, by contributing to NER factor recruitment, orchestrates chromatin remodeling. The subtle transcriptional differences found between various TFIIH variants thus participate in the phenotypic variability observed among XP, XP/CS, and TTD individuals. PMID:25620205

The rem mutations in the ATP-binding groove of the Rad3/XPD helicase lead to Xeroderma pigmentosum-Cockayne syndrome-like phenotypes.

PubMed

Herrera-Moyano, Emilia; Moriel-Carretero, María; Montelone, Beth A; Aguilera, Andrés

2014-12-01

The eukaryotic TFIIH complex is involved in Nucleotide Excision Repair and transcription initiation. We analyzed three yeast mutations of the Rad3/XPD helicase of TFIIH known as rem (recombination and mutation phenotypes). We found that, in these mutants, incomplete NER reactions lead to replication fork breaking and the subsequent engagement of the homologous recombination machinery to restore them. Nevertheless, the penetrance varies among mutants, giving rise to a phenotype gradient. Interestingly, the mutations analyzed reside at the ATP-binding groove of Rad3 and in vivo experiments reveal a gain of DNA affinity upon damage of the mutant Rad3 proteins. Since mutations at the ATP-binding groove of XPD in humans are present in the Xeroderma pigmentosum-Cockayne Syndrome (XP-CS), we recreated rem mutations in human cells, and found that these are XP-CS-like. We propose that the balance between the loss of helicase activity and the gain of DNA affinity controls the capacity of TFIIH to open DNA during NER, and its persistence at both DNA lesions and promoters. This conditions NER efficiency and transcription resumption after damage, which in human cells would explain the XP-CS phenotype, opening new perspectives to understand the molecular basis of the role of XPD in human disease.

Freezing pattern and frost killing temperature of apple (Malus domestica) wood under controlled conditions and in nature.

PubMed

Pramsohler, Manuel; Hacker, Jürgen; Neuner, Gilbert

2012-07-01

The freezing pattern and frost killing temperatures of apple (Malus domestica Borkh.) xylem were determined by differential thermal analysis and infrared differential thermal analysis (IDTA). Results from detached or attached twigs in controlled freezing experiments and during natural field freezing of trees were compared. Non-lethal freezing of apoplastic water in apple xylem as monitored during natural winter frosts in the field occurred at -1.9 ± 0.4 °C and did not change seasonally. The pattern of whole tree freezing was variable and specific to the environmental conditions. On detached twigs high-temperature freezing exotherms (HTEs) occurred 2.8 K below the temperature observed under natural frosts in the field with a seasonal mean of -4.7 ± 0.5 °C. Microporous apple xylem showed freezing without a specific pattern within a few seconds in IDTA images during HTEs, which is in contrast to macroporous xylem where a 2D freezing pattern mirrors anatomical structures. The pith tissue always remained unfrozen. Increasing twig length increased ice nucleation temperature; for increased twig diameter the effect was not significant. In attached twigs frozen in field portable freezing chambers, HTEs were recorded at a similar mean temperature (-4.6 ± 1.0 °C) to those for detached twigs. Upon lethal intracellular freezing of apple xylem parenchyma cells (XPCs) low-temperature freezing exotherms (LTEs) can be recorded. Low-temperature freezing exotherms determined on detached twigs varied significantly between a winter minimum of -36.9 °C and a summer maximum -12.7 °C. Within the temperature range wherein LTEs were recorded by IDTA in summer (-12.7 ± 0.5 to -20.3 ± 1.1 °C) various tiny clearly separated discontinuous freezing events could be detected similar to that in other species with contrasting XPC anatomy. These freezing events appeared to be initially located in the primary and only later in the secondary xylem. During the LTE no freezing events in the bark and central pith tissue were recorded. Attached twigs were exposed to various freezing temperatures at which LTEs occur. Even if 60% of XPCs were frost-damaged twigs were able to recuperate and showed full re-growth indicating a high regeneration capacity even after severe frost damage to XPCs.

The rem Mutations in the ATP-Binding Groove of the Rad3/XPD Helicase Lead to Xeroderma pigmentosum-Cockayne Syndrome-Like Phenotypes

PubMed Central

Montelone, Beth A.; Aguilera, Andrés

2014-01-01

The eukaryotic TFIIH complex is involved in Nucleotide Excision Repair and transcription initiation. We analyzed three yeast mutations of the Rad3/XPD helicase of TFIIH known as rem (recombination and mutation phenotypes). We found that, in these mutants, incomplete NER reactions lead to replication fork breaking and the subsequent engagement of the homologous recombination machinery to restore them. Nevertheless, the penetrance varies among mutants, giving rise to a phenotype gradient. Interestingly, the mutations analyzed reside at the ATP-binding groove of Rad3 and in vivo experiments reveal a gain of DNA affinity upon damage of the mutant Rad3 proteins. Since mutations at the ATP-binding groove of XPD in humans are present in the Xeroderma pigmentosum-Cockayne Syndrome (XP-CS), we recreated rem mutations in human cells, and found that these are XP-CS-like. We propose that the balance between the loss of helicase activity and the gain of DNA affinity controls the capacity of TFIIH to open DNA during NER, and its persistence at both DNA lesions and promoters. This conditions NER efficiency and transcription resumption after damage, which in human cells would explain the XP-CS phenotype, opening new perspectives to understand the molecular basis of the role of XPD in human disease. PMID:25500814

TFIIH subunit alterations causing xeroderma pigmentosum and trichothiodystrophy specifically disturb several steps during transcription.

PubMed

Singh, Amita; Compe, Emanuel; Le May, Nicolas; Egly, Jean-Marc

2015-02-05

Mutations in genes encoding the ERCC3 (XPB), ERCC2 (XPD), and GTF2H5 (p8 or TTD-A) subunits of the transcription and DNA-repair factor TFIIH lead to three autosomal-recessive disorders: xeroderma pigmentosum (XP), XP associated with Cockayne syndrome (XP/CS), and trichothiodystrophy (TTD). Although these diseases were originally associated with defects in DNA repair, transcription deficiencies might be also implicated. By using retinoic acid receptor beta isoform 2 (RARB2) as a model in several cells bearing mutations in genes encoding TFIIH subunits, we observed that (1) the recruitment of the TFIIH complex was altered at the activated RARB2 promoter, (2) TFIIH participated in the recruitment of nucleotide excision repair (NER) factors during transcription in a manner different from that observed during NER, and (3) the different TFIIH variants disturbed transcription by having distinct consequences on post-translational modifications of histones, DNA-break induction, DNA demethylation, and gene-loop formation. The transition from heterochromatin to euchromatin was disrupted depending on the variant, illustrating the fact that TFIIH, by contributing to NER factor recruitment, orchestrates chromatin remodeling. The subtle transcriptional differences found between various TFIIH variants thus participate in the phenotypic variability observed among XP, XP/CS, and TTD individuals. Copyright © 2015 The American Society of Human Genetics. Published by Elsevier Inc. All rights reserved.

High speed systems for time-resolved experiments with synchrotron radiation

NASA Astrophysics Data System (ADS)

Koziol, Anna; Maj, Piotr

2018-02-01

The UFXC32k is a single photon counting hybrid pixel detector with 75 μm pixel pitch. It was designed to cope with high X-ray intensities and therefore it is a very good candiate for synchrotron applications. In order to use this detector in an application, a dedicated setup must be designed and built allowing proper operation of the detector within the experiment. The paper presents two setups built for the purpose of Pump-Probe-Probe experiments at the Synchrotron SOLEIL and XPCS experiments at the APS.

Elevated Urinary Levels of 8-Hydroxy-2'-deoxyguanosine in a Japanese Child of Xeroderma Pigmentosum/Cockayne Syndrome Complex with Infantile Onset of Nephrotic Syndrome.

PubMed

Kondo, Daiki; Noguchi, Atsuko; Tamura, Hiroaki; Tsuchida, Satoko; Takahashi, Ikuko; Kubota, Hiroki; Yano, Tamami; Oyama, Chikako; Sawaishi, Yukio; Moriwaki, Shinichi; Takahashi, Tsutomu

2016-07-01

Nucleotide excision repair (NER) is an essential biological pathway protecting against ultraviolet light-induced DNA damage. Deficient NER causes a group of rare genetic disorders including two autosomal recessive diseases, xeroderma pigmentosum (XP) and Cockayne syndrome (CS). In addition to the cutaneous photosensitivity shared in XP and CS, CS is featured by growth failure, neurological deterioration, microcephaly, and deep sunken eyes. XP/CS complex is an extremely rare type of NER disorder with a distinct phenotype that is characterized by the skin and eye pathology of XP and the somatic and neurological abnormalities of CS. Some of CS cases have been reported to be complicated with renal failure, but the genetic background or the etiology of the renal failure has not been reported. We herein report a 1-year-old Japanese boy with XP/CS complex, complicated by nephrotic syndrome. Diagnosis was confirmed by the presence of compound heterozygous mutations, G47R (c.139G>A) and R616G (c.1846C>G), in the excision repair cross-complementation group 2 (ERCC2) gene. The kidney biopsies, performed at the age of 1 year and 2 months, revealed diffuse expansion of the mesangial matrix and segmental glomerulosclerosis under light microscopy, and diffused thin capillary walls with partially lamellated regions under electron microscopy. Notably, high levels of urinary 8-hydroxy-2'-deoxyguanosin, known as an oxidative stress marker, were observed during the clinical course. The patient died at the age of 1 year and 11 months because of renal failure. We suggest the involvement of oxidative stress in the pathogenesis of nephrotic syndrome in NER disorders.

Clinical heterogeneity within xeroderma pigmentosum associated with mutations in the DNA repair and transcription gene ERCC3

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

Vermeulen, W.; Kleijer, W.J.; Bootsma, D.

1994-02-01

The human DNA excision repair gene ERCC3 specifically corrects the nucleotide excision repair (NER) defect of xeroderma pigmentosum (XP) complementation group B. In addition to its function in NER, the ERCC3 DNA helicase was recently identified as one of the components of the human BTF2/TFIIH transcription factor complex, which is required for initiation of transcription of class II genes. To date, a single patient (XP11BE) has been assigned to this XP group B (XP-B), with the remarkable conjunction of two autosomal recessive DNA repair deficiency disorders: XP and Cockayne syndrome (CS). The intriguing involvement of the ERCC3 protein in themore » vital process of transcription may provide an explanation for the rarity, severity, and wide spectrum of clinical features in this complementation group. Here the authors report the identification of two new XP-B patients: XPCS1BA and XPCS2BA (siblings), by microneedle injection of the cloned ERCC3 repair gene as well as by cell hybridization. Molecular analysis of the ERCC3 gene in both patients revealed a single base substitution causing a missense mutation in a region that is completely conserved in yeast, Drosophila, mouse, and human ERCC3. As in patient XP11BE, the expression of only one allele (paternal) is detected. The mutation causes a virtually complete inactivation of the NER function of the protein. Despite this severe NER defect, both patients display a late onset of neurologic impairment, mild cutaneous symptoms, and a striking absence of skin tumors even at an age of >40 years. Analysis of the frequency of hprt[sup [minus

Topics in Chemical Instrumentation. The Fourier Transform in Chemistry-NMR: Part 4. Two-Dimensional Methods.

ERIC Educational Resources Information Center

Williams, Kathryn R.; King, Roy W.

1990-01-01

Examined are some of the types of two-dimensional spectra. Their application to nuclear magnetic resonance for the elucidation of molecular structure is discussed. Included are J spectroscopy, H-H correlation spectroscopy, heteronuclear correlation spectroscopy, carbon-carbon correlation, nuclear Overhauser effect correlation, experimental…

Two-dimensional correlation spectroscopy — Biannual survey 2007-2009

NASA Astrophysics Data System (ADS)

Noda, Isao

2010-06-01

The publication activities in the field of 2D correlation spectroscopy are surveyed with the emphasis on papers published during the last two years. Pertinent review articles and conference proceedings are discussed first, followed by the examination of noteworthy developments in the theory and applications of 2D correlation spectroscopy. Specific topics of interest include Pareto scaling, analysis of randomly sampled spectra, 2D analysis of data obtained under multiple perturbations, evolution of 2D spectra along additional variables, comparison and quantitative analysis of multiple 2D spectra, orthogonal sample design to eliminate interfering cross peaks, quadrature orthogonal signal correction and other data transformation techniques, data pretreatment methods, moving window analysis, extension of kernel and global phase angle analysis, covariance and correlation coefficient mapping, variant forms of sample-sample correlation, and different display methods. Various static and dynamic perturbation methods used in 2D correlation spectroscopy, e.g., temperature, composition, chemical reactions, H/D exchange, physical phenomena like sorption, diffusion and phase transitions, optical and biological processes, are reviewed. Analytical probes used in 2D correlation spectroscopy include IR, Raman, NIR, NMR, X-ray, mass spectrometry, chromatography, and others. Application areas of 2D correlation spectroscopy are diverse, encompassing synthetic and natural polymers, liquid crystals, proteins and peptides, biomaterials, pharmaceuticals, food and agricultural products, solutions, colloids, surfaces, and the like.

Intracellular applications of fluorescence correlation spectroscopy: prospects for neuroscience.

PubMed

Kim, Sally A; Schwille, Petra

2003-10-01

Based on time-averaging fluctuation analysis of small fluorescent molecular ensembles in equilibrium, fluorescence correlation spectroscopy has recently been applied to investigate processes in the intracellular milieu. The exquisite sensitivity of fluorescence correlation spectroscopy provides access to a multitude of measurement parameters (rates of diffusion, local concentration, states of aggregation and molecular interactions) in real time with fast temporal and high spatial resolution. The introduction of dual-color cross-correlation, imaging, two-photon excitation, and coincidence analysis coupled with fluorescence correlation spectroscopy has expanded the utility of the technique to encompass a wide range of promising applications in living cells that may provide unprecedented insight into understanding the molecular mechanisms of intracellular neurobiological processes.

Optical Spectroscopy and Imaging of Correlated Spin Orbit Phases

DTIC Science & Technology

2016-06-14

Unlimited UU UU UU UU 14-06-2016 15-Mar-2013 14-Mar-2016 Final Report: Optical Spectroscopy and Imaging of Correlated Spin-Orbit Phases The views...Box 12211 Research Triangle Park, NC 27709-2211 Ultrafast optical spectroscopy , nonlinear optical spectroscopy , iridates, cuprates REPORT...California Blvd. Pasadena, CA 91125 -0001 ABSTRACT Number of Papers published in peer-reviewed journals: Final Report: Optical Spectroscopy and

Recent advancement in the field of two-dimensional correlation spectroscopy

NASA Astrophysics Data System (ADS)

Noda, Isao

2008-07-01

The recent advancement in the field of 2D correlation spectroscopy is reviewed with the emphasis on a number of papers published during the last two years. Topics covered by this comprehensive review include books, review articles, and noteworthy developments in the theory and applications of 2D correlation spectroscopy. New 2D correlation techniques are discussed, such as kernel analysis and augmented 2D correlation, model-based correlation, moving window analysis, global phase angle, covariance and correlation coefficient mapping, sample-sample correlation, hybrid and hetero correlation, pretreatment and transformation of data, and 2D correlation combined with other chemometrics techniques. Perturbation methods of both static (e.g., temperature, composition, pressure and stress, spatial distribution and orientation) and dynamic types (e.g., rheo-optical and acoustic, chemical reactions and kinetics, H/D exchange, sorption and diffusion) currently in use are examined. Analytical techniques most commonly employed in 2D correlation spectroscopy are IR, Raman, and NIR, but the growing use of other probes is also noted, including fluorescence, emission, Raman optical activity and vibrational circular dichroism, X-ray absorption and scattering, NMR, mass spectrometry, and even chromatography. The field of applications for 2D correlation spectroscopy is very diverse, encompassing synthetic polymers, liquid crystals, Langmuir-Blodgett films, proteins and peptides, natural polymers and biomaterials, pharmaceuticals, food and agricultural products, water, solutions, inorganic, organic, hybrid or composite materials, and many more.

[Classification of results of studying blood plasma with laser correlation spectroscopy based on semiotics of preclinical and clinical states].

PubMed

Ternovoĭ, K S; Kryzhanovskiĭ, G N; Musiĭchuk, Iu I; Noskin, L A; Klopov, N V; Noskin, V A; Starodub, N F

1998-01-01

The usage of laser correlation spectroscopy for verification of preclinical and clinical states is substantiated. Developed "semiotic" classifier for solving the problems of preclinical and clinical states is presented. The substantiation of biological algorithms as well as the mathematical support and software for the proposed classifier for the data of laser correlation spectroscopy of blood plasma are presented.

The roles of carbohydrates, proteins and lipids in the process of aggregation of natural marine organic matter investigated by means of 2D correlation spectroscopy applied to infrared spectra.

PubMed

Mecozzi, Mauro; Pietrantonio, Eva; Pietroletti, Marco

2009-01-01

In this paper the marine organic matter soluble in an alkaline medium called extractable humic substance (EHS), was extracted from three sediment samples of Tyrrhenian Sea and separated by precipitation at pH 2 in the two fractions of fulvic acids (FAs) and humic acids (HAs). FAs were further fractionated in seven sub-samples of different molecular weight (mw) by means of seven different ultrafiltration membranes operating in the range between mw<1 kDa and mw>100 kDa. Then the qualitative composition of each sample of fractionated FAs and HAs was studied by means of one-dimensional Fourier transform infrared spectroscopy in reflectance mode (FTIR-DRIFT) and by two-dimensional (2D) correlation spectroscopy both in wavelength-wavelength (WW) and in sample-sample (SS) mode. The application of 2D correlation WW spectroscopy allows to elucidate the different roles played by carbohydrates and proteins with respect to some lipid compounds such as fatty acids and ester fatty acids during the process of aggregate formations from mw approximately 1 kDa to higher size aggregates. In addition, 2D correlation WW spectroscopy allows to observe some peculiar interactions between carbohydrates and proteins in the formation of EHS aggregates, interactions which vary from a sample to another sample. The results of 2D correlation SS spectroscopy confirm the general evidences obtained by 2D WW spectroscopy and moreover, they also describe the formation of EHS aggregates as a complex process where evolutionary links and connectivity between aggregates of neighbour molecular size ranges are not evident. Two-dimensional correlation spectroscopy applied to FTIR spectroscopy shows to be a powerful tool for the investigation of the mechanisms involved in EHS aggregation because it supports the acquisition of structural information which sometimes can be hardly obtained by one-dimensional FTIR spectroscopy.

New sesquiterpenes from Euonymus europaeus (Celastraceae).

PubMed

Descoins, Charles; Bazzocchi, Isabel López; Ravelo, Angel Gutiérrez

2002-02-01

A new sesquiterpene evoninate alkaloid (1), and two sesquiterpenes (2, 3) with a dihydro-beta-agarofuran skeleton, along with three known sesquiterpenes (4-6), were isolated from the seeds of Euonymus europaeus. Their structures were elucidated by high resolution mass analysis, and one- and two-dimensional (1D and 2D) NMR spectroscopy, including homonuclear and heteronuclear correlation [correlation spectroscopy (COSY), rotating frame Overhauser enhancement spectroscopy (ROESY), heteronuclear single quantum coherence (HSQC), and heteronuclear multiple bond correlation (HMBC)] experiments.

Frontiers of Two-Dimensional Correlation Spectroscopy. Part 1. New concepts and noteworthy developments

NASA Astrophysics Data System (ADS)

Noda, Isao

2014-07-01

A comprehensive survey review of new and noteworthy developments, which are advancing forward the frontiers in the field of 2D correlation spectroscopy during the last four years, is compiled. This review covers books, proceedings, and review articles published on 2D correlation spectroscopy, a number of significant conceptual developments in the field, data pretreatment methods and other pertinent topics, as well as patent and publication trends and citation activities. Developments discussed include projection 2D correlation analysis, concatenated 2D correlation, and correlation under multiple perturbation effects, as well as orthogonal sample design, predicting 2D correlation spectra, manipulating and comparing 2D spectra, correlation strategy based on segmented data blocks, such as moving-window analysis, features like determination of sequential order and enhanced spectral resolution, statistical 2D spectroscopy using covariance and other statistical metrics, hetero-correlation analysis, and sample-sample correlation technique. Data pretreatment operations prior to 2D correlation analysis are discussed, including the correction for physical effects, background and baseline subtraction, selection of reference spectrum, normalization and scaling of data, derivatives spectra and deconvolution technique, and smoothing and noise reduction. Other pertinent topics include chemometrics and statistical considerations, peak position shift phenomena, variable sampling increments, computation and software, display schemes, such as color coded format, slice and power spectra, tabulation, and other schemes.

Pushing x-ray photon correlation spectroscopy beyond the continuous frame rate limit

DOE PAGES

Dufresne, Eric M.; Narayanan, Suresh; Sandy, Alec R.; ...

2016-01-06

We demonstrate delayed-frame X-ray Photon Correlation Spectroscopy with 120 microsecond time resolution, limited only by sample scattering rates, with a prototype Pixel-array detector capable of taking two image frames separated by 153 ns or less. Although the overall frame rate is currently limited to about 4 frame pairs per second, we easily measured millisecond correlation functions. In conclusion, this technology, coupled to the use of brighter synchrotrons such as Petra III or the NSLS-II should enable X-ray Photon Correlation Spectroscopy on microsecond time scales on a wider variety of materials.

Second Harmonic Correlation Spectroscopy: Theory and Principles for Determining Surface Binding Kinetics.

PubMed

Sly, Krystal L; Conboy, John C

2017-06-01

A novel application of second harmonic correlation spectroscopy (SHCS) for the direct determination of molecular adsorption and desorption kinetics to a surface is discussed in detail. The surface-specific nature of second harmonic generation (SHG) provides an efficient means to determine the kinetic rates of adsorption and desorption of molecular species to an interface without interference from bulk diffusion, which is a significant limitation of fluorescence correlation spectroscopy (FCS). The underlying principles of SHCS for the determination of surface binding kinetics are presented, including the role of optical coherence and optical heterodyne mixing. These properties of SHCS are extremely advantageous and lead to an increase in the signal-to-noise (S/N) of the correlation data, increasing the sensitivity of the technique. The influence of experimental parameters, including the uniformity of the TEM00 laser beam, the overall photon flux, and collection time are also discussed, and are shown to significantly affect the S/N of the correlation data. Second harmonic correlation spectroscopy is a powerful, surface-specific, and label-free alternative to other correlation spectroscopic methods for examining surface binding kinetics.

Point-point and point-line moving-window correlation spectroscopy and its applications

NASA Astrophysics Data System (ADS)

Zhou, Qun; Sun, Suqin; Zhan, Daqi; Yu, Zhiwu

2008-07-01

In this paper, we present a new extension of generalized two-dimensional (2D) correlation spectroscopy. Two new algorithms, namely point-point (P-P) correlation and point-line (P-L) correlation, have been introduced to do the moving-window 2D correlation (MW2D) analysis. The new method has been applied to a spectral model consisting of two different processes. The results indicate that P-P correlation spectroscopy can unveil the details and re-constitute the entire process, whilst the P-L can provide general feature of the concerned processes. Phase transition behavior of dimyristoylphosphotidylethanolamine (DMPE) has been studied using MW2D correlation spectroscopy. The newly proposed method verifies that the phase transition temperature is 56 °C, same as the result got from a differential scanning calorimeter. To illustrate the new method further, a lysine and lactose mixture has been studied under thermo perturbation. Using the P-P MW2D, the Maillard reaction of the mixture was clearly monitored, which has been very difficult using conventional display of FTIR spectra.

Hardware simulator for optical correlation spectroscopy with Gaussian statistics and arbitrary correlation functions.

PubMed

Molteni, Matteo; Weigel, Udo M; Remiro, Francisco; Durduran, Turgut; Ferri, Fabio

2014-11-17

We present a new hardware simulator (HS) for characterization, testing and benchmarking of digital correlators used in various optical correlation spectroscopy experiments where the photon statistics is Gaussian and the corresponding time correlation function can have any arbitrary shape. Starting from the HS developed in [Rev. Sci. Instrum. 74, 4273 (2003)], and using the same I/O board (PCI-6534 National Instrument) mounted on a modern PC (Intel Core i7-CPU, 3.07GHz, 12GB RAM), we have realized an instrument capable of delivering continuous streams of TTL pulses over two channels, with a time resolution of Δt = 50ns, up to a maximum count rate of 〈I〉 ∼ 5MHz. Pulse streams, typically detected in dynamic light scattering and diffuse correlation spectroscopy experiments were generated and measured with a commercial hardware correlator obtaining measured correlation functions that match accurately the expected ones.

Spectroscopic techniques to study the immune response in human saliva

NASA Astrophysics Data System (ADS)

Nepomnyashchaya, E.; Savchenko, E.; Velichko, E.; Bogomaz, T.; Aksenov, E.

2018-01-01

Studies of the immune response dynamics by means of spectroscopic techniques, i.e., laser correlation spectroscopy and fluorescence spectroscopy, are described. The laser correlation spectroscopy is aimed at measuring sizes of particles in biological fluids. The fluorescence spectroscopy allows studying of the conformational and other structural changings in immune complex. We have developed a new scheme of a laser correlation spectrometer and an original signal processing algorithm. We have suggested a new fluorescence detection scheme based on a prism and an integrating pin diode. The developed system based on the spectroscopic techniques allows studies of complex process in human saliva and opens some prospects for an individual treatment of immune diseases.

Discrimination of Fritillary according to geographical origin with Fourier transform infrared spectroscopy and two-dimensional correlation IR spectroscopy.

PubMed

Hua, Rui; Sun, Su-Qin; Zhou, Qun; Noda, Isao; Wang, Bao-Qin

2003-09-19

Fritillaria is a traditional Chinese herbal medicine for eliminating phlegm and relieving a cough with a long history in China and some other Asian countries. The objective of this study is to develop a nondestructive and accurate method to discriminate Fritillaria of different geographical origins, which is a troublesome work by existing analytical methods. We conducted a systematic study on five kinds of Fritillaria by Fourier transform infrared spectroscopy, second derivative infrared spectroscopy, and two-dimensional (2D) correlation infrared spectroscopy under thermal perturbation. Because Fritillaria consist of a large amount of starch, the conventional IR spectra of different Fritillaria only have very limited spectral feature differences. Based on these differences, we can separate different Fritillaria to a limited extent, but this method was deemed not very practical. The second derivative IR spectra of Fritillaria could enhance spectrum resolution, amplify the differences between the IR spectra of different Fritillaria, and provide some dissimilarity in their starch content, when compared with the spectrum of pure starch. Finally, we applied thermal perturbation to Fritillaria and analyzed the resulting spectra by the 2D correlation method to distinguish different Fritillaria easily and clearly. The distinction of very similar Fritillaria was possible because the spectral resolution was greatly enhanced by the 2D correlation spectroscopy. In addition, with the dynamic information of molecular structure provided by 2D correlation IR spectra, we studied the differences in the stability of active components of Fritillaria. The differences embodied mainly on the intensity ratio of the auto-peak at 985 cm(-1) and other auto-peaks. The 2D correlation IR spectroscopy (2D IR) of Fritillaria can be a new and powerful method to discriminate Fritillaria.

Diagnosis of non-exudative (DRY) age related macular degeneration by non-invasive photon-correlation spectroscopy.

PubMed

Fankhauser, Franz Ii; Ott, Maria; Munteanu, Mihnea

2016-01-01

Photon-correlation spectroscopy (PCS) (quasi-elastic light scattering spectroscopy, dynamic light scattering spectroscopy) allows the non-invasively reveal of local dynamics and local heterogeneities of macromolecular systems. The capability of this technique to diagnose the retinal pathologies by in-vivo investigations of spatial anomalies of retinas displaying non-exudative senile macular degeneration was evaluated. Further, the potential use of the technique for the diagnosis of the macular degeneration was analyzed and displayed by the Receiver Operating Curve (ROC). The maculae and the peripheral retina of 73 normal eyes and of 26 eyes afflicted by an early stage of non-exudative senile macular degeneration were characterized by time-correlation functions and analyzed in terms of characteristic decay times and apparent size distributions. The characteristics of the obtained time-correlation functions of the eyes afflicted with nonexudative macular degeneration and of normal eyes differed significantly, which could be referred to a significant change of the nano- and microstructure of the investigated pathologic maculas. Photon-correlation spectroscopy is able to assess the macromolecular and microstructural aberrations in the macula afflicted by non-exudative, senile macular degeneration. It has been demonstrated that macromolecules of this disease show a characteristic abnormal behavior in the macula.

Electromagnetically-induced-transparency intensity-correlation power broadening in a buffer gas

NASA Astrophysics Data System (ADS)

Zheng, Aojie; Green, Alaina; Crescimanno, Michael; O'Leary, Shannon

2016-04-01

Electromagnetically-induced-transparency (EIT) noise correlation spectroscopy holds promise as a simple, robust method for performing high-resolution spectroscopy used in optical magnetometry and clocks. Of relevance to these applications, we report on the role of buffer gas pressure and magnetic field gradients on power broadening of Zeeman-EIT noise correlation resonances.

Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy

DOE PAGES

Dong, Hui; Lewis, Nicholas H. C.; Oliver, Thomas A. A.; ...

2015-05-07

Changes in the electronic structure of pigments in protein environments and of polar molecules in solution inevitably induce a re-adaption of molecular nuclear structure. Both changes of electronic and vibrational energies can be probed with visible or infrared lasers, such as two-dimensional electronic spectroscopy or vibrational spectroscopy. The extent to which the two changes are correlated remains elusive. The recent demonstration of two-dimensional electronic-vibrational (2DEV) spectroscopy potentially enables a direct measurement of this correlation experimentally. However, it has hitherto been unclear how to characterize the correlation from the spectra. In this report, we present a theoretical formalism to demonstrate themore » slope of the nodal line between the excited state absorption and ground state bleach peaks in the spectra as a characterization of the correlation between electronic and vibrational transition energies. In conclusion, we also show the dynamics of the nodal line slope is correlated to the vibrational spectral dynamics. Additionally, we demonstrate the fundamental 2DEV spectral line-shape of a monomer with newly developed response functions« less

Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy

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

Dong, Hui; Lewis, Nicholas H. C.; Oliver, Thomas A. A.

2015-05-07

Changes in the electronic structure of pigments in protein environments and of polar molecules in solution inevitably induce a re-adaption of molecular nuclear structure. Both changes of electronic and vibrational energies can be probed with visible or infrared lasers, such as two-dimensional electronic spectroscopy or vibrational spectroscopy. The extent to which the two changes are correlated remains elusive. The recent demonstration of two-dimensional electronic-vibrational (2DEV) spectroscopy potentially enables a direct measurement of this correlation experimentally. However, it has hitherto been unclear how to characterize the correlation from the spectra. In this paper, we present a theoretical formalism to demonstrate themore » slope of the nodal line between the excited state absorption and ground state bleach peaks in the spectra as a characterization of the correlation between electronic and vibrational transition energies. We also show the dynamics of the nodal line slope is correlated to the vibrational spectral dynamics. Additionally, we demonstrate the fundamental 2DEV spectral line-shape of a monomer with newly developed response functions.« less

In Vivo Fluorescence Correlation and Cross-Correlation Spectroscopy

NASA Astrophysics Data System (ADS)

Mütze, Jörg; Ohrt, Thomas; Petrášek, Zdeněk; Schwille, Petra

In this manuscript, we describe the application of Fluorescence Correlation Spectroscopy (FCS), Fluorescence Cross-Correlation Spectroscopy (FCCS), and scanning FCS (sFCS) to two in vivo systems. In the first part, we describe the application of two-photon standard and scanning FCS in Caenorhabditis elegans embryos. The differentiation of a single fertilized egg into a complex organism in C. elegans is regulated by a number of protein-dependent processes. The oocyte divides asymmetrically into two daughter cells of different developmental fate. Two of the involved proteins, PAR-2 and NMY-2, are studied. The second investigated system is the mechanism of RNA interference in human cells. An EGFP based cell line that allows to study the dynamics and localization of the RNA-induced silencing complex (RISC) with FCS in vivo is created, which has so far been inaccessible with other experimental methods. Furthermore, Fluorescence Cross-Correlation Spectroscopy is employed to highlight the asymmetric incorporation of labeled siRNAs into RISC.

Advancements of two dimensional correlation spectroscopy in protein researches

NASA Astrophysics Data System (ADS)

Tao, Yanchun; Wu, Yuqing; Zhang, Liping

2018-05-01

The developments of two-dimensional correlation spectroscopy (2DCOS) applications in protein studies are discussed, especially for the past two decades. The powerful utilities of 2DCOS combined with various analytical techniques in protein studies are summarized. The emphasis is on the vibration spectroscopic techniques including IR, NIR, Raman and optical activity (ROA), as well as vibration circular dichroism (VCD) and fluorescence spectroscopy. In addition, some new developments, such as hetero-spectral 2DCOS, moving-window correlation, and model based correlation, are also reviewed for their utility in the investigation of the secondary structure, denaturation, folding and unfolding changes of protein. Finally, the new possibility and challenges of 2DCOS in protein research are highlighted as well.

Fluorescence correlation spectroscopy of diffusion probed with a Gaussian Lorentzian spatial distribution

NASA Astrophysics Data System (ADS)

Marrocco, Michele

2007-11-01

Fluorescence correlation spectroscopy is fundamental in many physical, chemical and biological studies of molecular diffusion. However, the concept of fluorescence correlation is founded on the assumption that the analytical description of the correlation decay of diffusion can be achieved if the spatial profile of the detected volume obeys a three-dimensional Gaussian distribution. In the present Letter, the analytical result is instead proven for the fundamental Gaussian-Lorentzian profile.

The X-ray correlation spectroscopy instrument at the Linac Coherent Light Source

DOE PAGES

Alonso-Mori, Roberto; Caronna, Chiara; Chollet, Matthieu; ...

2015-03-03

The X-ray Correlation Spectroscopy instrument is dedicated to the study of dynamics in condensed matter systems using the unique coherence properties of free-electron lasers. It covers a photon energy range of 4–25 keV. The intrinsic temporal characteristics of the Linac Coherent Light Source, in particular the 120 Hz repetition rate, allow for the investigation of slow dynamics (milliseconds) by means of X-ray photon correlation spectroscopy. Double-pulse schemes could probe dynamics on the picosecond timescale. In addition, a description of the instrument capabilities and recent achievements is presented.

The measurement of bacterial translation by photon correlation spectroscopy.

PubMed Central

Stock, G B; Jenkins, T C

1978-01-01

Photon correlation spectroscopy is shown to be a practical technique for the accurate determination of translational speeds of bacteria. Though other attempts have been made to use light scattering as a probe of various aspects of bacterial motility, no other comprehensive studies to establish firmly the basic capabilities and limitations of the technique have been published. The intrinsic accuracy of the assay of translational speeds by photon correlation spectroscopy is investigated by analysis of synthetic autocorrelation data; consistently accurate estimates of the mean and second moment of the speed distribution can be calculated. Extensive analyses of experimental preparations of Salmonella typhimurium examine the possible sources of experimental difficulty with the assay. Cinematography confirms the bacterial speed estimates obtained by photon correlation techniques. PMID:346073

EIT amplitude noise spectroscopy

NASA Astrophysics Data System (ADS)

Whitenack, Benjamin; Tormey, Devan; O'Leary, Shannon; Crescimanno, Michael

2017-04-01

EIT Noise spectroscopy is usually studied by computing a correlation statistic based on temporal intensity variations of the two (circular polarization) propagation eigenstates. Studying the intensity noise correlations that result from amplitude mixing that we perform before and after the cell allows us to recast it in terms of the underlying amplitude noise. This leads to new tests of the quantum optics theory model and suggests an approach to the use of noise spectroscopy for vector magnetometry.

Quantitative evaluation of cross correlation between two finite-length time series with applications to single-molecule FRET.

PubMed

Hanson, Jeffery A; Yang, Haw

2008-11-06

The statistical properties of the cross correlation between two time series has been studied. An analytical expression for the cross correlation function's variance has been derived. On the basis of these results, a statistically robust method has been proposed to detect the existence and determine the direction of cross correlation between two time series. The proposed method has been characterized by computer simulations. Applications to single-molecule fluorescence spectroscopy are discussed. The results may also find immediate applications in fluorescence correlation spectroscopy (FCS) and its variants.

The X-ray Correlation Spectroscopy instrument at the Linac Coherent Light Source

PubMed Central

Alonso-Mori, Roberto; Caronna, Chiara; Chollet, Matthieu; Curtis, Robin; Damiani, Daniel S.; Defever, Jim; Feng, Yiping; Flath, Daniel L.; Glownia, James M.; Lee, Sooheyong; Lemke, Henrik T.; Nelson, Silke; Bong, Eric; Sikorski, Marcin; Song, Sanghoon; Srinivasan, Venkat; Stefanescu, Daniel; Zhu, Diling; Robert, Aymeric

2015-01-01

The X-ray Correlation Spectroscopy instrument is dedicated to the study of dynamics in condensed matter systems using the unique coherence properties of free-electron lasers. It covers a photon energy range of 4–25 keV. The intrinsic temporal characteristics of the Linac Coherent Light Source, in particular the 120 Hz repetition rate, allow for the investigation of slow dynamics (milli­seconds) by means of X-ray photon correlation spectroscopy. Double-pulse schemes could probe dynamics on the picosecond timescale. A description of the instrument capabilities and recent achievements is presented. PMID:25931061

Chemical profiling and adulteration screening of Aquilariae Lignum Resinatum by Fourier transform infrared (FT-IR) spectroscopy and two-dimensional correlation infrared (2D-IR) spectroscopy.

PubMed

Qu, Lei; Chen, Jian-Bo; Zhang, Gui-Jun; Sun, Su-Qin; Zheng, Jing

2017-03-05

As a kind of expensive perfume and valuable herb, Aquilariae Lignum Resinatum (ALR) is often adulterated for economic motivations. In this research, Fourier transform infrared (FT-IR) spectroscopy is employed to establish a simple and quick method for the adulteration screening of ALR. First, the principal chemical constituents of ALR are characterized by FT-IR spectroscopy at room temperature and two-dimensional correlation infrared (2D-IR) spectroscopy with thermal perturbation. Besides the common cellulose and lignin compounds, a certain amount of resin is the characteristic constituent of ALR. Synchronous and asynchronous 2D-IR spectra indicate that the resin (an unstable secondary metabolite) is more sensitive than cellulose and lignin (stable structural constituents) to the thermal perturbation. Using a certified ALR sample as the reference, the infrared spectral correlation threshold is determined by 30 authentic samples and 6 adulterated samples. The spectral correlation coefficient of an authentic ALR sample to the standard reference should be not less than 0.9886 (p=0.01). Three commercial adulterated ALR samples are identified by the correlation threshold. Further interpretation of the infrared spectra of the adulterated samples indicates the common adulterating methods - counterfeiting with other kind of wood, adding ingredient such as sand to increase the weight, and adding the cheap resin such as rosin to increase the content of resin compounds. Results of this research prove that FT-IR spectroscopy can be used as a simple and accurate quality control method of ALR. Copyright © 2016 Elsevier B.V. All rights reserved.

Chemical profiling and adulteration screening of Aquilariae Lignum Resinatum by Fourier transform infrared (FT-IR) spectroscopy and two-dimensional correlation infrared (2D-IR) spectroscopy

NASA Astrophysics Data System (ADS)

Qu, Lei; Chen, Jian-bo; Zhang, Gui-Jun; Sun, Su-qin; Zheng, Jing

2017-03-01

As a kind of expensive perfume and valuable herb, Aquilariae Lignum Resinatum (ALR) is often adulterated for economic motivations. In this research, Fourier transform infrared (FT-IR) spectroscopy is employed to establish a simple and quick method for the adulteration screening of ALR. First, the principal chemical constituents of ALR are characterized by FT-IR spectroscopy at room temperature and two-dimensional correlation infrared (2D-IR) spectroscopy with thermal perturbation. Besides the common cellulose and lignin compounds, a certain amount of resin is the characteristic constituent of ALR. Synchronous and asynchronous 2D-IR spectra indicate that the resin (an unstable secondary metabolite) is more sensitive than cellulose and lignin (stable structural constituents) to the thermal perturbation. Using a certified ALR sample as the reference, the infrared spectral correlation threshold is determined by 30 authentic samples and 6 adulterated samples. The spectral correlation coefficient of an authentic ALR sample to the standard reference should be not less than 0.9886 (p = 0.01). Three commercial adulterated ALR samples are identified by the correlation threshold. Further interpretation of the infrared spectra of the adulterated samples indicates the common adulterating methods - counterfeiting with other kind of wood, adding ingredient such as sand to increase the weight, and adding the cheap resin such as rosin to increase the content of resin compounds. Results of this research prove that FT-IR spectroscopy can be used as a simple and accurate quality control method of ALR.

Fluorescence correlation spectroscopy: the case of subdiffusion.

PubMed

Lubelski, Ariel; Klafter, Joseph

2009-03-18

The theory of fluorescence correlation spectroscopy is revisited here for the case of subdiffusing molecules. Subdiffusion is assumed to stem from a continuous-time random walk process with a fat-tailed distribution of waiting times and can therefore be formulated in terms of a fractional diffusion equation (FDE). The FDE plays the central role in developing the fluorescence correlation spectroscopy expressions, analogous to the role played by the simple diffusion equation for regular systems. Due to the nonstationary nature of the continuous-time random walk/FDE, some interesting properties emerge that are amenable to experimental verification and may help in discriminating among subdiffusion mechanisms. In particular, the current approach predicts 1), a strong dependence of correlation functions on the initial time (aging); 2), sensitivity of correlation functions to the averaging procedure, ensemble versus time averaging (ergodicity breaking); and 3), that the basic mean-squared displacement observable depends on how the mean is taken.

Xeroderma pigmentosum--Cockayne syndrome complex: a further case.

PubMed Central

Hamel, B C; Raams, A; Schuitema-Dijkstra, A R; Simons, P; van der Burgt, I; Jaspers, N G; Kleijer, W J

1996-01-01

We report on a male patient born to healthy, first cousin, Moroccan parents. During the pregnancy growth retardation was observed. Birth weight, length, and OFC were all well below the 3rd centile. Facial anomalies, microphthalmia, cleft palate, small penis, and flexion contractures of large joints were noted. Cerebral MRI showed dysmyelination. The clinical course was characterised by feeding difficulties, growth failure, lack of development, photosensitivity, and death at 7 months. The main differential diagnoses were COFS syndrome and early onset Cockayne syndrome (CS). UV exposure of cultured fibroblasts showed inhibition of nucleic acids synthesis. Further DNA repair studies showed extreme cellular sensitivity to UV and xeroderma pigmentosum (XP)-like defective nucleotide excision repair (NER), which in combination with the clinical symptoms indicated the very rare XP-CS complex. Complementation analysis showed that the XPG gene is affected in this patient. In cases suspected of having COFS syndrome and early onset CS, extensive DNA repair studies are needed to reach the definitive diagnosis, thereby allowing reliable genetic counselling and prenatal diagnosis. Images PMID:8818951

Laser correlation spectroscopy in the diagnosis of tumor diseases of the female reproductive system (preliminary results)

NASA Astrophysics Data System (ADS)

Korneeva, A. A.; Sekerskaya, M. N.; Zhordaniya, K. I.; Sapezhinskiy, V. S.; Golubtsova, N. V.; Barmashov, A. E.; Gonchukov, S. A.; Ivanov, A. V.

2017-01-01

The study of blood serum of cancer patients by laser correlation spectroscopy to determine the possibility of differentiation of benign and malignant tumors of the female reproductive system. We analyzed the data and assessed the applicability of the method mentioned above target.

Measuring and imaging diffusion with multiple scan speed image correlation spectroscopy.

PubMed

Gröner, Nadine; Capoulade, Jérémie; Cremer, Christoph; Wachsmuth, Malte

2010-09-27

The intracellular mobility of biomolecules is determined by transport and diffusion as well as molecular interactions and is crucial for many processes in living cells. Methods of fluorescence microscopy like confocal laser scanning microscopy (CLSM) can be used to characterize the intracellular distribution of fluorescently labeled biomolecules. Fluorescence correlation spectroscopy (FCS) is used to describe diffusion, transport and photo-physical processes quantitatively. As an alternative to FCS, spatially resolved measurements of mobilities can be implemented using a CLSM by utilizing the spatio-temporal information inscribed into the image by the scan process, referred to as raster image correlation spectroscopy (RICS). Here we present and discuss an extended approach, multiple scan speed image correlation spectroscopy (msICS), which benefits from the advantages of RICS, i.e. the use of widely available instrumentation and the extraction of spatially resolved mobility information, without the need of a priori knowledge of diffusion properties. In addition, msICS covers a broad dynamic range, generates correlation data comparable to FCS measurements, and allows to derive two-dimensional maps of diffusion coefficients. We show the applicability of msICS to fluorophores in solution and to free EGFP in living cells.

Determination of organic compounds in water using ultraviolet LED

NASA Astrophysics Data System (ADS)

Kim, Chihoon; Ji, Taeksoo; Eom, Joo Beom

2018-04-01

This paper describes a method of detecting organic compounds in water using an ultraviolet LED (280 nm) spectroscopy system and a photodetector. The LED spectroscopy system showed a high correlation between the concentration of the prepared potassium hydrogen phthalate and that calculated by multiple linear regression, indicating an adjusted coefficient of determination ranging from 0.953-0.993. In addition, a comparison between the performance of the spectroscopy system and the total organic carbon analyzer indicated that the difference in concentration was small. Based on the close correlation between the spectroscopy and photodetector absorbance values, organic measurement with a photodetector could be configured for monitoring.

Correlative Raman spectroscopy and focused ion beam for targeted phase boundary analysis of titania polymorphs

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

Mangum, John S.; Chan, Lisa H.; Schmidt, Ute

Site-specific preparation of specimens using focused ion beam instruments for transmission electron microscopy is at the forefront of targeting regions of interest for nanoscale characterization. Typical methods of pinpointing desired features include electron backscatter diffraction for differentiating crystal structures and energy-dispersive X-Ray spectroscopy for probing compositional variations. Yet there are situations, notably in the titanium dioxide system, where these techniques can fail. Differentiating between the brookite and anatase polymorphs of titania is either excessively laborious or impossible with the aforementioned techniques. However, due to differences in bonding structure, Raman spectroscopy serves as an ideal candidate for polymorph differentiation. In thismore » work, a correlative approach utilizing Raman spectroscopy for targeted focused ion beam specimen preparation was employed. Dark field imaging and diffraction in the transmission electron microscope confirmed the region of interest located via Raman spectroscopy and demonstrated the validity of this new method. Correlative Raman spectroscopy, scanning electron microscopy, and focused ion beam is shown to be a promising new technique for identifying site-specific preparation of nanoscale specimens in cases where conventional approaches do not suffice.« less

Correlative Raman spectroscopy and focused ion beam for targeted phase boundary analysis of titania polymorphs.

PubMed

Mangum, John S; Chan, Lisa H; Schmidt, Ute; Garten, Lauren M; Ginley, David S; Gorman, Brian P

2018-05-01

Site-specific preparation of specimens using focused ion beam instruments for transmission electron microscopy is at the forefront of targeting regions of interest for nanoscale characterization. Typical methods of pinpointing desired features include electron backscatter diffraction for differentiating crystal structures and energy-dispersive X-Ray spectroscopy for probing compositional variations. Yet there are situations, notably in the titanium dioxide system, where these techniques can fail. Differentiating between the brookite and anatase polymorphs of titania is either excessively laborious or impossible with the aforementioned techniques. However, due to differences in bonding structure, Raman spectroscopy serves as an ideal candidate for polymorph differentiation. In this work, a correlative approach utilizing Raman spectroscopy for targeted focused ion beam specimen preparation was employed. Dark field imaging and diffraction in the transmission electron microscope confirmed the region of interest located via Raman spectroscopy and demonstrated the validity of this new method. Correlative Raman spectroscopy, scanning electron microscopy, and focused ion beam is shown to be a promising new technique for identifying site-specific preparation of nanoscale specimens in cases where conventional approaches do not suffice. Copyright © 2018 Elsevier B.V. All rights reserved.

Correlative Raman spectroscopy and focused ion beam for targeted phase boundary analysis of titania polymorphs

DOE PAGES

Mangum, John S.; Chan, Lisa H.; Schmidt, Ute; ...

2018-02-23

Site-specific preparation of specimens using focused ion beam instruments for transmission electron microscopy is at the forefront of targeting regions of interest for nanoscale characterization. Typical methods of pinpointing desired features include electron backscatter diffraction for differentiating crystal structures and energy-dispersive X-Ray spectroscopy for probing compositional variations. Yet there are situations, notably in the titanium dioxide system, where these techniques can fail. Differentiating between the brookite and anatase polymorphs of titania is either excessively laborious or impossible with the aforementioned techniques. However, due to differences in bonding structure, Raman spectroscopy serves as an ideal candidate for polymorph differentiation. In thismore » work, a correlative approach utilizing Raman spectroscopy for targeted focused ion beam specimen preparation was employed. Dark field imaging and diffraction in the transmission electron microscope confirmed the region of interest located via Raman spectroscopy and demonstrated the validity of this new method. Correlative Raman spectroscopy, scanning electron microscopy, and focused ion beam is shown to be a promising new technique for identifying site-specific preparation of nanoscale specimens in cases where conventional approaches do not suffice.« less

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.

Magnetic resonance spectroscopy of normal appearing white matter in early relapsing-remitting multiple sclerosis: correlations between disability and spectroscopy

PubMed Central

Ruiz-Peña, Juan Luis; Piñero, Pilar; Sellers, Guillermo; Argente, Joaquín; Casado, Alfredo; Foronda, Jesus; Uclés, Antonio; Izquierdo, Guillermo

2004-01-01

Background What currently appears to be irreversible axonal loss in normal appearing white matter, measured by proton magnetic resonance spectroscopy is of great interest in the study of Multiple Sclerosis. Our aim is to determine the axonal damage in normal appearing white matter measured by magnetic resonance spectroscopy and to correlate this with the functional disability measured by Multiple Sclerosis Functional Composite scale, Neurological Rating Scale, Ambulation Index scale, and Expanded Disability Scale Score. Methods Thirty one patients (9 male and 22 female) with relapsing remitting Multiple Sclerosis and a Kurtzke Expanded Disability Scale Score of 0–5.5 were recruited from four hospitals in Andalusia, Spain and included in the study. Magnetic resonance spectroscopy scans and neurological disability assessments were performed the same day. Results A statistically significant correlation was found (r = -0.38 p < 0.05) between disability (measured by Expanded Disability Scale Score) and N-Acetyl Aspartate (NAA/Cr ratio) levels in normal appearing white matter in these patients. No correlation was found between the NAA/Cr ratio and disability measured by any of the other disability assessment scales. Conclusions There is correlation between disability (measured by Expanded Disability Scale Score) and the NAA/Cr ratio in normal appearing white matter. The lack of correlation between the NAA/Cr ratio and the Multiple Sclerosis Functional Composite score indicates that the Multiple Sclerosis Functional Composite is not able to measure irreversible disability and would be more useful as a marker in stages where axonal damage is not a predominant factor. PMID:15191618

Early Amyloidogenic Oligomerization Studied through Fluorescence Lifetime Correlation Spectroscopy

PubMed Central

Paredes, Jose M.; Casares, Salvador; Ruedas-Rama, Maria J.; Fernandez, Elena; Castello, Fabio; Varela, Lorena; Orte, Angel

2012-01-01

Amyloidogenic protein aggregation is a persistent biomedical problem. Despite active research in disease-related aggregation, the need for multidisciplinary approaches to the problem is evident. Recent advances in single-molecule fluorescence spectroscopy are valuable for examining heterogenic biomolecular systems. In this work, we have explored the initial stages of amyloidogenic aggregation by employing fluorescence lifetime correlation spectroscopy (FLCS), an advanced modification of conventional fluorescence correlation spectroscopy (FCS) that utilizes time-resolved information. FLCS provides size distributions and kinetics for the oligomer growth of the SH3 domain of α-spectrin, whose N47A mutant forms amyloid fibrils at pH 3.2 and 37 °C in the presence of salt. The combination of FCS with additional fluorescence lifetime information provides an exciting approach to focus on the initial aggregation stages, allowing a better understanding of the fibrillization process, by providing multidimensional information, valuable in combination with other conventional methodologies. PMID:22949804

Frontiers of two-dimensional correlation spectroscopy. Part 2. Perturbation methods, fields of applications, and types of analytical probes

NASA Astrophysics Data System (ADS)

Noda, Isao

2014-07-01

Noteworthy experimental practices, which are advancing forward the frontiers of the field of two-dimensional (2D) correlation spectroscopy, are reviewed with the focus on various perturbation methods currently practiced to induce spectral changes, pertinent examples of applications in various fields, and types of analytical probes employed. Types of perturbation methods found in the published literature are very diverse, encompassing both dynamic and static effects. Although a sizable portion of publications report the use of dynamic perturbatuions, much greater number of studies employ static effect, especially that of temperature. Fields of applications covered by the literature are also very broad, ranging from fundamental research to practical applications in a number of physical, chemical and biological systems, such as synthetic polymers, composites and biomolecules. Aside from IR spectroscopy, which is the most commonly used tool, many other analytical probes are used in 2D correlation analysis. The ever expanding trend in depth, breadth and versatility of 2D correlation spectroscopy techniques and their broad applications all point to the robust and healthy state of the field.

Scanning, non-contact, hybrid broadband diffuse optical spectroscopy and diffuse correlation spectroscopy system.

PubMed

Johansson, Johannes D; Mireles, Miguel; Morales-Dalmau, Jordi; Farzam, Parisa; Martínez-Lozano, Mar; Casanovas, Oriol; Durduran, Turgut

2016-02-01

A scanning system for small animal imaging using non-contact, hybrid broadband diffuse optical spectroscopy (ncDOS) and diffuse correlation spectroscopy (ncDCS) is presented. The ncDOS uses a two-dimensional spectrophotometer retrieving broadband (610-900 nm) spectral information from up to fifty-seven source-detector distances between 2 and 5 mm. The ncDCS data is simultaneously acquired from four source-detector pairs. The sample is scanned in two dimensions while tracking variations in height. The system has been validated with liquid phantoms, demonstrated in vivo on a human fingertip during an arm cuff occlusion and on a group of mice with xenoimplanted renal cell carcinoma.

Pancreatic tissue assessment using fluorescence and reflectance spectroscopy

NASA Astrophysics Data System (ADS)

Chandra, Malavika; Heidt, David; Simeone, Diane; McKenna, Barbara; Scheiman, James; Mycek, Mary-Ann

2007-07-01

The ability of multi-modal optical spectroscopy to detect signals from pancreatic tissue was demonstrated by studying human pancreatic cancer xenografts in mice and freshly excised human pancreatic tumor tissue. Measured optical spectra and fluorescence decays were correlated with tissue morphological and biochemical properties. The measured spectral features and decay times correlated well with expected pathological differences in normal, pancreatitis and adenocarcinoma tissue states. The observed differences between the fluorescence and reflectance properties of normal, pancreatitis and adenocarcinoma tissue indicate a possible application of multi-modal optical spectroscopy to differentiating between the three tissue classifications.

Correlation between near infrared spectroscopy and electrical techniques in measuring skin moisture content

NASA Astrophysics Data System (ADS)

Mohamad, M.; Sabbri, A. R. M.; Mat Jafri, M. Z.; Omar, A. F.

2014-11-01

Near infrared (NIR) spectroscopy technique serves as an important tool for the measurement of moisture content of skin owing to the advantages it has over the other techniques. The purpose of the study is to develop a correlation between NIR spectrometer with electrical conventional techniques for skin moisture measurement. A non-invasive measurement of moisture content of skin was performed on different part of human face and hand under control environment (temperature 21 ± 1 °C, relative humidity 45 ± 5 %). Ten healthy volunteers age between 21-25 (male and female) participated in this study. The moisture content of skin was measured using DermaLab® USB Moisture Module, Scalar Moisture Checker and NIR spectroscopy (NIRQuest). Higher correlation was observed between NIRQuest and Dermalab moisture probe with a coefficient of determination (R2) above 70 % for all the subjects. However, the value of R2 between NIRQuest and Moisture Checker was observed to be lower with the R2 values ranges from 51.6 to 94.4 %. The correlation of NIR spectroscopy technique successfully developed for measuring moisture content of the skin. The analysis of this correlation can help to establish novel instruments based on an optical system in clinical used especially in the dermatology field.

Study on Senna alata and its different extracts by Fourier transform infrared spectroscopy and two-dimensional correlation infrared spectroscopy

NASA Astrophysics Data System (ADS)

Adiana, M. A.; Mazura, M. P.

2011-04-01

Senna alata L. commonly known as candle bush belongs to the family of Fabaceae and the plant has been reported to possess anti-inflammatory, analgesic, laxative and antiplatelet-aggregating activity. In order to develop a rapid and effective analysis method for studying integrally the main constituents in the medicinal materials and their extracts, discriminating the extracts from different extraction process, comparing the categories of chemical constituents in the different extracts and monitoring the qualities of medicinal materials, we applied Fourier transform infrared spectroscopy (FT-IR) associated with second derivative infrared spectroscopy and two-dimensional infrared correlation spectroscopy (2D-IR) to study the main constituents of S. alata and its different extracts (extracted by hexane, dichloromethane, ethyl acetate and methanol in turn). The findings indicated that FT-IR and 2D-IR can provide many holistic variation rules of chemical constituents. Use of the macroscopical fingerprint characters of FT-IR and 2D-IR spectrum can identify the main chemical constituents in medicinal materials and their extracts, but also compare the components differences among similar samples. In a conclusion, FT-IR spectroscopy combined with 2D correlation analysis provides a powerful method for the quality control of traditional medicines.

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.

Distinction of three wood species by Fourier transform infrared spectroscopy and two-dimensional correlation IR spectroscopy

NASA Astrophysics Data System (ADS)

Huang, Anmin; Zhou, Qun; Liu, Junliang; Fei, Benhua; Sun, Suqin

2008-07-01

Dalbergia odorifera T. Chen, Pterocarpus santalinus L.F. and Pterocarpus soyauxii are three kinds of the most valuable wood species, which are hard to distinguish. In this paper, differentiation of D. odorifera, P. santalinus and P. soyauxii was carried out by using Fourier transform infrared spectroscopy (FT-IR), second derivative IR spectra and two-dimensional correlation infrared (2D-IR) spectroscopy. The three woods have their characteristic peaks in conventional IR spectra. For example, D. odorifera has obvious absorption peaks at 1640 and 1612 cm -1; P. santalinus has only one peak at 1614 cm -1; and P. soyauxii has one peak at 1619 cm -1 and one shoulder peak at 1597 cm -1. To enhance spectrum resolution and amplify the differences between the IR spectra of different woods, the second derivative technology was adopted to examine the three wood samples. More differences could be observed in the region of 800-1700 cm -1. Then, the thermal perturbation is applied to distinguish different wood samples in an easier way, because of the spectral resolution being enhanced by the 2D correlation spectroscopy. In the region of 1300-1800 cm -1, D. odorifera has five auto-peaks at 1518, 1575, 1594, 1620 and 1667 cm -1; P. santalinus has four auto-peaks at 1469, 1518, 1627 and 1639 cm -1 and P. soyauxii has only two auto-peaks at 1627 and 1639 cm -1. It is proved that the 2D correlation IR spectroscopy can be a new method to distinguish D. odorifera, P. santalinus and P. soyauxii.

Ghost Spectroscopy with Classical Thermal Light Emitted by a Superluminescent Diode

NASA Astrophysics Data System (ADS)

Janassek, Patrick; Blumenstein, Sébastien; Elsäßer, Wolfgang

2018-02-01

We propose and realize the first classical ghost-imaging (GI) experiment in the frequency or wavelength domain, thus performing ghost spectroscopy using thermal light exhibiting photon bunching. The required wavelength correlations are provided by light emitted by spectrally broadband near-infrared amplified spontaneous emission of a semiconductor-based superluminescent diode. They are characterized by wavelength-resolved intensity cross-correlation measurements utilizing two-photon-absorption interferometry. Finally, a real-world spectroscopic application of this ghost spectroscopy with a classical light scheme is demonstrated in which an absorption band of trichloromethane (chloroform) at 1214 nm is reconstructed with a spectral resolution of 10 nm as a proof-of-principle experiment. This ghost-spectroscopy work fills the gap of a hitherto missing analogy between the spatial and the spectral domain in classical GI modalities, with the expectation of contributing towards a broader dissemination of correlated photon ghost modalities, hence paving the way towards more applications which exploit the favorable advantages.

Vectorized data acquisition and fast triple-correlation integrals for Fluorescence Triple Correlation Spectroscopy

PubMed Central

Ridgeway, William K; Millar, David P; Williamson, James R

2013-01-01

Fluorescence Correlation Spectroscopy (FCS) is widely used to quantitate reaction rates and concentrations of molecules in vitro and in vivo. We recently reported Fluorescence Triple Correlation Spectroscopy (F3CS), which correlates three signals together instead of two. F3CS can analyze the stoichiometries of complex mixtures and detect irreversible processes by identifying time-reversal asymmetries. Here we report the computational developments that were required for the realization of F3CS and present the results as the Triple Correlation Toolbox suite of programs. Triple Correlation Toolbox is a complete data analysis pipeline capable of acquiring, correlating and fitting large data sets. Each segment of the pipeline handles error estimates for accurate error-weighted global fitting. Data acquisition was accelerated with a combination of off-the-shelf counter-timer chips and vectorized operations on 128-bit registers. This allows desktop computers with inexpensive data acquisition cards to acquire hours of multiple-channel data with sub-microsecond time resolution. Off-line correlation integrals were implemented as a two delay time multiple-tau scheme that scales efficiently with multiple processors and provides an unprecedented view of linked dynamics. Global fitting routines are provided to fit FCS and F3CS data to models containing up to ten species. Triple Correlation Toolbox is a complete package that enables F3CS to be performed on existing microscopes. PMID:23525193

2D Vis/NIR correlation spectroscopy of cooked chicken meats

NASA Astrophysics Data System (ADS)

Liu, Yongliang; Chen, Yud-Ren; Ozaki, Yukihiro

2000-03-01

Cooking of chicken meats was investigated by the generalized two-dimensional visible/near-infrared (2D Vis/NIR) correlation spectroscopy. Synchronous and asynchronous spectra in the 400-700 nm visible region suggested that the 445 and 560 nm bands be ascribed to deoxymyoglobin and oxymyoglobin, and at least one of the 475, 520, and 585 nm bands is assignable to the denatured species (metmyoglobin). The asynchronous 2D NIR correlation spectrum showed that CH bands change their spectral intensities before the OH/NH groups during the cooking process, indicating that CH fractions are easily oxidized and degraded. In addition, strong correlation peaks were observed correlating the bands in the visible and NIR spectral regions.

Spatiotemporal image correlation spectroscopy (STICS) theory, verification, and application to protein velocity mapping in living CHO cells.

PubMed

Hebert, Benedict; Costantino, Santiago; Wiseman, Paul W

2005-05-01

We introduce a new extension of image correlation spectroscopy (ICS) and image cross-correlation spectroscopy (ICCS) that relies on complete analysis of both the temporal and spatial correlation lags for intensity fluctuations from a laser-scanning microscopy image series. This new approach allows measurement of both diffusion coefficients and velocity vectors (magnitude and direction) for fluorescently labeled membrane proteins in living cells through monitoring of the time evolution of the full space-time correlation function. By using filtering in Fourier space to remove frequencies associated with immobile components, we are able to measure the protein transport even in the presence of a large fraction (>90%) of immobile species. We present the background theory, computer simulations, and analysis of measurements on fluorescent microspheres to demonstrate proof of principle, capabilities, and limitations of the method. We demonstrate mapping of flow vectors for mixed samples containing fluorescent microspheres with different emission wavelengths using space time image cross-correlation. We also present results from two-photon laser-scanning microscopy studies of alpha-actinin/enhanced green fluorescent protein fusion constructs at the basal membrane of living CHO cells. Using space-time image correlation spectroscopy (STICS), we are able to measure protein fluxes with magnitudes of mum/min from retracting lamellar regions and protrusions for adherent cells. We also demonstrate the measurement of correlated directed flows (magnitudes of mum/min) and diffusion of interacting alpha5 integrin/enhanced cyan fluorescent protein and alpha-actinin/enhanced yellow fluorescent protein within living CHO cells. The STICS method permits us to generate complete transport maps of proteins within subregions of the basal membrane even if the protein concentration is too high to perform single particle tracking measurements.

Surface Transient Binding-Based Fluorescence Correlation Spectroscopy (STB-FCS), a Simple and Easy-to-Implement Method to Extend the Upper Limit of the Time Window to Seconds.

PubMed

Peng, Sijia; Wang, Wenjuan; Chen, Chunlai

2018-05-10

Fluorescence correlation spectroscopy is a powerful single-molecule tool that is able to capture kinetic processes occurring at the nanosecond time scale. However, the upper limit of its time window is restricted by the dwell time of the molecule of interest in the confocal detection volume, which is usually around submilliseconds for a freely diffusing biomolecule. Here, we present a simple and easy-to-implement method, named surface transient binding-based fluorescence correlation spectroscopy (STB-FCS), which extends the upper limit of the time window to seconds. We further demonstrated that STB-FCS enables capture of both intramolecular and intermolecular kinetic processes whose time scales cross several orders of magnitude.

Recent advances in multidimensional ultrafast spectroscopy

NASA Astrophysics Data System (ADS)

Oliver, Thomas A. A.

2018-01-01

Multidimensional ultrafast spectroscopies are one of the premier tools to investigate condensed phase dynamics of biological, chemical and functional nanomaterial systems. As they reach maturity, the variety of frequency domains that can be explored has vastly increased, with experimental techniques capable of correlating excitation and emission frequencies from the terahertz through to the ultraviolet. Some of the most recent innovations also include extreme cross-peak spectroscopies that directly correlate the dynamics of electronic and vibrational states. This review article summarizes the key technological advances that have permitted these recent advances, and the insights gained from new multidimensional spectroscopic probes.

Recent advances in multidimensional ultrafast spectroscopy

PubMed Central

2018-01-01

Multidimensional ultrafast spectroscopies are one of the premier tools to investigate condensed phase dynamics of biological, chemical and functional nanomaterial systems. As they reach maturity, the variety of frequency domains that can be explored has vastly increased, with experimental techniques capable of correlating excitation and emission frequencies from the terahertz through to the ultraviolet. Some of the most recent innovations also include extreme cross-peak spectroscopies that directly correlate the dynamics of electronic and vibrational states. This review article summarizes the key technological advances that have permitted these recent advances, and the insights gained from new multidimensional spectroscopic probes. PMID:29410844

Correlation spectrometer for filtering of (quasi) elastic neutron scattering with variable resolution

NASA Astrophysics Data System (ADS)

Magazù, Salvatore; Mezei, Ferenc; Migliardo, Federica

2018-05-01

In a variety of applications of inelastic neutron scattering spectroscopy the goal is to single out the elastic scattering contribution from the total scattered spectrum as a function of momentum transfer and sample environment parameters. The elastic part of the spectrum is defined in such a case by the energy resolution of the spectrometer. Variable elastic energy resolution offers a way to distinguish between elastic and quasi-elastic intensities. Correlation spectroscopy lends itself as an efficient, high intensity approach for accomplishing this both at continuous and pulsed neutron sources. On the one hand, in beam modulation methods the Liouville theorem coupling between intensity and resolution is relaxed and time-of-flight velocity analysis of the neutron velocity distribution can be performed with 50 % duty factor exposure for all available resolutions. On the other hand, the (quasi)elastic part of the spectrum generally contains the major part of the integrated intensity at a given detector, and thus correlation spectroscopy can be applied with most favorable signal to statistical noise ratio. The novel spectrometer CORELLI at SNS is an example for this type of application of the correlation technique at a pulsed source. On a continuous neutron source a statistical chopper can be used for quasi-random time dependent beam modulation and the total time-of-flight of the neutron from the statistical chopper to detection is determined by the analysis of the correlation between the temporal fluctuation of the neutron detection rate and the statistical chopper beam modulation pattern. The correlation analysis can either be used for the determination of the incoming neutron velocity or for the scattered neutron velocity, depending of the position of the statistical chopper along the neutron trajectory. These two options are considered together with an evaluation of spectrometer performance compared to conventional spectroscopy, in particular for variable resolution elastic neutron scattering (RENS) studies of relaxation processes and the evolution of mean square displacements. A particular focus of our analysis is the unique feature of correlation spectroscopy of delivering high and resolution independent beam intensity, thus the same statistical chopper scan contains both high intensity and high resolution information at the same time, and can be evaluated both ways. This flexibility for variable resolution data handling represents an additional asset for correlation spectroscopy in variable resolution work. Changing the beam width for the same statistical chopper allows us to additionally trade resolution for intensity in two different experimental runs, similarly for conventional single slit chopper spectroscopy. The combination of these two approaches is a capability of particular value in neutron spectroscopy studies requiring variable energy resolution, such as the systematic study of quasi-elastic scattering and mean square displacement. Furthermore the statistical chopper approach is particularly advantageous for studying samples with low scattering intensity in the presence of a high, sample independent background.

Intracellular dynamics and fate of polystyrene nanoparticles in A549 Lung epithelial cells monitored by image (cross-) correlation spectroscopy and single particle tracking.

PubMed

Deville, Sarah; Penjweini, Rozhin; Smisdom, Nick; Notelaers, Kristof; Nelissen, Inge; Hooyberghs, Jef; Ameloot, Marcel

2015-10-01

Novel insights in nanoparticle (NP) uptake routes of cells, their intracellular trafficking and subcellular targeting can be obtained through the investigation of their temporal and spatial behavior. In this work, we present the application of image (cross-) correlation spectroscopy (IC(C)S) and single particle tracking (SPT) to monitor the intracellular dynamics of polystyrene (PS) NPs in the human lung carcinoma A549 cell line. The ensemble kinetic behavior of NPs inside the cell was characterized by temporal and spatiotemporal image correlation spectroscopy (TICS and STICS). Moreover, a more direct interpretation of the diffusion and flow detected in the NP motion was obtained by SPT by monitoring individual NPs. Both techniques demonstrate that the PS NP transport in A549 cells is mainly dependent on microtubule-assisted transport. By applying spatiotemporal image cross-correlation spectroscopy (STICCS), the correlated motions of NPs with the early endosomes, late endosomes and lysosomes are identified. PS NPs were equally distributed among the endolysosomal compartment during the time interval of the experiments. The cotransport of the NPs with the lysosomes is significantly larger compared to the other cell organelles. In the present study we show that the complementarity of ICS-based techniques and SPT enables a consistent elaborate model of the complex behavior of NPs inside biological systems. Copyright © 2015 Elsevier B.V. All rights reserved.

Brain oxygen saturation assessment in neonates using T2-prepared blood imaging of oxygen saturation and near-infrared spectroscopy.

PubMed

Alderliesten, Thomas; De Vis, Jill B; Lemmers, Petra Ma; Hendrikse, Jeroen; Groenendaal, Floris; van Bel, Frank; Benders, Manon Jnl; Petersen, Esben T

2017-03-01

Although near-infrared spectroscopy is increasingly being used to monitor cerebral oxygenation in neonates, it has a limited penetration depth. The T 2 -prepared Blood Imaging of Oxygen Saturation (T 2 -BIOS) magnetic resonance sequence provides an oxygen saturation estimate on a voxel-by-voxel basis, without needing a respiratory calibration experiment. In 15 neonates, oxygen saturation measured by T 2 -prepared blood imaging of oxygen saturation and near-infrared spectroscopy were compared. In addition, these measures were compared to cerebral blood flow and venous oxygen saturation in the sagittal sinus. A strong linear relation was found between the oxygen saturation measured by magnetic resonance imaging and the oxygen saturation measured by near-infrared spectroscopy ( R 2  = 0.64, p < 0.001). Strong linear correlations were found between near-infrared spectroscopy oxygen saturation, and magnetic resonance imaging measures of frontal cerebral blood flow, whole brain cerebral blood flow and venous oxygen saturation in the sagittal sinus ( R 2  = 0.71, 0.50, 0.65; p < 0.01). The oxygen saturation obtained by T 2 -prepared blood imaging of oxygen saturation correlated with venous oxygen saturation in the sagittal sinus ( R 2  = 0.49, p = 0.023), but no significant correlations could be demonstrated with frontal and whole brain cerebral blood flow. These results suggest that measuring oxygen saturation by T 2 -prepared blood imaging of oxygen saturation is feasible, even in neonates. Strong correlations between the various methods work as a cross validation for near-infrared spectroscopy and T 2 -prepared blood imaging of oxygen saturation, confirming the validity of using of these techniques for determining cerebral oxygenation.

Metallic scattering lifetime measurements with terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Lea, Graham Bryce

The momentum scattering lifetime is a fundamental parameter of metallic conduction that can be measured with terahertz time-domain spectroscopy. This technique has an important strength over optical reflectance spectroscopy: it is capable of measuring both the phase and the amplitude of the probing radiation. This allows simultaneous, independent measurements of the scattering lifetime and resistivity. Broadly, it is the precision of the phase measurement that determines the precision of scattering lifetime measurements. This thesis describes milliradian-level phase measurement refinements in the experimental technique and measures the conductivity anisotropy in the correlated electron system CaRuO3. These phase measurement refinements translate to femtosecond-level refinements in scattering lifetime measurements of thin metallic films. Keywords: terahertz time-domain spectroscopy, calcium ruthenate, ruthenium oxides, correlated electrons, experimental technique.

Polarization and amplitude probes in Hanle effect EIT noise spectroscopy of a buffer gas cell

NASA Astrophysics Data System (ADS)

O'Leary, Shannon; Zheng, Aojie; Crescimanno, Michael

2015-05-01

Noise correlation spectroscopy on systems manifesting Electromagnetically Induced Transparency (EIT) holds promise as a simple, robust method for performing high-resolution spectroscopy used in applications such as EIT-based atomic magnetometry and clocks. While this noise conversion can diminish the precision of EIT applications, noise correlation techniques transform the noise into a useful spectroscopic tool that can improve the application's precision. We study intensity noise, originating from the large phase noise of a semiconductor diode laser's light, in Rb vapor EIT in the Hanle configuration. We report here on our recent experimental work on and complementary theoretical modeling of the effects of light polarization preparation and post-selection on the correlation spectrum and on the independent noise channel traces. We also explain methodology and recent results for delineating the effects of residual laser amplitude fluctuations on the correlation noise resonance as compared to other contributing processes. Understanding these subtleties are essential for optimizing EIT-noise applications.

Fluorescence lifetime correlation spectroscopy for precise concentration detection in vivo by background subtraction

NASA Astrophysics Data System (ADS)

Gärtner, Maria; Mütze, Jörg; Ohrt, Thomas; Schwille, Petra

2009-07-01

In vivo studies of single molecule dynamics by means of Fluorescence correlation spectroscopy can suffer from high background. Fluorescence lifetime correlation spectroscopy provides a tool to distinguish between signal and unwanted contributions via lifetime separation. By studying the motion of the RNA-induced silencing complex (RISC) within two compartments of a human cell, the nucleus and the cytoplasm, we observed clear differences in concentration as well as mobility of the protein complex between those two locations. Especially in the nucleus, where the fluorescence signal is very weak, a correction for background is crucial to provide reliable results of the particle number. Utilizing the fluorescent lifetime of the different contributions, we show that it is possible to distinguish between the fluorescent signal and the autofluorescent background in vivo in a single measurement.

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

Chaurasia, Neha; Mishra, Yogesh; Rai, Lal Chand

Phytochelatin synthase (PCS) is involved in the synthesis of phytochelatins (PCs), plays role in heavy metal detoxification. The present study describes for first time the functional expression and characterization of pcs gene of Anabaena sp. PCC 7120 in Escherichia coli in terms of offering protection against heat, salt, carbofuron (pesticide), cadmium, copper, and UV-B stress. The involvement of pcs gene in tolerance to above abiotic stresses was investigated by cloning of pcs gene in expression vector pGEX-5X-2 and its transformation in E. coli BL21 (DE3). The E. coli cells transformed with pGEX-5X-pcs showed better growth than control cells (pGEX-5X-2) undermore » temperature (47 deg. C), NaCl (6% w/v), carbofuron (0.025 mg ml{sup -1}), CdCl{sub 2} (4 mM), CuCl{sub 2} (1 mM), and UV-B (10 min) exposure. The enhanced expression of pcs gene revealed by RT-PCR analysis under above stresses at different time intervals further advocates its role in tolerance against above abiotic stresses.« less

XPD Helicase Structures And Activities: Insights Into the Cancer And Aging Phenotypes From XPD Mutations

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

Fan, L.; Fuss, J.O.; Cheng, Q.J.

2009-05-18

Mutations in XPD helicase, required for nucleotide excision repair (NER) as part of the transcription/repair complex TFIIH, cause three distinct phenotypes: cancer-prone xeroderma pigmentosum (XP), or aging disorders Cockayne syndrome (CS), and trichothiodystrophy (TTD). To clarify molecular differences underlying these diseases, we determined crystal structures of the XPD catalytic core from Sulfolobus acidocaldarius and measured mutant enzyme activities. Substrate-binding grooves separate adjacent Rad51/RecA-like helicase domains (HD1, HD2) and an arch formed by 4FeS and Arch domains. XP mutations map along the HD1 ATP-binding edge and HD2 DNA-binding channel and impair helicase activity essential for NER. XP/CS mutations both impair helicasemore » activity and likely affect HD2 functional movement. TTD mutants lose or retain helicase activity but map to sites in all four domains expected to cause framework defects impacting TFIIH integrity. These results provide a foundation for understanding disease consequences of mutations in XPD and related 4Fe-4S helicases including FancJ.« less

XPD Helicase Structures and Activities: Insights into the Cancer and Aging Phenotypes from XPD Mutations

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

Tainer, John; Fan, Li; Fuss, Jill O.

2008-06-02

Mutations in XPD helicase, required for nucleotide excision repair (NER) as part of the transcription/repair complex TFIIH, cause three distinct phenotypes: cancer-prone xeroderma pigmentosum (XP), or aging disorders Cockayne syndrome (CS), and trichothiodystrophy (TTD). To clarify molecular differences underlying these diseases, we determined crystal structures of the XPD catalytic core from Sulfolobus acidocaldarius and measured mutant enzyme activities. Substrate-binding grooves separate adjacent Rad51/RecA-like helicase domains (HD1, HD2) and an arch formed by 4FeS and Arch domains. XP mutations map along the HD1 ATP-binding edge and HD2 DNA-binding channel and impair helicase activity essential for NER. XP/CS mutations both impair helicasemore » activity and likely affect HD2 functional movement. TTD mutants lose or retain helicase activity but map to sites in all four domains expected to cause framework defects impacting TFIIH integrity. These results provide a foundation for understanding disease consequences of mutations in XPD and related 4Fe-4S helicases including FancJ.« less

Relationship between changes in rat behavior and integral biochemical indexes determined by laser correlation spectroscopy after photothrombosis of the prefrontal cortex.

PubMed

Romanova, G A; Shakova, F M; Kovaleva, O I; Pivovarov, V V; Khlebnikova, N N; Karganov, M Yu

2004-02-01

Experiments on rats showed that Noopept improved retention and retrieval of conditioned passive avoidance response after phototrombosis of the prefrontal cortex (a procedure impairing retention of memory traces). The impairment of mnesic functions was accompanied by changes in integral biochemical indexes of the plasma determined by laser correlation spectroscopy. Treatment of behavioral disorders with Noopepet normalized biochemical indexes.

Two-dimensional correlation spectroscopy in polymer study

PubMed Central

Park, Yeonju; Noda, Isao; Jung, Young Mee

2015-01-01

This review outlines the recent works of two-dimensional correlation spectroscopy (2DCOS) in polymer study. 2DCOS is a powerful technique applicable to the in-depth analysis of various spectral data of polymers obtained under some type of perturbation. The powerful utility of 2DCOS combined with various analytical techniques in polymer studies and noteworthy developments of 2DCOS used in this field are also highlighted. PMID:25815286

Noninvasive Spatially Offset and Transmission Raman Mapping of Breast Tissue: A Multimodal Approach Towards the In Vivo Assessment of Tissue Pathology

DTIC Science & Technology

2013-06-01

spectroscopy on tissue biopsies to correlate spectral bands with healthy and diseased breast tissue. Observed spectral changes are compared to infrared...capabilities and performance. Additionally, we conduct spectroscopy on tissue biopsies to correlate spectral bands with healthy and diseased ... disease states, ie hyperplasia, dysplasia, malignant, benign. The instrumentation has been built and characterized using archived tissue that was

Topographical and Chemical Imaging of a Phase Separated Polymer Using a Combined Atomic Force Microscopy/Infrared Spectroscopy/Mass Spectrometry Platform

DOE PAGES

Tai, Tamin; Karácsony, Orsolya; Bocharova, Vera; ...

2016-02-18

This article describes how the use of a hybrid atomic force microscopy/infrared spectroscopy/mass spectrometry imaging platform was demonstrated for the acquisition and correlation of nanoscale sample surface topography and chemical images based on infrared spectroscopy and mass spectrometry.

Direct Quantification of Solute Diffusivity in Agarose and Articular Cartilage Using Correlation Spectroscopy.

PubMed

Shoga, Janty S; Graham, Brian T; Wang, Liyun; Price, Christopher

2017-10-01

Articular cartilage is an avascular tissue; diffusive transport is critical for its homeostasis. While numerous techniques have been used to quantify diffusivity within porous, hydrated tissues and tissue engineered constructs, these techniques have suffered from issues regarding invasiveness and spatial resolution. In the present study, we implemented and compared two separate correlation spectroscopy techniques, fluorescence correlation spectroscopy (FCS) and raster image correlation spectroscopy (RICS), for the direct, and minimally-invasive quantification of fluorescent solute diffusion in agarose and articular cartilage. Specifically, we quantified the diffusional properties of fluorescein and Alexa Fluor 488-conjugated dextrans (3k and 10k) in aqueous solutions, agarose gels of varying concentration (i.e. 1, 3, 5%), and in different zones of juvenile bovine articular cartilage explants (i.e. superficial, middle, and deep). In agarose, properties of solute diffusion obtained via FCS and RICS were inversely related to molecule size, gel concentration, and applied strain. In cartilage, the diffusional properties of solutes were similarly dependent upon solute size, cartilage zone, and compressive strain; findings that agree with work utilizing other quantification techniques. In conclusion, this study established the utility of FCS and RICS as simple and minimally invasive techniques for quantifying microscale solute diffusivity within agarose constructs and articular cartilage explants.

Analytical Raman spectroscopic study for discriminant analysis of different animal-derived feedstuff: Understanding the high correlation between Raman spectroscopy and lipid characteristics.

PubMed

Gao, Fei; Xu, Lingzhi; Zhang, Yuejing; Yang, Zengling; Han, Lujia; Liu, Xian

2018-02-01

The objectives of the current study were to explore the correlation between Raman spectroscopy and lipid characteristics and to assess the potential of Raman spectroscopic methods for distinguishing the different sources of animal-originated feed based on lipid characteristics. A total of 105 lipid samples derived from five animal species have been analyzed by gas chromatography (GC) and FT-Raman spectroscopy. High correlations (r 2 >0.94) were found between the characteristic peak ratio of the Raman spectra (1654/1748 and 1654/1445) and the degree of unsaturation of the animal lipids. The results of FT-Raman data combined with chemometrics showed that the fishmeal, poultry, porcine and ruminant (bovine and ovine) MBMs could be well separated based on their lipid spectral characteristics. This study demonstrated that FT-Raman spectroscopy can mostly exhibit the lipid structure specificity of different species of animal-originated feed and can be used to discriminate different animal-originated feed samples. Copyright © 2017. Published by Elsevier Ltd.

Photon statistics and speckle visibility spectroscopy with partially coherent X-rays.

PubMed

Li, Luxi; Kwaśniewski, Paweł; Orsi, Davide; Wiegart, Lutz; Cristofolini, Luigi; Caronna, Chiara; Fluerasu, Andrei

2014-11-01

A new approach is proposed for measuring structural dynamics in materials from multi-speckle scattering patterns obtained with partially coherent X-rays. Coherent X-ray scattering is already widely used at high-brightness synchrotron lightsources to measure dynamics using X-ray photon correlation spectroscopy, but in many situations this experimental approach based on recording long series of images (i.e. movies) is either not adequate or not practical. Following the development of visible-light speckle visibility spectroscopy, the dynamic information is obtained instead by analyzing the photon statistics and calculating the speckle contrast in single scattering patterns. This quantity, also referred to as the speckle visibility, is determined by the properties of the partially coherent beam and other experimental parameters, as well as the internal motions in the sample (dynamics). As a case study, Brownian dynamics in a low-density colloidal suspension is measured and an excellent agreement is found between correlation functions measured by X-ray photon correlation spectroscopy and the decay in speckle visibility with integration time obtained from the analysis presented here.

Thermal perturbation correlation of calcium binding Human centrin 3 and its structural changes

NASA Astrophysics Data System (ADS)

Pastrana-Rios, Belinda

2014-07-01

Perturbation-correlation moving-window two-dimensional (PCMW2D) correlation spectroscopy was applied for the determination of the individual transition temperatures of different vibrational modes located within structural components of a calcium binding protein known as Human centrin 3. This crucial information served to understand the contribution individual calcium binding sites made towards the stability of the EF-hand and therefore the protein without the use of probes. We are convinced that the general application of PCMW2D correlation spectroscopy can be applied to the study of proteins in general to ascertain the differences in the stability of structural motifs within proteins and its relationship to the actual transition temperature of unfolding.

The examinations of microorganisms by correlation optics method

NASA Astrophysics Data System (ADS)

Bilyi, Olexander I.

2004-06-01

In report described methods of correlation optics, which are based on the analysis of intensity changes of quasielastic light scattering by micro-organisms and allow the type of correlation function to obtain information about the size of dispersive particles. The principle of new optical method of verification is described. In this method the gauging of intensity of an indirect illumination is carried out by static spectroscopy and processing of observed data by a method of correlation spectroscopy. The given mode of gauging allows measuring allocation of micro-organisms in size interval of 0.1 - 10.0 microns. In the report results of examinations of cultures Pseudomonas aeruginosa, Escherichia coli, Micrococcus lutteus, Lamprocystis and Triocapsa bacteriachlorofil are considered.

Ex vivo measurement of postmortem tissue changes in the crystalline lens by Brillouin spectroscopy and confocal reflectance microscopy.

PubMed

Reiss, Stephan; Sperlich, K; Hovakimyan, M; Martius, P; Guthoff, R F; Stolz, H; Stachs, O

2012-08-01

Use of Brillouin spectroscopy in ophthalmology enables noninvasive, spatially resolved determination of the rheological properties of crystalline lens tissue. Furthermore, the Brillouin shift correlates with the protein concentration inside the lens. In vitro measurements on extracted porcine lenses demonstrate that results obtained with Brillouin spectroscopy depend strongly on time after death. The intensity of the Brillouin signal decreases significantly as early as 5 h postmortem. Moreover, the fluctuation of the Brillouin frequency shift inside the lens increases with postmortem time. Images of lens tissue taken with a confocal reflectance microscope between measurements reveal a degenerative aging process. These tissue changes correlate with our results from Brillouin spectroscopy. It is concluded that only in vivo measurements appropriately reflect the rheological properties of the eye lens and its protein concentration.

Characterization of an antibiotic produced by Bacillus subtilis JW-1 that suppresses Ralstonia solanacearum.

PubMed

Kwon, Jae Won; Kim, Shin Duk

2014-01-01

Bacillus subtilis JW-1 was isolated from rhizosphere soil as a potential biocontrol agent of bacterial wilt caused by Ralstonia solanacearum. Seed treatment followed by a soil drench application with this strain resulted in >80% reduction in bacterial wilt disease compared with that in the untreated control under greenhouse conditions. The antibacterial compound produced by strain JW-1 was purified by bioactivity-guided fractionation. Based on mass spectroscopy and nuclear magnetic resonance spectral data ((1)H, (13)C, (1)H-(1)H correlation spectroscopies, rotating frame nuclear Overhauser effect spectroscopy, and heteronuclear multiple-bond correlation spectroscopy), the structure of this compound was elucidated as a cyclic lipopeptide composed of a heptapeptide (Gln-Leu-Leu-Val-Asp-Leu-Leu) bonded to a β-hydroxy-iso-hexadecanoic acid arranged in a lactone ring system.

Determination of melamine of milk based on two-dimensional correlation infrared spectroscopy

NASA Astrophysics Data System (ADS)

Yang, Ren-jie; Liu, Rong; Xu, Kexin

2012-03-01

The adulteration of milk with harmful substances is a threat to public health and beyond question a serious crime. In order to develop a rapid, cost-effective, high-throughput analysis method for detecting of adulterants in milk, the discriminative analysis of melamine is established in milk based on the two-dimensional (2D) correlation infrared spectroscopy in present paper. Pure milk samples and adulterated milk samples with different content of melamine were prepared. Then the Fourier Transform Infrared spectra of all samples were measured at room temperature. The characteristics of pure milk and adulterated milk were studied by one-dimensional spectra. The 2D NIR and 2D IR correlation spectroscopy were calculated under the perturbation of adulteration concentration. In the range from 1400 to 1800 cm-1, two strong autopeaks were aroused by melamine in milk at 1464 cm-1 and 1560 cm-1 in synchronous spectrum. At the same time, the 1560 cm-1 band does not share cross peak with the 1464 cm-1 band, which further confirm that the two bands have the same origin. Also in the range from 4200 to 4800 cm-1, the autopeak was shown at 4648 cm-1 in synchronous spectrum of melamine in milk. 2D NIR-IR hetero-spectral correlation analysis confirmed that the bands at 1464, 1560 and 4648 cm-1 had the same origin. The results demonstrated that the adulterant can be discriminated correctly by 2D correlation infrared spectroscopy.

Fluorescence correlation spectroscopy, Raster image correlation spectroscopy and Number & Brightness on a commercial confocal laser scanning microscope with analog detectors (Nikon C1)

PubMed Central

Moens, Pierre D.J.; Gratton, Enrico; Salvemini, Iyrri L.

2010-01-01

Fluorescence correlation spectroscopy (FCS) was developed in 1972 by Magde, Elson and Webb (Magde et al., 1972). Photon counting detectors and avalanche photodiodes have become standards in FCS to the point that there is a widespread belief that these detectors are essential to perform FCS experiments, despite the fact that FCS was developed using analog detectors. Spatial and temporal intensity fluctuation correlations using analog detection on a commercial Olympus Fluoview 300 microscope has been reported by Brown et al. (2008). However, each analog instrument has its own idiosyncrasies that need to be understood before using the instrument for FCS. In this work we explore the capabilities of the Nikon C1, a low cost confocal microscope, to obtain single point FCS, Raster-scan Image Correlation Spectroscopy (RICS) and Number & Brightness data both in solution and incorporated into the membrane of Giant Unilamellar Vesicles (GUVs). We show that it is possible to obtain dynamic information about fluorescent molecules from single point FCS, RICS and Number & Brightness using the Nikon C1. We highlighted the fact that care should be taken in selecting the acquisition parameters in order to avoid possible artifacts due to the detector noise. However, due to relatively large errors in determining the distribution of digital levels for a given microscope setting, the system is probably only adequate for determining relative brightness within the same image. PMID:20734406

Numerical Evaluation of Parameter Correlation in the Hartmann-Tran Line Profile

NASA Astrophysics Data System (ADS)

Adkins, Erin M.; Reed, Zachary; Hodges, Joseph T.

2017-06-01

The partially correlated quadratic, speed-dependent hard-collision profile (pCqSDHCP), for simplicity referred to as the Hartmann-Tran profile (HTP), has been recommended as a generalized lineshape for high resolution spectroscopy. The HTP parameterizes complex collisional effects such as Dicke narrowing, speed dependent narrowing, and correlations between velocity-changing and dephasing collisions, while also simplifying to simpler profiles that are widely used, such as the Voigt profile. As advanced lineshape profiles are adopted by more researchers, it is important to understand the limitations that data quality has on the ability to retrieve physically meaningful parameters using sophisticated lineshapes that are fit to spectra of finite signal-to-noise ratio. In this work, spectra were simulated using the HITRAN Application Programming Interface (HAPI) across a full range of line parameters. Simulated spectra were evaluated to quantify the precision with which fitted lineshape parameters can be determined at a given signal-to-noise ratio, focusing on the numerical correlation between the retrieved Dicke narrowing frequency and the velocity-changing and dephasing collisions correlation parameter. Tran, H., N. Ngo, and J.-M. Hartmann, Journal of Quantitative Spectroscopy and Radiative Transfer 2013. 129: p. 89-100. Tennyson, et al., Pure Appl. Chem. 2014, 86: p. 1931-1943. Kochanov, R.V., et al., Journal of Quantitative Spectroscopy and Radiative Transfer 2016. 177: p. 15-30. Tran, H., N. Ngo, and J.-M. Hartmann, Journal of Quantitative Spectroscopy and Radiative Transfer 2013. 129: p. 199-203.

Recent mathematical developments in 2D correlation spectroscopy

NASA Astrophysics Data System (ADS)

Noda, I.

2000-03-01

Recent mathematical developments in the field of 2D correlation spectroscopy, especially those related to the statistical theory, are reported. The notion of correlation phase angle is introduced. The significance of correlation phase angle between dynamic fluctuations of signals measured at two different spectral variables may be linked to more commonly known statistical concepts, such as coherence and correlation coefficient. This treatment provides the direct mathematical connection between the synchronous 2D correlation spectrum with a continuous form of the variance-covariance matrix. Moreover, it gives the background for the formal definition of the disrelation spectrum, which may be used as a heuristic substitution for the asynchronous 2D spectrum. The 2D correlation intensity may be separated into two independent factors representing the normalized extent of signal fluctuation coherence (i.e., correlation coefficient) and the magnitude of spectral intensity changes (i.e., variance). Such separation offers a convenient way to artificially enhance the discriminating power of 2D correlation spectra.

Nanosecond X-ray Photon Correlation Spectroscopy on Magnetic Skyrmions

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

Seaberg, M. H.; Holladay, B.; Lee, J. C. T.

We report an X-ray photon correlation spectroscopy method that exploits the recent development of the two-pulse mode at the Linac Coherent Light Source. By using coherent resonant X-ray magnetic scattering, we studied spontaneous fluctuations on nanosecond timescales in thin films of multilayered Fe/Gd that exhibit ordered stripe and skyrmion lattice phases. The correlation time of the fluctuations was found to differ between the skyrmion phase and near the stripe-skyrmion boundary. As a result, this technique will enable a significant new area of research on the study of equilibrium fluctuations in condensed matter.

Nanosecond X-ray Photon Correlation Spectroscopy on Magnetic Skyrmions

DOE PAGES

Seaberg, M. H.; Holladay, B.; Lee, J. C. T.; ...

2017-08-09

We report an X-ray photon correlation spectroscopy method that exploits the recent development of the two-pulse mode at the Linac Coherent Light Source. By using coherent resonant X-ray magnetic scattering, we studied spontaneous fluctuations on nanosecond timescales in thin films of multilayered Fe/Gd that exhibit ordered stripe and skyrmion lattice phases. The correlation time of the fluctuations was found to differ between the skyrmion phase and near the stripe-skyrmion boundary. As a result, this technique will enable a significant new area of research on the study of equilibrium fluctuations in condensed matter.

Correlation between the local stress and the grain misorientation in the polycrystalline Al2O3 measured by near-field luminescence spectroscopy

NASA Astrophysics Data System (ADS)

Tomimatsu, Toru; Takigawa, Ryo

2018-06-01

Owing to its high spatial resolution, near-field spectroscopy is a useful method for sensing the stress in a narrow region of submicron order. Here, on the basis of the highly resolved images obtained by near-field luminescence spectroscopy, we propose a statistical method of analyzing grain anisotropy-induced stress in polycrystalline Al2O3. We focus on two characteristics of a spectra: the intensity ratio and peak shift of luminescence of two lines (R1 and R2) from Al2O3 to discuss crystal orientation and stress, respectively. By incorporating the concept of the crystal misorientation parameter using intensity ratio, an apparent correlation between the magnitude of stress and the misorientation is found. This correlation analysis provides an important insight for the investigation of local thermal stress in Al2O3.

A scalable correlator for multichannel diffuse correlation spectroscopy.

PubMed

Stapels, Christopher J; Kolodziejski, Noah J; McAdams, Daniel; Podolsky, Matthew J; Fernandez, Daniel E; Farkas, Dana; Christian, James F

2016-02-01

Diffuse correlation spectroscopy (DCS) is a technique which enables powerful and robust non-invasive optical studies of tissue micro-circulation and vascular blood flow. The technique amounts to autocorrelation analysis of coherent photons after their migration through moving scatterers and subsequent collection by single-mode optical fibers. A primary cost driver of DCS instruments are the commercial hardware-based correlators, limiting the proliferation of multi-channel instruments for validation of perfusion analysis as a clinical diagnostic metric. We present the development of a low-cost scalable correlator enabled by microchip-based time-tagging, and a software-based multi-tau data analysis method. We will discuss the capabilities of the instrument as well as the implementation and validation of 2- and 8-channel systems built for live animal and pre-clinical settings.

Spatial fluorescence cross-correlation spectroscopy between core and ring pinholes

NASA Astrophysics Data System (ADS)

Blancquaert, Yoann; Delon, Antoine; Derouard, Jacques; Jaffiol, Rodolphe

2006-04-01

Fluorescence Correlation Spectroscopy (FCS) is an attractive method to measure molecular concentration, mobility parameters and chemical kinetics. However its ability to descriminate different diffusing species needs to be improved. Recently, we have proposed a simplified spatial Fluorescence cross Correlation Spectroscopy (sFCCS) method, allowing, with only one focused laser beam to obtain two confocal volumes spatially shifted. Now, we present a new sFCCS optical geometry where the two pinholes, a ring and core, are encapsulated one in the other. In this approach all physical and chemical processes that occur in a single volume, like singlet-triplet dynamics and photobleaching, can be eliminated; moreover, this new optical geometry optimises the collection of fluorescence. The first cross Correlation curves for Rhodamine 6G (Rh6G) in Ethanol are presented, in addition to the effect of the size of fluorescent particules (nano-beads, diameters : 20, 100 and 200 nm). The relative simplicity of the method leads us to propose sFCCS as an appropriate method for the determination of diffusion parameters of fluorophores in solution or cells. Nevertheless, progresses in the ingeniering of the optical Molecular Detection Efficiency volumes are highly desirable, in order to improve the descrimination between the cross correlated volumes.

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.

A 32-channel photon counting module with embedded auto/cross-correlators for real-time parallel fluorescence correlation spectroscopy

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

Gong, S.; Labanca, I.; Rech, I.

2014-10-15

Fluorescence correlation spectroscopy (FCS) is a well-established technique to study binding interactions or the diffusion of fluorescently labeled biomolecules in vitro and in vivo. Fast FCS experiments require parallel data acquisition and analysis which can be achieved by exploiting a multi-channel Single Photon Avalanche Diode (SPAD) array and a corresponding multi-input correlator. This paper reports a 32-channel FPGA based correlator able to perform 32 auto/cross-correlations simultaneously over a lag-time ranging from 10 ns up to 150 ms. The correlator is included in a 32 × 1 SPAD array module, providing a compact and flexible instrument for high throughput FCS experiments.more » However, some inherent features of SPAD arrays, namely afterpulsing and optical crosstalk effects, may introduce distortions in the measurement of auto- and cross-correlation functions. We investigated these limitations to assess their impact on the module and evaluate possible workarounds.« less

Integrative two-dimensional correlation spectroscopy (i2DCOS) for the intuitive identification of adulterated herbal materials

NASA Astrophysics Data System (ADS)

Chen, Jianbo; Wang, Yue; Rong, Lixin; Wang, Jingjuan

2018-07-01

IR, Raman and other separation-free and label-free spectroscopic techniques have been the promising methods for the rapid and low-cost quality control of complex mixtures such as food and herb. However, as the overlapped signals from different ingredients usually make it difficult to extract useful information, chemometrics tools are often needed to find out spectral features of interest. With designed perturbations, two-dimensional correlation spectroscopy (2DCOS) is a powerful technique to resolve the overlapped spectral bands and enhance the apparent spectral resolution. In this research, the integrative two-dimensional correlation spectroscopy (i2DCOS) is defined for the first time overcome some disadvantages of synchronous and asynchronous correlation spectra for identification. The integrative 2D correlation spectra weight the asynchronous cross peaks by the corresponding synchronous cross peaks, which combines the signal-to-noise ratio advantage of synchronous correlation spectra and the spectral resolution advantage of asynchronous correlation spectra. The feasibility of the integrative 2D correlation spectra for the quality control of complex mixtures is examined by the identification of adulterated Fritillariae Bulbus powders. Compared with model-based pattern recognition and multivariate calibration methods, i2DCOS can provide intuitive identification results but not require the number of samples. The results show the potential of i2DCOS in the intuitive quality control of herbs and other complex mixtures, especially when the number of samples is not large.

Correlating brain blood oxygenation level dependent (BOLD) fractal dimension mapping with magnetic resonance spectroscopy (MRS) in Alzheimer's disease.

PubMed

Warsi, Mohammed A; Molloy, William; Noseworthy, Michael D

2012-10-01

To correlate temporal fractal structure of resting state blood oxygen level dependent (rsBOLD) functional magnetic resonance imaging (fMRI) with in vivo proton magnetic resonance spectroscopy ((1)H-MRS), in Alzheimer's disease (AD) and healthy age-matched normal controls (NC). High temporal resolution (4 Hz) rsBOLD signal and single voxel (left putamen) magnetic resonance spectroscopy data was acquired in 33 AD patients and 13 NC. The rsBOLD data was analyzed using two types of fractal dimension (FD) analysis based on relative dispersion and frequency power spectrum. Comparisons in FD were performed between AD and NC, and FD measures were correlated with (1)H-MRS findings. Temporal fractal analysis of rsBOLD, was able to differentiate AD from NC subjects (P = 0.03). Low FD correlated with markers of AD severity including decreased concentrations of N-acetyl aspartate (R = 0.44, P = 0.015) and increased myoinositol (mI) (R = -0.45, P = 0.012). Based on these results we suggest fractal analysis of rsBOLD could provide an early marker of AD.

Fluorescence correlation spectroscopy and fluorescence cross-correlation spectroscopy reveal the cytoplasmic origination of loaded nuclear RISC in vivo in human cells

PubMed Central

Mütze, Jörg; Staroske, Wolfgang; Weinmann, Lasse; Höck, Julia; Crell, Karin; Meister, Gunter; Schwille, Petra

2008-01-01

Studies of RNA interference (RNAi) provide evidence that in addition to the well-characterized cytoplasmic mechanisms, nuclear mechanisms also exist. The mechanism by which the nuclear RNA-induced silencing complex (RISC) is formed in mammalian cells, as well as the relationship between the RNA silencing pathways in nuclear and cytoplasmic compartments is still unknown. Here we show by applying fluorescence correlation and cross-correlation spectroscopy (FCS/FCCS) in vivo that two distinct RISC exist: a large ∼3 MDa complex in the cytoplasm and a 20-fold smaller complex of ∼158 kDa in the nucleus. We further show that nuclear RISC, consisting only of Ago2 and a short RNA, is loaded in the cytoplasm and imported into the nucleus. The loaded RISC accumulates in the nucleus depending on the presence of a target, based on an miRNA-like interaction with impaired cleavage of the cognate RNA. Together, these results suggest a new RISC shuttling mechanism between nucleus and cytoplasm ensuring concomitant gene regulation by small RNAs in both compartments. PMID:18842624

Fluorescence correlation spectroscopy and fluorescence cross-correlation spectroscopy reveal the cytoplasmic origination of loaded nuclear RISC in vivo in human cells.

PubMed

Ohrt, Thomas; Mütze, Jörg; Staroske, Wolfgang; Weinmann, Lasse; Höck, Julia; Crell, Karin; Meister, Gunter; Schwille, Petra

2008-11-01

Studies of RNA interference (RNAi) provide evidence that in addition to the well-characterized cytoplasmic mechanisms, nuclear mechanisms also exist. The mechanism by which the nuclear RNA-induced silencing complex (RISC) is formed in mammalian cells, as well as the relationship between the RNA silencing pathways in nuclear and cytoplasmic compartments is still unknown. Here we show by applying fluorescence correlation and cross-correlation spectroscopy (FCS/FCCS) in vivo that two distinct RISC exist: a large approximately 3 MDa complex in the cytoplasm and a 20-fold smaller complex of approximately 158 kDa in the nucleus. We further show that nuclear RISC, consisting only of Ago2 and a short RNA, is loaded in the cytoplasm and imported into the nucleus. The loaded RISC accumulates in the nucleus depending on the presence of a target, based on an miRNA-like interaction with impaired cleavage of the cognate RNA. Together, these results suggest a new RISC shuttling mechanism between nucleus and cytoplasm ensuring concomitant gene regulation by small RNAs in both compartments.

Correlation between the structure and the piezoelectric properties of lead-free (K,Na,Li)(Nb,Ta,Sb)O3 ceramics studied by XRD and Raman spectroscopy.

PubMed

Rubio-Marcos, Fernando; Marchet, Pascal; Romero, Juan José; Fernández, Jose F

2011-09-01

This article reviews on the use of Raman spectroscopy for the study of (K,Na,Li)(Nb,Ta,Sb)O(3) lead-free piezoceramics. Currently, this material appears to be one of the most interesting and promising alternatives to the well-known PZT piezoelectric materials. In this work, we prepare piezoceramics with different stoichiometries and study their structural, ferroelectric, and piezoelectric properties. By using both Raman spectroscopy and X-ray diffraction, we establish a direct correlation between the structure and the properties. The results demonstrate that the wavenumber of the A(1g) vibration is proportional to the tetragonality, the remnant polarization, and the piezoelectric coefficients of these materials. Thus, Raman spectroscopy appears as a very useful technique for a fast evaluation of the crystalline structure and the ferroelectric/ piezoelectric properties.

Quantification of transuranic elements by time interval correlation spectroscopy of the detected neutrons

PubMed

Baeten; Bruggeman; Paepen; Carchon

2000-03-01

The non-destructive quantification of transuranic elements in nuclear waste management or in safeguards verifications is commonly performed by passive neutron assay techniques. To minimise the number of unknown sample-dependent parameters, Neutron Multiplicity Counting (NMC) is applied. We developed a new NMC-technique, called Time Interval Correlation Spectroscopy (TICS), which is based on the measurement of Rossi-alpha time interval distributions. Compared to other NMC-techniques, TICS offers several advantages.

VIS-NIR spectroscopy as a process analytical technology for compositional characterization of film biopolymers and correlation with their mechanical properties.

PubMed

Barbin, Douglas Fernandes; Valous, Nektarios A; Dias, Adriana Passos; Camisa, Jaqueline; Hirooka, Elisa Yoko; Yamashita, Fabio

2015-11-01

There is an increasing interest in the use of polysaccharides and proteins for the production of biodegradable films. Visible and near-infrared (VIS-NIR) spectroscopy is a reliable analytical tool for objective analyses of biological sample attributes. The objective is to investigate the potential of VIS-NIR spectroscopy as a process analytical technology for compositional characterization of biodegradable materials and correlation to their mechanical properties. Biofilms were produced by single-screw extrusion with different combinations of polybutylene adipate-co-terephthalate, whole oat flour, glycerol, magnesium stearate, and citric acid. Spectral data were recorded in the range of 400-2498nm at 2nm intervals. Partial least square regression was used to investigate the correlation between spectral information and mechanical properties. Results show that spectral information is influenced by the major constituent components, as they are clustered according to polybutylene adipate-co-terephthalate content. Results for regression models using the spectral information as predictor of tensile properties achieved satisfactory results, with coefficients of prediction (R(2)C) of 0.83, 0.88 and 0.92 (calibration models) for elongation, tensile strength, and Young's modulus, respectively. Results corroborate the correlation of NIR spectra with tensile properties, showing that NIR spectroscopy has potential as a rapid analytical technology for non-destructive assessment of the mechanical properties of the films. Copyright © 2015 Elsevier B.V. All rights reserved.

Low-power adiabatic sequences for in-vivo localized two-dimensional chemical shift correlated MR spectroscopy

PubMed Central

Andronesi, Ovidiu C.; Ramadan, Saadallah; Mountford, Carolyn E.; Sorensen, A. Gregory

2011-01-01

Novel low-power adiabatic sequences are demonstrated for in-vivo localized two-dimensional (2D) correlated MR spectroscopy, such as COSY (Correlated Spectroscopy) and TOCSY (Total Correlated Spectroscopy). The design is based on three new elements for in-vivo 2D MRS: the use of gradient modulated constant adiabaticity GOIA-W(16,4) pulses for i) localization (COSY and TOCSY) and ii) mixing (TOCSY), and iii) the use of longitudinal mixing (z-filter) for magnetization transfer during TOCSY. GOIA-W(16,4) provides accurate signal localization, and more importantly, lowers the SAR for both TOCSY mixing and localization. Longitudinal mixing improves considerably (five-folds) the efficiency of TOCSY transfer. These are markedly different from previous 1D editing TOCSY sequences using spatially non-selective pulses and transverse mixing. Fully adiabatic (adiabatic mixing with adiabatic localization) and semi-adiabatic (adiabatic mixing with non-adiabatic localization) methods for 2D TOCSY are compared. Results are presented for simulations, phantoms, and in-vivo 2D spectra from healthy volunteers and patients with brain tumors obtained on 3T clinical platforms equipped with standard hardware. To the best of our knowledge this is the first demonstration of in-vivo adiabatic 2D TOCSY and fully adiabatic 2D COSY. It is expected that these methodological developments will advance the in-vivo applicability of multi(spectrally)dimensional MRS to reliably identify metabolic biomarkers. PMID:20890988

The contribution of Raman spectroscopy to the analytical quality control of cytotoxic drugs in a hospital environment: eliminating the exposure risks for staff members and their work environment.

PubMed

Bourget, Philippe; Amin, Alexandre; Vidal, Fabrice; Merlette, Christophe; Troude, Pénélope; Baillet-Guffroy, Arlette

2014-08-15

The purpose of the study was to perform a comparative analysis of the technical performance, respective costs and environmental effect of two invasive analytical methods (HPLC and UV/visible-FTIR) as compared to a new non-invasive analytical technique (Raman spectroscopy). Three pharmacotherapeutic models were used to compare the analytical performances of the three analytical techniques. Statistical inter-method correlation analysis was performed using non-parametric correlation rank tests. The study's economic component combined calculations relative to the depreciation of the equipment and the estimated cost of an AQC unit of work. In any case, analytical validation parameters of the three techniques were satisfactory, and strong correlations between the two spectroscopic techniques vs. HPLC were found. In addition, Raman spectroscopy was found to be superior as compared to the other techniques for numerous key criteria including a complete safety for operators and their occupational environment, a non-invasive procedure, no need for consumables, and a low operating cost. Finally, Raman spectroscopy appears superior for technical, economic and environmental objectives, as compared with the other invasive analytical methods. Copyright © 2014 Elsevier B.V. All rights reserved.

Copper ESEEM and HYSCORE through ultra-wideband chirp EPR spectroscopy.

PubMed

Segawa, Takuya F; Doll, Andrin; Pribitzer, Stephan; Jeschke, Gunnar

2015-07-28

The main limitation of pulse electron paramagnetic resonance (EPR) spectroscopy is its narrow excitation bandwidth. Ultra-wideband (UWB) excitation with frequency-swept chirp pulses over several hundreds of megahertz overcomes this drawback. This allows to excite electron spin echo envelope modulation (ESEEM) from paramagnetic copper centers in crystals, whereas up to now, only ESEEM of ligand nuclei like protons or nitrogens at lower frequencies could be detected. ESEEM spectra are recorded as two-dimensional correlation experiments, since the full digitization of the electron spin echo provides an additional Fourier transform EPR dimension. Thus, UWB hyperfine-sublevel correlation experiments generate a novel three-dimensional EPR-correlated nuclear modulation spectrum.

In vivo flow speed measurement of capillaries by photoacoustic correlation spectroscopy.

PubMed

Chen, Sung-Liang; Xie, Zhixing; Carson, Paul L; Wang, Xueding; Guo, L Jay

2011-10-15

We recently proposed photoacoustic correlation spectroscopy (PACS) and demonstrated a proof-of-concept experiment. Here we use the technique for in vivo flow speed measurement in capillaries in a chick embryo model. The photoacoustic microscopy system is used to render high spatial resolution and high sensitivity, enabling sufficient signals from single red blood cells. The probe beam size is calibrated by a blood-mimicking phantom. The results indicate the feasibility of using PACS to study flow speeds in capillaries.

PyCorrFit-generic data evaluation for fluorescence correlation spectroscopy.

PubMed

Müller, Paul; Schwille, Petra; Weidemann, Thomas

2014-09-01

We present a graphical user interface (PyCorrFit) for the fitting of theoretical model functions to experimental data obtained by fluorescence correlation spectroscopy (FCS). The program supports many data file formats and features a set of tools specialized in FCS data evaluation. The Python source code is freely available for download from the PyCorrFit web page at http://pycorrfit.craban.de. We offer binaries for Ubuntu Linux, Mac OS X and Microsoft Windows. © The Author 2014. Published by Oxford University Press.

Two-Photon Fluorescence Correlation Spectroscopy

NASA Technical Reports Server (NTRS)

Zimmerli, Gregory A.; Fischer, David G.

2002-01-01

We will describe a two-photon microscope currently under development at the NASA Glenn Research Center. It is composed of a Coherent Mira 900 tunable, pulsed Titanium:Sapphire laser system, an Olympus Fluoview 300 confocal scanning head, and a Leica DM IRE inverted microscope. It will be used in conjunction with a technique known as fluorescence correlation spectroscopy (FCS) to study intracellular protein dynamics. We will briefly explain the advantages of the two-photon system over a conventional confocal microscope, and provide some preliminary experimental results.

Continuous quantum measurement in spin environments

NASA Astrophysics Data System (ADS)

Xie, Dong; Wang, An Min

2015-08-01

We derive a stochastic master equation (SME) which describes the decoherence dynamics of a system in spin environments conditioned on the measurement record. Markovian and non-Markovian nature of environment can be revealed by a spectroscopy method based on weak continuous quantum measurement. On account of that correlated environments can lead to a non-local open system which exhibits strong non-Markovian effects although the local dynamics are Markovian, the spectroscopy method can be used to demonstrate that there is correlation between two environments.

Diffuse correlation spectroscopy for non-invasive, micro-vascular cerebral blood flow measurement

PubMed Central

Durduran, Turgut; Yodh, Arjun G.

2013-01-01

Diffuse correlation spectroscopy (DCS) uses the temporal fluctuations of near-infrared (NIR) light to measure cerebral blood flow (CBF) non-invasively. Here, we provide a brief history of DCS applications in brain with an emphasis on the underlying physical ideas, common instrumentation and validation. Then we describe recent clinical research that employs DCS-measured CBF as a biomarker of patient well-being, and as an indicator of hemodynamic and metabolic response to functional stimuli. PMID:23770408

Trifasciatosides A-J, Steroidal Saponins from Sansevieria trifasciata.

PubMed

Teponno, Rémy Bertrand; Tanaka, Chiaki; Jie, Bai; Tapondjou, Léon Azefack; Miyamoto, Tomofumi

2016-01-01

Four previously unreported steroidal saponins, trifasciatosides A-D (1-4), three pairs of previously undescribed steroidal saponins, trifasciatosides E-J (5a, b-7a, b) including acetylated ones, together with twelve known compounds were isolated from the n-butanol soluble fraction of the methanol extract of Sansevieria trifasciata. Their structures were elucidated on the basis of detailed spectroscopic analysis, including (1)H-NMR, (13)C-NMR, (1)H-(1)H correlated spectroscopy (COSY), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond connectivity (HMBC), total correlated spectroscopy (TOCSY), nuclear Overhauser enhancement and exchange spectroscopy (NOESY), electrospray ionization-time of flight (ESI-TOF)-MS and chemical methods. Compounds 2, 4, and 7a, b exhibited moderate antiproliferative activity against HeLa cells.

An Overview of Microbiology Research in Japan, with Notes on Medical History, Education and Health Care.

DTIC Science & Technology

1981-07-01

Kyogoku: infrared spectroscopy , Raman spectroscop , and nuclear magnetic resonance spectroscopy of protein and protein models; resonance Raman spectra...Research projects - tritium labeling techniques; heavy metal accumulations in deciduous teeth; chemistry of the mycotoxin fusarenon; EM of phage P22 DNA...fluorescence correlation spectroscopy . - Biological Activities of Biopolymers - Dr. M. Kageyama, Director: Analysis of Pseudomonas aeruginosa bacteriocins

Inexpensive electronics and software for photon statistics and correlation spectroscopy.

PubMed

Gamari, Benjamin D; Zhang, Dianwen; Buckman, Richard E; Milas, Peker; Denker, John S; Chen, Hui; Li, Hongmin; Goldner, Lori S

2014-07-01

Single-molecule-sensitive microscopy and spectroscopy are transforming biophysics and materials science laboratories. Techniques such as fluorescence correlation spectroscopy (FCS) and single-molecule sensitive fluorescence resonance energy transfer (FRET) are now commonly available in research laboratories but are as yet infrequently available in teaching laboratories. We describe inexpensive electronics and open-source software that bridges this gap, making state-of-the-art research capabilities accessible to undergraduates interested in biophysics. We include a discussion of the intensity correlation function relevant to FCS and how it can be determined from photon arrival times. We demonstrate the system with a measurement of the hydrodynamic radius of a protein using FCS that is suitable for the undergraduate teaching laboratory. The FPGA-based electronics, which are easy to construct, are suitable for more advanced measurements as well, and several applications are described. As implemented, the system has 8 ns timing resolution, can control up to four laser sources, and can collect information from as many as four photon-counting detectors.

Inexpensive electronics and software for photon statistics and correlation spectroscopy

PubMed Central

Gamari, Benjamin D.; Zhang, Dianwen; Buckman, Richard E.; Milas, Peker; Denker, John S.; Chen, Hui; Li, Hongmin; Goldner, Lori S.

2016-01-01

Single-molecule-sensitive microscopy and spectroscopy are transforming biophysics and materials science laboratories. Techniques such as fluorescence correlation spectroscopy (FCS) and single-molecule sensitive fluorescence resonance energy transfer (FRET) are now commonly available in research laboratories but are as yet infrequently available in teaching laboratories. We describe inexpensive electronics and open-source software that bridges this gap, making state-of-the-art research capabilities accessible to undergraduates interested in biophysics. We include a discussion of the intensity correlation function relevant to FCS and how it can be determined from photon arrival times. We demonstrate the system with a measurement of the hydrodynamic radius of a protein using FCS that is suitable for the undergraduate teaching laboratory. The FPGA-based electronics, which are easy to construct, are suitable for more advanced measurements as well, and several applications are described. As implemented, the system has 8 ns timing resolution, can control up to four laser sources, and can collect information from as many as four photon-counting detectors. PMID:26924846

A Novel Diterpene Glycoside with Nine Glucose Units from Stevia rebaudiana Bertoni

PubMed Central

Prakash, Indra; Ma, Gil; Bunders, Cynthia; Charan, Romila D.; Ramirez, Catherine; Devkota, Krishna P.; Snyder, Tara M.

2017-01-01

Following our interest in new diterpene glycosides with better taste profiles than that of Rebaudioside M, we have recently isolated and characterized Rebaudioside IX—a novel steviol glycoside—from a commercially-supplied extract of Stevia rebaudiana Bertoni. This molecule contains a hexasaccharide group attached at C-13 of the central diterpene core, and contains three additional glucose units when compared with Rebaudioside M. Here we report the complete structure elucidation—based on extensive Nuclear Magnetic Resonance (NMR) analysis (1H, 13C, Correlation Spectroscopy (COSY), Heteronuclear Single Quantum Coherence-Distortionless Enhancement Polarization Transfer (HSQC-DEPT), Heteronuclear Multiple Bond Correlation (HMBC), 1D Total Correlation Spectroscopy (TOCSY), Nuclear Overhauser Effect Spectroscopy (NOESY)) and mass spectral data—of this novel diterpene glycoside with nine sugar moieties and containing a relatively rare 1→6 α-linked glycoside. A steviol glycoside bearing nine glucose units is unprecedented in the literature, and could have an impact on the natural sweetener catalog. PMID:28146121

A Novel Diterpene Glycoside with Nine Glucose Units from Stevia rebaudiana Bertoni.

PubMed

Prakash, Indra; Ma, Gil; Bunders, Cynthia; Charan, Romila D; Ramirez, Catherine; Devkota, Krishna P; Snyder, Tara M

2017-01-31

Following our interest in new diterpene glycosides with better taste profiles than that of Rebaudioside M, we have recently isolated and characterized Rebaudioside IX-a novel steviol glycoside-from a commercially-supplied extract of Stevia rebaudiana Bertoni. This molecule contains a hexasaccharide group attached at C-13 of the central diterpene core, and contains three additional glucose units when compared with Rebaudioside M. Here we report the complete structure elucidation-based on extensive Nuclear Magnetic Resonance (NMR) analysis (1H, 13C, Correlation Spectroscopy (COSY), Heteronuclear Single Quantum Coherence-Distortionless Enhancement Polarization Transfer (HSQC-DEPT), Heteronuclear Multiple Bond Correlation (HMBC), 1D Total Correlation Spectroscopy (TOCSY), Nuclear Overhauser Effect Spectroscopy (NOESY)) and mass spectral data-of this novel diterpene glycoside with nine sugar moieties and containing a relatively rare 16 α-linked glycoside. A steviol glycoside bearing nine glucose units is unprecedented in the literature, and could have an impact on the natural sweetener catalog.

Continuous gradient temperature Raman spectroscopy of unsaturated fatty acids

USDA-ARS?s Scientific Manuscript database

A new innovative technique gradient temperature, Raman spectroscopy (GTRS), identifies Raman frequency shifts in solid or liquid samples, and correlates them with specific temperature ranges within which flexible structures absorb heat. GTRS can easily detect changes that occur within one celcius te...

Protein oligomerization monitored by fluorescence fluctuation spectroscopy: Self-assembly of Rubisco activase

USDA-ARS?s Scientific Manuscript database

A methodology is presented to characterize complex protein assembly pathways by fluorescence correlation spectroscopy. We have derived the total autocorrelation function describing the behavior of mixtures of labeled and unlabeled protein under equilibrium conditions. Our modeling approach allows us...

Tempo-spatially resolved scattering correlation spectroscopy under dark-field illumination and its application to investigate dynamic behaviors of gold nanoparticles in live cells.

PubMed

Liu, Heng; Dong, Chaoqing; Ren, Jicun

2014-02-19

In this study, a new tempo-spatially resolved fluctuation spectroscopy under dark-field illumination is described, named dark-field illumination-based scattering correlation spectroscopy (DFSCS). DFSCS is a single-particle method, whose principle is similar to that of fluorescence correlation spectroscopy (FCS). DFSCS correlates the fluctuations of the scattered light from single nanoparticle under dark-field illumination. We developed a theoretical model for translational diffusion of nanoparticles in DFSCS system. The results of computer simulations documented that this model was able to well describe the diffusion behaviors of nanoparticles in uniformly illuminated field. The experimental setup of DFSCS was achieved by introducing a dark-field condenser to the frequently used bright-field microscope and an electron multiplying charge-coupled device (EMCCD) as the array detector. In the optimal condition, a stack of 500 000 frames were collected simultaneously on 64 detection channels for a single measurement with acquisition rate of 0.5 ms per frame. We systematically investigated the effect of certain factors such as particle concentration, viscosity of the solution, and heterogeneity of gold nanoparticles (GNPs) samples on DFSCS measurements. The experiment data confirmed theoretical model proposed. Furthermore, this new method was successfully used for investigating dynamic behaviors of GNPs in live cells. Our preliminary results demonstrate that DFSCS is a practical and affordable tool for ordinary laboratories to investigate the dynamic information of nanoparticles in vitro as well as in vivo.

HR-MAS MR Spectroscopy of Breast Cancer Tissue Obtained with Core Needle Biopsy: Correlation with Prognostic Factors

PubMed Central

Choi, Ji Soo; Baek, Hyeon-Man; Kim, Suhkmann; Kim, Min Jung; Youk, Ji Hyun; Moon, Hee Jung; Kim, Eun-Kyung; Han, Kyung Hwa; Kim, Dong-hyun; Kim, Seung Il; Koo, Ja Seung

2012-01-01

The purpose of this study was to examine the correlation between high-resolution magic angle spinning (HR-MAS) magnetic resonance (MR) spectroscopy using core needle biopsy (CNB) specimens and histologic prognostic factors currently used in breast cancer patients. After institutional review board approval and informed consent were obtained for this study, CNB specimens were collected from 36 malignant lesions in 34 patients. Concentrations and metabolic ratios of various choline metabolites were estimated by HR-MAS MR spectroscopy using CNB specimens. HR-MAS spectroscopic values were compared according to histopathologic variables [tumor size, lymph node metastasis, histologic grade, status of estrogens receptor (ER), progesterone receptor (PR), HER2 (a receptor for human epidermal growth factor), and Ki-67, and triple negativity]. Multivariate analysis was performed with Orthogonal Projections to Latent Structure-Discriminant Analysis (OPLS-DA). HR-MAS MR spectroscopy quantified and discriminated choline metabolites in all CNB specimens of the 36 breast cancers. Several metabolite markers [free choline (Cho), phosphocholine (PC), creatine (Cr), taurine, myo-inositol, scyllo-inositol, total choline (tCho), glycine, Cho/Cr, tCho/Cr, PC/Cr] on HR-MAS MR spectroscopy were found to correlate with histologic prognostic factors [ER, PR, HER2, histologic grade, triple negativity, Ki-67, poor prognosis]. OPLS-DA multivariate models were generally able to discriminate the status of histologic prognostic factors (ER, PR, HER2, Ki-67) and prognosis groups. Our study suggests that HR-MAS MR spectroscopy using CNB specimens can predict tumor aggressiveness prior to surgery in breast cancer patients. In addition, it may be helpful in the detection of reliable markers for breast cancer characterization. PMID:23272149

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

Cross-correlation spin noise spectroscopy of heterogeneous interacting spin systems

DOE PAGES

Roy, Dibyendu; Yang, Luyi; Crooker, Scott A.; ...

2015-04-30

Interacting multi-component spin systems are ubiquitous in nature and in the laboratory. As such, investigations of inter-species spin interactions are of vital importance. Traditionally, they are studied by experimental methods that are necessarily perturbative: e.g., by intentionally polarizing or depolarizing one spin species while detecting the response of the other(s). Here, we describe and demonstrate an alternative approach based on multi-probe spin noise spectroscopy, which can reveal inter-species spin interactions - under conditions of strict thermal equilibrium - by detecting and cross-correlating the stochastic fluctuation signals exhibited by each of the constituent spin species. Specifically, we consider a two-component spinmore » ensemble that interacts via exchange coupling, and we determine cross-correlations between their intrinsic spin fluctuations. The model is experimentally confirmed using “two-color” optical spin noise spectroscopy on a mixture of interacting Rb and Cs vapors. Noise correlations directly reveal the presence of inter-species spin exchange, without ever perturbing the system away from thermal equilibrium. These non-invasive and noise-based techniques should be generally applicable to any heterogeneous spin system in which the fluctuations of the constituent components are detectable.« less

A total internal reflection-fluorescence correlation spectroscopy setup with pulsed diode laser excitation

NASA Astrophysics Data System (ADS)

Weger, Lukas; Hoffmann-Jacobsen, Kerstin

2017-09-01

Fluorescence correlation spectroscopy (FCS) measures fluctuations in a (sub-)femtoliter volume to analyze the diffusive behavior of fluorescent particles. This highly sensitive method has proven to be useful for the analysis of dynamic biological systems as well as in chemistry, physics, and material sciences. It is routinely performed with commercial fluorescence microscopes, which provide a confined observation volume by the confocal technique. The evanescent wave of total internal reflectance (TIR) is used in home-built systems to permit a surface sensitive FCS analysis. We present a combined confocal and TIR-FCS setup which uses economic low-power pulsed diode lasers for excitation. Excitation and detection are coupled to time-correlated photon counting hardware. This allows simultaneous fluorescence lifetime and FCS measurements in a surface-sensitive mode. Moreover, the setup supports fluorescence lifetime correlation spectroscopy at surfaces. The excitation can be easily switched between TIR and epi-illumination to compare the surface properties with those in liquid bulk. The capabilities of the presented setup are demonstrated by measuring the diffusion coefficients of a free dye molecule, a labeled polyethylene glycol, and a fluorescent nanoparticle in confocal as well as in TIR-FCS.

Photo-stability study of a solution-processed small molecule solar cell system: correlation between molecular conformation and degradation

PubMed Central

Newman, Michael J.; Speller, Emily M.; Barbé, Jérémy; Luke, Joel; Li, Meng; Li, Zhe; Wang, Zhao-Kui; Jain, Sagar M.; Kim, Ji-Seon; Lee, Harrison Ka Hin; Tsoi, Wing Chung

2018-01-01

Abstract Solution-processed organic small molecule solar cells (SMSCs) have achieved efficiency over 11%. However, very few studies have focused on their stability under illumination and the origin of the degradation during the so-called burn-in period. Here, we studied the burn-in period of a solution-processed SMSC using benzodithiophene terthiophene rhodamine:[6,6]-phenyl C71 butyric acid methyl ester (BTR:PC71BM) with increasing solvent vapour annealing time applied to the active layer, controlling the crystallisation of the BTR phase. We find that the burn-in behaviour is strongly correlated to the crystallinity of BTR. To look at the possible degradation mechanisms, we studied the fresh and photo-aged blend films with grazing incidence X-ray diffraction, UV–vis absorbance, Raman spectroscopy and photoluminescence (PL) spectroscopy. Although the crystallinity of BTR affects the performance drop during the burn-in period, the degradation is found not to originate from the crystallinity changes of the BTR phase, but correlates with changes in molecular conformation – rotation of the thiophene side chains, as resolved by Raman spectroscopy which could be correlated to slight photobleaching and changes in PL spectra. PMID:29511397

Photo-stability study of a solution-processed small molecule solar cell system: correlation between molecular conformation and degradation.

PubMed

Newman, Michael J; Speller, Emily M; Barbé, Jérémy; Luke, Joel; Li, Meng; Li, Zhe; Wang, Zhao-Kui; Jain, Sagar M; Kim, Ji-Seon; Lee, Harrison Ka Hin; Tsoi, Wing Chung

2018-01-01

Solution-processed organic small molecule solar cells (SMSCs) have achieved efficiency over 11%. However, very few studies have focused on their stability under illumination and the origin of the degradation during the so-called burn-in period. Here, we studied the burn-in period of a solution-processed SMSC using benzodithiophene terthiophene rhodamine:[6,6]-phenyl C 71 butyric acid methyl ester (BTR:PC 71 BM) with increasing solvent vapour annealing time applied to the active layer, controlling the crystallisation of the BTR phase. We find that the burn-in behaviour is strongly correlated to the crystallinity of BTR. To look at the possible degradation mechanisms, we studied the fresh and photo-aged blend films with grazing incidence X-ray diffraction, UV-vis absorbance, Raman spectroscopy and photoluminescence (PL) spectroscopy. Although the crystallinity of BTR affects the performance drop during the burn-in period, the degradation is found not to originate from the crystallinity changes of the BTR phase, but correlates with changes in molecular conformation - rotation of the thiophene side chains, as resolved by Raman spectroscopy which could be correlated to slight photobleaching and changes in PL spectra.

Two-Voxel Localization Sequence for in Vivo Two-Dimensional Homonuclear Correlation Spectroscopy

NASA Astrophysics Data System (ADS)

Delmas, Florence; Beloeil, Jean-Claude; van der Sanden, Boudewijn P. J.; Nicolay, Klaas; Gillet, Brigitte

2001-03-01

The combination of localized 2D 1H MR correlation spectroscopy and Hadamard encoding allows the simultaneous acquisition of multiple volumes of interest without an increase in the experimental duration, compared to single-voxel acquisition. In the present study, 2D correlation spectra were acquired simultaneously within 20 to 40 min in two voxels located in each hemisphere of the rat brain. An intervoxel distance of 20% of the voxel size was sufficient to limit spatial contamination. The following cerebral metabolites gave detectable crosspeaks: N-acetylaspartate, the glutamate/glutamine pool, aspartate, phosphoethanolamine, glucose, glutathione, taurine, myo-inositols, lactate, threonine, γ-aminobutyric acid, and alanine. Most of the metabolites were measured without contamination of other resonances.

Copper ESEEM and HYSCORE through ultra-wideband chirp EPR spectroscopy

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

Segawa, Takuya F.; Doll, Andrin; Pribitzer, Stephan

2015-07-28

The main limitation of pulse electron paramagnetic resonance (EPR) spectroscopy is its narrow excitation bandwidth. Ultra-wideband (UWB) excitation with frequency-swept chirp pulses over several hundreds of megahertz overcomes this drawback. This allows to excite electron spin echo envelope modulation (ESEEM) from paramagnetic copper centers in crystals, whereas up to now, only ESEEM of ligand nuclei like protons or nitrogens at lower frequencies could be detected. ESEEM spectra are recorded as two-dimensional correlation experiments, since the full digitization of the electron spin echo provides an additional Fourier transform EPR dimension. Thus, UWB hyperfine-sublevel correlation experiments generate a novel three-dimensional EPR-correlated nuclearmore » modulation spectrum.« less

Chemotherapeutic drug-specific alteration of microvascular blood flow in murine breast cancer as measured by diffuse correlation spectroscopy

PubMed Central

Ramirez, Gabriel; Proctor, Ashley R.; Jung, Ki Won; Wu, Tong Tong; Han, Songfeng; Adams, Russell R.; Ren, Jingxuan; Byun, Daniel K.; Madden, Kelley S.; Brown, Edward B.; Foster, Thomas H.; Farzam, Parisa; Durduran, Turgut; Choe, Regine

2016-01-01

The non-invasive, in vivo measurement of microvascular blood flow has the potential to enhance breast cancer therapy monitoring. Here, longitudinal blood flow of 4T1 murine breast cancer (N=125) under chemotherapy was quantified with diffuse correlation spectroscopy based on layer models. Six different treatment regimens involving doxorubicin, cyclophosphamide, and paclitaxel at clinically relevant doses were investigated. Treatments with cyclophosphamide increased blood flow as early as 3 days after administration, whereas paclitaxel induced a transient blood flow decrease at 1 day after administration. Early blood flow changes correlated strongly with the treatment outcome and distinguished treated from untreated mice individually for effective treatments. PMID:27699124

Reconciling STS and ARPES data for the correlated superconductor LiFeAs

NASA Astrophysics Data System (ADS)

Hong, Jongbae; Abergel, David

The inconsistency between the density of states revealed by scanning tunneling spectroscopy (STS) and that given by angle-resolved photoemission spectroscopy (ARPES) is a substantial problem for understanding the nature of strongly correlated superconductors such as Fe-based LiFeAs and the cuprates. We reveal that the two side peaks commonly appearing in both pnictide and cuprate superconductors are the result of the non-equilibrium behavior associated with singlet cotunneling from the tip to the strongly correlated sample. We accurately reproduce the STS line shape of the Fe-based LiFeAs using a sample density of states which coincides with ARPES data, thereby producing a unified description for these materials.

Discrimination of different genuine Danshen and their extracts by Fourier transform infrared spectroscopy combined with two-dimensional correlation infrared spectroscopy

NASA Astrophysics Data System (ADS)

Liu, Xin-hu; Xu, Chang-hua; Sun, Su-qin; Huang, Jian; Zhang, Ke; Li, Guo-yu; Zhu, Yun; Zhou, Qun; Zhang, Zhi-cheng; Wang, Jin-hui

2012-11-01

In this study, six varieties of Danshen from different populations and genuine ("Daodi" in Chinese transliteration) regions were discriminated and identified by a three-step infrared spectroscopy method (Fourier transform-infrared spectroscopy (FT-IR) coupled with second derivative infrared spectroscopy (SD-IR) and two dimensional correlation infrared spectroscopy (2D-IR)). Though only small differences were found among the FT-IR spectra of the six Danshen samples, the positions and intensities of peaks at 3393, 3371, 1613, 1050, and 1036 cm-1 could be considered as the key factors to discriminate them. More significant differences were exhibited in their SD-IR, particularly for the peaks around 1080, 1144, 695, 665, 800, 1610, 1510, 1450, 1117 and 1077 cm-1. The visual 2D-IR spectra provided dynamic chemical structure information of the six Danshen samples with presenting different particular auto-peak clusters, respectively. Moreover, the contents of salvianolic acid B in all samples were measured quantitatively by a validated ultra performance liquid chromatography (UPLC), which was consistent with the FT-IR findings. This study provides a promising method for characteristics and quality control of the complicated and extremely similar herbal medicine like Danshen, which is more cost effective and time saving.

Novel estimation of the humification degree of soil organic matter by laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Ferreira, Edilene Cristina; Ferreira, Ednaldo José; Villas-Boas, Paulino Ribeiro; Senesi, Giorgio Saverio; Carvalho, Camila Miranda; Romano, Renan Arnon; Martin-Neto, Ladislau; Milori, Débora Marcondes Bastos Pereira

2014-09-01

Soil organic matter (SOM) constitutes an important reservoir of terrestrial carbon and can be considered an alternative for atmospheric carbon storage, contributing to global warming mitigation. Soil management can favor atmospheric carbon incorporation into SOM or its release from SOM to atmosphere. Thus, the evaluation of the humification degree (HD), which is an indication of the recalcitrance of SOM, can provide an estimation of the capacity of carbon sequestration by soils under various managements. The HD of SOM can be estimated by using various analytical techniques including fluorescence spectroscopy. In the present work, the potential of laser-induced breakdown spectroscopy (LIBS) to estimate the HD of SOM was evaluated for the first time. Intensities of emission lines of Al, Mg and Ca from LIBS spectra showing correlation with fluorescence emissions determined by laser-induced fluorescence spectroscopy (LIFS) reference technique were used to obtain a multivaried calibration model based on the k-nearest neighbor (k-NN) method. The values predicted by the proposed model (A-LIBS) showed strong correlation with LIFS results with a Pearson's coefficient of 0.87. The HD of SOM obtained after normalizing A-LIBS by total carbon in the sample showed a strong correlation to that determined by LIFS (0.94), thus suggesting the great potential of LIBS for this novel application.

Determination of nuclear quadrupole moments – An example of the synergy of ab initio calculations and microwave spectroscopy

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

Kellö, Vladimir

Highly correlated scalar relativistic calculations of electric field gradients at nuclei in diatomic molecules in combination with accurate nuclear quadrupole coupling constants obtained from microwave spectroscopy are used for determination of nuclear quadrupole moments.

Super-resolved FT-IR spectroscopy: Strategies, challenges, and opportunities for membrane biophysics.

PubMed

Li, Jessica J; Yip, Christopher M

2013-10-01

Direct correlation of molecular conformation with local structure is critical to studies of protein- and peptide-membrane interactions, particularly in the context of membrane-facilitated aggregation, and disruption or disordering. Infrared spectroscopy has long been a mainstay for determining molecular conformation, following folding dynamics, and characterizing reactions. While tremendous advances have been made in improving the spectral and temporal resolution of infrared spectroscopy, it has only been with the introduction of scanned-probe techniques that exploit the raster-scanning tip as either a source, scattering tool, or measurement probe that researchers have been able to obtain sub-diffraction limit IR spectra. This review will examine the history of correlated scanned-probe IR spectroscopies, from their inception to their use in studies of molecular aggregates, membrane domains, and cellular structures. The challenges and opportunities that these platforms present for examining dynamic phenomena will be discussed. This article is part of a Special Issue entitled: FTIR in membrane proteins and peptide studies. Copyright © 2013 Elsevier B.V. All rights reserved.

Validation of mid-infrared spectroscopy for macronutrient analysis of human milk.

PubMed

Parat, S; Groh-Wargo, S; Merlino, S; Wijers, C; Super, D M

2017-07-01

Human milk has considerable variation in its composition. Hence, the nutrient profile is only an estimate and can result in under- or over-estimation of the intake of preterm infants. Mid-infrared (MIR) spectroscopy is an evolving technique for analyzing human milk but needs validation before use in clinical practice. Human milk samples from 35 mothers delivering at 35 weeks to term gestation were analyzed for macronutrients by MIR spectroscopy and by standard laboratory methods using Kjeldahl assay for protein, Mojonnier assay for fat and high-pressure liquid chromatography assay for lactose. MIR analysis of the macronutrients in human milk correlated well with standard laboratory tests with intraclass correlation coefficients of 0.997 for fat, 0.839 for protein and 0.776 for lactose. Agreement between the two methods was excellent for fat, and moderate for protein and lactose (P<0.001). This methodological paper provides evidence that MIR spectroscopy can be used to analyze macronutrient composition of human milk. Agreement between the methodologies varies by macronutrient.

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

Marrow Adipose Tissue Quantification of the Lumbar Spine by Using Dual-Energy CT and Single-Voxel 1H MR Spectroscopy: A Feasibility Study

PubMed Central

Daley, Scott M.; Kalra, Mannudeep K.; Brown, J. Keenan; Miller, Karen K.; Torriani, Martin

2015-01-01

Purpose To test the performance of dual-energy computed tomography (CT) in the assessment of marrow adipose tissue (MAT) content of the lumbar spine by using proton (hydrogen 1 [1H]) magnetic resonance (MR) spectroscopy as a reference standard and to determine the influence of MAT on the assessment of bone mineral density (BMD). Materials and Methods This study was institutional review board approved and complied with HIPAA guidelines. Written informed consent was obtained. Twelve obese osteopenic but otherwise healthy subjects (mean age ± standard deviation, 43 years ± 13) underwent 3-T 1H MR spectroscopy of the L2 vertebra by using a point-resolved spatially localized spectroscopy sequence without water suppression. The L2 vertebra was scanned with dual-energy CT (80 and 140 kV) by using a dual-source multi–detector row CT scanner with a calibration phantom. Mean basis material composition relative to the phantom was estimated in the L2 vertebra. Volumetric BMD was measured with and without correction for MAT. Bland-Altman 95% limits of agreement and Pearson correlation coefficients were calculated. Results There was excellent agreement between 1H MR spectroscopy and dual-energy CT, with a mean difference in fat fraction of −0.02 between the techniques, with a 95% confidence interval of −0.24, 0.20. There was a strong correlation between marrow fat fraction obtained with 1H MR spectroscopy and that obtained with dual-energy CT (r = 0.91, P < .001). The presence of MAT led to underestimation of BMD, and this bias increased with increasing MAT content (P < .001). Conclusion Dual-energy CT can be used to assess MAT content and BMD of the lumbar spine in a single examination and provides data that closely agree and correlate with 1H MR spectroscopy data. © RSNA, 2015 PMID:25988401

Evidence of an Improper Displacive Phase Transition in Cd2 Re2 O7 via Time-Resolved Coherent Phonon Spectroscopy

NASA Astrophysics Data System (ADS)

Harter, J. W.; Kennes, D. M.; Chu, H.; de la Torre, A.; Zhao, Z. Y.; Yan, J.-Q.; Mandrus, D. G.; Millis, A. J.; Hsieh, D.

2018-01-01

We have used a combination of ultrafast coherent phonon spectroscopy, ultrafast thermometry, and time-dependent Landau theory to study the inversion symmetry breaking phase transition at Tc=200 K in the strongly spin-orbit coupled correlated metal Cd2 Re2 O7 . We establish that the structural distortion at Tc is a secondary effect through the absence of any softening of its associated phonon mode, which supports a purely electronically driven mechanism. However, the phonon lifetime exhibits an anomalously strong temperature dependence that decreases linearly to zero near Tc. We show that this behavior naturally explains the spurious appearance of phonon softening in previous Raman spectroscopy experiments and should be a prevalent feature of correlated electron systems with linearly coupled order parameters.

Probing organic field effect transistors in situ during operation using SFG.

PubMed

Ye, Hongke; Abu-Akeel, Ashraf; Huang, Jia; Katz, Howard E; Gracias, David H

2006-05-24

In this communication, we report results obtained using surface-sensitive IR+Visible Sum Frequency Generation (SFG) nonlinear optical spectroscopy on interfaces of organic field effect transistors during operation. We observe remarkable correlations between trends in the surface vibrational spectra and electrical properties of the transistor, with changes in gate voltage (VG). These results suggest that field effects on electronic conduction in thin film organic semiconductor devices are correlated to interfacial nonlinear optical characteristics and point to the possibility of using SFG spectroscopy to monitor electronic properties of OFETs.

In vivo time-gated diffuse correlation spectroscopy at quasi-null source-detector separation.

PubMed

Pagliazzi, M; Sekar, S Konugolu Venkata; Di Sieno, L; Colombo, L; Durduran, T; Contini, D; Torricelli, A; Pifferi, A; Mora, A Dalla

2018-06-01

We demonstrate time domain diffuse correlation spectroscopy at quasi-null source-detector separation by using a fast time-gated single-photon avalanche diode without the need of time-tagging electronics. This approach allows for increased photon collection, simplified real-time instrumentation, and reduced probe dimensions. Depth discriminating, quasi-null distance measurement of blood flow in a human subject is presented. We envision the miniaturization and integration of matrices of optical sensors of increased spatial resolution and the enhancement of the contrast of local blood flow changes.

Novel developments and applications of two-dimensional correlation spectroscopy

NASA Astrophysics Data System (ADS)

Park, Yeonju; Noda, Isao; Jung, Young Mee

2016-11-01

A comprehensive survey review of new and noteworthy developments of 2D correlation spectroscopy (2DCOS) and its applications for the last two years is compiled. This review covers not only journal articles and book chapters but also books, proceedings, and review articles published on 2DCOS, numerous significant new concepts of 2DCOS, patents and publication trends. Noteworthy experimental practices in the field of 2DCOS, including types of analytical probes employed, various perturbation methods used in experiments, and pertinent examples of fundamental and practical applications, are also reviewed.

Vectorized data acquisition and fast triple-correlation integrals for Fluorescence Triple Correlation Spectroscopy

NASA Astrophysics Data System (ADS)

Ridgeway, William K.; Millar, David P.; Williamson, James R.

2013-04-01

Fluorescence Correlation Spectroscopy (FCS) is widely used to quantify reaction rates and concentrations of molecules in vitro and in vivo. We recently reported Fluorescence Triple Correlation Spectroscopy (F3CS), which correlates three signals together instead of two. F3CS can analyze the stoichiometries of complex mixtures and detect irreversible processes by identifying time-reversal asymmetries. Here we report the computational developments that were required for the realization of F3CS and present the results as the Triple Correlation Toolbox suite of programs. Triple Correlation Toolbox is a complete data analysis pipeline capable of acquiring, correlating and fitting large data sets. Each segment of the pipeline handles error estimates for accurate error-weighted global fitting. Data acquisition was accelerated with a combination of off-the-shelf counter-timer chips and vectorized operations on 128-bit registers. This allows desktop computers with inexpensive data acquisition cards to acquire hours of multiple-channel data with sub-microsecond time resolution. Off-line correlation integrals were implemented as a two delay time multiple-tau scheme that scales efficiently with multiple processors and provides an unprecedented view of linked dynamics. Global fitting routines are provided to fit FCS and F3CS data to models containing up to ten species. Triple Correlation Toolbox is a complete package that enables F3CS to be performed on existing microscopes. Catalogue identifier: AEOP_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEOP_v1_0.html Program obtainable from: CPC Program Library, Queen’s University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 50189 No. of bytes in distributed program, including test data, etc.: 6135283 Distribution format: tar.gz Programming language: C/Assembly. Computer: Any with GCC and library support. Operating system: Linux and OS X (data acq. for Linux only due to library availability), not tested on Windows. RAM: ≥512 MB. Classification: 16.4. External routines: NIDAQmx (National Instruments), Gnu Scientific Library, GTK+, PLplot (optional) Nature of problem: Fluorescence Triple Correlation Spectroscopy required three things: data acquisition at faster speeds than were possible without expensive custom hardware, triple-correlation routines that could process 1/2 TB data sets rapidly, and fitting routines capable of handling several to a hundred fit parameters and 14,000 + data points, each with error estimates. Solution method: A novel data acquisition concept mixed signal processing with off-the-shelf hardware and data-parallel processing using 128-bit registers found in desktop CPUs. Correlation algorithms used fractal data structures and multithreading to reduce data analysis times. Global fitting was implemented with robust minimization routines and provides feedback that allows the user to critically inspect initial guesses and fits. Restrictions: Data acquisition only requires a National Instruments data acquisition card (it was tested on Linux using card PCIe-6251) and a simple home-built circuit. Unusual features: Hand-coded ×86-64 assembly for data acquisition loops (platform-independent C code also provided). Additional comments: A complete collection of tools to perform Fluorescence Triple Correlation Spectroscopy-from data acquisition to two-tau correlation of large data sets, to model fitting. Running time: 1-5 h of data analysis per hour of data collected. Varies depending on data-acquisition length, time resolution, data density and number of cores used for correlation integrals.

Identification of anisodamine tablets by Raman and near-infrared spectroscopy with chemometrics.

PubMed

Li, Lian; Zang, Hengchang; Li, Jun; Chen, Dejun; Li, Tao; Wang, Fengshan

2014-06-05

Vibrational spectroscopy including Raman and near-infrared (NIR) spectroscopy has become an attractive tool for pharmaceutical analysis. In this study, effective calibration models for the identification of anisodamine tablet and its counterfeit and the distinguishment of manufacturing plants, based on Raman and NIR spectroscopy, were built, respectively. Anisodamine counterfeit tablets were identified by Raman spectroscopy with correlation coefficient method, and the results showed that the predictive accuracy was 100%. The genuine anisodamine tablets from 5 different manufacturing plants were distinguished by NIR spectroscopy using partial least squares discriminant analysis (PLS-DA) models based on interval principal component analysis (iPCA) method. And the results showed the recognition rate and rejection rate were 100% respectively. In conclusion, Raman spectroscopy and NIR spectroscopy combined with chemometrics are feasible and potential tools for rapid pharmaceutical tablet discrimination. Copyright © 2014 Elsevier B.V. All rights reserved.

Relaxation processes in disaccharide sugar glasses

NASA Astrophysics Data System (ADS)

Hwang, Yoon-Hwae; Kwon, Hyun-Joung; Seo, Jeong-Ah; Shin, Dong-Myeong; Ha, Ji-Hye; Kim, Hyung-Kook

2013-02-01

We represented relaxation processes of disaccharide sugars (anhydrous trehalose and maltose) in supercooled and glassy states by using several spectroscopy techniques which include a broadband dielectric loss spectroscopy, photon correlation spectroscopy and X-ray diffraction (Retvield analysis) methods which are powerful tools to measure the dynamics in glass forming materials. In a dielectric loss spectroscopy study, we found that anhydrous trehalose and maltose glasses have an extra relaxation process besides α-, JG β- and γ-relaxations which could be related to a unique property of glycoside bond in disaccharides. In photon correlation spectroscopy study, we found an interesting compressed exponential relaxation at temperatures above 140°C. The q-1 dependence of its relaxation time corresponds to an ultraslow ballistic motion due to the local structure rearrangements. In the same temperature range, we found the glycosidic bond structure changes in trehalose molecule from the Raman and the Retvield X-ray diffraction measurements indicating that the observed compressed exponential relaxation in supercooled liquid trehalose could be resulted in the glycosidic bond structure change. Therefore, the overall results from this study might support the fact that the superior bioprotection ability of disaccharide sugar glasses might originate from this unique relaxation process of glycosidic bond.

[Near infrared reflectance spectroscopy (NIRS): a novel approach to reconstructing historical changes of primary productivity in Antarctic lake].

PubMed

Chen, Qian-Qian; Liu, Xiao-Dong; Liu, Wen-Qi; Jiang, Shan

2011-10-01

Compared with traditional chemical analysis methods, reflectance spectroscopy has the advantages of speed, minimal or no sample preparation, non-destruction, and low cost. In order to explore the potential application of spectroscopy technology in the paleolimnological study on Antarctic lakes, we took a lake sediment core in Mochou Lake at Zhongshan Station of Antarctic, and analyzed the near infrared reflectance spectroscopy (NIRS) data in the sedimentary samples. The results showed that the factor loadings of principal component analysis (PCA) displayed very similar depth-profile change pattern with the S2 index, a reliable proxy for the change in historical lake primary productivity. The correlation analysis showed that the values of PCA factor loading and S2 were correlated significantly, suggesting that it is feasible to infer paleoproductivity changes recorded in Antarctic lakes using NIRS technology. Compared to the traditional method of the trough area between 650 and 700 nm, the authors found that the PCA statistical approach was more accurate for reconstructing the change in historical lake primary productivity. The results reported here demonstrate that reflectance spectroscopy can provide a rapid method for the reconstruction of lake palaeoenviro nmental change in the remote Antarctic regions.

Understanding Zeeman EIT Noise Correlation Spectra in Buffered Rb Vapor

NASA Astrophysics Data System (ADS)

O'Leary, Shannon; Zheng, Aojie; Crescimanno, Michael

2014-05-01

Noise correlation spectroscopy on systems manifesting Electromagnetically Induced Transparency (EIT) holds promise as a simple, robust method for performing high-resolution spectroscopy used in applications such as EIT-based atomic magnetometry and clocks. During laser light's propagation through a resonant medium, interaction with the medium converts laser phase noise into intensity noise. While this noise conversion can diminish the precision of EIT applications, noise correlation techniques transform the noise into a useful spectroscopic tool that can improve the application's precision. Using a single diode laser with large phase noise, we examine laser intensity noise and noise correlations from Zeeman EIT in a buffered Rb vapor. Of particular interest is a narrow noise correlation feature, resonant with EIT, that has been shown in earlier work to be power-broadening resistant at low powers. We report here on our recent experimental work and complementary theoretical modeling on EIT noise spectra, including a study of power broadening of the narrow noise correlation feature. Understanding the nature of the noise correlation spectrum is essential for optimizing EIT-noise applications.

Structural environments of carboxyl groups in natural organic molecules from terrestrial systems. Part 2: 2D NMR spectroscopy

NASA Astrophysics Data System (ADS)

Deshmukh, Ashish P.; Pacheco, Carlos; Hay, Michael B.; Myneni, Satish C. B.

2007-07-01

Carboxyl groups are abundant in natural organic molecules (NOM) and play a major role in their reactivity. The structural environments of carboxyl groups in IHSS soil and river humic samples were investigated using 2D NMR (heteronuclear and homonuclear correlation) spectroscopy. Based on the 1H- 13C heteronuclear multiple-bond correlation (HMBC) spectroscopy results, the carboxyl environments in NOM were categorized as Type I (unsubstituted and alkyl-substituted aliphatic/alicyclic), Type II (functionalized carbon substituted), Type IIIa, b (heteroatom and olefin substituted), and Type IVa, b (5-membered heterocyclic aromatic and 6-membered aromatic). The most intense signal in the HMBC spectra comes from the Type I carboxyl groups, including the 2JCH and 3JCH couplings of unsubstituted aliphatic and alicyclic acids, though this spectral region also includes the 3JCH couplings of Type II and III structures. Type II and III carboxyls have small but detectable 2JCH correlations in all NOM samples except for the Suwannee River humic acid. Signals from carboxyls bonded to 5-membered aromatic heterocyclic fragments (Type IVa) are observed in the soil HA and Suwannee River FA, while correlations to 6-membered aromatics (Type IVb) are only observed in Suwannee River HA. In general, aromatic carboxylic acids may be present at concentrations lower than previously imagined in these samples. Vibrational spectroscopy results for these NOM samples, described in an accompanying paper [Hay M. B. and Myneni S. C. B. (2007) Structural environments of carboxyl groups in natural organic molecules from terrestrial systems. Part 1: Infrared spectroscopy. Geochim. Cosmochim. Acta (in press)], suggest that Type II and Type III carboxylic acids with α substituents (e.g., -OH, -OR, or -CO 2H) constitute the majority of carboxyl structures in all humic substances examined. Furoic and salicylic acid structures (Type IV) are also feasible fragments, albeit as minor constituents. The vibrational spectroscopy results also suggest that much of the "Type I" signal observed in the HMBC spectrum is due to carboxylic acid esters and possibly α-substituted alicyclic acids.

EIT Noise Resonance Power Broadening: a probe for coherence dynamics

NASA Astrophysics Data System (ADS)

Crescimanno, Michael; O'Leary, Shannon; Snider, Charles

2012-06-01

EIT noise correlation spectroscopy holds promise as a simple, robust method for performing high resolution spectroscopy used in devices as diverse as magnetometers and clocks. One useful feature of these noise correlation resonances is that they do not power broaden with the EIT window. We report on measurements of the eventual power broadening (at higher optical powers) of these resonances and a simple, quantitative theoretical model that relates the observed power broadening slope with processes such as two-photon detuning gradients and coherence diffusion. These processes reduce the ground state coherence relative to that of a homogeneous system, and thus the power broadening slope of the EIT noise correlation resonance may be a simple, useful probe for coherence dynamics.

Noncontact diffuse correlation spectroscopy for noninvasive deep tissue blood flow measurement

NASA Astrophysics Data System (ADS)

Lin, Yu; He, Lian; Shang, Yu; Yu, Guoqiang

2012-01-01

A noncontact diffuse correlation spectroscopy (DCS) probe has been developed using two separated optical paths for the source and detector. This unique design avoids the interference between the source and detector and allows large source-detector separations for deep tissue blood flow measurements. The noncontact probe has been calibrated against a contact probe in a tissue-like phantom solution and human muscle tissues; flow changes concurrently measured by the two probes are highly correlated in both phantom (R2=0.89, p<10-5) and real-tissue (R2=0.77, p<10-5, n=9) tests. The noncontact DCS holds promise for measuring blood flow in vulnerable (e.g., pressure ulcer) and soft (e.g., breast) tissues without distorting tissue hemodynamic properties.

Exploitation of Geometric Occlusion and Covariance Spectroscopy in a Gamma Sensor Array

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

Mukhopadhyay, Sanjoy; Maurer, Richard; Wolff, Ronald

2013-09-01

The National Security Technologies, LLC, Remote Sensing Laboratory has recently used an array of six small-footprint (1-inch diameter by 3-inch long) cylindrical crystals of thallium-doped sodium iodide scintillators to obtain angular information from discrete gamma ray–emitting point sources. Obtaining angular information in a near-field measurement for a field-deployed gamma sensor is a requirement for radiological emergency work. Three of the sensors sit at the vertices of a 2-inch isosceles triangle, while the other three sit on the circumference of a 3-inch-radius circle centered in this triangle. This configuration exploits occlusion of sensors, correlation from Compton scattering within a detector array,more » and covariance spectroscopy, a spectral coincidence technique. Careful placement and orientation of individual detectors with reference to other detectors in an array can provide improved angular resolution for determining the source position by occlusion mechanism. By evaluating the values of, and the uncertainties in, the photopeak areas, efficiencies, branching ratio, peak area correction factors, and the correlations between these quantities, one can determine the precise activity of a particular radioisotope from a mixture of radioisotopes that have overlapping photopeaks that are ordinarily hard to deconvolve. The spectral coincidence technique, often known as covariance spectroscopy, examines the correlations and fluctuations in data that contain valuable information about radiation sources, transport media, and detection systems. Covariance spectroscopy enhances radionuclide identification techniques, provides directional information, and makes weaker gamma-ray emission—normally undetectable by common spectroscopic analysis—detectable. A series of experimental results using the concept of covariance spectroscopy are presented.« less

A definitive analytical spectroscopic study of Indian yellow, an ancient pigment used for dating purposes.

PubMed

de Faria, Dalva L A; Edwards, Howell G M; Careaga, Valeria; Walt, Nicholas; Maier, Marta S

2017-02-01

The Raman spectrum of tartrazine has been mistakenly reported as being that of Indian yellow in the literature, which has serious consequences for the identification of this pigment in art works regarding their authentication. Unlike tartrazine, Indian yellow (a natural mixture of the magnesium and calcium salts of euxanthic acid) exhibits in its Raman spectrum a strong fluorescent background when visible excitation is used, however, excitation in the near infrared (1064nm) permitted the observation of the Raman bands from the raw pigment with the main features placed at 1346, 1368, 1425, 1441 and 1626cm -1 . Indian yellow identification was assured by 1 H and 13 C Nuclear Magnetic Resonance characterization and the complete assignment of the proton and carbon resonances was accomplished using heteronuclear single quantum correlation (HSQC), heteronuclear multiple bond correlation (HMBC), nuclear overhauser effect spectroscopy (NOESY) and 1 H- 1 H correlation spectroscopy (COSY). Scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and X-ray fluorescence (XRF) analyzes were also conducted on a genuine sample of this historical pigment. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

PubMed Central

Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.; Park, Sunkyu; Kim, Seong H.

2015-01-01

A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlate with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. It was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component. PMID:26463274

Probing transcription factor diffusion dynamics in the living mammalian embryo with photoactivatable fluorescence correlation spectroscopy.

PubMed

Kaur, Gurpreet; Costa, Mauro W; Nefzger, Christian M; Silva, Juan; Fierro-González, Juan Carlos; Polo, Jose M; Bell, Toby D M; Plachta, Nicolas

2013-01-01

Transcription factors use diffusion to search the DNA, yet the mechanisms controlling transcription factor diffusion during mammalian development remain poorly understood. Here we combine photoactivation and fluorescence correlation spectroscopy to study transcription factor diffusion in developing mouse embryos. We show that the pluripotency-associated transcription factor Oct4 displays both fast and Brownian and slower subdiffusive behaviours that are controlled by DNA interactions. Following cell lineage specification, the slower DNA-interacting diffusion fraction distinguishes pluripotent from extraembryonic cell nuclei. Similar to Oct4, Sox2 shows slower diffusion in pluripotent cells while Cdx2 displays opposite dynamics, suggesting that slow diffusion may represent a general feature of transcription factors in lineages where they are essential. Slow Oct4 subdiffusive behaviours are conserved in embryonic stem cells and induced pluripotent stem cells (iPS cells), and lost during differentiation. We also show that Oct4 diffusion depends on its interaction with ERG-associated protein with SET domain. Photoactivation and fluorescence correlation spectroscopy provides a new intravital approach to study transcription factor diffusion in complex in vivo systems.

Combined multi-distance frequency domain and diffuse correlation spectroscopy system with simultaneous data acquisition and real-time analysis.

PubMed

Carp, Stefan A; Farzam, Parisa; Redes, Norin; Hueber, Dennis M; Franceschini, Maria Angela

2017-09-01

Frequency domain near infrared spectroscopy (FD-NIRS) and diffuse correlation spectroscopy (DCS) have emerged as synergistic techniques for the non-invasive assessment of tissue health. Combining FD-NIRS oximetry with DCS measures of blood flow, the tissue oxygen metabolic rate can be quantified, a parameter more closely linked to underlying physiology and pathology than either NIRS or DCS estimates alone. Here we describe the first commercially available integrated instrument, called the "MetaOx", designed to enable simultaneous FD-NIRS and DCS measurements at rates of 10 + Hz, and offering real-time data evaluation. We show simultaneously acquired characterization data demonstrating performance equivalent to individual devices and sample in vivo measurements of pulsation resolved blood flow, forearm occlusion hemodynamic changes and muscle oxygen metabolic rate monitoring during stationary bike exercise.

Combined multi-distance frequency domain and diffuse correlation spectroscopy system with simultaneous data acquisition and real-time analysis

PubMed Central

Carp, Stefan A.; Farzam, Parisa; Redes, Norin; Hueber, Dennis M.; Franceschini, Maria Angela

2017-01-01

Frequency domain near infrared spectroscopy (FD-NIRS) and diffuse correlation spectroscopy (DCS) have emerged as synergistic techniques for the non-invasive assessment of tissue health. Combining FD-NIRS oximetry with DCS measures of blood flow, the tissue oxygen metabolic rate can be quantified, a parameter more closely linked to underlying physiology and pathology than either NIRS or DCS estimates alone. Here we describe the first commercially available integrated instrument, called the “MetaOx”, designed to enable simultaneous FD-NIRS and DCS measurements at rates of 10 + Hz, and offering real-time data evaluation. We show simultaneously acquired characterization data demonstrating performance equivalent to individual devices and sample in vivo measurements of pulsation resolved blood flow, forearm occlusion hemodynamic changes and muscle oxygen metabolic rate monitoring during stationary bike exercise. PMID:29026684

Investigation of Antioxidant Activity of Pomegranate Juices by Means of Electron Paramagnetic Resonance and UV-Vis Spectroscopy.

PubMed

Kozik, Violetta; Jarzembek, Krystyna; Jędrzejowska, Agnieszka; Bąk, Andrzej; Polak, Justyna; Bartoszek, Mariola; Pytlakowska, Katarzyna

2015-01-01

Pomegranate fruit (Punica granatum L.) is a source of numerous phenolic compounds, and it contains flavonoids such as anthocyanins, anthocyanidins, cyanidins, catechins and other complexes of flavonoids, ellagitannins, and hydrolyzed tannins. Pomegranate juice shows antioxidant, antiproliferative, and anti-atherosclerotic properties. The antioxidant capacity (TEAC) of the pomegranate juices was measured using electron paramagnetic resonance (EPR) spectroscopy and 1,1-diphenyl-2-picrylhydrazyl (DPPH•) as a source of free radicals, and the total phenolic (TP) content was measured using UV-Vis spectroscopy. All the examined pomegranate juices exhibited relatively high antioxidant properties. The TEAC values determined by means of EPR spectroscopy using Trolox (TE) as a free radical scavenger were in the range of 463.12 to 1911.91 μmol TE/100 mL juice. The TP content measured by the Folin-Ciocalteu method, using gallic acid (GA) as a free radical scavenger, widely varied in the investigated pomegranate juice samples and ranged from 1673.62 to 5263.87 mg GA/1 L juice. The strongest antioxidant properties were observed with the fresh pomegranate juices obtained from the fruits originating from Israel, Lebanon, and Azerbaijan. Correlation analysis of numerical data obtained by means of EPR spectroscopy (TEAC) and UV-Vis spectroscopy (TP) gave correlation coefficient (r)=0.90 and determination coefficient (r2)=0.81 (P<0.05).

Picosecond time-resolved photoluminescence using picosecond excitation correlation spectroscopy

NASA Astrophysics Data System (ADS)

Johnson, M. B.; McGill, T. C.; Hunter, A. T.

1988-03-01

We present a study of the temporal decay of photoluminescence (PL) as detected by picosecond excitation correlation spectroscopy (PECS). We analyze the correlation signal that is obtained from two simple models; one where radiative recombination dominates, the other where trapping processes dominate. It is found that radiative recombination alone does not lead to a correlation signal. Parallel trapping type processes are found to be required to see a signal. To illustrate this technique, we examine the temporal decay of the PL signal for In-alloyed, semi-insulating GaAs substrates. We find that the PL signal indicates a carrier lifetime of roughly 100 ps, for excitation densities of 1×1016-5×1017 cm-3. PECS is shown to be an easy technique to measure the ultrafast temporal behavior of PL processes because it requires no ultrafast photon detection. It is particularly well suited to measuring carrier lifetimes.

Fluorescence correlation spectroscopy: novel variations of an established technique.

PubMed

Haustein, Elke; Schwille, Petra

2007-01-01

Fluorescence correlation spectroscopy (FCS) is one of the major biophysical techniques used for unraveling molecular interactions in vitro and in vivo. It allows minimally invasive study of dynamic processes in biological specimens with extremely high temporal and spatial resolution. By recording and correlating the fluorescence fluctuations of single labeled molecules through the exciting laser beam, FCS gives information on molecular mobility and photophysical and photochemical reactions. By using dual-color fluorescence cross-correlation, highly specific binding studies can be performed. These have been extended to four reaction partners accessible by multicolor applications. Alternative detection schemes shift accessible time frames to slower processes (e.g., scanning FCS) or higher concentrations (e.g., TIR-FCS). Despite its long tradition, FCS is by no means dated. Rather, it has proven to be a highly versatile technique that can easily be adapted to solve specific biological questions, and it continues to find exciting applications in biology and medicine.

Metabolite profiling in retinoblastoma identifies novel clinicopathological subgroups

PubMed Central

Kohe, Sarah; Brundler, Marie-Anne; Jenkinson, Helen; Parulekar, Manoj; Wilson, Martin; Peet, Andrew C; McConville, Carmel M

2015-01-01

Background: Tumour classification, based on histopathology or molecular pathology, is of value to predict tumour behaviour and to select appropriate treatment. In retinoblastoma, pathology information is not available at diagnosis and only exists for enucleated tumours. Alternative methods of tumour classification, using noninvasive techniques such as magnetic resonance spectroscopy, are urgently required to guide treatment decisions at the time of diagnosis. Methods: High-resolution magic-angle spinning magnetic resonance spectroscopy (HR-MAS MRS) was undertaken on enucleated retinoblastomas. Principal component analysis and cluster analysis of the HR-MAS MRS data was used to identify tumour subgroups. Individual metabolite concentrations were determined and were correlated with histopathological risk factors for each group. Results: Multivariate analysis identified three metabolic subgroups of retinoblastoma, with the most discriminatory metabolites being taurine, hypotaurine, total-choline and creatine. Metabolite concentrations correlated with specific histopathological features: taurine was correlated with differentiation, total-choline and phosphocholine with retrolaminar optic nerve invasion, and total lipids with necrosis. Conclusions: We have demonstrated that a metabolite-based classification of retinoblastoma can be obtained using ex vivo magnetic resonance spectroscopy, and that the subgroups identified correlate with histopathological features. This result justifies future studies to validate the clinical relevance of these subgroups and highlights the potential of in vivo MRS as a noninvasive diagnostic tool for retinoblastoma patient stratification. PMID:26348444

Multiple-step relayed correlation spectroscopy: sequential resonance assignments in oligosaccharides.

PubMed Central

Homans, S W; Dwek, R A; Fernandes, D L; Rademacher, T W

1984-01-01

A general property of the high-resolution proton NMR spectra of oligosaccharides is the appearance of low-field well-resolved resonances corresponding to the anomeric (H1) and H2 protons. The remaining skeletal protons resonate in the region 3-4 ppm, giving rise to an envelope of poorly resolved resonances. Assignments can be made from the H1 and H2 protons to their J-coupled neighbors (H2 and H3) within this main envelope by using 1H-1H correlated spectroscopy. However, the tight coupling (J congruent to delta) between further protons results in poor spectral dispersion with consequent assignment ambiguities. We describe here three-step two-dimensional relayed correlation spectroscopy and show how it can be used to correlate the resolved anomeric (H1) and H2 protons with remote (H4, H5) protons directly through a linear network of couplings using sequential magnetization transfer around the oligosaccharide rings. Resonance assignments are then obtained by inspection of cross-peaks that appear in well-resolved regions of the two-dimensional spectrum. This offers a general solution to the assignment problem in oligosaccharides and, importantly, these assignments will subsequently allow for the three-dimensional solution conformation to be determined by using one-dimensional and two-dimensional nuclear Overhauser experiments. PMID:6593701

k-Space Image Correlation Spectroscopy: A Method for Accurate Transport Measurements Independent of Fluorophore Photophysics

PubMed Central

Kolin, David L.; Ronis, David; Wiseman, Paul W.

2006-01-01

We present the theory and application of reciprocal space image correlation spectroscopy (kICS). This technique measures the number density, diffusion coefficient, and velocity of fluorescently labeled macromolecules in a cell membrane imaged on a confocal, two-photon, or total internal reflection fluorescence microscope. In contrast to r-space correlation techniques, we show kICS can recover accurate dynamics even in the presence of complex fluorophore photobleaching and/or “blinking”. Furthermore, these quantities can be calculated without nonlinear curve fitting, or any knowledge of the beam radius of the exciting laser. The number densities calculated by kICS are less sensitive to spatial inhomogeneity of the fluorophore distribution than densities measured using image correlation spectroscopy. We use simulations as a proof-of-principle to show that number densities and transport coefficients can be extracted using this technique. We present calibration measurements with fluorescent microspheres imaged on a confocal microscope, which recover Stokes-Einstein diffusion coefficients, and flow velocities that agree with single particle tracking measurements. We also show the application of kICS to measurements of the transport dynamics of α5-integrin/enhanced green fluorescent protein constructs in a transfected CHO cell imaged on a total internal reflection fluorescence microscope using charge-coupled device area detection. PMID:16861272

Investigating the effect of poly-l-lactic acid nanoparticles carrying hypericin on the flow-biased diffusive motion of HeLa cell organelles.

PubMed

Penjweini, Rozhin; Deville, Sarah; Haji Maghsoudi, Omid; Notelaers, Kristof; Ethirajan, Anitha; Ameloot, Marcel

2017-07-19

In this study, we investigate in human cervical epithelial HeLa cells the intracellular dynamics and the mutual interaction with the organelles of the poly-l-lactic acid nanoparticles (PLLA NPs) carrying the naturally occurring hydrophobic photosensitizer hypericin. Temporal and spatiotemporal image correlation spectroscopy was used for the assessment of the intracellular diffusion and directed motion of the nanocarriers by tracking the hypericin fluorescence. Using image cross-correlation spectroscopy and specific fluorescent labelling of endosomes, lysosomes and mitochondria, the NPs dynamics in association with the cell organelles was studied. Static colocalization experiments were interpreted according to the Manders' overlap coefficient. Nanoparticles associate with a small fraction of the whole-organelle population. The organelles moving with NPs exhibit higher directed motion compared to those moving without them. The rate of the directed motion drops substantially after the application of nocodazole. The random component of the organelle motions is not influenced by the NPs. Image correlation and cross-correlation spectroscopy are most appropriate to unravel the motion of the PLLA nanocarrier and to demonstrate that the rate of the directed motion of organelles is influenced by their interaction with the nanocarriers. Not all PLLA-hypericin NPs are associated with organelles. © 2017 Royal Pharmaceutical Society.

Integrated fluorescence correlation spectroscopy device for point-of-care clinical applications

PubMed Central

Olson, Eben; Torres, Richard; Levene, Michael J.

2013-01-01

We describe an optical system which reduces the cost and complexity of fluorescence correlation spectroscopy (FCS), intended to increase the suitability of the technique for clinical use. Integration of the focusing optics and sample chamber into a plastic component produces a design which is simple to align and operate. We validate the system by measurements on fluorescent dye, and compare the results to a commercial instrument. In addition, we demonstrate its application to measurements of concentration and multimerization of the clinically relevant protein von Willebrand factor (vWF) in human plasma. PMID:23847733

Direct correlations of structural and optical properties of three-dimensional GaN/InGaN core/shell micro-light emitting diodes

NASA Astrophysics Data System (ADS)

Sadat Mohajerani, Matin; Müller, Marcus; Hartmann, Jana; Zhou, Hao; Wehmann, Hergo-H.; Veit, Peter; Bertram, Frank; Christen, Jürgen; Waag, Andreas

2016-05-01

Three-dimensional (3D) InGaN/GaN quantum-well (QW) core-shell light emitting diodes (LEDs) are a promising candidate for the future solid state lighting. In this contribution, we study direct correlations of structural and optical properties of the core-shell LEDs using highly spatially-resolved cathodoluminescence spectroscopy (CL) in combination with scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM). Temperature-dependent resonant photoluminescence (PL) spectroscopy has been performed to understand recombination mechanisms and to estimate the internal quantum efficiency (IQE).

Detection of elemental mercury by multimode diode laser correlation spectroscopy.

PubMed

Lou, Xiutao; Somesfalean, Gabriel; Svanberg, Sune; Zhang, Zhiguo; Wu, Shaohua

2012-02-27

We demonstrate a method for elemental mercury detection based on correlation spectroscopy employing UV laser radiation generated by sum-frequency mixing of two visible multimode diode lasers. Resonance matching of the multimode UV laser is achieved in a wide wavelength range and with good tolerance for various operating conditions. Large mode-hops provide an off-resonance baseline, eliminating interferences from other gas species with broadband absorption. A sensitivity of 1 μg/m3 is obtained for a 1-m path length and 30-s integration time. The performance of the system shows promise for mercury monitoring in industrial applications.

Enhancing the sensitivity of fluorescence correlation spectroscopy by using time-correlated single photon counting.

PubMed

Lamb, D C; Müller, B K; Bräuchle, C

2005-10-01

Fluorescence correlation spectroscopy (FCS) and fluorescence cross-correlation spectroscopy (FCCS) are methods that extract information about a sample from the influence of thermodynamic equilibrium fluctuations on the fluorescence intensity. This method allows dynamic information to be obtained from steady state equilibrium measurements and its popularity has dramatically increased in the last 10 years due to the development of high sensitivity detectors and its combination with confocal microscopy. Using time-correlated single-photon counting (TCSPC) detection and pulsed excitation, information over the duration of the excited state can be extracted and incorporated in the analysis. In this short review, we discuss new methodologies that have recently emerged which incorporated fluorescence lifetime information or TCSPC data in the FCS and FCCS analysis. Time-gated FCS discriminates between which photons are to be incorporated in the analysis dependent upon their arrival time after excitation. This allows for accurate FCS measurements in the presence of fluorescent background, determination of sample homogeneity, and the ability to distinguish between static and dynamic heterogeneities. A similar method, time-resolved FCS can be used to resolve the individual correlation functions from multiple fluorophores through the different fluorescence lifetimes. Pulsed interleaved excitation (PIE) encodes the excitation source into the TCSPC data. PIE can be used to perform dual-channel FCCS with a single detector and allows elimination of spectral cross-talk with dual-channel detection. For samples that undergo fluorescence resonance energy transfer (FRET), quantitative FCCS measurements can be performed in spite of the FRET and the static FRET efficiency can be determined.

The Equilibrium Constant for Bromothymol Blue: A General Chemistry Laboratory Experiment Using Spectroscopy

ERIC Educational Resources Information Center

Klotz, Elsbeth; Doyle, Robert; Gross, Erin; Mattson, Bruce

2011-01-01

A simple, inexpensive, and environmentally friendly undergraduate laboratory experiment is described in which students use visible spectroscopy to determine a numerical value for an equilibrium constant, K[subscript c]. The experiment correlates well with the lecture topic of equilibrium even though the subject of the study is an acid-base…

Abdominal near-infrared spectroscopy measurements are lower in preterm infants at risk for necrotizing enterocolitis

USDA-ARS?s Scientific Manuscript database

Near-infrared spectroscopy is a noninvasive method of measuring local tissue oxygenation (StO[2]). Abdominal StO[2] measurements in preterm piglets are directly correlated with changes in intestinal blood flow and markedly reduced by necrotizing enterocolitis. The objectives of this study were to us...

Investigation of the Brill transition in nylon 6,6 by Raman, THz-Raman, and two-dimensional correlation spectroscopy.

PubMed

Bertoldo Menezes, D; Reyer, A; Musso, M

2018-02-05

The Brill transition is a phase transition process in polyamides related with structural changes between the hydrogen bonds of the lateral functional groups (CO) and (NH). In this study, we have used the potential of Raman spectroscopy for exploring this phase transition in polyamide 6,6 (nylon 6,6), due to the sensitivity of this spectroscopic technique to small intermolecular changes affecting vibrational properties of relevant functional groups. During a step by step heating and cooling process of the sample we collected Raman spectra allowing us from two-dimensional Raman correlation spectroscopy to identify which spectral regions suffered the largest influence during the Brill transition, and from Terahertz Stokes and anti-Stokes Raman spectroscopy to obtain complementary information, e.g. on the temperature of the sample. This allowed us to grasp signatures of the Brill transition from peak parameters of vibrational modes associated with (CC) skeletal stretches and (CNH) bending, and to verify the Brill transition temperature at around 160°C, as well as the reversibility of this phase transition. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Development of an Early Warning Fire Detection System using Correlation Spectroscopy

NASA Technical Reports Server (NTRS)

Goswami, K.; Voevodkin, G.; Rubstov, V.; Lieberman, R.; Piltch, N.

2001-01-01

Combustion byproducts are numerous. A few examples of the gaseous byproducts include carbon dioxide, carbon monoxide, hydrogen chloride, hydrogen cyanide and ammonia. For detecting these chemical species, classic absorption spectroscopy has been used for many decades, but the sensitivity of steady-state methods is often unsuitable for the detection of trace compounds at the low levels (parts per million to parts per billion) appropriate for scientific purposes. This is particularly so for monitoring equipment, which must be compact and cost-effective, and which is often subjected to shock, vibration, and other environmental effects that can severely degrade the performance of high-sensitivity spectrometers in an aircraft. Steady-state techniques also suffer from a lack of specificity; the deconvolution of the spectra of complex mixtures is a laborious and error prone process. These problems are exacerbated in remote fiber-optic monitoring where, for practical reasons, the fundamental absorbance region of the spectrum (often between 3 and 8 microns) is inaccessible, and the low-strength, closely spaced, near-infrared overtone absorbance bands must be used. We circumvented these challenges by employing correlation spectroscopy, a variation of modulation spectroscopy.

Gallium interstitial in irradiated germanium: Deep level transient spectroscopy

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

Kolkovsky, Vl.; Petersen, M. Christian; Larsen, A. Nylandsted

Two electronic levels at 0.34 eV above the valence band and 0.32 eV below the conduction band, in gallium doped, p-type Ge irradiated with 2 MeV electrons have been studied by deep level transient spectroscopy (DLTS) with both majority- and minority-carrier injections, and Laplace DLTS spectroscopy. It is concluded that these levels, having donor and acceptor characters, respectively, are correlated with interstitial Ga atoms, formed by the Watkins-replacement mechanism via self-interstitials.

Gallium interstitial in irradiated germanium: Deep level transient spectroscopy

NASA Astrophysics Data System (ADS)

Kolkovsky, Vl.; Petersen, M. Christian; Mesli, A.; van Gheluwe, J.; Clauws, P.; Larsen, A. Nylandsted

2008-12-01

Two electronic levels at 0.34 eV above the valence band and 0.32 eV below the conduction band, in gallium doped, p -type Ge irradiated with 2 MeV electrons have been studied by deep level transient spectroscopy (DLTS) with both majority- and minority-carrier injections, and Laplace DLTS spectroscopy. It is concluded that these levels, having donor and acceptor characters, respectively, are correlated with interstitial Ga atoms, formed by the Watkins-replacement mechanism via self-interstitials.

Revealing time bunching effect in single-molecule enzyme conformational dynamics.

PubMed

Lu, H Peter

2011-04-21

In this perspective, we focus our discussion on how the single-molecule spectroscopy and statistical analysis are able to reveal enzyme hidden properties, taking the study of T4 lysozyme as an example. Protein conformational fluctuations and dynamics play a crucial role in biomolecular functions, such as in enzymatic reactions. Single-molecule spectroscopy is a powerful approach to analyze protein conformational dynamics under physiological conditions, providing dynamic perspectives on a molecular-level understanding of protein structure-function mechanisms. Using single-molecule fluorescence spectroscopy, we have probed T4 lysozyme conformational motions under the hydrolysis reaction of a polysaccharide of E. coli B cell walls by monitoring the fluorescence resonant energy transfer (FRET) between a donor-acceptor probe pair tethered to T4 lysozyme domains involving open-close hinge-bending motions. Based on the single-molecule spectroscopic results, molecular dynamics simulation, a random walk model analysis, and a novel 2D statistical correlation analysis, we have revealed a time bunching effect in protein conformational motion dynamics that is critical to enzymatic functions. Bunching effect implies that conformational motion times tend to bunch in a finite and narrow time window. We show that convoluted multiple Poisson rate processes give rise to the bunching effect in the enzymatic reaction dynamics. Evidently, the bunching effect is likely common in protein conformational dynamics involving in conformation-gated protein functions. In this perspective, we will also discuss a new approach of 2D regional correlation analysis capable of analyzing fluctuation dynamics of complex multiple correlated and anti-correlated fluctuations under a non-correlated noise background. Using this new method, we are able to map out any defined segments along the fluctuation trajectories and determine whether they are correlated, anti-correlated, or non-correlated; after which, a cross correlation analysis can be applied for each specific segment to obtain a detailed fluctuation dynamics analysis.

[Pattern recognition of decorative papers with different visual characteristics using visible spectroscopy coupled with principal component analysis (PCA)].

PubMed

Zhang, Mao-mao; Yang, Zhong; Lu, Bin; Liu, Ya-na; Sun, Xue-dong

2015-02-01

As one of the most important decorative materials for the modern household products, decorative papers impregnated with melamine not only have better decorative performance, but also could greatly improve the surface properties of materials. However, the appearance quality (such as color-difference evaluation and control) of decorative papers, as an important index for the surface quality of decorative paper, has been a puzzle for manufacturers and consumers. Nowadays, human eye is used to discriminate whether there exist color difference in the factory, which is not only of low efficiency but also prone to bring subjective error. Thus, it is of great significance to find an effective method in order to realize the fast recognition and classification of the decorative papers. In the present study, the visible spectroscopy coupled with principal component analysis (PCA) was used for the pattern recognition of decorative papers with different visual characteristics to investigate the feasibility of visible spectroscopy to rapidly recognize the types of decorative papers. The results showed that the correlation between visible spectroscopy and visual characteristics (L*, a* and b*) was significant, and the correlation coefficients wereup to 0.85 and some was even more than 0. 99, which might suggest that the visible spectroscopy reflected some information about visual characteristics on the surface of decorative papers. When using the visible spectroscopy coupled with PCA to recognize the types of decorative papers, the accuracy reached 94%-100%, which might suggest that the visible spectroscopy was a very potential new method for the rapid, objective and accurate recognition of decorative papers with different visual characteristics.

Detection of structurally similar adulterants in botanical dietary supplements by thin-layer chromatography and surface enhanced Raman spectroscopy combined with two-dimensional correlation spectroscopy.

PubMed

Li, Hao; Zhu, Qing xia; Chwee, Tsz sian; Wu, Lin; Chai, Yi feng; Lu, Feng; Yuan, Yong fang

2015-07-09

Thin-layer chromatography (TLC) coupled with surface enhanced Raman spectroscopy (SERS) has been widely used for the study of various complex systems, especially for the detection of adulterants in botanical dietary supplements (BDS). However, this method is not sufficient to distinguish structurally similar adulterants in BDS since the analogs have highly similar chromatographic and/or spectroscopic behaviors. Taking into account the fact that higher cost and more time will be required for comprehensive chromatographic separation, more efforts with respect to spectroscopy are now focused on analyzing the overlapped SERS peaks. In this paper, the combination of a TLC-SERS method with two-dimensional correlation spectroscopy (2DCOS), with duration of exposure to laser as the perturbation, is applied to solve this problem. Besides the usual advantages of the TLC-SERS method, such as its simplicity, rapidness, and sensitivity, more advantages are presented here, such as enhanced selectivity and good reproducibility, which are obtained by 2DCOS. Two chemicals with similar structures are successfully differentiated from the complex BDS matrices. The study provides a more accurate qualitative screening method for detection of BDS with adulterants, and offers a new universal approach for the analysis of highly overlapped SERS peaks. Copyright © 2015 Elsevier B.V. All rights reserved.

On the use of two-time correlation functions for X-ray photon correlation spectroscopy data analysis.

PubMed

Bikondoa, Oier

2017-04-01

Multi-time correlation functions are especially well suited to study non-equilibrium processes. In particular, two-time correlation functions are widely used in X-ray photon correlation experiments on systems out of equilibrium. One-time correlations are often extracted from two-time correlation functions at different sample ages. However, this way of analysing two-time correlation functions is not unique. Here, two methods to analyse two-time correlation functions are scrutinized, and three illustrative examples are used to discuss the implications for the evaluation of the correlation times and functional shape of the correlations.

Thermally induced conformational changes in polyethylene studied by two-dimensional near-infrared infrared hetero-spectral correlation spectroscopy

NASA Astrophysics Data System (ADS)

Watanabe, Shin; Noda, Isao; Ozaki, Yukihiro

2008-07-01

The amount of nonplanar gauche bonds was monitored as a function of increasing temperature in three different polyethylene (PE) samples by means of mid-infrared (MIR) and near-infrared (NIR) spectroscopy. The hetero-spectral two-dimensional (2D) correlation analysis was carried out between the NIR spectral region of 4365-4235 cm -1 and the well-established MIR spectral region of 1375-1265 cm -1, where bands due to nonplanar conformer are detected. This approach allowed us to identify the NIR band at 4265 cm -1, which behaves in a way similar to MIR bands originating from conformational-defect sequences. By combining the result of our current study and that of our previous report obtained on different types of PE, it is suggested that the NIR band originates from conformational-defect sequences in PE. This finding opens up a unique and useful way to study the state of conformational disorder in PE crystal by NIR spectroscopy, monitoring the intensity of the NIR band at 4265 cm -1. The use of NIR spectroscopy allows researchers to directly probe the degree in the formation of conformational-defect sequences in thick, real-world PE samples that cannot be studied by conventional MIR spectroscopy. The 2D correlation spectroscopy analysis among the MIR CH 2 wagging conformational-defect-mode bands on linear low-density PE (LLDPE) and low-density PE (LDPE) revealed the formation of nonplanar conformer represented by the band at 1368 cm -1 proceeds prior to those by other band at 1308 cm -1. This result agrees well with our previous finding on high-density PE (HDPE). We therefore propose with strong confidence that the bands at 1368 and 1308 cm -1 arise from different conformational-defect sequences, even though both of the bands have been proposed to arise from the same conformer of gtg' ( kink) + gtg sequence.

Nonlinear two-dimensional terahertz photon echo and rotational spectroscopy in the gas phase.

PubMed

Lu, Jian; Zhang, Yaqing; Hwang, Harold Y; Ofori-Okai, Benjamin K; Fleischer, Sharly; Nelson, Keith A

2016-10-18

Ultrafast 2D spectroscopy uses correlated multiple light-matter interactions for retrieving dynamic features that may otherwise be hidden under the linear spectrum; its extension to the terahertz regime of the electromagnetic spectrum, where a rich variety of material degrees of freedom reside, remains an experimental challenge. We report a demonstration of ultrafast 2D terahertz spectroscopy of gas-phase molecular rotors at room temperature. Using time-delayed terahertz pulse pairs, we observe photon echoes and other nonlinear signals resulting from molecular dipole orientation induced by multiple terahertz field-dipole interactions. The nonlinear time domain orientation signals are mapped into the frequency domain in 2D rotational spectra that reveal J-state-resolved nonlinear rotational dynamics. The approach enables direct observation of correlated rotational transitions and may reveal rotational coupling and relaxation pathways in the ground electronic and vibrational state.

Hydrogen Bond Lifetimes and Energetics for Solute-Solvent Complexes Studied with 2D-IR Vibrational Echo Spectroscopy

PubMed Central

Zheng, Junrong; Fayer, Michael D.

2008-01-01

Weak π hydrogen bonded solute-solvent complexes are studied with ultrafast two dimensional infrared (2D-IR) vibrational echo chemical exchange spectroscopy, temperature dependent IR absorption spectroscopy, and density functional theory calculations. Eight solute-solvent complexes composed of a number of phenol derivatives and various benzene derivatives are investigated. The complexes are formed between the phenol derivative (solute) in a mixed solvent of the benzene derivative and CCl4. The time dependence of the 2D-IR vibrational echo spectra of the phenol hydroxyl stretch is used to directly determine the dissociation and formation rates of the hydrogen bonded complexes. The dissociation rates of the weak hydrogen bonds are found to be strongly correlated with their formation enthalpies. The correlation can be described with an equation similar to the Arrhenius equation. The results are discussed in terms of transition state theory. PMID:17373792

Steelmaking process control using remote ultraviolet atomic emission spectroscopy

NASA Astrophysics Data System (ADS)

Arnold, Samuel

Steelmaking in North America is a multi-billion dollar industry that has faced tremendous economic and environmental pressure over the past few decades. Fierce competition has driven steel manufacturers to improve process efficiency through the development of real-time sensors to reduce operating costs. In particular, much attention has been focused on end point detection through furnace off gas analysis. Typically, off-gas analysis is done with extractive sampling and gas analyzers such as Non-dispersive Infrared Sensors (NDIR). Passive emission spectroscopy offers a more attractive approach to end point detection as the equipment can be setup remotely. Using high resolution UV spectroscopy and applying sophisticated emission line detection software, a correlation was observed between metal emissions and the process end point during field trials. This correlation indicates a relationship between the metal emissions and the status of a steelmaking melt which can be used to improve overall process efficiency.

Identification of geographical origin of Lignosus samples using Fourier transform infrared and two-dimensional infrared correlation spectroscopy

NASA Astrophysics Data System (ADS)

Choong, Yew-Keong; Xu, Chang-Hua; Lan, Jin; Chen, Xiang-Dong; Jamal, Jamia Azdina

2014-07-01

Lignosus spp. is a medicinal mushroom that has been used as a folk remedy for 'clearing heat', eliminating phlegm, 'moistening the lungs' and as an anti-breast cancer agent. The objective of this study was to identify the active chemical constituents of the mushroom limited number of sample by using Fourier transform infrared (FTIR) and two-dimensional correlation Fourier transform infrared spectroscopy (2DIR). The sample M26/08 was purchased from a Chinese medicine shop in Kuala Lumpur, while M49/07 and M23/08 were collected from Semenyih and Kuala Lipis respectively. The three samples have strong absorption peaks corresponding to the stretching vibration of conjugated carbonyl Cdbnd O group. Both fresh sample M49/07 and M23/08 showed an identical peak of 1655 cm-1, whereby M26/08 contained stretching vibration of 1648 cm-1. The peaks from 1260 cm-1 onwards were assignation of carbohydrate content including saccharides. Spectrum of M26/08 showed region from 1260 cm-1 to 950 cm-1 which was 99.4% similar to M23/08. The chemical constitutes of M26/08 and M23/08 were closely correlated (r = 0.97), whereas the correlation coefficient of M26/08 and M49/07 was 0.94. The use of second derivative and 2DIR spectroscopy enhanced the distinct differences to a more significant level. Although the geographical origin of M26/08 was unknown, its origin was determined by comparing with M49/07 and M23/08. The visual and colorful 2DIR spectra provided dynamic structural information of the chemical components analyzed and demonstrated a powerful and useful approach using the spectroscopy of different samples.

Relationships between astrogliosis and 1H MR spectroscopic measures of brain choline/creatine and myo-inositol/creatine in a primate model.

PubMed

Kim, John P; Lentz, Margaret R; Westmoreland, Susan V; Greco, Jane B; Ratai, Eva M; Halpern, Elkan; Lackner, Andrew A; Masliah, Eliezer; González, R Gilberto

2005-04-01

In vivo 1H MR spectroscopy demonstrates elevated choline (Cho)/creatine (Cr) and myo-inositol (MI)/Cr in many neurologic diseases that has been ascribed to gliosis. We tested the hypotheses that in vivo Cho/Cr and/or MI/Cr levels are correlated with glial fibrillary acidic protein (GFAP) immunostains and that the changes are water-soluble metabolites. We performed postmortem 1H MR spectroscopy and GFAP immunohistochemistry in brains from seven rhesus macaques acutely infected with simian immunodeficiency virus (SIV) and in four controls and compared the findings with previous in vivo MR spectroscopic results. Changes in neuropathologic and MR spectroscopic markers after infection and relationships among plasma viral load, GFAP immunostaining results, and ex vivo and in vivo MR spectroscopic measures were statistically evaluated. On GFAP immunostaining and in vivo MR spectroscopy, GFAP, Cho/Cr and MI/Cr were highest near the time of peak plasma viral load at 11 days postinfection (dpi). Immunostains returned to baseline by 14 dpi, whereas Cho/Cr and MI/Cr had different time courses, with the former dropping below baseline and the latter remaining elevated. Viral load and immunostains were significantly correlated. No correlation was found between ex vivo Cho/Cr or MI/Cr and viral load or between metabolite ratios from in vivo and ex vivo MR spectroscopy. In acute SIV infection, plasma viral load was significantly correlated with brain GFAP immunostains and in vivo 1H MR spectroscopic Cho/Cr. In vivo changes in Cho/Cr and MI/Cr were principally due to contributions other than those of low-molecular-weight water-soluble metabolites.

Microvascular versus macrovascular cerebral vasomotor reactivity in patients with severe internal carotid artery stenosis or occlusion.

PubMed

Zirak, Peyman; Delgado-Mederos, Raquel; Dinia, Lavinia; Martí-Fàbregas, Joan; Durduran, Turgut

2014-02-01

In patients with severe internal carotid artery steno-occlusive lesions (ISOL), impaired cerebrovascular reactivity (CVR) is predictive of future ischemic stroke (IS) or transient ischemic attack (TIA). Therefore, the evaluation of CVR in ISOL patients may be a means to evaluate the risk for IS/TIA and decide on an intervention. Our aim was (1) to explore the feasibility of concurrent near-infrared spectroscopy (NIRS-DOS), diffuse correlation spectroscopy, and transcranial Doppler for CVR assessment in ISOL patients, and (2) to compare macrovascular and microvascular CVR in ISOL patients and explore its potential for IS/TIA risk stratification. Twenty-seven ISOL patients were recruited. The changes in continuous microvascular and macrovascular hemodynamics upon acetazolamide injection were used to determine CVR. Oxyhemoglobin (HbO2, by near-infrared spectroscopy), microvascular cerebral blood flow (CBF, by diffuse correlation spectroscopy) and CBF velocity (by transcranial Doppler) showed significant increases upon acetazolamide injection in all subjects (P < .03). Only macrovascular CVR (P = .024) and none of the microvascular measures were significantly dependent on the presence of ISOL. In addition, while CBF was significantly correlated with HbO2, neither of these microvascular measures correlated with macrovascular CBF velocity. We demonstrated the simultaneous, continuous, and noninvasive evaluation of CVR at both the microvasculature and macrovasculature. We found that macrovascular CVR response depends on the presence of ISOL, whereas the microvascular CVR did not significantly depend on the ISOL presence, possibly due to the role of collaterals other than those of the circle of Willis. The concurrent microvascular and macrovascular CVR measurement in the ISOL patients might improve future IS/TIA risk assessment. Copyright © 2014 AUR. Published by Elsevier Inc. All rights reserved.

Evaluation of different grades of ginseng using Fourier-transform infrared and two-dimensional infrared correlation spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Yan-ling; Chen, Jian-bo; Lei, Yu; Zhou, Qun; Sun, Su-qin; Noda, Isao

2010-06-01

Ginseng is one of the most widely used herbal medicines which have many kinds of pharmaceutical values. The discrimination of grades of ginseng includes the cultivation types and the growth years herein. To evaluate the different grades of ginseng, the fibrous roots and rhizome roots of ginseng were analyzed by Fourier-transform infrared and two-dimensional infrared correlation spectroscopy in this paper. The fibrous root and rhizome root of ginseng have different content of starch, calcium oxalate and other components. For the fibrous roots of ginseng, mountain cultivation ginseng (MCG), garden cultivation ginseng (GCG) and transplanted cultivation ginseng (TCG) have clear difference in the infrared spectra and second derivative spectra in the range of 1800-400 cm -1, and clearer difference was observed in the range of 1045-1160 and 1410-1730 cm -1 in 2D synchronous correlation spectra. Three kinds of ginseng can be clustered very well by using SIMCA analysis on the basis of PCA as well. For the rhizome roots, the content of calcium oxalate and starch change with growth years in the IR spectra, and some useful procedure can be obtained by the analysis of 2D IR synchronous spectra in the range of 1050-1415 cm -1. Also, ginsengs cultivated in different growth years were clustered perfectly by using SIMCA analysis. The results suggested that different grades of ginseng can be well recognized using the mid-infrared spectroscopy assisted by 2D IR correlation spectroscopy, which provide the macro-fingerprint characteristics of ginseng in different parts and supplied a rapid, effective approach for the evaluation of the quality of ginseng.

Solution structure of the DNA-binding domain of the heat shock transcription factor determined by multidimensional heteronuclear magnetic resonance spectroscopy.

PubMed Central

Damberger, F. F.; Pelton, J. G.; Harrison, C. J.; Nelson, H. C.; Wemmer, D. E.

1994-01-01

The solution structure of the 92-residue DNA-binding domain of the heat shock transcription factor from Kluyveromyces lactis has been determined using multidimensional NMR methods. Three-dimensional (3D) triple resonance, 1H-13C-13C-1H total correlation spectroscopy, and 15N-separated total correlation spectroscopy-heteronuclear multiple quantum correlation experiments were used along with various 2D spectra to make nearly complete assignments for the backbone and side-chain 1H, 15N, and 13C resonances. Five-hundred eighty-three NOE constraints identified in 3D 13C- and 15N-separated NOE spectroscopy (NOESY)-heteronuclear multiple quantum correlation spectra and a 4-dimensional 13C/13C-edited NOESY spectrum, along with 35 phi, 9 chi 1, and 30 hydrogen bond constraints, were used to calculate 30 structures by hybrid distance geometry/stimulated annealing protocol, of which 24 were used for structural comparison. The calculations revealed that a 3-helix bundle packs against a small 4-stranded antiparallel beta-sheet. The backbone RMS deviation (RMSD) for the family of structures was 1.03 +/- 0.19 A with respect to the average structure. The topology is analogous to that of the C-terminal domain of the catabolite gene activator protein and appears to be in the helix-turn-helix family of DNA-binding proteins. The overall fold determined by the NMR data is consistent with recent crystallographic work on this domain (Harrison CJ, Bohm AA, Nelson HCM, 1994, Science 263:224) as evidenced by RMSD between backbone atoms in the NMR and X-ray structures of 1.77 +/- 0.20 A. Several differences were identified some of which may be due to protein-protein interactions in the crystal. PMID:7849597

Multimodality Intracoronary Imaging With Near-Infrared Spectroscopy and Intravascular Ultrasound in Asymptomatic Individuals With High Calcium Scores.

PubMed

Madder, Ryan D; VanOosterhout, Stacie; Klungle, David; Mulder, Abbey; Elmore, Matthew; Decker, Jeffrey M; Langholz, David; Boyden, Thomas F; Parker, Jessica; Muller, James E

2017-10-01

This study sought to determine the frequency of large lipid-rich plaques (LRP) in the coronary arteries of individuals with high coronary artery calcium scores (CACS) and to determine whether the CACS correlates with coronary lipid burden. Combined near-infrared spectroscopy and intravascular ultrasound was performed in 57 vessels in 20 asymptomatic individuals (90% on statins) with no prior history of coronary artery disease who had a screening CACS ≥300 Agatston units. Among 268 10-mm coronary segments, near-infrared spectroscopy images were analyzed for LRP, defined as a bright yellow block on the near-infrared spectroscopy block chemogram. Lipid burden was assessed as the lipid core burden index (LCBI), and large LRP were defined as a maximum LCBI in 4 mm ≥400. Vessel plaque volume was measured by quantitative intravascular ultrasound. Vessel-level CACS significantly correlated with plaque volume by intravascular ultrasound ( r =0.69; P <0.0001) but not with LCBI by near-infrared spectroscopy ( r =0.24; P =0.07). Despite a high CACS, no LRP was detected in 8 (40.0%) subjects. Large LRP having a maximum LCBI in 4 mm ≥400 were infrequent, found in only 5 (25.0%) of 20 subjects and in only 5 (1.9%) of 268 10-mm coronary segments analyzed. Among individuals with a CACS ≥300 Agatston units mostly on statins, CACS correlated with total plaque volume but not LCBI. This observation may have implications on coronary risk among individuals with a high CACS considering that it is coronary LRP, rather than calcification, that underlies the majority of acute coronary events. © 2017 American Heart Association, Inc.

Discrimination of wild-growing and cultivated Lentinus edodes by tri-step infrared spectroscopy

NASA Astrophysics Data System (ADS)

Lin, Haojian; Liu, Gang; Yang, Weimei; An, Ran; Ou, Quanhong

2018-01-01

It's not easy to discriminate dried wild-growing Lentinus edodes (WL) and cultivated Lentinus edodes (CL) by conventional method based on the morphological inspection of fruiting bodies. In this paper, fruiting body samples of WL and CL are discriminated by a tri-step IR spectroscopy method, including Fourier transform infrared (FT-IR) spectroscopy, second derivatives infrared (SD-IR) spectroscopy and two-dimensional correlation infrared (2D-IR) spectroscopy under thermal perturbation. The results show that the FT-IR spectra of WL and CL are similar in holistic spectral profile. More significant differences are exhibited in their SD-IR spectra in the range of 1700 - 900 cm-1. Furthermore, more evident differences have been observed in their synchronous 2D-IR spectra in the range of 2970 - 2900, 1678 - 1390, 1250 -1104 and 1090 - 1030 cm-1. The CL has thirteen auto-peaks at 2958, 2921, 1649, 1563, 1450, 1218, 1192, 1161, 1140, 1110, 1082, 1065 and 1047 cm-1, in which the four strongest auto-peaks are at 2921, 1563, 1192 and 1082 cm-1. The WL shows fifteen auto-peaks at 2960, 2937, 2921, 1650, 1615, 1555, 1458, 1219, 1190, 1138, 1111, 1084, 1068, 1048 and 1033 cm-1, in which the four strongest auto-peaks are at 2921, 1650, 1190 and 1068 cm-1. This study shows the potential of FT-IR spectroscopy and 2D correlation analysis in a simple and quick distinction of wild-growing and cultivated mushrooms.

Longitudinal evaluation of patients with oral potentially malignant disorders using optical imaging and spectroscopy

NASA Astrophysics Data System (ADS)

Schwarz, Richard A.; Pierce, Mark C.; Mondrik, Sharon; Gao, Wen; Quinn, Mary K.; Bhattar, Vijayashree; Williams, Michelle D.; Vigneswaran, Nadarajah; Gillenwater, Ann M.; Richards-Kortum, Rebecca

2012-02-01

Dysplastic and cancerous alterations in oral tissue can be detected noninvasively in vivo using optical techniques including autofluorescence imaging, high-resolution imaging, and spectroscopy. Interim results are presented from a longitudinal study in which optical imaging and spectroscopy were used to evaluate the progression of lesions over time in patients at high risk for development of oral cancer. Over 100 patients with oral potentially malignant disorders have been enrolled in the study to date. Areas of concern in the oral cavity are measured using widefield autofluorescence imaging and depth-sensitive optical spectroscopy during successive clinical visits. Autofluorescence intensity patterns and autofluorescence spectra are tracked over time and correlated with clinical observations. Patients whose lesions progress and who undergo surgery are also measured in the operating room immediately prior to surgery using autofluorescence imaging and spectroscopy, with the addition of intraoperative high-resolution imaging to characterize nuclear size, nuclear crowding, and tissue architecture at selected sites. Optical measurements are compared to histopathology results from biopsies and surgical specimens collected from the measured sites. Autofluorescence imaging and spectroscopy measurements are continued during post-surgery followup visits. We examined correlations between clinical impression and optical classification over time with an average followup period of 4 months. The data collected to date suggest that multimodal optical techniques may aid in noninvasive monitoring of the progression of oral premalignant lesions, biopsy site selection, and accurate delineation of lesion extent during surgery.

Source Determination of Red Gel Pen Inks using Raman Spectroscopy and Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy combined with Pearson's Product Moment Correlation Coefficients and Principal Component Analysis.

PubMed

Mohamad Asri, Muhammad Naeim; Mat Desa, Wan Nur Syuhaila; Ismail, Dzulkiflee

2018-01-01

The potential combination of two nondestructive techniques, that is, Raman spectroscopy (RS) and attenuated total reflectance-fourier transform infrared (ATR-FTIR) spectroscopy with Pearson's product moment correlation (PPMC) coefficient (r) and principal component analysis (PCA) to determine the actual source of red gel pen ink used to write a simulated threatening note, was examined. Eighteen (18) red gel pens purchased from Japan and Malaysia from November to December 2014 where one of the pens was used to write a simulated threatening note were analyzed using RS and ATR-FTIR spectroscopy, respectively. The spectra of all the red gel pen inks including the ink deposited on the simulated threatening note gathered from the RS and ATR-FTIR analyses were subjected to PPMC coefficient (r) calculation and principal component analysis (PCA). The coefficients r = 0.9985 and r = 0.9912 for pairwise combination of RS and ATR-FTIR spectra respectively and similarities in terms of PC1 and PC2 scores of one of the inks to the ink deposited on the simulated threatening note substantiated the feasibility of combining RS and ATR-FTIR spectroscopy with PPMC coefficient (r) and PCA for successful source determination of red gel pen inks. The development of pigment spectral library had allowed the ink deposited on the threatening note to be identified as XSL Poppy Red (CI Pigment Red 112). © 2017 American Academy of Forensic Sciences.

Functional Near-Infrared Spectroscopy for the Assessment of Speech Related Tasks

ERIC Educational Resources Information Center

Dieler, A. C.; Tupak, S. V.; Fallgatter, A. J.

2012-01-01

Over the past years functional near-infrared spectroscopy (fNIRS) has substantially contributed to the understanding of language and its neural correlates. In contrast to other imaging techniques, fNIRS is well suited to study language function in healthy and psychiatric populations due to its cheap and easy application in a quiet and natural…

Shelf life study of egg albumin in pasteurized and non-pasteurized eggs using visible-near infrared spectroscopy

USDA-ARS?s Scientific Manuscript database

A twelve week shelf life study was conducted on the egg albumen from both pasteurized and non-pasteurized shell eggs using visible-near infrared spectroscopy. The goal of the study was to correlate the chemical changes detected in the spectra to the measurement of Haugh units (measure of interior eg...

Convective-diffusion-based fluorescence correlation spectroscopy for detection of a trace amount of E. coli in water.

PubMed

Qing, De-Kui; Mengüç, M Pinar; Payne, Fred A; Danao, Mary-Grace C

2003-06-01

Fluorescence correlation spectroscopy (FCS) is adapted for a new procedure to detect trace amounts of Escherichia coli in water. The present concept is based on convective diffusion rather than Brownian diffusion and employs confocal microscopy as in traditional FCS. With this system it is possible to detect concentrations as small as 1.5 x 10(5) E. coli per milliliter (2.5 x 10(-16) M). This concentration corresponds to an approximately 1.0-nM level of Rhodamine 6G dyes. A detailed analysis of the optical system is presented, and further improvements for the procedure are discussed.

Investigation of human serum albumin (HSA) binding specificity of certain photosensitizers related to pyropheophorbide-a and bacteriopurpurinimide by circular dichroism spectroscopy and its correlation with in vivo photosensitizing efficacy.

PubMed

Chen, Yihui; Miclea, Razvan; Srikrishnan, Thamarapu; Balasubramanian, Sathyamangalam; Dougherty, Thomas J; Pandey, Ravindra K

2005-07-01

A series of pyropheophorbide-a and bacteriopurpurinimides were investigated to understand the correlation between HSA (site II) binding affinity and in vivo photosensitizing activity. In our study, photosensitizers that bound to site II of HSA produced a significant difference in the circular dichroism spectra of the corresponding complexes, especially at Soret band region of the photosensitizers. Our results suggest that CD spectroscopy of the photosensitizer-HSA complexes could be a valuable tool in screening new photosensitizers before evaluating them for in vivo efficacy.

Recent Developments in Fluorescence Correlation Spectroscopy for Diffusion Measurements in Planar Lipid Membranes

PubMed Central

Macháň, Radek; Hof, Martin

2010-01-01

Fluorescence correlation spectroscopy (FCS) is a single molecule technique used mainly for determination of mobility and local concentration of molecules. This review describes the specific problems of FCS in planar systems and reviews the state of the art experimental approaches such as 2-focus, Z-scan or scanning FCS, which overcome most of the artefacts and limitations of standard FCS. We focus on diffusion measurements of lipids and proteins in planar lipid membranes and review the contributions of FCS to elucidating membrane dynamics and the factors influencing it, such as membrane composition, ionic strength, presence of membrane proteins or frictional coupling with solid support. PMID:20386647

X-ray photoelectron spectroscopy study of radiofrequency sputtered chromium bromide, molybdenum disilicide, and molybdenum disulfide coatings and their friction properties

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Brainard, W. A.

1977-01-01

Radiofrequency sputtered coatings of CRB2, MOSI2, and MOS2 were examined by X-ray photoelectron spectroscopy. The effects of sputtering target history, deposition time, RF power level, and substrate bias on film composition were studied. Friction tests were run on RF sputtered surfaces of 440-C steel to correlate XPS data with lubricating properties. Significant deviations from stoichiometry and high oxide levels for all three compounds were related to target outgassing. The effect of biasing on these two factors depended on the compound. Improved stoichiometry correlated well with good friction and wear properties.

Improvement of photon correlation spectroscopy method for measuring nanoparticle size by using attenuated total reflectance.

PubMed

Krishtop, Victor; Doronin, Ivan; Okishev, Konstantin

2012-11-05

Photon correlation spectroscopy is an effective method for measuring nanoparticle sizes and has several advantages over alternative methods. However, this method suffers from a disadvantage in that its measuring accuracy reduces in the presence of convective flows of fluid containing nanoparticles. In this paper, we propose a scheme based on attenuated total reflectance in order to reduce the influence of convection currents. The autocorrelation function for the light-scattering intensity was found for this case, and it was shown that this method afforded a significant decrease in the time required to measure the particle sizes and an increase in the measuring accuracy.

Employing NMR Spectroscopy To Evaluate Transmission of Electronic Effects in 4-Substituted Chalcones

NASA Astrophysics Data System (ADS)

Wachter-Jurcsak, Nanette; Zamani, Hossein

1999-05-01

Described is an organic synthesis experiment that demonstrates the electronic transmission by substituents. The effect of substitution at the para-position of the styryl ring of 1,3-diphenyl-2-propenones (chalcones) by typical electron-donating or -accepting groups can be observed by proton and carbon-13 NMR spectroscopy. A linear correlation is observed when the differences in chemical shift measurements for H are plotted against the corresponding Hammett substituent constant values. Good correlation between carbon-13 chemical shifts of the alpha carbon are also observed. The syntheses of the 4-substituted chalcones is presented as well as a brief discussion of the theory.

On the use of band-target entropy minimization to simplify the interpretation of two-dimensional correlation spectroscopy.

PubMed

Widjaja, Effendi; Tan, Boon Hong; Garland, Marc

2006-03-01

Two-dimensional (2D) correlation spectroscopy has been extensively applied to analyze various vibrational spectroscopic data, especially infrared and Raman. However, when it is applied to real-world experimental data, which often contains various imperfections (such as noise interference, baseline fluctuations, and band-shifting) and highly overlapping bands, many artifacts and misleading features in synchronous and asynchronous maps will emerge, and this will lead to difficulties with interpretation. Therefore, an approach that counters many artifacts and therefore leads to simplified interpretation of 2D correlation analysis is certainly useful. In the present contribution, band-target entropy minimization (BTEM) is employed as a spectral pretreatment to handle many of the artifact problems before the application of 2D correlation analysis. BTEM is employed to elucidate the pure component spectra of mixtures and their corresponding concentration profiles. Two alternate forms of analysis result. In the first, the normally vxv problem is converted to an equivalent nvxnv problem, where n represents the number of species present. In the second, the pure component spectra are transformed into simple distributions, and an equivalent and less computationally intensive nv'xnv' problem results (v'

Near-infrared spectroscopy assessment of cerebral oxygen metabolism in the developing premature brain.

PubMed

Roche-Labarbe, Nadège; Fenoglio, Angela; Aggarwal, Alpna; Dehaes, Mathieu; Carp, Stefan A; Franceschini, Maria Angela; Grant, Patricia Ellen

2012-03-01

Little is known about cerebral blood flow, cerebral blood volume (CBV), oxygenation, and oxygen consumption in the premature newborn brain. We combined quantitative frequency-domain near-infrared spectroscopy measures of cerebral hemoglobin oxygenation (SO(2)) and CBV with diffusion correlation spectroscopy measures of cerebral blood flow index (BF(ix)) to determine the relationship between these measures, gestational age at birth (GA), and chronological age. We followed 56 neonates of various GA once a week during their hospital stay. We provide absolute values of SO(2) and CBV, relative values of BF(ix), and relative cerebral metabolic rate of oxygen (rCMRO(2)) as a function of postmenstrual age (PMA) and chronological age for four GA groups. SO(2) correlates with chronological age (r=-0.54, P value ≤0.001) but not with PMA (r=-0.07), whereas BF(ix) and rCMRO(2) correlate better with PMA (r=0.37 and 0.43, respectively, P value ≤0.001). Relative CMRO2 during the first month of life is lower when GA is lower. Blood flow index and rCMRO(2) are more accurate biomarkers of the brain development than SO(2) in the premature newborns.

Low-temperature thermal reduction of graphene oxide: In situ correlative structural, thermal desorption, and electrical transport measurements

NASA Astrophysics Data System (ADS)

Lipatov, Alexey; Guinel, Maxime J.-F.; Muratov, Dmitry S.; Vanyushin, Vladislav O.; Wilson, Peter M.; Kolmakov, Andrei; Sinitskii, Alexander

2018-01-01

Elucidation of the structural transformations in graphene oxide (GO) upon reduction remains an active and important area of research. We report the results of in situ heating experiments, during which electrical, mass spectrometry, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy (TEM) measurements were carried out correlatively. The simultaneous electrical and temperature programmed desorption measurements allowed us to correlate the onset of the increase in the electrical conductivity of GO by five orders of magnitude at about 150 °C with the maxima of the rates of desorption of H2O, CO, and CO2. Interestingly, this large conductivity change happens at an intermediate level of the reduction of GO, which likely corresponds to the point when the graphitic domains become large enough to enable percolative electronic transport. We demonstrate that the gas desorption is intimately related to (i) the changes in the chemical structure of GO detected by XPS and Raman spectroscopy and (ii) the formation of nanoscopic holes in GO sheets revealed by TEM. These in situ observations provide a better understanding of the mechanism of the GO thermal reduction.

2D FTIR correlation spectroscopy and EPR analysis of Urtica dioica leaves from areas of different environmental pollution

NASA Astrophysics Data System (ADS)

Moskal, Paulina; Wesełucha-Birczyńska, Aleksandra; Łabanowska, Maria; Kurdziel, Magdalena; Filek, Maria

2018-01-01

Leaves of Urtica dioica collected from two areas of different environmental pollution were analysed by fourier transform infrared spectroscopy (FTIR) and electron paramagnetic resonance (EPR) spectroscopy. Analysis of FTIR spectra allows to describe main component of plant like proteins, lipids and carbohydrates. Although the FTIR spectra of plants from these two geographical locations of different environmental pollution appear to be relatively similar, 2D correlation shows completely different patterns. Synchronous and asynchronous correlation maps showed sequences of changes occurring during development of plant, manly in Amide I and Amide II, lignin, lipids and cellulose. In addition, 2D analysis revealed another sequence of changes as the function of plant growth depending on the degree of the environmental pollution. Two various kinds of paramagnetic species, transition metal ions (Mn(II), Fe(III)) and stable organic radicals (chlorophyll, semiquinone, tyrosyl and carbon centered) were found in leaves of nettle collected at different stages of development and growing in clean and polluted environment. In plants growing in polluted area the injuries of protein molecules bonding metal ions and the disturbances of photosynthesis and redox equilibrium in cells, as well as instability of polysaccharide structure of cell walls were observed.

Iron in typical and atypical parkinsonism - Mössbauer spectroscopy and MRI studies

NASA Astrophysics Data System (ADS)

Kuliński, R.; Bauminger, E. R.; Friedman, A.; Duda, P.; Gałązka-Friedman, J.

2016-12-01

Iron may play important role in neurodegeneration. The results of comparative studies of human brain areas (control and pathological) performed by Mössbauer spectroscopy (MS) and magnetic resonance imaging (MRI) techniques are presented. Mössbauer spectroscopy demonstrated a higher concentration of iron in atypical parkinsonism (progressive supranuclear palsy PSP) in the brain areas Substantia Nigra (SN) and Globus Pallidus (GP) involved in this pathological process, compared to control, while the concentration of iron in pathological tissues in typical parkinsonism (Parkinson's disease - PD) did not differ from that in control. These results were compared with the changes in 1/T1 and 1/T2 (T1 and T2 being the relaxation times determined by MRI). A good linear correlation curve was found between the concentration of iron as determined by MS in different areas of control human brains and between 1/T1 and 1/T2. Whereas the finding in PSP-GP (the brain area involved in PSP) also fitted to such a correlation, this was not so for the correlation between pathological SN - the brain area involved in both diseases - and 1/T2, indicating a dependence of T2 on other factors than just the concentration of iron.

A time-correlation function approach to nuclear dynamical effects in X-ray spectroscopy

NASA Astrophysics Data System (ADS)

Karsten, Sven; Bokarev, Sergey I.; Aziz, Saadullah G.; Ivanov, Sergei D.; Kühn, Oliver

2017-06-01

Modern X-ray spectroscopy has proven itself as a robust tool for probing the electronic structure of atoms in complex environments. Despite working on energy scales that are much larger than those corresponding to nuclear motions, taking nuclear dynamics and the associated nuclear correlations into account may be of importance for X-ray spectroscopy. Recently, we have developed an efficient protocol to account for nuclear dynamics in X-ray absorption and resonant inelastic X-ray scattering spectra [Karsten et al., J. Phys. Chem. Lett. 8, 992 (2017)], based on ground state molecular dynamics accompanied with state-of-the-art calculations of electronic excitation energies and transition dipoles. Here, we present an alternative derivation of the formalism and elaborate on the developed simulation protocol using gas phase and bulk water as examples. The specific spectroscopic features stemming from the nuclear motions are analyzed and traced down to the dynamics of electronic energy gaps and transition dipole correlation functions. The observed tendencies are explained on the basis of a simple harmonic model, and the involved approximations are discussed. The method represents a step forward over the conventional approaches that treat the system in full complexity and provides a reasonable starting point for further improvements.

A time-correlation function approach to nuclear dynamical effects in X-ray spectroscopy.

PubMed

Karsten, Sven; Bokarev, Sergey I; Aziz, Saadullah G; Ivanov, Sergei D; Kühn, Oliver

2017-06-14

Modern X-ray spectroscopy has proven itself as a robust tool for probing the electronic structure of atoms in complex environments. Despite working on energy scales that are much larger than those corresponding to nuclear motions, taking nuclear dynamics and the associated nuclear correlations into account may be of importance for X-ray spectroscopy. Recently, we have developed an efficient protocol to account for nuclear dynamics in X-ray absorption and resonant inelastic X-ray scattering spectra [Karsten et al., J. Phys. Chem. Lett. 8, 992 (2017)], based on ground state molecular dynamics accompanied with state-of-the-art calculations of electronic excitation energies and transition dipoles. Here, we present an alternative derivation of the formalism and elaborate on the developed simulation protocol using gas phase and bulk water as examples. The specific spectroscopic features stemming from the nuclear motions are analyzed and traced down to the dynamics of electronic energy gaps and transition dipole correlation functions. The observed tendencies are explained on the basis of a simple harmonic model, and the involved approximations are discussed. The method represents a step forward over the conventional approaches that treat the system in full complexity and provides a reasonable starting point for further improvements.

Rapid and direct screening of H:C ratio in Archean kerogen via microRaman Spectroscopy

NASA Astrophysics Data System (ADS)

Ferralis, N.; Matys, E. D.; Allwood, A.; Knoll, A. H.; Summons, R. E.

2015-12-01

Rapid evaluation of the preservation of biosignatures in ancient kerogens is essential for the evaluation of the usability of Earth analogues as proxies of Martian geological materials. No single, non-destructive and non-invasive technique currently exists to rapidly determine such state of preservation of the organic matter in relation to its geological and mineral environment. Due to its non-invasive nature, microRaman spectroscopy is emerging as a candidate technique for the qualitative determination maturity of organic matter, by correlating Raman spectral features and aromatic carbon cluster size. Here we will present a novel quantitative method in which before-neglected Raman spectral features are correlated directly and with excellent accuracy with the H:C ratio. In addition to providing a chemical justification of the found direct correlation, we will show its applicability and predictive capabilities in evaluating H:C in Archean kerogens. This novel method opens new opportunities for the use of Raman spectroscopy and mapping. This includes the non-invasively determination of kerogen preservation and microscale chemical diversity within a particular Earth analogue, to be potentially extended to evaluate Raman spectra acquired directly on Mars.

Intracellular localization and dynamics of Hypericin loaded PLLA nanocarriers by image correlation spectroscopy.

PubMed

Penjweini, Rozhin; Deville, Sarah; D'Olieslaeger, Lien; Berden, Mandy; Ameloot, Marcel; Ethirajan, Anitha

2015-11-28

The study of cell-nanoparticle interactions is an important aspect for understanding drug delivery using nanocarriers. In this regard, advances in fluorescence based microscopy are useful for the investigation of temporal and spatial behavior of nanoparticles (NPs) within the intracellular environment. In this work, we focus on the delivery of the naturally-occurring hydrophobic photosensitizer Hypericin in human lung carcinoma A549 cells by using biodegradable poly L-lactic acid NPs. For the first time, Hypericin containing NPs are prepared by combining the miniemulsion technique with the solvent evaporation method. This approach yields an efficient loading of the NPs with Hypericin and allows for additional cargo molecules. To monitor the release of Hypercin from the NPs, an additional fluorescent lipophilic dye Coumarin-6 is incorporated in the NPs. Temporal and spatiotemporal image correlation spectroscopy is used to determine the fate of the NPs carrying the potential cargo. Both directed and non-directed motions are detected. By using image cross-correlation spectroscopy and specific fluorescent labeling of endosomes, lysosomes and mitochondria, the dynamics of the cargo loaded NPs in association with the organelles is studied. Copyright © 2015 Elsevier B.V. All rights reserved.

Quantitative analysis of bayberry juice acidity based on visible and near-infrared spectroscopy

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

Shao Yongni; He Yong; Mao Jingyuan

Visible and near-infrared (Vis/NIR) reflectance spectroscopy has been investigated for its ability to nondestructively detect acidity in bayberry juice. What we believe to be a new, better mathematic model is put forward, which we have named principal component analysis-stepwise regression analysis-backpropagation neural network (PCA-SRA-BPNN), to build a correlation between the spectral reflectivity data and the acidity of bayberry juice. In this model, the optimum network parameters,such as the number of input nodes, hidden nodes, learning rate, and momentum, are chosen by the value of root-mean-square (rms) error. The results show that its prediction statistical parameters are correlation coefficient (r) ofmore » 0.9451 and root-mean-square error of prediction(RMSEP) of 0.1168. Partial least-squares (PLS) regression is also established to compare with this model. Before doing this, the influences of various spectral pretreatments (standard normal variate, multiplicative scatter correction, S. Golay first derivative, and wavelet package transform) are compared. The PLS approach with wavelet package transform preprocessing spectra is found to provide the best results, and its prediction statistical parameters are correlation coefficient (r) of 0.9061 and RMSEP of 0.1564. Hence, these two models are both desirable to analyze the data from Vis/NIR spectroscopy and to solve the problem of the acidity prediction of bayberry juice. This supplies basal research to ultimately realize the online measurements of the juice's internal quality through this Vis/NIR spectroscopy technique.« less

Correlation between bulk- and surface chemistry of Cr-tanned leather and the release of Cr(III) and Cr(VI).

PubMed

Hedberg, Yolanda S; Lidén, Carola; Odnevall Wallinder, Inger

2014-09-15

About 1-3% of the adult general population in Europe is allergic to chromium (Cr). The assessment of the potential release of Cr(III) and Cr(VI) from leather is hence important from a human health and environmental risk perspective. The Cr(VI) content in leather was recently restricted in the European Union. The aim of this study was to assess possible correlations between the bulk and surface chemistry of leather, released Cr(III) and Cr(VI), and capacities of co-released leather specific species to reduce and complex released Cr. Four differently tanned leathers were characterized by scanning electron microscopy with energy dispersive spectroscopy, X-ray photoelectron spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and the diphenylcarbazide colorimetric method. Their characteristics were compared with results on Cr(III) and Cr(VI) release into artificial sweat (ASW, pH<6.5) and phosphate buffer (PB, pH 7.5-8.0), measured by means of spectrophotometry and atomic absorption spectroscopy. Co-released leather-specific species were shown to reduce Cr(VI), both in ASW and in PB. Their reduction capacities correlated with findings of the surface content of Cr and of released Cr. Leather samples without this capacity, and with less aromatic surface groups visible by ATR-FTIR, revealed Cr(VI) both at the surface and in solution (PB). Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

Integration of 3D 1H-magnetic resonance spectroscopy data into neuronavigation systems for tumor biopsies

NASA Astrophysics Data System (ADS)

Kanberoglu, Berkay; Moore, Nina Z.; Frakes, David; Karam, Lina J.; Debbins, Josef P.; Preul, Mark C.

2013-03-01

Many important applications in clinical medicine can benefit from the fusion of spectroscopy data with anatomical images. For example, the correlation of metabolite profiles with specific regions of interest in anatomical tumor images can be useful in characterizing and treating heterogeneous tumors that appear structurally homogeneous. Such applications can build on the correlation of data from in-vivo Proton Magnetic Resonance Spectroscopy Imaging (1HMRSI) with data from genetic and ex-vivo Nuclear Magnetic Resonance spectroscopy. To establish that correlation, tissue samples must be neurosurgically extracted from specifically identified locations with high accuracy. Toward that end, this paper presents new neuronavigation technology that enhances current clinical capabilities in the context of neurosurgical planning and execution. The proposed methods improve upon the current state-of-the-art in neuronavigation through the use of detailed three dimensional (3D) 1H-MRSI data. MRSI spectra are processed and analyzed, and specific voxels are selected based on their chemical contents. 3D neuronavigation overlays are then generated and applied to anatomical image data in the operating room. Without such technology, neurosurgeons must rely on memory and other qualitative resources alone for guidance in accessing specific MRSI-identified voxels. In contrast, MRSI-based overlays provide quantitative visual cues and location information during neurosurgery. The proposed methods enable a progressive new form of online MRSI-guided neuronavigation that we demonstrate in this study through phantom validation and clinical application.

Detection of Nitrogen Content in Rubber Leaves Using Near-Infrared (NIR) Spectroscopy with Correlation-Based Successive Projections Algorithm (SPA).

PubMed

Tang, Rongnian; Chen, Xupeng; Li, Chuang

2018-05-01

Near-infrared spectroscopy is an efficient, low-cost technology that has potential as an accurate method in detecting the nitrogen content of natural rubber leaves. Successive projections algorithm (SPA) is a widely used variable selection method for multivariate calibration, which uses projection operations to select a variable subset with minimum multi-collinearity. However, due to the fluctuation of correlation between variables, high collinearity may still exist in non-adjacent variables of subset obtained by basic SPA. Based on analysis to the correlation matrix of the spectra data, this paper proposed a correlation-based SPA (CB-SPA) to apply the successive projections algorithm in regions with consistent correlation. The result shows that CB-SPA can select variable subsets with more valuable variables and less multi-collinearity. Meanwhile, models established by the CB-SPA subset outperform basic SPA subsets in predicting nitrogen content in terms of both cross-validation and external prediction. Moreover, CB-SPA is assured to be more efficient, for the time cost in its selection procedure is one-twelfth that of the basic SPA.

The Correlation Between Dislocations and Vacancy Defects Using Positron Annihilation Spectroscopy

NASA Astrophysics Data System (ADS)

Pang, Jinbiao; Li, Hui; Zhou, Kai; Wang, Zhu

2012-07-01

An analysis program for positron annihilation lifetime spectra is only applicable to isolated defects, but is of no use in the presence of defective correlations. Such limitations have long caused problems for positron researchers in their studies of complicated defective systems. In order to solve this problem, we aim to take a semiconductor material, for example, to achieve a credible average lifetime of single crystal silicon under plastic deformation at different temperatures using positron life time spectroscopy. By establishing reasonable positron trapping models with defective correlations and sorting out four lifetime components with multiple parameters, as well as their respective intensities, information is obtained on the positron trapping centers, such as the positron trapping rates of defects, the density of the dislocation lines and correlation between the dislocation lines, and the vacancy defects, by fitting with the average lifetime with the aid of Matlab software. These results give strong grounds for the existence of dislocation-vacancy correlation in plastically deformed silicon, and lay a theoretical foundation for the analysis of positron lifetime spectra when the positron trapping model involves dislocation-related defects.

[Identification of impurity peaks in the HPLC chromatogram by LC-MS and two-dimensional chromatographic correlation spectroscopy].

PubMed

Chen, Zhen-Zhen; Zhang, Dou-Sheng; Wang, Nan; Feng, Fang; Hu, Chang-Qin

2012-04-01

A novel qualitative analytical method by using two-dimensional chromatographic correlation spectroscopy techniques for recognizing impurity peaks of HPLC methods of quality control and LC-MS chromatographic system was established. The structures of major degradation products of ceftizoxime and cefdinir were identified by LC-MS and MassWorks application; the standard chromatographic and spectral data of the degradation impurities were obtained by high-performance liquid chromatography with diode array detection. The impurity peaks of two-dimensional chromatography were matched by comparison of spectra and calculating correlation coefficients. Peaks in chromatography can be identified accurately and rapidly in different chromatographic systems such as column and mobile phase changed. The method provides a new way and thought to identify the peaks in quality control of impurities without reference impurity substances.

Comparison of methods applied in photoinduced transient spectroscopy to determining the defect center parameters: The correlation procedure and the signal analysis based on inverse Laplace transformation

NASA Astrophysics Data System (ADS)

Suproniuk, M.; Pawłowski, M.; Wierzbowski, M.; Majda-Zdancewicz, E.; Pawłowski, Ma.

2018-04-01

The procedure for determination of trap parameters by photo-induced transient spectroscopy is based on the Arrhenius plot that illustrates a thermal dependence of the emission rate. In this paper, we show that the Arrhenius plot obtained by the correlation method is shifted toward lower temperatures as compared to the one obtained with the inverse Laplace transformation. This shift is caused by the model adequacy error of the correlation method and introduces errors to a calculation procedure of defect center parameters. The effect is exemplified by comparing the results of the determination of trap parameters with both methods based on photocurrent transients for defect centers observed in tin-doped neutron-irradiated silicon crystals and in gallium arsenide grown with the Vertical Gradient Freeze method.

The CAT-ACT Beamline at ANKA: A new high energy X-ray spectroscopy facility for CATalysis and ACTinide research

NASA Astrophysics Data System (ADS)

Zimina, A.; Dardenne, K.; Denecke, M. A.; Grunwaldt, J. D.; Huttel, E.; Lichtenberg, H.; Mangold, S.; Pruessmann, T.; Rothe, J.; Steininger, R.; Vitova, T.

2016-05-01

A new hard X-ray beamline for CATalysis and ACTinide research has been built at the synchrotron radiation facility ANKA. The beamline design is dedicated to X-ray spectroscopy, including ‘flux hungry’ photon-in/photon-out and correlative techniques with a special infrastructure for radionuclide and catalysis research. The CAT-ACT beamline will help serve the growing need for high flux/hard X-ray spectroscopy in these communities. The design, the first spectra and the current status of this project are reported.

Density Functional Calculations for Prediction of 57Fe Mössbauer Isomer Shifts and Quadrupole Splittings in β-Diketiminate Complexes

PubMed Central

2017-01-01

The relative ease of Mössbauer spectroscopy and of density functional theory (DFT) calculations encourages the use of Mössbauer parameters as a validation method for calculations, and the use of calculations as a double check on crystallographic structures. A number of studies have proposed correlations between the computationally determined electron density at the iron nucleus and the observed isomer shift, but deviations from these correlations in low-valent iron β-diketiminate complexes encouraged us to determine a new correlation for these compounds. The use of B3LYP/def2-TZVP in the ORCA platform provides an excellent balance of accuracy and speed. We provide here not only this new correlation and a clear guide to its use but also a systematic analysis of the limitations of this approach. We also highlight the impact of crystallographic inaccuracies, DFT model truncation, and spin states, with intent to assist experimentalists to use Mössbauer spectroscopy and calculations together. PMID:28691111

Analyzing Baryon Acoustic Oscillations in Sparse Spectroscopic Samples via Cross-Correlation with Dense Photometry

NASA Astrophysics Data System (ADS)

Patej, Anna; Eisenstein, Daniel J.

2018-04-01

We develop a formalism for measuring the cosmological distance scale from baryon acoustic oscillations (BAO) using the cross-correlation of a sparse redshift survey with a denser photometric sample. This reduces the shot noise that would otherwise affect the auto-correlation of the sparse spectroscopic map. As a proof of principle, we make the first on-sky application of this method to a sparse sample defined as the z > 0.6 tail of the Sloan Digital Sky Survey's (SDSS) BOSS/CMASS sample of galaxies and a dense photometric sample from SDSS DR9. We find a 2.8σ preference for the BAO peak in the cross-correlation at an effective z = 0.64, from which we measure the angular diameter distance DM(z = 0.64) = (2418 ± 73 Mpc)(rs/rs, fid). Accordingly, we expect that using this method to combine sparse spectroscopy with the deep, high quality imaging that is just now becoming available will enable higher precision BAO measurements than possible with the spectroscopy alone.

A correlative study on data from pork carcass and processed meat (Bauernspeck) for automatic estimation of chemical parameters by means of near-infrared spectroscopy.

PubMed

Boschetti, Lucio; Ottavian, Matteo; Facco, Pierantonio; Barolo, Massimiliano; Serva, Lorenzo; Balzan, Stefania; Novelli, Enrico

2013-11-01

The use of near-infrared spectroscopy (NIRS) is proposed in this study for the characterization of the quality parameters of a smoked and dry-cured meat product known as Bauernspeck (originally from Northern Italy), as well as of some technological traits of the pork carcass used for its manufacturing. In particular, NIRS is shown to successfully estimate several key quality parameters (including water activity, moisture, dry matter, ash and protein content), suggesting its suitability for real time application in replacement of expensive and time consuming chemical analysis. Furthermore, a correlative approach based on canonical correlation analysis was used to investigate the spectral regions that are mostly correlated to the characteristics of interest. The identification of these regions, which can be linked to the absorbance of the main functional chemical groups, is intended to provide a better understanding of the chemical structure of the substrate under investigation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Real-time autocorrelator for fluorescence correlation spectroscopy based on graphical-processor-unit architecture: method, implementation, and comparative studies

NASA Astrophysics Data System (ADS)

Laracuente, Nicholas; Grossman, Carl

2013-03-01

We developed an algorithm and software to calculate autocorrelation functions from real-time photon-counting data using the fast, parallel capabilities of graphical processor units (GPUs). Recent developments in hardware and software have allowed for general purpose computing with inexpensive GPU hardware. These devices are more suited for emulating hardware autocorrelators than traditional CPU-based software applications by emphasizing parallel throughput over sequential speed. Incoming data are binned in a standard multi-tau scheme with configurable points-per-bin size and are mapped into a GPU memory pattern to reduce time-expensive memory access. Applications include dynamic light scattering (DLS) and fluorescence correlation spectroscopy (FCS) experiments. We ran the software on a 64-core graphics pci card in a 3.2 GHz Intel i5 CPU based computer running Linux. FCS measurements were made on Alexa-546 and Texas Red dyes in a standard buffer (PBS). Software correlations were compared to hardware correlator measurements on the same signals. Supported by HHMI and Swarthmore College

Insight into resolution enhancement in generalized two-dimensional correlation spectroscopy.

PubMed

Ma, Lu; Sikirzhytski, Vitali; Hong, Zhenmin; Lednev, Igor K; Asher, Sanford A

2013-03-01

Generalized two-dimensional correlation spectroscopy (2D-COS) can be used to enhance spectral resolution in order to help differentiate highly overlapped spectral bands. Despite the numerous extensive 2D-COS investigations, the origin of the 2D spectral resolution enhancement mechanism(s) is not completely understood. In the work here, we studied the 2D-COS of simulated spectra in order to develop new insights into the dependence of 2D-COS spectral features on the overlapping band separations, their intensities and bandwidths, and their band intensity change rates. We found that the features in the 2D-COS maps that are derived from overlapping bands were determined by the spectral normalized half-intensities and the total intensity changes of the correlated bands. We identified the conditions required to resolve overlapping bands. In particular, 2D-COS peak resolution requires that the normalized half-intensities of a correlating band have amplitudes between the maxima and minima of the normalized half-intensities of the overlapping bands.

Insight into Resolution Enhancement in Generalized Two-Dimensional Correlation Spectroscopy

PubMed Central

Ma, Lu; Sikirzhytski, Vitali; Hong, Zhenmin; Lednev, Igor K.; Asher, Sanford A.

2014-01-01

Generalized two-dimensional correlation spectroscopy (2D COS) can be used to enhance spectral resolution in order to help differentiate highly overlapped spectral bands. Despite the numerous extensive 2D COS investigations, the origin of the 2D spectral resolution enhancement mechanism(s) are not completely understood. In the work here we studied the 2D COS of simulated spectra in order to develop new insights into the dependence of the 2D COS spectral features on the overlapping band separations, their intensities and bandwidths, and their band intensity change rates. We find that the features in the 2D COS maps that derive from overlapping bands are determined by the spectral normalized half-intensities and the total intensity changes of the correlated bands. We identify the conditions required to resolve overlapping bands. In particular, 2D COS peak resolution requires that the normalized half-intensities of a correlating band have amplitudes between the maxima and minima of the normalized half-intensities of the overlapping bands. PMID:23452492

Prediction of individual milk proteins including free amino acids in bovine milk using mid-infrared spectroscopy and their correlations with milk processing characteristics.

PubMed

McDermott, A; Visentin, G; De Marchi, M; Berry, D P; Fenelon, M A; O'Connor, P M; Kenny, O A; McParland, S

2016-04-01

The aim of this study was to evaluate the effectiveness of mid-infrared spectroscopy in predicting milk protein and free amino acid (FAA) composition in bovine milk. Milk samples were collected from 7 Irish research herds and represented cows from a range of breeds, parities, and stages of lactation. Mid-infrared spectral data in the range of 900 to 5,000 cm(-1) were available for 730 milk samples; gold standard methods were used to quantify individual protein fractions and FAA of these samples with a view to predicting these gold standard protein fractions and FAA levels with available mid-infrared spectroscopy data. Separate prediction equations were developed for each trait using partial least squares regression; accuracy of prediction was assessed using both cross validation on a calibration data set (n=400 to 591 samples) and external validation on an independent data set (n=143 to 294 samples). The accuracy of prediction in external validation was the same irrespective of whether undertaken on the entire external validation data set or just within the Holstein-Friesian breed. The strongest coefficient of correlation obtained for protein fractions in external validation was 0.74, 0.69, and 0.67 for total casein, total β-lactoglobulin, and β-casein, respectively. Total proteins (i.e., total casein, total whey, and total lactoglobulin) were predicted with greater accuracy then their respective component traits; prediction accuracy using the infrared spectrum was superior to prediction using just milk protein concentration. Weak to moderate prediction accuracies were observed for FAA. The greatest coefficient of correlation in both cross validation and external validation was for Gly (0.75), indicating a moderate accuracy of prediction. Overall, the FAA prediction models overpredicted the gold standard values. Near-unity correlations existed between total casein and β-casein irrespective of whether the traits were based on the gold standard (0.92) or mid-infrared spectroscopy predictions (0.95). Weaker correlations among FAA were observed than the correlations among the protein fractions. Pearson correlations between gold standard protein fractions and the milk processing characteristics of rennet coagulation time, curd firming time, curd firmness, heat coagulating time, pH, and casein micelle size were weak to moderate and ranged from -0.48 (protein and pH) to 0.50 (total casein and a30). Pearson correlations between gold standard FAA and these milk processing characteristics were also weak to moderate and ranged from -0.60 (Val and pH) to 0.49 (Val and K20). Results from this study indicate that mid-infrared spectroscopy has the potential to predict protein fractions and some FAA in milk at a population level. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Molecular dynamics simulation of nonlinear spectroscopies of intermolecular motions in liquid water.

PubMed

Yagasaki, Takuma; Saito, Shinji

2009-09-15

Water is the most extensively studied of liquids because of both its ubiquity and its anomalous thermodynamic and dynamic properties. The properties of water are dominated by hydrogen bonds and hydrogen bond network rearrangements. Fundamental information on the dynamics of liquid water has been provided by linear infrared (IR), Raman, and neutron-scattering experiments; molecular dynamics simulations have also provided insights. Recently developed higher-order nonlinear spectroscopies open new windows into the study of the hydrogen bond dynamics of liquid water. For example, the vibrational lifetimes of stretches and a bend, intramolecular features of water dynamics, can be accurately measured and are found to be on the femtosecond time scale at room temperature. Higher-order nonlinear spectroscopy is expressed by a multitime correlation function, whereas traditional linear spectroscopy is given by a one-time correlation function. Thus, nonlinear spectroscopy yields more detailed information on the dynamics of condensed media than linear spectroscopy. In this Account, we describe the theoretical background and methods for calculating higher order nonlinear spectroscopy; equilibrium and nonequilibrium molecular dynamics simulations, and a combination of both, are used. We also present the intermolecular dynamics of liquid water revealed by fifth-order two-dimensional (2D) Raman spectroscopy and third-order IR spectroscopy. 2D Raman spectroscopy is sensitive to couplings between modes; the calculated 2D Raman signal of liquid water shows large anharmonicity in the translational motion and strong coupling between the translational and librational motions. Third-order IR spectroscopy makes it possible to examine the time-dependent couplings. The 2D IR spectra and three-pulse photon echo peak shift show the fast frequency modulation of the librational motion. A significant effect of the translational motion on the fast frequency modulation of the librational motion is elucidated by introducing the "translation-free" molecular dynamics simulation. The isotropic pump-probe signal and the polarization anisotropy decay show fast transfer of the librational energy to the surrounding water molecules, followed by relaxation to the hot ground state. These theoretical methods do not require frequently used assumptions and can thus be called ab initio methods; together with multidimensional nonlinear spectroscopies, they provide powerful methods for examining the inter- and intramolecular details of water dynamics.

Near infrared spectroscopy for mastitis diagnosis: Two-dimensional correlation study in short wavelength region

NASA Astrophysics Data System (ADS)

Tsenkova, Roumiana; Murayama, Koichi; Kawano, Sumio; Wu, Yuqing; Toyoda, Kiyohiko; Ozaki, Yukihiro

2000-03-01

We describe the application of two-dimensional correlation spectroscopic (2DCOS) technique for mastitic diagnosis. Seven average spectra in the short wavelength region (700-1100 nm) of mastitic levels separated from healthy to disease were subjected to 2DCOS analysis. Synchronous correlation map clearly showed water and fat bands. Asynchronous correlation map indicated the dynamical variations of milk constituents in milk occurred when a cow gets mastitis.

Quantifying time-of-flight-resolved optical field dynamics in turbid media with interferometric near-infrared spectroscopy (iNIRS) (Conference Presentation)

NASA Astrophysics Data System (ADS)

Borycki, Dawid; Kholiqov, Oybek; Zhou, Wenjun; Srinivasan, Vivek J.

2017-03-01

Sensing and imaging methods based on the dynamic scattering of coherent light, including laser speckle, laser Doppler, and diffuse correlation spectroscopy quantify scatterer motion using light intensity (speckle) fluctuations. The underlying optical field autocorrelation (OFA), rather than being measured directly, is typically inferred from the intensity autocorrelation (IA) through the Siegert relationship, by assuming that the scattered field obeys Gaussian statistics. In this work, we demonstrate interferometric near-infrared spectroscopy (iNIRS) for measurement of time-of-flight (TOF) resolved field and intensity autocorrelations in fluid tissue phantoms and in vivo. In phantoms, we find a breakdown of the Siegert relationship for short times-of-flight due to a contribution from static paths whose optical field does not decorrelate over experimental time scales, and demonstrate that eliminating such paths by polarization gating restores the validity of the Siegert relationship. Inspired by these results, we developed a method, called correlation gating, for separating the OFA into static and dynamic components. Correlation gating enables more precise quantification of tissue dynamics. To prove this, we show that iNIRS and correlation gating can be applied to measure cerebral hemodynamics of the nude mouse in vivo using dynamically scattered (ergodic) paths and not static (non-ergodic) paths, which may not be impacted by blood. More generally, correlation gating, in conjunction with TOF resolution, enables more precise separation of diffuse and non-diffusive contributions to OFA than is possible with TOF resolution alone. Finally, we show that direct measurements of OFA are statistically more efficient than indirect measurements based on IA.

Correlated Raman micro-spectroscopy and scanning electron microscopy analyses of flame retardants in environmental samples: a micro-analytical tool for probing chemical composition, origin and spatial distribution.

PubMed

Ghosal, Sutapa; Wagner, Jeff

2013-07-07

We present correlated application of two micro-analytical techniques: scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) and Raman micro-spectroscopy (RMS) for the non-invasive characterization and molecular identification of flame retardants (FRs) in environmental dusts and consumer products. The SEM/EDS-RMS technique offers correlated, morphological, molecular, spatial distribution and semi-quantitative elemental concentration information at the individual particle level with micrometer spatial resolution and minimal sample preparation. The presented methodology uses SEM/EDS analyses for rapid detection of particles containing FR specific elements as potential indicators of FR presence in a sample followed by correlated RMS analyses of the same particles for characterization of the FR sub-regions and surrounding matrices. The spatially resolved characterization enabled by this approach provides insights into the distributional heterogeneity as well as potential transfer and exposure mechanisms for FRs in the environment that is typically not available through traditional FR analysis. We have used this methodology to reveal a heterogeneous distribution of highly concentrated deca-BDE particles in environmental dust, sometimes in association with identifiable consumer materials. The observed coexistence of deca-BDE with consumer material in dust is strongly indicative of its release into the environment via weathering/abrasion of consumer products. Ingestion of such enriched FR particles in dust represents a potential for instantaneous exposure to high FR concentrations. Therefore, correlated SEM/RMS analysis offers a novel investigative tool for addressing an area of important environmental concern.

Two-Dimensional NMR Evidence for Cleavage of Lignin and Xylan Substituents in Wheat Straw Through Hydrothermal Pretreatment and Enzymatic Hydrolysis

Treesearch

Daniel J. Yelle; Prasad Kaparaju; Christopher G. Hunt; Kolby Hirth; Hoon Kim; John Ralph; Claus Felby

2012-01-01

Solution-state two-dimensional (2D) nuclear magnetic resonance (NMR) spectroscopy of plant cell walls is a powerful tool for characterizing changes in cell wall chemistry during the hydrothermal pretreatment process of wheat straw for second-generation bioethanol production. One-bond 13C-1H NMR correlation spectroscopy, via...

Perspective: Two-dimensional resonance Raman spectroscopy

NASA Astrophysics Data System (ADS)

Molesky, Brian P.; Guo, Zhenkun; Cheshire, Thomas P.; Moran, Andrew M.

2016-11-01

Two-dimensional resonance Raman (2DRR) spectroscopy has been developed for studies of photochemical reaction mechanisms and structural heterogeneity in complex systems. The 2DRR method can leverage electronic resonance enhancement to selectively probe chromophores embedded in complex environments (e.g., a cofactor in a protein). In addition, correlations between the two dimensions of the 2DRR spectrum reveal information that is not available in traditional Raman techniques. For example, distributions of reactant and product geometries can be correlated in systems that undergo chemical reactions on the femtosecond time scale. Structural heterogeneity in an ensemble may also be reflected in the 2D spectroscopic line shapes of both reactive and non-reactive systems. In this perspective article, these capabilities of 2DRR spectroscopy are discussed in the context of recent applications to the photodissociation reactions of triiodide and myoglobin. We also address key differences between the signal generation mechanisms for 2DRR and off-resonant 2D Raman spectroscopies. Most notably, it has been shown that these two techniques are subject to a tradeoff between sensitivity to anharmonicity and susceptibility to artifacts. Overall, recent experimental developments and applications of the 2DRR method suggest great potential for the future of the technique.

Study on fast measurement of sugar content of yogurt using Vis/NIR spectroscopy techniques

NASA Astrophysics Data System (ADS)

He, Yong; Feng, Shuijuan; Wu, Di; Li, Xiaoli

2006-09-01

In order to measuring the sugar content of yogurt rapidly, a fast measurement of sugar content of yogurt using Vis/NIR-spectroscopy techniques was established. 25 samples selected separately from five different brands of yogurt were measured by Vis/NIR-spectroscopy. The sugar content of yogurt on positions scanned by spectrum were measured by a sugar content meter. The mathematical model between sugar content and Vis/NIR spectral measurements was established and developed based on partial least squares (PLS). The correlation coefficient of sugar content based on PLS model is more than 0.894, and standard error of calibration (SEC) is 0.356, standard error of prediction (SEP) is 0.389. Through predicting the sugar content quantitatively of 35 samples of yogurt from 5 different brands, the correlation coefficient between predictive value and measured value of those samples is more than 0.934. The results show the good to excellent prediction performance. The Vis/NIR spectroscopy technique had significantly greater accuracy for determining the sugar content. It was concluded that the Vis/NIRS measurement technique seems reliable to assess the fast measurement of sugar content of yogurt, and a new method for the measurement of sugar content of yogurt was established.

Determining conformational order and crystallinity in polycaprolactone via Raman spectroscopy

PubMed Central

Kotula, Anthony P.; Snyder, Chad R.; Migler, Kalman B.

2017-01-01

Raman spectroscopy is a popular method for non-invasive analysis of biomaterials containing polycaprolactone in applications such as tissue engineering and drug delivery. However there remain fundamental challenges in interpretation of such spectra in the context of existing dielectric spectroscopy and differential scanning calorimetry results in both the melt and semi-crystalline states. In this work, we develop a thermodynamically informed analysis method which utilizes basis spectra – ideal spectra of the polymer chain conformers comprising the measured Raman spectrum. In polycaprolactone we identify three basis spectra in the carbonyl region; measurement of their temperature dependence shows that one is linearly proportional to crystallinity, a second correlates with dipole-dipole interactions that are observed in dielectric spectroscopy and a third which correlates with amorphous chain behavior. For other spectral regions, e.g. C-COO stretch, a comparison of the basis spectra to those from density functional theory calculations in the all-trans configuration allows us to indicate whether sharp spectral peaks can be attributed to single chain modes in the all-trans state or to crystalline order. Our analysis method is general and should provide important insights to other polymeric materials. PMID:28824207

Two-dimensional correlation spectroscopy reveals the underlying compositions for FT-NIR identification of the medicinal bulbs of the genus Fritillaria

NASA Astrophysics Data System (ADS)

Chen, Jianbo; Wang, Yue; Liu, Aoxue; Rong, Lixin; Wang, Jingjuan

2018-03-01

Fritillariae Bulbus, the dried bulbs of several species of the genus Fritillaria, is often used in traditional Chinese medicine for the treatment of cough and pulmonary diseases. However, the similar appearances make it difficult to identify different kinds of Fritillariae Bulbus. In this research, Fourier transform near-infrared (FT-NIR) spectroscopy with a reflection fiber probe is employed for the direct testing and automatic identification of different kinds of Fritillariae Bulbus to ensure the authenticity, efficacy and safety. The bulbs can be measured directly without pulverizing. According to the two-dimensional (2D) correlation analysis and statistical analysis, the height ratio of the two peaks near 4860 cm-1 and 4750 cm-1 in the second derivative spectra is specific to the species of Fritillariae Bulbus. This indicates that the relative amount of protein and carbohydrate may be critical to identify Fritillariae Bulbus. With the help of the SIMCA model, the four kinds of Fritillariae Bulbus can be identified correctly by FT-NIR spectroscopy. The results show the potential of FT-NIR spectroscopy with a reflection fiber probe in the rapid testing and identification of Fritillariae Bulbus.

Correlation of surface enhanced Raman spectroscopy and nanoparticle aggregation with rhodamine 6G

NASA Astrophysics Data System (ADS)

Hoff, Christopher A.

Surface enhanced Raman spectroscopy (SERS) has fascinated the analytical chemistry field for decades. The SERS phenomenon has progressively leveraged the inherently insensitive Raman phenomenon from a novelty vibrational spectroscopy method into one capable of single molecule detection, with attendant molecular level selectivity and information. Yet, even after 40 years since its discovery, the core mechanism behind this phenomenon is still debated. This thesis presents results from a series of photometric titrations wherein solutions of 30 nm Au@Ag nanoparticles (NPs) were titrated with rhodamine 6G (R6G), spanning five orders of magnitude in R6G concentration, and which elucidate the conditions required for the onset of SERS by R6G in this system. The experiments illustrated the correlation between the Raman response and the plasmonic (via UV-Vis spectroscopy) properties of the nanoparticle solutions. It was found that the onset of R6G SERS was related much more closely to the aggregation of the nanoparticles in solution than to their R6G adsorbed surface coverage. However, triggering aggregation with sodium chloride appeared to enhance SERS by an independent mechanism, which is operative only at low, i.e., [NaCl] > 100 mM concentration.

Multiple spatially resolved reflection spectroscopy for in vivo determination of carotenoids in human skin and blood

NASA Astrophysics Data System (ADS)

Darvin, Maxim E.; Magnussen, Björn; Lademann, Juergen; Köcher, Wolfgang

2016-09-01

Non-invasive measurement of carotenoid antioxidants in human skin is one of the important tasks to investigate the skin physiology in vivo. Resonance Raman spectroscopy and reflection spectroscopy are the most frequently used non-invasive techniques in dermatology and skin physiology. In the present study, an improved method based on multiple spatially resolved reflection spectroscopy (MSRRS) was introduced. The results obtained were compared with those obtained using the ‘gold standard’ resonance Raman spectroscopy method and showed strong correlations for the total carotenoid concentration (R  =  0.83) as well as for lycopene (R  =  0.80). The measurement stability was confirmed to be better than 10% within the total temperature range from 5 °C to  +  30 °C and pressure contact between the skin and the MSRRS sensor from 800 Pa to 18 000 Pa. In addition, blood samples taken from the subjects were analyzed for carotenoid concentrations. The MSRRS sensor was calibrated on the blood carotenoid concentrations resulting in being able to predict with a correlation of R  =  0.79. On the basis of blood carotenoids it could be demonstrated that the MSRRS cutaneous measurements are not influenced by Fitzpatrick skin types I-VI. The MSRRS sensor is commercially available under the brand name biozoom.

Two-trace two-dimensional (2T2D) correlation spectroscopy - A method for extracting useful information from a pair of spectra

NASA Astrophysics Data System (ADS)

Noda, Isao

2018-05-01

Two-trace two-dimensional (2T2D) correlation spectroscopy, where a pair of spectra are compared as 2D maps by a form of cross correlation analysis, is introduced. In 2T2D, spectral intensity changes of bands arising from the same origin, which cannot change independently of each other, are synchronized. Meanwhile, those arising from different sources may and often do change asynchronously. By taking advantage of this property, one can distinguish and classify a number of contributing bands present in the original pair of spectra in a systematic manner. Highly overlapped neighboring bands originating from different sources can also be identified by the presence of asynchronous cross peaks, thus enhancing the apparent spectral resolution. Computational procedure to obtain 2T2D correlation spectra and their interpretation method, as well as an illustrative description of the basic concept in the vector phase space, are provided. 2T2D spectra may also be viewed as individual building blocks of the generalized 2D correlation spectra derived from a series of more than two spectral data. Some promising application potentials of 2T2D correlation and integration with established advanced 2D correlation techniques are discussed.

Atmospheric pollution measurement by optical cross correlation methods - A concept

NASA Technical Reports Server (NTRS)

Fisher, M. J.; Krause, F. R.

1971-01-01

Method combines standard spectroscopy with statistical cross correlation analysis of two narrow light beams for remote sensing to detect foreign matter of given particulate size and consistency. Method is applicable in studies of generation and motion of clouds, nuclear debris, ozone, and radiation belts.

Application of mid-infrared spectroscopy in analyzing different segmented production of Angelica by AB-8 macroporous resin

NASA Astrophysics Data System (ADS)

Guo, Yizhen; Wang, Jingjuan; Lu, Lina; Sun, Suqin; Liu, Yang; Xiao, Yao; Qin, Youwen; Xiao, Lijuan; Wen, Haoran; Qu, Lei

2016-01-01

As complicated mixture systems, chemical components of Angelica are very difficult to identify and discriminate, so as not to control its quality effectively. In recent years, Mid-infrared spectroscopy has been innovatively employed to identify and assess the quality of Traditional Chinese medicine (TCM) products. 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 (2D-IR), are applied to study and identify Angelica raw material, the decoction and different segmented production of AB-8 macroporous resin. FT-IR spectrum indicates that Angelica raw material is rich in sucrose and the correlation coefficient is 0.8465. The decoction of Angelica contains varieties of polysaccharides components and the content is gradually decreased with increasing concentration of ethanol. In addition, the decoction of Angelica contains a certain amount of protein components and 50% ethanol eluate has more protein than other eluates. Their second derivative spectra amplify the differences and reveal the potentially characteristic IR absorption bands, then we conclude that the decoction of Angelica contains a certain amount of ferulic acid and ligustilide. And 30% ethanol eluate, 50% ethanol eluate and 70% ethanol eluate are similar to ligustilide. Further, 2D-IR spectra enhance the spectral resolution and obtain much new information for discriminating the similar complicated samples. It is demonstrated that the above three-step infrared spectroscopy could be applicable for effective, visual and accurate analysis and identification of very complicated and similar mixture systems of traditional Chinese medicines.

Scanning fluorescence correlation spectroscopy comes full circle.

PubMed

Gunther, German; Jameson, David M; Aguilar, Joao; Sánchez, Susana A

2018-02-07

In this article, we review the application of fluorescence correlation spectroscopy (FCS) methods to studies on live cells. We begin with a brief overview of the theory underlying FCS, highlighting the type of information obtainable. We then focus on circular scanning FCS. Specifically, we discuss instrumentation and data analysis and offer some considerations regarding sample preparation. Two examples from the literature are discussed in detail. First, we show how this method, coupled with the photon counting histogram analysis, can provide information on yeast ribosomal structures in live cells. The combination of scanning FCS with dual channel detection in the study of lipid domains in live cells is also illustrated. Copyright © 2018 Elsevier Inc. All rights reserved.

Lithographically fabricated silicon microreactor for in situ characterization of heterogeneous catalysts—Enabling correlative characterization techniques

NASA Astrophysics Data System (ADS)

Baier, S.; Rochet, A.; Hofmann, G.; Kraut, M.; Grunwaldt, J.-D.

2015-06-01

We report on a new modular setup on a silicon-based microreactor designed for correlative spectroscopic, scattering, and analytic on-line gas investigations for in situ studies of heterogeneous catalysts. The silicon microreactor allows a combination of synchrotron radiation based techniques (e.g., X-ray diffraction and X-ray absorption spectroscopy) as well as infrared thermography and Raman spectroscopy. Catalytic performance can be determined simultaneously by on-line product analysis using mass spectrometry. We present the design of the reactor, the experimental setup, and as a first example for an in situ study, the catalytic partial oxidation of methane showing the applicability of this reactor for in situ studies.

Lithographically fabricated silicon microreactor for in situ characterization of heterogeneous catalysts—Enabling correlative characterization techniques.

PubMed

Baier, S; Rochet, A; Hofmann, G; Kraut, M; Grunwaldt, J-D

2015-06-01

We report on a new modular setup on a silicon-based microreactor designed for correlative spectroscopic, scattering, and analytic on-line gas investigations for in situ studies of heterogeneous catalysts. The silicon microreactor allows a combination of synchrotron radiation based techniques (e.g., X-ray diffraction and X-ray absorption spectroscopy) as well as infrared thermography and Raman spectroscopy. Catalytic performance can be determined simultaneously by on-line product analysis using mass spectrometry. We present the design of the reactor, the experimental setup, and as a first example for an in situ study, the catalytic partial oxidation of methane showing the applicability of this reactor for in situ studies.

Understanding individual defects in CdTe thin-film solar cells via STEM: From atomic structure to electrical activity

DOE PAGES

Li, Chen; Poplawsky, Jonathan; Yan, Yanfa; ...

2017-07-01

Here in this paper we review a systematic study of the structure-property correlations of a series of defects in CdTe solar cells. A variety of experimental methods, including aberration-corrected scanning transmission electron microscopy, electron energy loss spectroscopy, energy dispersive X-ray spectroscopy, and electron-beam-induced current have been combined with density-functional theory. The research traces the connections between the structures and electrical activities of individual defects including intra-grain partial dislocations, grain boundaries and the CdTe/CdS interface. The interpretations of the physical origin underlying the structure-property correlation provide insights that should further the development of future CdTe solar cells.

Instrumental sensing of stationary source emissions. [sulphur dioxide remote sensing for coal-burning power plants

NASA Technical Reports Server (NTRS)

Herget, W. F.; Conner, W. D.

1977-01-01

A variety of programs have been conducted within EPA to evaluate the capability of various ground-based remote-sensing techniques for measuring the SO2 concentration, velocity, and opacity of effluents from coal-burning power plants. The results of the remote measurements were compared with the results of instack measurements made using EPA reference methods. Attention is given to infrared gas-filter correlation radiometry for SO2 concentration, Fourier-transform infrared spectroscopy for SO2 concentration, ultraviolet matched-filter correlation spectroscopy for SO2 concentration, infrared and ultraviolet television for velocity and SO2 concentration, infrared laser-Doppler velocimetry for plume velocity, and visible laser radar for plume opacity.

Diffuse Optics for Tissue Monitoring and Tomography

PubMed Central

Durduran, T; Choe, R; Baker, W B; Yodh, A G

2015-01-01

This review describes the diffusion model for light transport in tissues and the medical applications of diffuse light. Diffuse optics is particularly useful for measurement of tissue hemodynamics, wherein quantitative assessment of oxy- and deoxy-hemoglobin concentrations and blood flow are desired. The theoretical basis for near-infrared or diffuse optical spectroscopy (NIRS or DOS, respectively) is developed, and the basic elements of diffuse optical tomography (DOT) are outlined. We also discuss diffuse correlation spectroscopy (DCS), a technique whereby temporal correlation functions of diffusing light are transported through tissue and are used to measure blood flow. Essential instrumentation is described, and representative brain and breast functional imaging and monitoring results illustrate the workings of these new tissue diagnostics. PMID:26120204

Electrically induced microflows probed by fluorescence correlation spectroscopy.

PubMed

Ybert, C; Nadal, F; Salomé, R; Argoul, F; Bourdieu, L

2005-03-01

We report on the experimental characterisation of electrically induced flows at the micrometer scale through Fluorescence Correlation Spectroscopy (FCS) measurements. We stress the potential of FCS as a useful characterisation technique in microfluidics devices for transport properties cartography. The experimental results obtained in a model situation are in agreement with previous calculations (F. Nadal, F. Argoul, P. Kestener, B. Pouligny, C. Ybert, A. Ajdari, Eur. Phys. J. E 9, 387 (2002)) predicting the structure and electric-field dependency of the induced flow. Additionally, the present study evidences a complex behaviour of the probe nanobeads under electric field whose precise understanding might prove relevant for situations where nano-objects interact with an external electric field.

In vivo preclinical verification of a multimodal diffuse reflectance and correlation spectroscopy system for sensing tissue perfusion

NASA Astrophysics Data System (ADS)

Pakela, Julia M.; Lee, Seung Yup; Hedrick, Taylor L.; Vishwanath, Karthik; Helton, Michael C.; Chung, Yooree G.; Kolodziejski, Noah J.; Staples, Christopher J.; McAdams, Daniel R.; Fernandez, Daniel E.; Christian, James F.; O'Reilly, Jameson; Farkas, Dana; Ward, Brent B.; Feinberg, Stephen E.; Mycek, Mary-Ann

2017-02-01

In reconstructive surgery, impeded blood flow in microvascular free flaps due to a compromise in arterial or venous patency secondary to blood clots or vessel spasms can rapidly result in flap failures. Thus, the ability to detect changes in microvascular free flaps is critical. In this paper, we report progress on in vivo pre-clinical testing of a compact, multimodal, fiber-based diffuse correlation and reflectance spectroscopy system designed to quantitatively monitor tissue perfusion in a porcine model's surgically-grafted free flap. We also describe the device's sensitivity to incremental blood flow changes and discuss the prospects for continuous perfusion monitoring in future clinical translational studies.

Boron difluoride dibenzoylmethane derivatives: Electronic structure and luminescence

NASA Astrophysics Data System (ADS)

Tikhonov, Sergey A.; Vovna, Vitaliy I.; Osmushko, Ivan S.; Fedorenko, Elena V.; Mirochnik, Anatoliy G.

2018-01-01

Electronic structure and optical properties of boron difluoride dibenzoylmethanate and four of its derivatives have been studied by X-ray photoelectron spectroscopy, absorption and luminescence spectroscopy and quantum chemistry (DFT, TDDFT). The relative quantum luminescence yields have been revealed to correlate with charge transfers of HOMO-LUMO transitions, energy barriers of aromatic substituents rotation and the lifetime of excited states in the investigated complexes. The bathochromic shift of intensive bands in the optical spectra has been observed to occur when the functional groups are introduced into p-positions of phenyl cycles due to destabilizing HOMO levels. Calculated energy intervals between electronic levels correlate well with XPS spectra structure of valence and core electrons.

Understanding individual defects in CdTe thin-film solar cells via STEM: From atomic structure to electrical activity

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

Li, Chen; Poplawsky, Jonathan; Yan, Yanfa

Here in this paper we review a systematic study of the structure-property correlations of a series of defects in CdTe solar cells. A variety of experimental methods, including aberration-corrected scanning transmission electron microscopy, electron energy loss spectroscopy, energy dispersive X-ray spectroscopy, and electron-beam-induced current have been combined with density-functional theory. The research traces the connections between the structures and electrical activities of individual defects including intra-grain partial dislocations, grain boundaries and the CdTe/CdS interface. The interpretations of the physical origin underlying the structure-property correlation provide insights that should further the development of future CdTe solar cells.

Sonochemically synthesized iron-doped zinc oxide nanoparticles: Influence of precursor composition on characteristics

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

Roy, Anirban; Maitra, Saikat; Ghosh, Sobhan

Highlights: • Sonochemical synthesis of iron-doped zinc oxide nanoparticles. • Green synthesis without alkali at room temperature. • Characterization by UV–vis spectroscopy, FESEM, XRD and EDX. • Influence of precursor composition on characteristics. • Composition and characteristics are correlated. - Abstract: Iron-doped zinc oxide nanoparticles have been synthesized sonochemically from aqueous acetyl acetonate precursors of different proportions. Synthesized nanoparticles were characterized with UV–vis spectroscopy, X-ray diffraction and microscopy. Influences of precursor mixture on the characteristics have been examined and modeled. Linear correlations have been proposed between dopant dosing, extent of doping and band gap energy. Experimental data corroborated with themore » proposed models.« less

Correlation between morphology, electron band structure, and resistivity of Pb atomic chains on the Si(5 5 3)-Au surface

NASA Astrophysics Data System (ADS)

Jałochowski, M.; Kwapiński, T.; Łukasik, P.; Nita, P.; Kopciuszyński, M.

2016-07-01

Structural and electron transport properties of multiple Pb atomic chains fabricated on the Si(5 5 3)-Au surface are investigated using scanning tunneling spectroscopy, reflection high electron energy diffraction, angular resolved photoemission electron spectroscopy and in situ electrical resistance. The study shows that Pb atomic chains growth modulates the electron band structure of pristine Si(5 5 3)-Au surface and hence changes its sheet resistivity. Strong correlation between chains morphology, electron band structure and electron transport properties is found. To explain experimental findings a theoretical tight-binding model of multiple atomic chains interacting on effective substrate is proposed.

Combined IR-Raman vs vibrational sum-frequency heterospectral correlation spectroscopy

NASA Astrophysics Data System (ADS)

Roy, Sandra; Beutier, Clémentine; Hore, Dennis K.

2018-06-01

Vibrational sum-frequency generation spectroscopy is a valuable probe of surface structure, particularly when the same molecules are present in one of the adjacent bulk solid or solution phases. As a result of the non-centrosymmetric requirement of SFG, the signal generated is a marker of the extent to which the molecules are ordered in an arrangement that breaks the up-down symmetry at the surface. In cases where the accompanying changes in the bulk are of interest in understanding and interpreting the surface structure, simultaneous analysis of the bulk IR absorption or bulk Raman scattering is helpful, and may be used in heterospectral surface-bulk two-dimensional correlation. We demonstrate that, in such cases, generating a new type of bulk spectrum that combines the IR and Raman amplitudes is a better candidate than the individual IR and Raman spectra for the purpose of correlation with the SFG signal.

Clinical Applications of Near-infrared Diffuse Correlation Spectroscopy and Tomography for Tissue Blood Flow Monitoring and Imaging

PubMed Central

Shang, Yu; Li, Ting; Yu, Guoqiang

2017-01-01

Blood flow is one such available observable promoting a wealth of physiological insight both individually and in combination with other metrics. Near-infrared diffuse correlation spectroscopy (DCS) and, to a lesser extent, diffuse correlation tomography (DCT), have increasingly received interest over the past decade as noninvasive methods for tissue blood flow measurements and imaging. DCS/DCT offers several attractive features for tissue blood flow measurements/imaging such as noninvasiveness, portability, high temporal resolution, and relatively large penetration depth (up to several centimeters). This review first introduces the basic principle and instrumentation of DCS/DCT, followed by presenting clinical application examples of DCS/DCT for the diagnosis and therapeutic monitoring of diseases in a variety of organs/tissues including brain, skeletal muscle, and tumor. Clinical study results demonstrate technical versatility of DCS/DCT in providing important information for disease diagnosis and intervention monitoring. PMID:28199219

Microsecond protein dynamics observed at the single-molecule level

NASA Astrophysics Data System (ADS)

Otosu, Takuhiro; Ishii, Kunihiko; Tahara, Tahei

2015-07-01

How polypeptide chains acquire specific conformations to realize unique biological functions is a central problem of protein science. Single-molecule spectroscopy, combined with fluorescence resonance energy transfer, is utilized to study the conformational heterogeneity and the state-to-state transition dynamics of proteins on the submillisecond to second timescales. However, observation of the dynamics on the microsecond timescale is still very challenging. This timescale is important because the elementary processes of protein dynamics take place and direct comparison between experiment and simulation is possible. Here we report a new single-molecule technique to reveal the microsecond structural dynamics of proteins through correlation of the fluorescence lifetime. This method, two-dimensional fluorescence lifetime correlation spectroscopy, is applied to clarify the conformational dynamics of cytochrome c. Three conformational ensembles and the microsecond transitions in each ensemble are indicated from the correlation signal, demonstrating the importance of quantifying microsecond dynamics of proteins on the folding free energy landscape.

Microsecond protein dynamics observed at the single-molecule level

PubMed Central

Otosu, Takuhiro; Ishii, Kunihiko; Tahara, Tahei

2015-01-01

How polypeptide chains acquire specific conformations to realize unique biological functions is a central problem of protein science. Single-molecule spectroscopy, combined with fluorescence resonance energy transfer, is utilized to study the conformational heterogeneity and the state-to-state transition dynamics of proteins on the submillisecond to second timescales. However, observation of the dynamics on the microsecond timescale is still very challenging. This timescale is important because the elementary processes of protein dynamics take place and direct comparison between experiment and simulation is possible. Here we report a new single-molecule technique to reveal the microsecond structural dynamics of proteins through correlation of the fluorescence lifetime. This method, two-dimensional fluorescence lifetime correlation spectroscopy, is applied to clarify the conformational dynamics of cytochrome c. Three conformational ensembles and the microsecond transitions in each ensemble are indicated from the correlation signal, demonstrating the importance of quantifying microsecond dynamics of proteins on the folding free energy landscape. PMID:26151767

Structure changes in metastable and unstable foams probed by multispeckle diffusing light spectroscopy

NASA Astrophysics Data System (ADS)

Yuvchenko, S. A.; Tzyipin, D. V.; Isaeva, A. A.; Isaeva, E. A.; Ushakova, O. V.; Macheev, M. S.; Zimnyakov, D. A.

2018-04-01

The temporal evolution of the metastable and unstable foams had been studied. Diffusion wave spectroscopy was chosen as the diagnostic method, with calculation of the correlation time of the fluctuations in the intensity of the probing radiation. It was established that the correlation time increases with the time according to the power law with different parameters, depending on the type of the evolution and was found to be equal to 0.5 for the case of the metastable and to 2,52 for the unstable foam. It was also determined that the behaviour of the correlation time agrees well with the evolution of the characteristic dimensions of the scatterers in the form of bubbles in the medium, which can be used for contactless monitoring of the foaming processes in the production of the foam-like materials for various applications, for example, in the synthesis of the biocompatible polymer matrices - scaffolds.

Fast determination of total ginsenosides content in ginseng powder by near infrared reflectance spectroscopy

NASA Astrophysics Data System (ADS)

Chen, Hua-cai; Chen, Xing-dan; Lu, Yong-jun; Cao, Zhi-qiang

2006-01-01

Near infrared (NIR) reflectance spectroscopy was used to develop a fast determination method for total ginsenosides in Ginseng (Panax Ginseng) powder. The spectra were analyzed with multiplicative signal correction (MSC) correlation method. The best correlative spectra region with the total ginsenosides content was 1660 nm~1880 nm and 2230nm~2380 nm. The NIR calibration models of ginsenosides were built with multiple linear regression (MLR), principle component regression (PCR) and partial least squares (PLS) regression respectively. The results showed that the calibration model built with PLS combined with MSC and the optimal spectrum region was the best one. The correlation coefficient and the root mean square error of correction validation (RMSEC) of the best calibration model were 0.98 and 0.15% respectively. The optimal spectrum region for calibration was 1204nm~2014nm. The result suggested that using NIR to rapidly determinate the total ginsenosides content in ginseng powder were feasible.

Partial correlation-based functional connectivity analysis for functional near-infrared spectroscopy signals

NASA Astrophysics Data System (ADS)

Akın, Ata

2017-12-01

A theoretical framework, a partial correlation-based functional connectivity (PC-FC) analysis to functional near-infrared spectroscopy (fNIRS) data, is proposed. This is based on generating a common background signal from a high passed version of fNIRS data averaged over all channels as the regressor in computing the PC between pairs of channels. This approach has been employed to real data collected during a Stroop task. The results show a strong significance in the global efficiency (GE) metric computed by the PC-FC analysis for neutral, congruent, and incongruent stimuli (NS, CS, IcS; GEN=0.10±0.009, GEC=0.11±0.01, GEIC=0.13±0.015, p=0.0073). A positive correlation (r=0.729 and p=0.0259) is observed between the interference of reaction times (incongruent-neutral) and interference of GE values (GEIC-GEN) computed from [HbO] signals.

Separation of overlapping vibrational peaks in terahertz spectra using two-dimensional correlation spectroscopy

NASA Astrophysics Data System (ADS)

Hoshina, Hiromichi; Ishii, Shinya; Otani, Chiko

2014-07-01

In this study, the terahertz (THz) absorption spectra of poly(3-hydroxybutyrate) (PHB) were measured during isothermal crystallization at 90-120 °C. The temporal changes in the absorption spectra were analyzed using two-dimensional correlation spectroscopy (2DCOS). In the asynchronous plot, cross peaks were observed around 2.4 THz, suggesting that two vibrational modes overlap in the raw spectrum. By comparing this to the peak at 2.9 THz corresponding to the stretching mode of the helical structure of PHB and the assignment obtained using polarization spectroscopy, we concluded that the high-frequency band could be attributed to the vibration of the helical structure and the low-frequency band to the vibration between the helical structures. The exact frequencies of the overlapping vibrational bands and their assignments provide a new means to inspect the thermal behavior of the intermolecular vibrational modes. The large red-shift of the interhelix vibrational mode suggests a large anharmonicity in the vibrational potential.

Controlled Terahertz Birefringence in Stretched Poly(lactic acid) Films Investigated by Terahertz Time-Domain Spectroscopy and Wide-Angle X-ray Scattering.

PubMed

Iwasaki, Hotsumi; Nakamura, Madoka; Komatsubara, Nozomu; Okano, Makoto; Nakasako, Masayoshi; Sato, Harumi; Watanabe, Shinichi

2017-07-20

We report a correlation between the dielectric property and structure of stretched poly(lactic acid) (PLA) films, revealed by polarization-sensitive terahertz time-domain spectroscopy and two-dimensional (2D) wide-angle X-ray scattering (WAXS). The experiments evidence that the dielectric function of the PLA film becomes more anisotropic with increasing draw ratio (DR). This behavior is explained by a classical Lorentz oscillator model assuming polarization-dependent absorption. The birefringence can be systematically altered from 0 to 0.13 by controlling DR. The combination of terahertz spectroscopy and 2D WAXS measurement reveals a clear correlation between the birefringence in the terahertz frequency domain and the degree of orientation of the PLA molecular chains. These findings imply that the birefringence is a result of the orientation of the PLA chains with anisotropic macromolecular vibration modes. Because of a good controllability of the birefringence, polymer-based materials will provide an attractive materials system for phase retarders in the terahertz frequency range.

Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbon Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy

PubMed Central

Nordvang, Emily C; Borodina, Elena; Ruiz-Martínez, Javier; Fehrmann, Rasmus; Weckhuysen, Bert M

2015-01-01

The catalytic activity of large zeolite H-ZSM-5 crystals in methanol (MTO) and ethanol-to-olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ single crystal UV/Vis and confocal fluorescence micro-spectroscopy, allowing the observation of the spatiotemporal formation of intermediates and coke species during the MTO and ETO conversions. It was observed that rapid deactivation at elevated temperatures was due to the fast formation of aromatics at the periphery of the H-ZSM-5 crystals, which are transformed into more poly-aromatic coke species at the external surface, preventing the diffusion of reactants and products into and out of the H-ZSM-5 crystal. Furthermore, we were able to correlate the operando UV/Vis spectroscopy results observed during catalytic testing with the single crystal in situ results. PMID:26463581

Neural Correlates of Infant Accent Discrimination: An fNIRS Study

ERIC Educational Resources Information Center

Cristia, Alejandrina; Minagawa-Kawai, Yasuyo; Egorova, Natalia; Gervain, Judit; Filippin, Luca; Cabrol, Dominique; Dupoux, Emmanuel

2014-01-01

The present study investigated the neural correlates of infant discrimination of very similar linguistic varieties (Quebecois and Parisian French) using functional Near InfraRed Spectroscopy. In line with previous behavioral and electrophysiological data, there was no evidence that 3-month-olds discriminated the two regional accents, whereas…

Poultry water holding capacity measurements using infrared spectroscopies correlated to traditional methods

USDA-ARS?s Scientific Manuscript database

Water holding capacity (WHC) in chicken meat is directly correlated with the quality of the meat. Lower water holding capacity is linked with decreased sensory qualities and therefore lower consumer satisfaction. Additionally, measurement of WHC is subject to wide variations which can depend on many...

Proton MR spectroscopy in predicting the increase of perfusion MR imaging for WHO grade II gliomas.

PubMed

Guillevin, Remy; Menuel, Carole; Abud, Lucas; Costalat, Robert; Capelle, Laurent; Hoang-Xuan, Khê; Habas, Christophe; Chiras, Jacques; Vallée, Jean-Noel

2012-03-01

To investigate the correlation between the metabolite ratios obtained from proton magnetic resonance (MR) spectroscopy and those obtained from MR perfusion parameters (relative cerebral blood volume [rCBV]) in a cohort of low-grade glioma (LGG). Patients underwent prospectively conventional MR, proton magnetic resonance spectroscopy ((1) HMRS), and perfusion-weighted images (PWI). Statistical analyses were performed to determine the correlative and independent predictive factors of rCBVmax and the metabolite ratio thresholds with optimum sensitivity and specificity. Thirty-one patients were included in this study. Linear correlations were observed between the metabolic ratios (lactate [Lac]/creatine [Cr], choline [Cho]/N-acetyl-aspartate [NAA], free-lipids/Cr) and rCBVmax (P < 0.05). These metabolic ratios were determined to be independent predictive factors of rCBVmax (P = 0.027, 0.011 and 0.032, respectively). According to the receiver operating characteristic curves, the cutoff values of the metabolic ratios to discriminate between the two populations of rCBVmax (<1.7 versus = 1.7) were 1.72, 1.54, and 1.40, respectively, with a sensitivity = 75% and a specificity >95% for Lac/Cr. This study demonstrated consistent correlations between the data from (1) HMRS and PWI. The Lac/Cr ratio predicts regional hemodynamic changes, which are themselves a useful biomarker of clinical prognosis in patients with LGG. As such, this ratio may provide a new parameter for making improved clinical decisions. Copyright © 2011 Wiley-Liss, Inc.

In vivo two-dimensional NMR correlation spectroscopy

NASA Astrophysics Data System (ADS)

Kraft, Robert A.

1999-10-01

The poor resolution of in-vivo one- dimensional nuclear magnetic resonance spectroscopy (NMR) has limited its clinical potential. Currently, only the large singlet methyl resonances arising from N-acetyl aspartate (NAA), choline, and creatine are quantitated in a clinical setting. Other metabolites such as myo- inositol, glutamine, glutamate, lactate, and γ- amino butyric acid (GABA) are of clinical interest but quantitation is difficult due to the overlapping resonances and limited spectral resolution. To improve the spectral resolution and distinguish between overlapping resonances, a series of two- dimensional chemical shift correlation spectroscopy experiments were developed for a 1.5 Tesla clinical imaging magnet. Two-dimensional methods are attractive for in vivo spectroscopy due to their ability to unravel overlapping resonances with the second dimension, simplifying the interpretation and quantitation of low field NMR spectra. Two-dimensional experiments acquired with mix-mode line shape negate the advantages of the second dimension. For this reason, a new experiment, REVOLT, was developed to achieve absorptive mode line shape in both dimensions. Absorptive mode experiments were compared to mixed mode experiments with respect to sensitivity, resolution, and water suppression. Detailed theoretical and experimental calculations of the optimum spin lock and radio frequency power deposition were performed. Two-dimensional spectra were acquired from human bone marrow and human brain tissue. The human brain tissue spectra clearly reveal correlations among the coupled spins of NAA, glutamine, glutamate, lactate, GABA, aspartate and myo-inositol obtained from a single experiment of 23 minutes from a volume of 59 mL. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617-253-5668; Fax 617-253-1690.)

Advances in quantitative UV-visible spectroscopy for clinical and pre-clinical application in cancer.

PubMed

Brown, J Quincy; Vishwanath, Karthik; Palmer, Gregory M; Ramanujam, Nirmala

2009-02-01

Methods of optical spectroscopy that provide quantitative, physically or physiologically meaningful measures of tissue properties are an attractive tool for the study, diagnosis, prognosis, and treatment of various cancers. Recent development of methodologies to convert measured reflectance and fluorescence spectra from tissue to cancer-relevant parameters such as vascular volume, oxygenation, extracellular matrix extent, metabolic redox states, and cellular proliferation have significantly advanced the field of tissue optical spectroscopy. The number of publications reporting quantitative tissue spectroscopy results in the UV-visible wavelength range has increased sharply in the past three years, and includes new and emerging studies that correlate optically measured parameters with independent measures such as immunohistochemistry, which should aid in increased clinical acceptance of these technologies.

Validating in vivo Raman spectroscopy of bone in human subjects

NASA Astrophysics Data System (ADS)

Esmonde-White, Francis W. L.; Morris, Michael D.

2013-03-01

Raman spectroscopy can non-destructively measure properties of bone related to mineral density, mineral composition, and collagen composition. Bone properties can be measured through the skin in animal and human subjects, but correlations between the transcutaneous and exposed bone measurements have only been reported for human cadavers. In this study, we examine human subjects to collect measurements transcutaneously, on surgically exposed bone, and on recovered bone fragments. This data will be used to demonstrate in vivo feasibility and to compare transcutaneous and exposed Raman spectroscopy of bone. A commercially available Raman spectrograph and optical probe operating at 785 nm excitation are used for the in vivo measurements. Requirements for applying Raman spectroscopy during a surgery are also discussed.

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.

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).

Development of a homogeneous assay format for p53 antibodies using fluorescence correlation spectroscopy

NASA Astrophysics Data System (ADS)

Neuweiler, Hannes; Scheffler, Silvia; Sauer, Markus

2005-08-01

The development of reliable methods for the detection of minute amounts of antibodies directly in homogeneous solution represents one of the major tasks in the current research field of molecular diagnostics. We demonstrate the potential of fluorescence correlation spectroscopy (FCS) in combination with quenched peptide-based fluorescence probes for sensitive detection of p53 antibodies directly in homogeneous solution. Single tryptophan (Trp) residues in the sequences of short, synthetic peptide epitopes of the human p53 protein efficiently quench the fluorescence of an oxazine fluorophore attached to the amino terminal ends of the peptides. The fluorescence quenching mechanism is thought to be a photoinduced electron transfer reaction from Trp to the dye enabled by the formation of intramolecular complexes between dye and Trp. Specific recognition of the epitope by the antibody confines the conformational flexibility of the peptide. Consequently, complex formation between dye and Trp is abolished and fluorescence is recovered. Using fluorescence correlation spectroscopy (FCS), antibody binding can be monitored observing two parameters simultaneously: the diffusional mobility of the peptide as well as the quenching amplitude induced by the conformational flexibility of the peptide change significantly upon antibody binding. Our data demonstrate that FCS in combination with fluorescence-quenched peptide epitopes opens new possibilities for the reliable detection of antibody binding events in homogeneous solution.

Advances in Neutron Spectroscopy and High Magnetic Field Instrumentation for studies of Correlated Electron Systems

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

Granroth, Garrett E

2011-01-01

Neutron Spectroscopy has provided critical information on the magnetism in correlated electron systems. Specifically quantum magnets, superconductors, and multi-ferroics are areas of productive research. A discussion of recent measurements on the SEQUOIA spectrometer will provide examples of how novel instrumentation concepts are used on the latest generation of spectrometers to extend our knowledge in such systems. The now ubiquitous function of sample rotation allows for full mapping of volumes ofmore » $Q$ and $$\\omega$$ space. An instrument focused on low angles could extend these maps to cover more of the first Brillioun zone. Innovative chopper cascades allow two unique modes of operation. Multiplexed measurements allow the simultaneous measurement of high and low energy features in an excitation spectrum. Alternatively by limiting the neutron bandwidth incident on the Fermi Chopper, background from subsequent time frames is removed, enabling the observation of weak, large energy transfer features. Finally the implementation of event-based detection for neutron experiments is time correlated experiments. Diffraction studies of the high field spin states in MnWO$$_4$$ using magnetic fields up to 30 T, provided by a pulsed magnet, illustrate this method. Expanding the high field studies to spectroscopy will require a novel instrument, focused around a world class DC magnet, like Zeemans proposed for the SNS.« less

Quantitative HRMAS proton total correlation spectroscopy applied to cultured melanoma cells treated by chloroethyl nitrosourea: demonstration of phospholipid metabolism alterations.

PubMed

Morvan, Daniel; Demidem, Aicha; Papon, Janine; Madelmont, Jean Claude

2003-02-01

Recent NMR spectroscopy developments, such as high-resolution magic angle spinning (HRMAS) probes and correlation-enhanced 2D sequences, now allow improved investigations of phospholipid (Plp) metabolism. Using these modalities we previously demonstrated that a mouse-bearing melanoma tumor responded to chloroethyl nitrosourea (CENU) treatment in vivo by altering its Plp metabolism. The aims of the present study were to investigate whether HRMAS proton total correlation spectroscopy (TOCSY) could be used as a quantitative technique to probe Plp metabolism, and to determine the Plp metabolism response of cultured B16 melanoma cells to CENU treatment in vitro. The exploited TOCSY signals of Plp derivatives arose from scalar coupling among the protons of neighbor methylene groups within base headgroups (choline and ethanolamine). For strongly expressed Plp derivatives, TOCSY signals were compared to saturation recovery signals and demonstrated a linear relationship. HRMAS proton TOCSY was thus used to provide concentrations of Plp derivatives during long-term follow-up of CENU-treated cell cultures. Strong Plp metabolism alteration was observed in treated cultured cells in vitro involving a down-regulation of phosphocholine, and a dramatic and irreversible increase of phosphoethanolamine. These findings are discussed in relation to previous in vivo data, and to Plp metabolism enzymatic involvement. Copyright 2003 Wiley-Liss, Inc.

Exploring the Dynamics of Cell Processes through Simulations of Fluorescence Microscopy Experiments

PubMed Central

Angiolini, Juan; Plachta, Nicolas; Mocskos, Esteban; Levi, Valeria

2015-01-01

Fluorescence correlation spectroscopy (FCS) methods are powerful tools for unveiling the dynamical organization of cells. For simple cases, such as molecules passively moving in a homogeneous media, FCS analysis yields analytical functions that can be fitted to the experimental data to recover the phenomenological rate parameters. Unfortunately, many dynamical processes in cells do not follow these simple models, and in many instances it is not possible to obtain an analytical function through a theoretical analysis of a more complex model. In such cases, experimental analysis can be combined with Monte Carlo simulations to aid in interpretation of the data. In response to this need, we developed a method called FERNET (Fluorescence Emission Recipes and Numerical routines Toolkit) based on Monte Carlo simulations and the MCell-Blender platform, which was designed to treat the reaction-diffusion problem under realistic scenarios. This method enables us to set complex geometries of the simulation space, distribute molecules among different compartments, and define interspecies reactions with selected kinetic constants, diffusion coefficients, and species brightness. We apply this method to simulate single- and multiple-point FCS, photon-counting histogram analysis, raster image correlation spectroscopy, and two-color fluorescence cross-correlation spectroscopy. We believe that this new program could be very useful for predicting and understanding the output of fluorescence microscopy experiments. PMID:26039162

2D FTIR correlation spectroscopy and EPR analysis of Urtica dioica leaves from areas of different environmental pollution.

PubMed

Moskal, Paulina; Wesełucha-Birczyńska, Aleksandra; Łabanowska, Maria; Kurdziel, Magdalena; Filek, Maria

2018-01-15

Leaves of Urtica dioica collected from two areas of different environmental pollution were analysed by fourier transform infrared spectroscopy (FTIR) and electron paramagnetic resonance (EPR) spectroscopy. Analysis of FTIR spectra allows to describe main component of plant like proteins, lipids and carbohydrates. Although the FTIR spectra of plants from these two geographical locations of different environmental pollution appear to be relatively similar, 2D correlation shows completely different patterns. Synchronous and asynchronous correlation maps showed sequences of changes occurring during development of plant, manly in Amide I and Amide II, lignin, lipids and cellulose. In addition, 2D analysis revealed another sequence of changes as the function of plant growth depending on the degree of the environmental pollution. Two various kinds of paramagnetic species, transition metal ions (Mn(II), Fe(III)) and stable organic radicals (chlorophyll, semiquinone, tyrosyl and carbon centered) were found in leaves of nettle collected at different stages of development and growing in clean and polluted environment. In plants growing in polluted area the injuries of protein molecules bonding metal ions and the disturbances of photosynthesis and redox equilibrium in cells, as well as instability of polysaccharide structure of cell walls were observed. Copyright © 2017 Elsevier B.V. All rights reserved.

Imaging spectroscopy links aspen genotype with below-ground processes at landscape scales

PubMed Central

Madritch, Michael D.; Kingdon, Clayton C.; Singh, Aditya; Mock, Karen E.; Lindroth, Richard L.; Townsend, Philip A.

2014-01-01

Fine-scale biodiversity is increasingly recognized as important to ecosystem-level processes. Remote sensing technologies have great potential to estimate both biodiversity and ecosystem function over large spatial scales. Here, we demonstrate the capacity of imaging spectroscopy to discriminate among genotypes of Populus tremuloides (trembling aspen), one of the most genetically diverse and widespread forest species in North America. We combine imaging spectroscopy (AVIRIS) data with genetic, phytochemical, microbial and biogeochemical data to determine how intraspecific plant genetic variation influences below-ground processes at landscape scales. We demonstrate that both canopy chemistry and below-ground processes vary over large spatial scales (continental) according to aspen genotype. Imaging spectrometer data distinguish aspen genotypes through variation in canopy spectral signature. In addition, foliar spectral variation correlates well with variation in canopy chemistry, especially condensed tannins. Variation in aspen canopy chemistry, in turn, is correlated with variation in below-ground processes. Variation in spectra also correlates well with variation in soil traits. These findings indicate that forest tree species can create spatial mosaics of ecosystem functioning across large spatial scales and that these patterns can be quantified via remote sensing techniques. Moreover, they demonstrate the utility of using optical properties as proxies for fine-scale measurements of biodiversity over large spatial scales. PMID:24733949

Dual-color dual-focus line-scanning FCS for quantitative analysis of receptor-ligand interactions in living specimens.

PubMed

Dörlich, René M; Chen, Qing; Niklas Hedde, Per; Schuster, Vittoria; Hippler, Marc; Wesslowski, Janine; Davidson, Gary; Nienhaus, G Ulrich

2015-05-07

Cellular communication in multi-cellular organisms is mediated to a large extent by a multitude of cell-surface receptors that bind specific ligands. An in-depth understanding of cell signaling networks requires quantitative information on ligand-receptor interactions within living systems. In principle, fluorescence correlation spectroscopy (FCS) based methods can provide such data, but live-cell applications have proven extremely challenging. Here, we have developed an integrated dual-color dual-focus line-scanning fluorescence correlation spectroscopy (2c2f lsFCS) technique that greatly facilitates live-cell and tissue experiments. Absolute ligand and receptor concentrations and their diffusion coefficients within the cell membrane can be quantified without the need to perform additional calibration experiments. We also determine the concentration of ligands diffusing in the medium outside the cell within the same experiment by using a raster image correlation spectroscopy (RICS) based analysis. We have applied this robust technique to study the interactions of two Wnt antagonists, Dickkopf1 and Dickkopf2 (Dkk1/2), to their cognate receptor, low-density-lipoprotein-receptor related protein 6 (LRP6), in the plasma membrane of living HEK293T cells. We obtained significantly lower affinities than previously reported using in vitro studies, underscoring the need to measure such data on living cells or tissues.

Electromagnetic Spectroscopy of Normal Breast Tissue Specimens Obtained From Reduction Surgeries: Comparison of Optical and Microwave Properties

PubMed Central

Lazebnik, Mariya; Zhu, Changfang; Palmer, Gregory M.; Harter, Josephine; Sewall, Sarah; Ramanujam, Nirmala; Hagness, Susan C.

2009-01-01

Techniques utilizing electromagnetic energy at microwave and optical frequencies have been shown to be promising for breast cancer detection and diagnosis. Since different biophysical mechanisms are exploited at these frequencies to discriminate between healthy and diseased tissue, combining these two modalities may result in a more powerful approach for breast cancer detection and diagnosis. Toward this end, we performed microwave dielectric spectroscopy and optical diffuse reflectance spectroscopy measurements at the same sites on freshly-excised normal breast tissues obtained from reduction surgeries at the University of Wisconsin Hospital, using microwave and optical probes with very similar sensing volumes. We found that the microwave dielectric constant and effective conductivity are correlated with tissue composition across the entire measurement frequency range (|r|~0.5–0.6, p<0.01), and that the optical absorption coefficient at 460 nm and optical scattering coefficient are correlated with tissue composition (|r|~ 0.4–0.6, p<0.02). Finally, we found that the optical absorption coefficient at 460 nm is correlated with the microwave dielectric constant and effective conductivity (r=−0.55, p<0.01). Our results suggest that combining optical and microwave modalities for analyzing breast tissue samples may serve as a crosscheck and provide complementary information about tissue composition. PMID:18838370

Electromagnetic spectroscopy of normal breast tissue specimens obtained from reduction surgeries: comparison of optical and microwave properties.

PubMed

Lazebnik, Mariya; Zhu, Changfang; Palmer, Gregory M; Harter, Josephine; Sewall, Sarah; Ramanujam, Nirmala; Hagness, Susan C

2008-10-01

Techniques utilizing electromagnetic energy at microwave and optical frequencies have been shown to be promising for breast cancer detection and diagnosis. Since different biophysical mechanisms are exploited at these frequencies to discriminate between healthy and diseased tissue, combining these two modalities may result in a more powerful approach for breast cancer detection and diagnosis. Toward this end, we performed microwave dielectric spectroscopy and optical diffuse reflectance spectroscopy measurements at the same sites on freshly excised normal breast tissues obtained from reduction surgeries at the University of Wisconsin Hospital, using microwave and optical probes with very similar sensing volumes. We found that the microwave dielectric constant and effective conductivity are correlated with tissue composition across the entire measurement frequency range (|r| approximately 0.5-0.6, p<0.01) and that the optical absorption coefficient at 460 nm and optical scattering coefficient are correlated with tissue composition (|r| approximately 0.4-0.6, p<0.02). Finally, we found that the optical absorption coefficient at 460 nm is correlated with the microwave dielectric constant and effective conductivity (r=-0.55, p<0.01). Our results suggest that combining optical and microwave modalities for analyzing breast tissue samples may serve as a crosscheck and provide complementary information about tissue composition.

Coherent Optical Transients and Spectral Line Narrowing Phenomena in Four Wave Mixing Spectroscopies: Theoretical and Experimental Studies.

NASA Astrophysics Data System (ADS)

Dugan, Mark Allen

1990-08-01

The theoretical basis for new signal transients and spectral features generated in field correlated four wave mixing (4WM) spectroscopies is developed. Special attention is given to those signal responses that are sensitive to phase/amplitude correlation among the input driving fields and not simply their intensity correlation. Thus, the cases of incoherent broadband excitation and of coherent short pulsed excitation will be discussed and compared. Applications to the coherent Raman spectroscopies, both electronically nonresonant and fully resonant, are analyzed. Novel interferometric oscillatory behavior is exposed in terms of field-matter detuning beats and matter-matter bi-level and tri-level quantum beats. In addition new detuning resonances are found that have sub-material linewidths and lock onto the mode frequency of the driven chromophore. These spectral features are a member of a class of bichromophore resonant lineshapes arising from nonlinear mixing with correlated driving fields. The origin of such bichromophore resonances can be based on a coupling between two field-matter superposition states driven by correlated fields on separate chromophores. Analytic results are presented and modelled to anticipate the experimental results presented in a following chapter. The onset of resolvable homogeneous electronic memory is reported in room temperature solutions of dye molecules. A narrowing of the homogeneous linewidths with increasing concentration of these dye solutions is observed in sub-picosecond photon echo experiments. This effect is attributed to aggregation which results in a delocalization of the electronic states over several molecules. Ultra -fast spectral diffusion in these dye aggregates is observed in stimulated photon echo measurements. Aggregate bands, seen in the linear absorption spectrum only at high concentrations, can be probed in more dilute solutions with nonlinear four wave mixing.

Mapping Diffusion in a Living Cell via the Phasor Approach

PubMed Central

Ranjit, Suman; Lanzano, Luca; Gratton, Enrico

2014-01-01

Diffusion of a fluorescent protein within a cell has been measured using either fluctuation-based techniques (fluorescence correlation spectroscopy (FCS) or raster-scan image correlation spectroscopy) or particle tracking. However, none of these methods enables us to measure the diffusion of the fluorescent particle at each pixel of the image. Measurement using conventional single-point FCS at every individual pixel results in continuous long exposure of the cell to the laser and eventual bleaching of the sample. To overcome this limitation, we have developed what we believe to be a new method of scanning with simultaneous construction of a fluorescent image of the cell. In this believed new method of modified raster scanning, as it acquires the image, the laser scans each individual line multiple times before moving to the next line. This continues until the entire area is scanned. This is different from the original raster-scan image correlation spectroscopy approach, where data are acquired by scanning each frame once and then scanning the image multiple times. The total time of data acquisition needed for this method is much shorter than the time required for traditional FCS analysis at each pixel. However, at a single pixel, the acquired intensity time sequence is short; requiring nonconventional analysis of the correlation function to extract information about the diffusion. These correlation data have been analyzed using the phasor approach, a fit-free method that was originally developed for analysis of FLIM images. Analysis using this method results in an estimation of the average diffusion coefficient of the fluorescent species at each pixel of an image, and thus, a detailed diffusion map of the cell can be created. PMID:25517145

Relationship among Glutamine, γ-Aminobutyric Acid, and Social Cognition in Autism Spectrum Disorders

PubMed Central

Sikoglu, Elif M.; Hodge, Steven M.; Edden, Richard A.E.; Foley, Ann; Kennedy, David N.; Moore, Constance M.; Frazier, Jean A.

2015-01-01

Abstract Objective: An imbalance of excitatory and inhibitory neurotransmission in autism spectrum disorder (ASD) has been proposed. We compared glutamate (Glu), glutamine (Gln), and γ-aminobutyric acid (GABA) levels in the anterior cingulate cortex (ACC) of 13 males with ASD and 14 typically developing (TD) males (ages 13–17), and correlated these levels with intelligence quotient (IQ) and measures of social cognition. Methods: Social cognition was evaluated by administration of the Social Responsiveness Scale (SRS) and the Reading the Mind in the Eyes Test (RMET). We acquired proton magnetic resonance spectroscopy (1H-MRS) data from the bilateral ACC using the single voxel point resolved spectroscopy sequence (PRESS) to quantify Glu and Gln, and Mescher–Garwood point-resolved spectroscopy sequence (MEGA-PRESS) to quantify GABA levels referenced to creatine (Cr). Results: There were higher Gln levels (p=0.04), and lower GABA/Cre levels (p=0.09) in the ASD group than in the TD group. There was no difference in Glu levels between groups. Gln was negatively correlated with RMET score (rho=−0.62, p=0.001) and IQ (rho=−0.56, p=0.003), and positively correlated with SRS scores (rho=0.53, p=0.007). GABA/Cre levels were positively correlated with RMET score (rho=0.34, p=0.09) and IQ (rho=0.36, p=0.07), and negatively correlated with SRS score (rho=−0.34, p=0.09). Conclusions: These data suggest an imbalance between glutamatergic neurotransmission and GABA-ergic neurotransmission in ASD. Higher Gln levels and lower GABA/Cre levels were associated with lower IQ and greater impairments in social cognition across groups. PMID:25919578

Correlation-driven charge migration following double ionization and attosecond transient absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hollstein, Maximilian; Santra, Robin; Pfannkuche, Daniela

2017-05-01

We theoretically investigate charge migration following prompt double ionization. Thereby, we extend the concept of correlation-driven charge migration, which was introduced by Cederbaum and coworkers for single ionization [Chem. Phys. Lett. 307, 205 (1999), 10.1016/S0009-2614(99)00508-4], to doubly ionized molecules. This allows us to demonstrate that compared to singly ionized molecules, in multiply ionized molecules, electron dynamics originating from electronic relaxation and correlation are particularly prominent. In addition, we also discuss how these correlation-driven electron dynamics might be evidenced and traced experimentally using attosecond transient absorption spectroscopy. For this purpose, we determine the time-resolved absorption cross section and find that the correlated electron dynamics discussed are reflected in it with exceptionally great detail. Strikingly, we find that features in the cross section can be traced back to electron hole populations and time-dependent partial charges and hence, can be interpreted with surprising ease. By taking advantage of element-specific core-to-valence transitions even atomic spatial resolution can be achieved. Thus, with the theoretical considerations presented, not only do we predict particularly diverse and correlated electron dynamics in molecules to follow prompt multiple ionization but we also identify a promising route towards their experimental investigation.

Selection of the NIR region for a regression model of the ethanol concentration in fermentation process by an online NIR and mid-IR dual-region spectrometer and 2D heterospectral correlation spectroscopy.

PubMed

Nishii, Takashi; Genkawa, Takuma; Watari, Masahiro; Ozaki, Yukihiro

2012-01-01

A new selection procedure of an informative near-infrared (NIR) region for regression model building is proposed that uses an online NIR/mid-infrared (mid-IR) dual-region spectrometer in conjunction with two-dimensional (2D) NIR/mid-IR heterospectral correlation spectroscopy. In this procedure, both NIR and mid-IR spectra of a liquid sample are acquired sequentially during a reaction process using the NIR/mid-IR dual-region spectrometer; the 2D NIR/mid-IR heterospectral correlation spectrum is subsequently calculated from the obtained spectral data set. From the calculated 2D spectrum, a NIR region is selected that includes bands of high positive correlation intensity with mid-IR bands assigned to the analyte, and used for the construction of a regression model. To evaluate the performance of this procedure, a partial least-squares (PLS) regression model of the ethanol concentration in a fermentation process was constructed. During fermentation, NIR/mid-IR spectra in the 10000 - 1200 cm(-1) region were acquired every 3 min, and a 2D NIR/mid-IR heterospectral correlation spectrum was calculated to investigate the correlation intensity between the NIR and mid-IR bands. NIR regions that include bands at 4343, 4416, 5778, 5904, and 5955 cm(-1), which result from the combinations and overtones of the C-H group of ethanol, were selected for use in the PLS regression models, by taking the correlation intensity of a mid-IR band at 2985 cm(-1) arising from the CH(3) asymmetric stretching vibration mode of ethanol as a reference. The predicted results indicate that the ethanol concentrations calculated from the PLS regression models fit well to those obtained by high-performance liquid chromatography. Thus, it can be concluded that the selection procedure using the NIR/mid-IR dual-region spectrometer combined with 2D NIR/mid-IR heterospectral correlation spectroscopy is a powerful method for the construction of a reliable regression model.

Differentiating pediatric epileptic brain tissue from normal brain tissue by using time-dependent diffuse reflectance spectroscopy in vivo: comprehensive data analysis method in the time domain

NASA Astrophysics Data System (ADS)

Oh, Sanghoon; Fernald, Bradley; Bhatia, Sanjiv; Ragheb, John; Sandberg, David; Johnson, Mahlon; Lin, Wei-Chiang

2009-05-01

This research investigated the feasibility of using time-dependent diffuse reflectance spectroscopy to differentiate pediatric epileptic brain tissue from normal brain tissue. The optical spectroscopic technique monitored the dynamic optical properties of the cerebral cortex that are associated with its physiological, morphological, and compositional characteristics. Due to the transient irregular epileptic discharge activity within the epileptic brain tissue it was hypothesized that the lesion would express abnormal dynamic optical behavior that would alter normal dynamic behavior. Thirteen pediatric epilepsy patients and seven pediatric brain tumor patients (normal controls) were recruited for this clinical study. Dynamic optical properties were obtained from the cortical surface intraoperatively using a timedependent diffuse reflectance spectroscopy system. This system consisted of a fiber-optic probe, a tungsten-halogen light source, and a spectrophotometer. It acquired diffuse reflectance spectra with a spectral range of 204 nm to 932 nm at a rate of 33 spectra per second for approximately 12 seconds. Biopsy samples were taken from electrophysiologically abnormal cortex and evaluated by a neuropathologist, which served as a gold standard for lesion classification. For data analysis, spectral intensity changes of diffuse reflectance in the time domain at two different wavelengths from each investigated site were compared. Negative correlation segment, defined by the periods where the intensity changes at the two wavelengths were opposite in their slope polarity, were extracted. The total duration of negative correlation, referred to as the "negative correlation time index", was calculated by integrating the negative correlation segments. The negative correlation time indices from all investigated sites were sub-grouped according to the corresponding histological classifications. The difference between the mean indices of two subgroups was evaluated by standard t-test. These comparison and calculation procedures were carried out for all possible wavelength combinations between 400 nm and 800 nm with 2 nm increments. The positive group consisted of seven pathologically abnormal test sites, and the negative group consisted of 13 normal test sites from non-epileptic tumor patients. A standard t-test showed significant difference between negative correlation time indices from the two groups at the wavelength combinations of 700-760 nm versus 550-580 nm. An empirical discrimination algorithm based on the negative correlation time indices in this range produced 100% sensitivity and 85% specificity. Based on these results time-dependent diffuse reflectance spectroscopy with optimized data analysis methods differentiates epileptic brain tissue from normal brain tissue adequately, therefore can be utilized for surgical guidance, and may enhance the surgical outcome of pediatric epilepsy surgery.

Dielectric and structural characterisation of chalcogenide glasses via terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Ravagli, A.; Naftaly, M.; Craig, C.; Weatherby, E.; Hewak, D. W.

2017-07-01

Terahertz time-domain spectroscopy (THz TDS) was used to investigate a series of chalcogenide glasses. In particular, the dielectric properties at terahertz frequencies were determined and correlated with the glass composition. The experimental results showed a strong relationship between the dielectric properties and the polarizability of the glasses studied. A new explanation based on the coordination number of the metallic cations was proposed to understand these observations.

Correlation Between Early-Stage Expansion and Spectral Emission of a Nanosecond Laser-Induced Plasma from Organic Material

DTIC Science & Technology

2008-01-01

atmosphere like ours (mix of nitrogen and oxygen) implies a more complex plasma chemistry . For example, one of these difficulties is the interpretation of...due to LSDW have also been observed. KEYWORDS Polymer ablation, Shadowgraphy, Time-resolved laser induced breakdown spectroscopy, Plasma ... chemistry , Organic materials analysis, Expansion of laser-induced plasma 1 INTRODUCTION Laser-Induced Breakdown Spectroscopy (LIBS) traditionally

Correlation of quality measurements to visible-near infrared spectra of pasteurized egg

USDA-ARS?s Scientific Manuscript database

A twelve week study was conducted on the egg albumen from both pasteurized and non-pasteurized shell eggs using visible-near infrared spectroscopy. Correlation of the chemical changes detected in the spectra to the measurement of Haugh units (measure of interior egg quality) was carried out using ch...

Chemometric correlation of shelf life, quality measurements, and visible-near infrared spectra of pasteurized eggs

USDA-ARS?s Scientific Manuscript database

A twelve week study was conducted on the egg albumen from both pasteurized and non-pasteurized shell eggs using visible-near infrared spectroscopy. Correlation of the chemical changes detected in the spectra to the measurement of Haugh units (measure of interior egg quality) was carried out using pr...

In vivo macular pigment measurements: a comparison of resonance Raman spectroscopy and heterochromatic flicker photometry

PubMed Central

Hogg, R E; Anderson, R S; Stevenson, M R; Zlatkova, M B; Chakravarthy, U

2007-01-01

Aim To investigate whether two methods of measuring macular pigment—namely, heterochromatic flicker photometry (HFP) and resonance Raman spectroscopy (RRS)—yield comparable data. Methods Macular pigment was measured using HFP and RRS in the right eye of 107 participants aged 20–79 years. Correlations between methods were sought and regression models generated. RRS was recorded as Raman counts and HFP as macular pigment optical density (MPOD). The average of the top three of five Raman counts was compared with MPOD obtained at 0.5° eccentricity, and an integrated measure (spatial profile; MPODsp) computed from four stimulus sizes on HFP. Results The coefficient of variation was 12.0% for MPODsp and 13.5% for Raman counts. MPODsp exhibited significant correlations with Raman counts (r = 0.260, p = 0.012), whereas MPOD at 0.5° did not correlate significantly (r = 0.163, p = 0.118). MPODsp was not significantly correlated with age (p = 0.062), whereas MPOD at 0.5° was positively correlated (p = 0.011). Raman counts showed a significant decrease with age (p = 0.002) and were significantly lower when pupil size was smaller (p = 0.015). Conclusions Despite a statistically significant correlation, the correlations were weak, with those in excess of 90% of the variance between MPODsp and Raman counts remaining unexplained, meriting further research. PMID:16825281

Time-Domain Nuclear Magnetic Resonance (TD-NMR) and Chemometrics for Determination of Fat Content in Commercial Products of Milk Powder.

PubMed

Nascimento, Paloma Andrade Martins; Barsanelli, Paulo Lopes; Rebellato, Ana Paula; Pallone, Juliana Azevedo Lima; Colnago, Luiz Alberto; Pereira, Fabíola Manhas Verbi

2017-03-01

This study shows the use of time-domain (TD)-NMR transverse relaxation (T2) data and chemometrics in the nondestructive determination of fat content for powdered food samples such as commercial dried milk products. Most proposed NMR spectroscopy methods for measuring fat content correlate free induction decay or echo intensities with the sample's mass. The need for the sample's mass limits the analytical frequency of NMR determination, because weighing the samples is an additional step in this procedure. Therefore, the method proposed here is based on a multivariate model of T2 decay, measured with Carr-Purcell-Meiboom-Gill pulse sequence and reference values of fat content. The TD-NMR spectroscopy method shows high correlation (r = 0.95) with the lipid content, determined by the standard extraction method of Bligh and Dyer. For comparison, fat content determination was also performed using a multivariate model with near-IR (NIR) spectroscopy, which is also a nondestructive method. The advantages of the proposed TD-NMR method are that it (1) minimizes toxic residue generation, (2) performs measurements with high analytical frequency (a few seconds per analysis), and (3) does not require sample preparation (such as pelleting, needed for NIR spectroscopy analyses) or weighing the samples.

Sensitivity of near-infrared spectroscopy and diffuse correlation spectroscopy to brain hemodynamics: simulations and experimental findings during hypercapnia

PubMed Central

Selb, Juliette; Boas, David A.; Chan, Suk-Tak; Evans, Karleyton C.; Buckley, Erin M.; Carp, Stefan A.

2014-01-01

Abstract. Near-infrared spectroscopy (NIRS) and diffuse correlation spectroscopy (DCS) are two diffuse optical technologies for brain imaging that are sensitive to changes in hemoglobin concentrations and blood flow, respectively. Measurements for both modalities are acquired on the scalp, and therefore hemodynamic processes in the extracerebral vasculature confound the interpretation of cortical hemodynamic signals. The sensitivity of NIRS to the brain versus the extracerebral tissue and the contrast-to-noise ratio (CNR) of NIRS to cerebral hemodynamic responses have been well characterized, but the same has not been evaluated for DCS. This is important to assess in order to understand their relative capabilities in measuring cerebral physiological changes. We present Monte Carlo simulations on a head model that demonstrate that the relative brain-to-scalp sensitivity is about three times higher for DCS (0.3 at 3 cm) than for NIRS (0.1 at 3 cm). However, because DCS has higher levels of noise due to photon-counting detection, the CNR is similar for both modalities in response to a physiologically realistic simulation of brain activation. Even so, we also observed higher CNR of the hemodynamic response during graded hypercapnia in adult subjects with DCS than with NIRS. PMID:25453036

Chemical transitions of Areca semen during the thermal processing revealed by temperature-resolved ATR-FTIR spectroscopy and two-dimensional correlation analysis

NASA Astrophysics Data System (ADS)

Wang, Zhibiao; Wang, Xu; Pei, Wenxuan; Li, Sen; Sun, Suqin; Zhou, Qun; Chen, Jianbo

2018-03-01

Areca semen is a common herb used in traditional Chinese medicine, but alkaloids in this herb are categorized as Group I carcinogens by IARC. It has been proven that the stir-baking process can reduce alkaloids in Areca semen while keep the activity for promoting digestion. However, the changes of compositions other than alkaloids during the thermal processing are unclear. Understanding the thermal chemical transitions of Areca semen is necessary to explore the processing mechanisms and optimize the procedures. In this research, FTIR spectroscopy with a temperature-controlled ATR accessory is employed to study the heating process of Areca semen. Principal component analysis and two-dimensional correlation spectroscopy are used to interpret the spectra to reveal the chemical transitions of Areca semen in different temperature ranges. The loss of a few volatile compounds in the testa and sperm happens below 105 °C, while some esters in the sperm decreases above 105 °C. As the heating temperature is close to 210 °C, Areca semen begins to be scorched and the decomposition of many compounds can be observed. This research shows the potential of the temperature-resolved ATR-FTIR spectroscopy in exploring the chemical transitions of the thermal processing of herbal materials.

Identification of crystalline structures in jet-cooled acetylene large clusters studied by two-dimensional correlation infrared spectroscopy

NASA Astrophysics Data System (ADS)

Matsumoto, Yoshiteru; Yoshiura, Ryuto; Honma, Kenji

2017-07-01

We investigated the crystalline structures of jet-cooled acetylene (C2H2) large clusters by laser spectroscopy and chemometrics. The CH stretching vibrations of the C2H2 large clusters were observed by infrared (IR) cavity ringdown spectroscopy. The IR spectra of C2H2 clusters were measured under the conditions of various concentrations of C2H2/He mixture gas for supersonic jets. Upon increasing the gas concentration from 1% to 10%, we observed a rapid intensity enhancement for a band in the IR spectra. The strong dependence of the intensity on the gas concentration indicates that the band was assigned to CH stretching vibrations of the large clusters. An analysis of the IR spectra by two-dimensional correlation spectroscopy revealed that the IR absorption due to the C2H2 large cluster is decomposed into two CH stretching vibrations. The vibrational frequencies of the two bands are almost equivalent to the IR absorption of the pure- and poly-crystalline orthorhombic structures in the aerosol particles. The characteristic temperature behavior of the IR spectra implies the existence of the other large cluster, which is discussed in terms of the phase transition of a bulk crystal.

Calibration of diffuse correlation spectroscopy blood flow index with venous-occlusion diffuse optical spectroscopy in skeletal muscle

PubMed Central

Li, Zhe; Baker, Wesley B.; Parthasarathy, Ashwin B.; Ko, Tiffany S.; Wang, Detian; Schenkel, Steven; Durduran, Turgut; Li, Gang; Yodh, Arjun G.

2015-01-01

Abstract. We investigate and assess the utility of a simple scheme for continuous absolute blood flow monitoring based on diffuse correlation spectroscopy (DCS). The scheme calibrates DCS using venous-occlusion diffuse optical spectroscopy (VO-DOS) measurements of arm muscle tissue at a single time-point. A calibration coefficient (γ) for the arm is determined, permitting conversion of DCS blood flow indices to absolute blood flow units, and a study of healthy adults (N=10) is carried out to ascertain the variability of γ. The average DCS calibration coefficient for the right (i.e., dominant) arm was γ=(1.24±0.15)×108 (mL·100  mL−1·min−1)/(cm2/s). However, variability can be significant and is apparent in our site-to-site and day-to-day repeated measurements. The peak hyperemic blood flow overshoot relative to baseline resting flow was also studied following arm-cuff ischemia; excellent agreement between VO-DOS and DCS was found (R2=0.95, slope=0.94±0.07, mean difference=−0.10±0.45). Finally, we show that incorporation of subject-specific absolute optical properties significantly improves blood flow calibration accuracy. PMID:26720870

Measuring speaker–listener neural coupling with functional near infrared spectroscopy

PubMed Central

Liu, Yichuan; Piazza, Elise A.; Simony, Erez; Shewokis, Patricia A.; Onaral, Banu; Hasson, Uri; Ayaz, Hasan

2017-01-01

The present study investigates brain-to-brain coupling, defined as inter-subject correlations in the hemodynamic response, during natural verbal communication. We used functional near-infrared spectroscopy (fNIRS) to record brain activity of 3 speakers telling stories and 15 listeners comprehending audio recordings of these stories. Listeners’ brain activity was significantly correlated with speakers’ with a delay. This between-brain correlation disappeared when verbal communication failed. We further compared the fNIRS and functional Magnetic Resonance Imaging (fMRI) recordings of listeners comprehending the same story and found a significant relationship between the fNIRS oxygenated-hemoglobin concentration changes and the fMRI BOLD in brain areas associated with speech comprehension. This correlation between fNIRS and fMRI was only present when data from the same story were compared between the two modalities and vanished when data from different stories were compared; this cross-modality consistency further highlights the reliability of the spatiotemporal brain activation pattern as a measure of story comprehension. Our findings suggest that fNIRS can be used for investigating brain-to-brain coupling during verbal communication in natural settings. PMID:28240295

Use of COD, TOC, and Fluorescence Spectroscopy to Estimate BOD in Wastewater.

PubMed

Christian, Evelyn; Batista, Jacimaria R; Gerrity, Daniel

2017-02-01

  Common to all National Pollutant Discharge Elimination System (NPDES) permits in the United States is a limit on biochemical oxygen demand (BOD). Chemical oxygen demand (COD), total organic carbon (TOC), and fluorescence spectroscopy are also capable of quantifying organic content, although the mechanisms of quantification and the organic fractions targeted differ for each test. This study explores correlations between BOD5 and these alternate test procedures using facility influent, primary effluent, and facility effluent samples from a full-scale water resource recovery facility. Relative reductions of the water quality parameters proved to be strong indicators of their suitability as surrogates for BOD5. Suitable correlations were generally limited to the combined datasets for the three sampling locations or the facility effluent alone. COD exhibited relatively strong linear correlations with BOD5 when considering the three sample points (r = 0.985) and the facility effluent alone (r = 0.914), while TOC exhibited a suitable linear correlation with BOD5 in the facility effluent (r = 0.902). Exponential regressions proved to be useful for estimating BOD5 based on TOC or fluorescence (r > 0.95).

[Using 2-DCOS to identify the molecular spectrum peaks for the isomer in the multi-component mixture gases Fourier transform infrared analysis].

PubMed

Zhao, An-Xin; Tang, Xiao-Jun; Zhang, Zhong-Hua; Liu, Jun-Hua

2014-10-01

The generalized two-dimensional correlation spectroscopy and Fourier transform infrared were used to identify hydrocarbon isomers in the mixed gases for absorption spectra resolution enhancement. The Fourier transform infrared spectrum of n-butane and iso-butane and the two-dimensional correlation infrared spectrum of concentration perturbation were used for analysis as an example. The all band and the main absorption peak wavelengths of Fourier transform infrared spectrum for single component gas showed that the spectra are similar, and if they were mixed together, absorption peaks overlap and peak is difficult to identify. The synchronous and asynchronous spectrum of two-dimensional correlation spectrum can clearly identify the iso-butane and normal butane and their respective characteristic absorption peak intensity. Iso-butane has strong absorption characteristics spectrum lines at 2,893, 2,954 and 2,893 cm(-1), and n-butane at 2,895 and 2,965 cm(-1). The analysis result in this paper preliminary verified that the two-dimensional infrared correlation spectroscopy can be used for resolution enhancement in Fourier transform infrared spectrum quantitative analysis.

Analysis and identification of two reconstituted tobacco sheets by three-level infrared spectroscopy

NASA Astrophysics Data System (ADS)

Wu, Xian-xue; Xu, Chang-hua; Li, Ming; Sun, Su-qin; Li, Jin-ming; Dong, Wei

2014-07-01

Two kinds of reconstituted tobacco (RT) from France (RTF) and China (RTC) were analyzed and identified by a three-level infrared spectroscopy method (Fourier-transform infrared spectroscopy (FT-IR) coupled with second derivative infrared spectroscopy (SD-IR) and two-dimensional infrared correlation spectroscopy (2D-IR)). The conventional IR spectra of RTF parallel samples were more consistent than those of RTC according to their overlapped parallel spectra and IR spectra correlation coefficients. FT-IR spectra of both two RTs were similar in holistic spectral profile except for small differences around 1430 cm-1, indicating that they have similar chemical constituents. By analysis of SD-IR spectra of RTFs and RTCs, more distinct fingerprint features, especially peaks at 1106 (1110), 1054 (1059) and 877 (874) cm-1, were disclosed. Even better reproducibility of five SD-IR spectra of RTF in 1750-1400 cm-1 could be seen intuitively from their stacked spectra and could be confirmed by further similarity evaluation of SD-IR spectra. Existence of calcium carbonate and calcium oxalate could be easily observed in two RTs by comparing their spectra with references. Furthermore, the 2D-IR spectra provided obvious, vivid and intuitive differences of RTF and RTC. Both two RTs had a pair of strong positive auto-peaks in 1600-1400 cm-1. Specifically, the autopeak at 1586 cm-1 in RTF was stronger than the one around 1421 cm-1, whereas the one at 1587 cm-1 in RTC was weaker than that at 1458 cm-1. Consequently, the RTs of two different brands were analyzed and identified thoroughly and RTF had better homogeneity than RTC. As a result, three-level infrared spectroscopy method has proved to be a simple, convenient and efficient method for rapid discrimination and homogeneousness estimation of RT.

Could near-infrared Raman spectroscopy be correlated with the METAVIR scores in liver lesions induced by hepatitis C virus?

NASA Astrophysics Data System (ADS)

Gaggini, Marcio Cesar Reino; Navarro, Ricardo Scarparo; Stefanini, Aline Reis; Sano, Rubens Sato; Silveira, Landulfo

2013-03-01

The liver is responsible for several basic functions in human body how the syntheses of the most main proteins and degradation process of toxins, drugs and alcohols. In present days, the viral hepatitis C is one of the highest causes of chronic hepatic illness worldwide, affecting around 3% of the world population. The liver biopsy is considered the gold standard for diagnosing hepatic fibrosis; however, the biopsies may be questioned because of potential sampling error, morbidity, possible mortality and relatively high costs. Spectroscopy techniques such as Raman spectroscopy have been used for diagnosis of human tissues, with favorable results. Raman spectroscopy has been employed to distinguish normal from hepatic lesions through spectral features mainly of proteins, nucleic acids and lipids. In this study, eleven patients with diagnoses of chronic hepatitis C underwent hepatic biopsies having two hepatic fragments collected: one was scored through METAVIR system and the other one was submitted to near-infrared Raman spectroscopy using a dispersive spectrometer (830 nm wavelength, 300 mW laser power and 20 s exposure time). Five spectra were collected in each fragment and submitted to Principal Components Analysis (PCA). Results showed a good correlation between the Raman spectroscopy features and the stage of hepatic fibrosis and inflammation. PCA showed that samples with higher degree of fibrosis presented higher amount of protein features (collagen), whereas samples of higher degree of inflammation presented higher features of hemoglobin, in accordance to the expected evolution of the chronic hepatitis. It has been found an important biomarker for the beginning of hepatic lesion (quinone) with a spectral feature at 1595 cm-1.

Dynamics of diamond nanoparticles in solution and cells.

PubMed

Neugart, Felix; Zappe, Andrea; Jelezko, Fedor; Tietz, C; Boudou, Jean Paul; Krueger, Anke; Wrachtrup, Jörg

2007-12-01

The fluorescence and motional dynamics of single diamond nanocrystals in buffer solution and in living cells is investigated. Stable hydrosols of nanodiamonds in buffer solutions are investigated by fluorescence correlation spectroscopy. Measurement of the effective hydrodynamic radius yields particles of 48 nm diameter, which is in excellent agreement with atomic force microscopy measurements made on the same particles. Fluorescence correlation spectroscopy measurements indicate that nanocrystals easily form aggregates when the buffer pH is changed. This tendency is reduced when the surface of the diamonds is covered with surfactants. Upon incubation, cells spontaneously take up nanocrystals that uniformly distribute in cells. Most of the particles get immobilized within a few minutes. The binding of streptavidin to biotinylated aggregates of 4 nm diameter nanodiamonds is demonstrated.

Lithographically fabricated silicon microreactor for in situ characterization of heterogeneous catalysts—Enabling correlative characterization techniques

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

Baier, S.; Rochet, A.; Hofmann, G.

2015-06-15

We report on a new modular setup on a silicon-based microreactor designed for correlative spectroscopic, scattering, and analytic on-line gas investigations for in situ studies of heterogeneous catalysts. The silicon microreactor allows a combination of synchrotron radiation based techniques (e.g., X-ray diffraction and X-ray absorption spectroscopy) as well as infrared thermography and Raman spectroscopy. Catalytic performance can be determined simultaneously by on-line product analysis using mass spectrometry. We present the design of the reactor, the experimental setup, and as a first example for an in situ study, the catalytic partial oxidation of methane showing the applicability of this reactor formore » in situ studies.« less

Easy monitoring of velocity fields in microfluidic devices using spatiotemporal image correlation spectroscopy.

PubMed

Travagliati, Marco; Girardo, Salvatore; Pisignano, Dario; Beltram, Fabio; Cecchini, Marco

2013-09-03

Spatiotemporal image correlation spectroscopy (STICS) is a simple and powerful technique, well established as a tool to probe protein dynamics in cells. Recently, its potential as a tool to map velocity fields in lab-on-a-chip systems was discussed. However, the lack of studies on its performance has prevented its use for microfluidics applications. Here, we systematically and quantitatively explore STICS microvelocimetry in microfluidic devices. We exploit a simple experimental setup, based on a standard bright-field inverted microscope (no fluorescence required) and a high-fps camera, and apply STICS to map liquid flow in polydimethylsiloxane (PDMS) microchannels. Our data demonstrates optimal 2D velocimetry up to 10 mm/s flow and spatial resolution down to 5 μm.

Trapping, Deformation, and Rotation of Giant Unilamellar Vesicles in Octode Dielectrophoretic Field Cages

PubMed Central

Korlach, J.; Reichle, C.; Müller, T.; Schnelle, T.; Webb, W. W.

2005-01-01

The behavior of freestanding lipid bilayer membranes under the influence of dielectric force potentials was studied by trapping, holding, and rotating individual giant unilamellar vesicles (GUVs) inside dielectrophoretic microfield cages. Using laser scanning confocal microscopy and three-dimensional image reconstructions of GUVs labeled with fluorescent membrane probes, field strength and frequency-dependent vesicle deformations were observed which are explained by calculations of the dielectric force potentials inside the cage. Dynamical membrane properties under the influence of the field cage were studied by fluorescence correlation spectroscopy, circumventing potential artifacts associated with measurements involving GUV immobilization on support surfaces. Lipid transport could be accelerated markedly by the applied fields, aided by hydrodynamic fluid streaming which was also studied by fluorescence correlation spectroscopy. PMID:15863477

Geomorphic Evidence for Martian Ground Ice and Climate Change

NASA Technical Reports Server (NTRS)

Kanner, L. C.; Allen, C. C.; Bell, M. S.

2004-01-01

Recent results from gamma-ray and neutron spectrometers on Mars Odyssey indicate the presence of a hydrogen-rich layer tens of centimeters thick in the uppermost meter in high latitudes (>60 ) on Mars. This hydrogen-rich layer correlates to regions of ice stability. Thus, the subsurface hydrogen is thought to be water ice constituting 35+/- 15% by weight near the north and south polar regions. We refine the location of subsurface ice deposits at a < km scale by combining existing spectroscopy data with surface features indicative of subsurface ice. A positive correlation between spectroscopy data and geomorphic ice indicators has been previously suggested for high latitudes. Here we expand the comparative study to northern mid latitudes (30 deg.N- 65 deg.N).

In situ detection of warfarin using time-correlated single-photon counting

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

Rosengren, Annika M.; Karlsson, Bjoern C.G.; Naeslund, Inga

Highlights: {yields} Direct in situ measurement of specific isomeric forms of the anticoagulant warfarin. {yields} TCSPC spectroscopy in conjunction with synthetic Sudlow I binding site receptors. {yields} Development of sensor principle for use in clinical and environmental monitoring. -- Abstract: Here we report on a novel method for the direct in situ measurement of specific isomeric forms of the anticoagulant warfarin using time correlated single-photon counting (TCSPC) spectroscopy in conjunction with synthetic Sudlow I binding site receptors. The method is highly robust over the clinically significant concentration range, and demonstrates the potential of the binding site mimics in conjunction withmore » the spectroscopic strategy employed here for the determination of this important pharmaceutical in clinical or even environmental samples.« less

Photoelectron spectroscopic and microspectroscopic probes of ferroelectrics

NASA Astrophysics Data System (ADS)

Tǎnase, Liviu C.; Abramiuc, Laura E.; Teodorescu, Cristian M.

2017-12-01

This contribution is a review of recent aspects connected with photoelectron spectroscopy of free ferroelectric surfaces, metals interfaced with these surfaces, graphene-like layers together with some exemplifications concerning molecular adsorption, dissociations and desorptions occurring from ferroelectrics. Standard photoelectron spectroscopy is used nowadays in correlation with other characterization techniques, such as piezoresponse force microscopy, high resolution transmission electron spectroscopy, and ferroelectric hysteresis cycles. In this work we will concentrate mainly on photoelectron spectroscopy and spectro-microscopy characterization of ferroelectric thin films, starting from atomically clean ferroelectric surfaces of lead zirco-titanate, then going towards heterostructures using this material in combination with graphene-like carbon layers or with metals. Concepts involving charge accumulation and depolarization near surface will be revisited by taking into account the newest findings in this area.

Evaluation of Hepatic Steatosis by Using Acoustic Structure Quantification US in a Rat Model: Comparison with Pathologic Examination and MR Spectroscopy.

PubMed

Lee, Dong Ho; Lee, Jae Young; Lee, Kyung Bun; Han, Joon Koo

2017-11-01

Purpose To determine factors that significantly affect the focal disturbance (FD) ratio calculated with an acoustic structure quantification (ASQ) technique in a dietary-induced fatty liver disease rat model and to assess the diagnostic performance of the FD ratio in the assessment of hepatic steatosis by using histopathologic examination as a standard of reference. Materials and Methods Twenty-eight male F344 rats were fed a methionine-choline-deficient diet with a variable duration (3.5 days [half week] or 1, 2, 3, 4, 5, or 6 weeks; four rats in each group). A control group of four rats was maintained on a standard diet. At the end of each diet period, ASQ ultrasonography (US) and magnetic resonance (MR) spectroscopy were performed. Then, the rat was sacrificed and histopathologic examination of the liver was performed. Receiver operating characteristic curve analysis was performed to assess the diagnostic performance of the FD ratio in the evaluation of the degree of hepatic steatosis. The Spearman correlation coefficient was calculated to assess the correlation between the ordinal values, and multivariate linear regression analysis was used to identify significant determinant factors for the FD ratio. Results The diagnostic performance of the FD ratio in the assessment of the degree of hepatic steatosis (area under the receiver operating characteristic curve: 1.000 for 5%-33% steatosis, 0.981 for >33% to 66% steatosis, and 0.965 for >66% steatosis) was excellent and was comparable to that of MR spectroscopy. There was a strong negative linear correlation between the FD ratio and the estimated fat fraction at MR spectroscopy (Spearman ρ, -0.903; P < .001). Multivariate linear regression analysis showed that the degree of hepatic steatosis (P < .001) and fibrosis stage (P = .022) were significant factors affecting the FD ratio. Conclusion The FD ratio may potentially provide good diagnostic performance in the assessment of the degree of hepatic steatosis, with a strong negative linear correlation with the estimated fat fraction at MR spectroscopy. The degree of steatosis and stage of fibrosis at histopathologic examination were significant factors that affected the FD ratio. © RSNA, 2017 Online supplemental material is available for this article.

Correlation between the plasma characteristics and the surface chemistry of plasma-treated polymers through partial least-squares analysis.

PubMed

Mavadat, Maryam; Ghasemzadeh-Barvarz, Massoud; Turgeon, Stéphane; Duchesne, Carl; Laroche, Gaétan

2013-12-23

We investigated the effect of various plasma parameters (relative density of atomic N and H, plasma temperature, and vibrational temperature) and process conditions (pressure and H2/(N2 + H2) ratio) on the chemical composition of modified poly(tetrafluoroethylene) (PTFE). The plasma parameters were measured by means of near-infrared (NIR) and UV-visible emission spectroscopy with and without actinometry. The process conditions of the N2-H2 microwave discharges were set at various pressures ranging from 100 to 2000 mTorr and H2/(N2+H2) gas mixture ratios between 0 and 0.4. The surface chemical composition of the modified polymers was determined by X-ray photoelectron spectroscopy (XPS). A mathematical model was constructed using the partial least-squares regression algorithm to correlate the plasma information (process condition and plasma parameters as determined by emission spectroscopy) with the modified surface characteristics. To construct the model, a set of data input variables containing process conditions and plasma parameters were generated, as well as a response matrix containing the surface composition of the polymer. This model was used to predict the composition of PTFE surfaces subjected to N2-H2 plasma treatment. Contrary to what is generally accepted in the literature, the present data demonstrate that hydrogen is not directly involved in the defluorination of the surface but rather produces atomic nitrogen and/or NH radicals that are shown to be at the origin of fluorine atom removal from the polymer surface. The results show that process conditions alone do not suffice in predicting the surface chemical composition and that the plasma characteristics, which cannot be easily correlated with these conditions, should be considered. Process optimization and control would benefit from plasma diagnostics, particularly infrared emission spectroscopy.

Improving Ramsey spectroscopy in the extreme-ultraviolet region with a random-sampling approach

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

Eramo, R.; Bellini, M.; European Laboratory for Non-linear Spectroscopy

2011-04-15

Ramsey-like techniques, based on the coherent excitation of a sample by delayed and phase-correlated pulses, are promising tools for high-precision spectroscopic tests of QED in the extreme-ultraviolet (xuv) spectral region, but currently suffer experimental limitations related to long acquisition times and critical stability issues. Here we propose a random subsampling approach to Ramsey spectroscopy that, by allowing experimentalists to reach a given spectral resolution goal in a fraction of the usual acquisition time, leads to substantial improvements in high-resolution spectroscopy and may open the way to a widespread application of Ramsey-like techniques to precision measurements in the xuv spectral region.

Analysis of disulphide bonds found in human hair by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Pina-Ruiz, A. L.; Cordova-Fraga, T.; Plascencia-Castro, A. S.; Hernandez-Rayas, A.; Ruvalcaba, J. M.

2017-04-01

Raman spectroscopy offers information-rich spectra, making it a technique easy to use in areas such as biology, chemistry, and in the field. Human hair spectra has been recorded obtaining interesting information about its composition. Correlating information obtained from these spectra to bone health and determining if Raman spectroscopy could be used as a diagnostic tool of bone health is proposed. Spectra from healthy women were compared to the spectra of women who have suffered a bone fracture, all which were aged 39-60. This technique has potential to become a regular diagnostic tool and further investigation to improve and validate this method are needed.

Two Keggin-type heteropolytungstates with transition metal as a central atom: Crystal structure and magnetic study with 2D-IR correlation spectroscopy

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

Chai, Feng; Chen, YiPing, E-mail: ypchen007@sina.com; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002

2013-06-01

Two Keggin-type heteropolytungstates, [Co(phen)₃]₃[CoW₁₂O₄₀]·9H₂O 1 (phen=1,10-phenanthroline) and [Fe(phen)₃]₂[FeW₁₂O₄₀]·H₃O·H₂O 2, have been synthesized via the hydrothermal technique and characterized by single crystal X-ray diffraction analyses, IR, XPS, TG analysis, UV–DRS, XRD, thermal-dependent and magnetic-dependent 2D-COS IR (two-dimensional infrared correlation spectroscopy). Crystal structure analysis reveals that the polyanions in compound 1 are linked into 3D supramolecule through hydrogen bonding interactions between lattice water molecules and terminal oxygen atoms of polyanion units, and [Co(phen)₃]²⁺ cations distributed in the polyanion framework with many hydrogen bonding interactions. The XPS spectra indicate that all the Co atoms in 1 are +2 oxidation state, the Fe atomsmore » in 2 existing with +2 and +3 mixed oxidation states. - Graphical abstract: The magnetic-dependent synchronous 2D correlation IR spectra of 1 (a), 2 (b) over 0–50 mT in the range of 600–1000 cm⁻¹, the obvious response indicate two Keggin polyanions skeleton susceptible to applied magnetic field. Highlights: • Two Keggin-type heteropolytungstates with transition metal as a central atom has been obtained. • Compound 1 forms into 3D supramolecular architecture through hydrogen bonding between water molecules and polyanions. • Magnetic-dependent 2D-IR correlation spectroscopy was introduced to discuss the magnetism of polyoxometalate.« less

Adulteration detection in milk using infrared spectroscopy combined with two-dimensional correlation analysis

NASA Astrophysics Data System (ADS)

He, Bin; Liu, Rong; Yang, Renjie; Xu, Kexin

2010-02-01

Adulteration of milk and dairy products has brought serious threats to human health as well as enormous economic losses to the food industry. Considering the diversity of adulterants possibly mixed in milk, such as melamine, urea, tetracycline, sugar/salt and so forth, a rapid, widely available, high-throughput, cost-effective method is needed for detecting each of the components in milk at once. In this paper, a method using Fourier Transform Infrared spectroscopy (FTIR) combined with two-dimensional (2D) correlation spectroscopy is established for the discriminative analysis of adulteration in milk. Firstly, the characteristic peaks of the raw milk are found in the 4000-400 cm-1 region by its original spectra. Secondly, the adulterant samples are respectively detected with the same method to establish a spectral database for subsequent comparison. Then, 2D correlation spectra of the samples are obtained which have high time resolution and can provide information about concentration-dependent intensity changes not readily accessible from one-dimensional spectra. And the characteristic peaks in the synchronous 2D correlation spectra of the suspected samples are compared with those of raw milk. The differences among their synchronous spectra imply that the suspected milk sample must contain some kinds of adulterants. Melamine, urea, tetracycline and glucose adulterants in milk are identified respectively. This nondestructive method can be used for a correct discrimination on whether the milk and dairy products are adulterated with deleterious substances and it provides a new simple and cost-effective alternative to test the components of milk.

Identification of authentic and adulterated Aquilariae Lignum Resinatum by Fourier transform infrared (FT-IR) spectroscopy and two-dimensional correlation analysis

NASA Astrophysics Data System (ADS)

Qu, Lei; Chen, Jian-bo; Zhou, Qun; Zhang, Gui-jun; Sun, Su-qin; Guo, Yi-zhen

2016-11-01

As a kind of expensive perfume and valuable herb, the commercial Aquilariae Lignum Resinatum (ALR) is often adulterated for economic motivations. In this research, Fourier transform infrared (FT-IR) spectroscopy and two-dimensional (2D) correlation analysis are employed to establish a simple and quick identification method for the authentic and adulterated ALR. In the conventional infrared spectra, the standard ALR has a strong peak at 1658 cm-1 referring to the conjugated carbonyl of resin, while this peak is absent in the adulterated samples. The position, intensity, and shape of the auto-peaks and cross-peaks of the authentic and adulterated ALR are much different in the synchronous 2D correlation spectra with thermal perturbation. In the range of 1700-1500 cm-1, the standard ALR has four obvious auto-peaks, while the strongest one is at 1659 cm-1. The adulterated sample w-1 has three obvious auto-peaks and the strongest one is at 1647 cm-1. The adulterated sample w-2 has three obvious auto-peaks and the strongest one is at 1519 cm-1. The adulterated sample w-3 has four obvious auto-peaks and the strongest one is at 1690 cm-1. The above auto-peaks confirm that the standard ALR contains a certain content of resin compounds, while the three counterfeits contain little or different resins. The results show the potential of FT-IR spectroscopy and 2D correlation analysis in the simple and quick identification of authentic and adulterated ALR.

Effect of Heat-treatment on Accuracy of Infrared Spectroscopy and Digital and Optical Brix Refractometers for Measuring Immunoglobulin G Concentration in Bovine Colostrum.

PubMed

Elsohaby, I; McClure, J T; Dow, N; Keefe, G P

2018-01-01

Heat-treatment of colostrum is a method developed to reduce calf exposure to pathogens. Infrared (IR) spectroscopy and Brix refractometers can be used for measuring colostral IgG concentration and assessing colostrum quality. To determine the impact of heat-treatment on accuracy of IR spectroscopy and Brix refractometers for measuring colostral IgG concentration and assessing colostrum quality before and after heat-treatment. A total of 60 Holstein dairy cows on 8 commercial dairy farms. A cross-sectional study was designed to determine the effect of heat-treatment at 60°C and 63°C each for 30 and 60 minutes duration on colostral IgG concentration measured by the reference radial immunodiffusion (RID) assay, IR spectroscopy, and digital and optical refractometers. Colostrum IgG concentration significantly decreased after heat-treatment at 63°C for 30 or 60 minutes as measured by RID, but the IgG values remained unchanged when measured by IR spectroscopy and refractometers. The lowest correlation coefficient found between IR spectroscopy (r = 0.70) and RID results was in colostrum heat-treated at 63°C for 60 minutes. For digital (r = 0.48) and optical (r = 0.50) refractometers, the lowest correlation coefficient was at 63°C for 30 minutes when compared to RID. The accuracy of the IR spectroscopy, digital and optical Brix refractometers was decreased from 91.7 to 80%, 81.7 to 45%, and 80 to 45%, respectively, when colostrum heat-treated at 63°C for 60 minutes. Radial immunodiffusion, IR spectroscopy, and Brix refractometers exhibit utility for measuring IgG concentration when colostrum heat-treated at 60°C but does not detect decrease IgG concentrations when heat-treated at 63°C. Copyright © 2017 The Authors. Journal of Veterinary Internal Medicine published by Wiley Periodicals, Inc. on behalf of the American College of Veterinary Internal Medicine.

Frequency response measurements in battery electrodes

NASA Technical Reports Server (NTRS)

Thomas, Daniel L.

1992-01-01

Electrical impedance spectroscopy was used to investigate the behavior of porous zinc, silver, cadmium, and nickel electrodes. State of charge could be correlated with impedance data for all but the nickel electrodes. State of health was correlated with impedance data for two AgZn cells, one apparently good and the other bad. The impedance data was fit to equivalent circuit models.

Hydrodynamic size-dependent cellular uptake of aqueous QDs probed by fluorescence correlation spectroscopy.

PubMed

Dong, Chaoqing; Irudayaraj, Joseph

2012-10-11

Aqueous quantum dots (QDs) directly synthesized with various thiol ligands have been investigated as imaging probes in living cells. However, the effect of the surface chemistry of these ligands on QDs' cellular uptakes and their intracellular fate remains poorly understood. In this work, four CdTe QDs were directly synthesized under aqueous conditions using four different thiols as stabilizers and their interactions with cells were investigated. Fluorescence correlation spectroscopy (FCS), X-ray photoelectron spectroscopy (XPS), and zeta potential measurements on QDs primarily show that the surface structure of these QDs is highly dependent on the thiol ligands used in the preparation of QDs' precursors, including its layer thicknesses, densities, and surface charges. Subsequently, FCS integrated with the maximum-entropy-method-based FCS (MEMFCS) was used to investigate the concentration distribution and dynamics of these QDs in living A-427 cells. Our findings indicate that QDs' surface characteristics affect cell membrane adsorption and subsequent internalization. More critically, we show that the cellular uptake of aqueous QDs is dependent on their hydrodynamic diameter and might have the potential to escape trapped environments to accumulate in the cytoplasm.

Specificity and mechanism of action of alpha-helical membrane-active peptides interacting with model and biological membranes by single-molecule force spectroscopy.

PubMed

Sun, Shiyu; Zhao, Guangxu; Huang, Yibing; Cai, Mingjun; Shan, Yuping; Wang, Hongda; Chen, Yuxin

2016-07-01

In this study, to systematically investigate the targeting specificity of membrane-active peptides on different types of cell membranes, we evaluated the effects of peptides on different large unilamellar vesicles mimicking prokaryotic, normal eukaryotic, and cancer cell membranes by single-molecule force spectroscopy and spectrum technology. We revealed that cationic membrane-active peptides can exclusively target negatively charged prokaryotic and cancer cell model membranes rather than normal eukaryotic cell model membranes. Using Acholeplasma laidlawii, 3T3-L1, and HeLa cells to represent prokaryotic cells, normal eukaryotic cells, and cancer cells in atomic force microscopy experiments, respectively, we further studied that the single-molecule targeting interaction between peptides and biological membranes. Antimicrobial and anticancer activities of peptides exhibited strong correlations with the interaction probability determined by single-molecule force spectroscopy, which illustrates strong correlations of peptide biological activities and peptide hydrophobicity and charge. Peptide specificity significantly depends on the lipid compositions of different cell membranes, which validates the de novo design of peptide therapeutics against bacteria and cancers.

Orientational alignment in solids from bidimensional isotropic-anisotropic nuclear magnetic resonance spectroscopy: applications to the analysis of aramide fibers.

PubMed

Sachleben, J R; Frydman, L

1997-02-01

The use of two-dimensional isotropic-anisotropic correlation spectroscopy for the analysis of orientational alignment in solids is presented. The theoretical background and advantages of this natural-abundance 13C NMR method of measurement are discussed, and demonstrated with a series of powder and single-crystal variable-angle correlation spectroscopy (VACSY) experiments on model systems. The technique is subsequently employed to analyze the orientational distributions of three polymer fibers: Kevlar 29, Kevlar 49 and Kevlar 149. Using complementary two-dimensional NMR data recorded on synthetic samples of poly(p-phenyleneterephthalamide), the precursor of Kevlar, it was found that these commercial fibers possess molecules distributed over a very narrow orientational range with respect to the macroscopic director. The widths measured for these director distribution arrangements were (12 +/- 1.5) degrees for Kevlar 29, (15 +/- 1.5) degrees for Kevlar 49, and (8 +/- 1.5) degrees for Kevlar 149. These figures compare well with previous results obtained for non-commercial fiber samples derived from the same polymer.

Enhancement of visible-light photoactivity by polypropylene coated plasmonic Au/TiO2 for dye degradation in water solution

NASA Astrophysics Data System (ADS)

D'Amato, C. A.; Giovannetti, R.; Zannotti, M.; Rommozzi, E.; Ferraro, S.; Seghetti, C.; Minicucci, M.; Gunnella, R.; Di Cicco, A.

2018-05-01

A new approach to obtain a heterogeneous photocatalytic material with gold nanoparticles and TiO2 semiconductor was performed exploiting the reducing ability of acetylacetone, a chemical present in the TiO2 paste formulation. Gold/TiO2 heterogeneous catalyst supported on polypropylene [PP@Au-TiO2]A was prepared; composition, structure and morphology of this new material were defined by using UV-Vis spectroscopy, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), X-ray diffraction (XRD), X-ray Fluorescence (XRF), Raman Spectroscopy, Photoluminescence and Diffuse Reflectance Spectroscopy. The new material was tested in the photocatalytic degradation of Alizarin Red S in water solution, as target pollutant, under visible light and correlated with structural and spectroscopic characterizations. [PP@Au-TiO2]A showed higher photocatalytic activity respect to pure [PP@TiO2]A with an improvement of photodegradation kinetic. The best performance was obtained using [PP@Au-TiO2]A sample with 0.006 wt.% of Au and the photocatalytic improvement was correlated with the band gap energy decrease of photocatalyst.

An effective approach to quantitative analysis of ternary amino acids in foxtail millet substrate based on terahertz spectroscopy.

PubMed

Lu, Shao Hua; Li, Bao Qiong; Zhai, Hong Lin; Zhang, Xin; Zhang, Zhuo Yong

2018-04-25

Terahertz time-domain spectroscopy has been applied to many fields, however, it still encounters drawbacks in multicomponent mixtures analysis due to serious spectral overlapping. Here, an effective approach to quantitative analysis was proposed, and applied on the determination of the ternary amino acids in foxtail millet substrate. Utilizing three parameters derived from the THz-TDS, the images were constructed and the Tchebichef image moments were used to extract the information of target components. Then the quantitative models were obtained by stepwise regression. The correlation coefficients of leave-one-out cross-validation (R loo-cv 2 ) were more than 0.9595. As for external test set, the predictive correlation coefficients (R p 2 ) were more than 0.8026 and the root mean square error of prediction (RMSE p ) were less than 1.2601. Compared with the traditional methods (PLS and N-PLS methods), our approach is more accurate, robust and reliable, and can be a potential excellent approach to quantify multicomponent with THz-TDS spectroscopy. Copyright © 2017 Elsevier Ltd. All rights reserved.

Two-dimensional correlation infrared spectroscopy applied to the identification of ephedrine and pseudoephedrine in illegally adulterated slimming herbal products.

PubMed

Miao, Li; Liu, Yan; Li, Hao; Qi, Yunpeng; Lu, Feng

2017-02-01

Two-dimensional correlation spectroscopy (2DCOS) was employed for the identification of ephedrine (Ep) and pseudoephedrine (Ps) present in illegally adulterated slimming herbal products (SHPs). Second derivative (SD) spectral pretreatment was used prior to 2DCOS analysis to highlight specific features not readily observable by Fourier transform infrared spectroscopy (FTIR), SD-FTIR, or original 2DCOS, leading to enhanced resolution and a reduced lower limit of detection (<1% in this study). After examining the power spectra of suspicious SHPs, bands containing characteristic peaks for Ep (701, 747, 1042, 1363, 1375, 1451, 1478 cm -1 etc) and/or Ps (703, 767, 1037, 1375, 1428, 1455, 1590 cm - 1, etc.) were selected to construct synchronous and asynchronous maps for further analysis, while the latter was applied to discriminate positive SHPs adulterated simultaneously with Ep and Ps. The proposed method is simple and economical and has the potential to identify other chemicals in illegally adulterated herbal products. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

State-of-the-Art Fluorescence Fluctuation-Based Spectroscopic Techniques for the Study of Protein Aggregation

PubMed Central

Kinjo, Masataka

2018-01-01

Neurodegenerative diseases, including amyotrophic lateral sclerosis (ALS), Alzheimer’s disease, Parkinson’s disease, and Huntington’s disease, are devastating proteinopathies with misfolded protein aggregates accumulating in neuronal cells. Inclusion bodies of protein aggregates are frequently observed in the neuronal cells of patients. Investigation of the underlying causes of neurodegeneration requires the establishment and selection of appropriate methodologies for detailed investigation of the state and conformation of protein aggregates. In the current review, we present an overview of the principles and application of several methodologies used for the elucidation of protein aggregation, specifically ones based on determination of fluctuations of fluorescence. The discussed methods include fluorescence correlation spectroscopy (FCS), imaging FCS, image correlation spectroscopy (ICS), photobleaching ICS (pbICS), number and brightness (N&B) analysis, super-resolution optical fluctuation imaging (SOFI), and transient state (TRAST) monitoring spectroscopy. Some of these methodologies are classical protein aggregation analyses, while others are not yet widely used. Collectively, the methods presented here should help the future development of research not only into protein aggregation but also neurodegenerative diseases. PMID:29570669

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.

Nondestructive evaluation of soluble solid content in strawberry by near infrared spectroscopy

NASA Astrophysics Data System (ADS)

Guo, Zhiming; Huang, Wenqian; Chen, Liping; Wang, Xiu; Peng, Yankun

This paper indicates the feasibility to use near infrared (NIR) spectroscopy combined with synergy interval partial least squares (siPLS) algorithms as a rapid nondestructive method to estimate the soluble solid content (SSC) in strawberry. Spectral preprocessing methods were optimized selected by cross-validation in the model calibration. Partial least squares (PLS) algorithm was conducted on the calibration of regression model. The performance of the final model was back-evaluated according to root mean square error of calibration (RMSEC) and correlation coefficient (R2 c) in calibration set, and tested by mean square error of prediction (RMSEP) and correlation coefficient (R2 p) in prediction set. The optimal siPLS model was obtained with after first derivation spectra preprocessing. The measurement results of best model were achieved as follow: RMSEC = 0.2259, R2 c = 0.9590 in the calibration set; and RMSEP = 0.2892, R2 p = 0.9390 in the prediction set. This work demonstrated that NIR spectroscopy and siPLS with efficient spectral preprocessing is a useful tool for nondestructively evaluation SSC in strawberry.

"Sizing" the oligomers of Azami Green fluorescent protein with FCS and antibunching

NASA Astrophysics Data System (ADS)

Temirov, Jamshid; Werner, James H.; Goodwin, Peter M.; Bradbury, Andrew R. M.

2012-02-01

Fluorescent proteins are invaluable molecules in fluorescence microscopy and spectroscopy. The size and brightness of fluorescent proteins often dictates the application they may be used for. While a monomeric protein may be the least perturbative structure for labeling a protein in a cell, often oligomers (dimers and tetramers) of fluorescent proteins can be more stable. However, from a quantitative microscopy standpoint, it is important to realize the photophysical properties of monomers do not necessarily multiply by their number when they form oligomers. In this work we studied oligomerization states of the Azami Green (AG) protein with fluorescence correlation spectroscopy (FCS) and photon antibunching or photon pair correlation spectroscopy (PPCS). FCS was used to measure the hydrodynamic size of the oligomers, whereas antibunching was used to count the number of fluorescent emitters in the oligomers. The results exhibited that the dimers of AG were single emitters and the tetramers were dual-emitters, indicative of dipole-dipole interactions and energy transfer between the monomeric units. We also used these methods to estimate the number of fluorescent proteins displayed on T7 phage molecules.

Proton magnetic resonance spectroscopy in focal cortical dysplasia at 3T.

PubMed

Tschampa, Henriette J; Urbach, Horst; Träber, Frank; Sprinkart, Alois M; Greschus, Susanne; Malter, Michael P; Surges, Rainer; Gieseke, Jürgen; Block, Wolfgang

2015-11-01

Focal cortical dysplasia (FCD) type II is a frequent cause of medically intractable epilepsy. On conventional MRI diagnosis may be difficult. The purpose of our study was to assess the metabolic characteristics of MRI-typical or neuropathologically confirmed FCD II lesions at 3T. In a prospective study, 13 patients with drug-resistant epilepsy and MRI diagnosis of FCD II (seven neuropathologically confirmed) were investigated by single-volume proton magnetic resonance spectroscopy ((1)H MRS). We performed an intra-individual comparison placing spectroscopic volumes of interest in the lesion and in the apparently normal contralateral hemisphere. Spectroscopic results were correlated with clinical data. Matched pair analysis revealed a significant increase in absolute choline (Cho) concentration in the lesion volume (+32%, p=0.015) compared to the control volume. This increase was associated with a significant decrease in N-acetyl-aspartate (NAA) concentration (-13%; p=0.008). Mean myo-inositol (Ins) levels were distinctly (+36%) but not significantly (p=0.051) elevated. Lesional creatine (Cr) concentration correlated significantly with the frequency of seizures (Spearman-Rho r=0.898; p=0.002), while concentrations of NAA, Cho and Ins did not correlate with clinical or imaging parameters. MR spectroscopy revealed a characteristic metabolic pattern in FCD II lesions that helps to distinguish normal from epileptogenic tissue. Copyright © 2015 British Epilepsy Association. Published by Elsevier Ltd. All rights reserved.

Factors affecting measurement of optic parameters by time-resolved near-infrared spectroscopy in breast cancer

NASA Astrophysics Data System (ADS)

Yoshizawa, Nobuko; Ueda, Yukio; Mimura, Tetsuya; Ohmae, Etsuko; Yoshimoto, Kenji; Wada, Hiroko; Ogura, Hiroyuki; Sakahara, Harumi

2018-02-01

The purpose of this study was to evaluate the effects of the thickness and depth of tumors on hemoglobin measurements in breast cancer by optical spectroscopy and to demonstrate tissue oxygen saturation (SO2) and reduced scattering coefficient (μs‧) in breast tissue and breast cancer in relation to the skin-to-chest wall distance. We examined 53 tumors from 44 patients. Total hemoglobin concentration (tHb), SO2, and μs‧ were measured by time-resolved spectroscopy (TRS). The skin-to-chest wall distance and the size and depth of tumors were measured by ultrasonography. There was a positive correlation between tHb and tumor thickness, and a negative correlation between tHb and tumor depth. SO2 in breast tissue decreased when the skin-to-chest wall distance decreased, and SO2 in tumors tended to be lower than in breast tissue. In breast tissue, there was a negative correlation between μs‧ and the skin-to-chest wall distance, and μs‧ in tumors was higher than in breast tissue. Measurement of tHb in breast cancer by TRS was influenced by tumor thickness and depth. Although SO2 seemed lower and μs‧ was higher in breast cancer than in breast tissue, the skin-to-chest wall distance may have affected the measurements.

Accelerating two-dimensional nuclear magnetic resonance correlation spectroscopy via selective coherence transfer

NASA Astrophysics Data System (ADS)

Ye, Qimiao; Chen, Lin; Qiu, Wenqi; Lin, Liangjie; Sun, Huijun; Cai, Shuhui; Wei, Zhiliang; Chen, Zhong

2017-01-01

Nuclear magnetic resonance (NMR) spectroscopy serves as an important tool for both qualitative and quantitative analyses of various systems in chemistry, biology, and medicine. However, applications of one-dimensional 1H NMR are often restrained by the presence of severe overlap among different resonances. The advent of two-dimensional (2D) 1H NMR constitutes a promising alternative by extending the crowded resonances into a plane and thereby alleviating the spectral congestions. However, the enhanced ability in discriminating resonances is achieved at the cost of extended experimental duration due to necessity of various scans with progressive delays to construct the indirect dimension. Therefore, in this study, we propose a selective coherence transfer (SECOT) method to accelerate acquisitions of 2D correlation spectroscopy by converting chemical shifts into spatial positions within the effective sample length and then performing an echo planar spectroscopic imaging module to record the spatial and spectral information, which generates 2D correlation spectrum after 2D Fourier transformation. The feasibility and effectiveness of SECOT have been verified by a set of experiments under both homogeneous and inhomogeneous magnetic fields. Moreover, evaluations of SECOT for quantitative analyses are carried out on samples with a series of different concentrations. Based on these experimental results, the SECOT may open important perspectives for fast, accurate, and stable investigations of various chemical systems both qualitatively and quantitatively.

Measurement of nanoscale three-dimensional diffusion in the interior of living cells by STED-FCS.

PubMed

Lanzanò, Luca; Scipioni, Lorenzo; Di Bona, Melody; Bianchini, Paolo; Bizzarri, Ranieri; Cardarelli, Francesco; Diaspro, Alberto; Vicidomini, Giuseppe

2017-07-06

The observation of molecular diffusion at different spatial scales, and in particular below the optical diffraction limit (<200 nm), can reveal details of the subcellular topology and its functional organization. Stimulated-emission depletion microscopy (STED) has been previously combined with fluorescence correlation spectroscopy (FCS) to investigate nanoscale diffusion (STED-FCS). However, stimulated-emission depletion fluorescence correlation spectroscopy has only been used successfully to reveal functional organization in two-dimensional space, such as the plasma membrane, while, an efficient implementation for measurements in three-dimensional space, such as the cellular interior, is still lacking. Here we integrate the STED-FCS method with two analytical approaches, the recent separation of photons by lifetime tuning and the fluorescence lifetime correlation spectroscopy, to simultaneously probe diffusion in three dimensions at different sub-diffraction scales. We demonstrate that this method efficiently provides measurement of the diffusion of EGFP at spatial scales tunable from the diffraction size down to ∼80 nm in the cytoplasm of living cells.The measurement of molecular diffusion at sub-diffraction scales has been achieved in 2D space using STED-FCS, but an implementation for 3D diffusion is lacking. Here the authors present an analytical approach to probe diffusion in 3D space using STED-FCS and measure the diffusion of EGFP at different spatial scales.

Two-dimensional infrared correlation spectroscopy study of the aggregation of cytochrome c in the presence of dimyristoylphosphatidylglycerol.

PubMed Central

Paquet, M J; Laviolette, M; Pézolet, M; Auger, M

2001-01-01

Two-dimensional infrared correlation spectroscopy (2D-IR) was used in this study to investigate the aggregation of cytochrome c in the presence of dimyristoylphosphatidylglycerol. The influence of temperature on the aggregation has been evaluated by monitoring the intensity of a band at 1616 cm(-1), which is characteristic of aggregated proteins, and the 2D-IR analysis has been used to determine the various secondary structure components of cytochrome c involved before and during its aggregation. The 2D-IR correlation analysis clearly reveals for the first time that aggregation starts to occur between nearly native proteins, which then unfold, yielding to further aggregation of the protein. Later in the aggregation process, the formation of intermolecular bonds and unfolding of the alpha-helices appear to be simultaneous. These results lead us to propose a two-step aggregation process. Finally, the results obtained during the heating period clearly indicate that before the protein starts to aggregate, there is a loosening of the tertiary structure of cytochrome c, resulting in a decrease of the beta-sheet content and an increase of the amount of beta-turns. This study clearly demonstrates the potential of 2D-IR spectroscopy to investigate the aggregation of proteins and this technique could therefore be applied to other proteins such as those involved in fibrilogenesis. PMID:11423415

Two-dimensional correlation spectroscopic analysis on the interaction between humic acids and aluminum coagulant.

PubMed

Jin, Pengkang; Song, Jina; Wang, Xiaochang C; Jin, Xin

2018-02-01

In this study, two-dimensional correlation spectroscopy integrated with synchronous fluorescence and infrared absorption spectroscopy was employed to investigate the interaction between humic acids and aluminum coagulant at slightly acidic and neutral pH. Higher fluorescence quenching was produced for fulvic-like and humic-like fractions at pH5. At pH5, the humic-like fractions originating from the carboxylic acid, carboxyl and polysaccharide compounds were bound to aluminum first, followed by the fulvic-like fractions originating from the carboxyl and polysaccharide compounds. This finding also demonstrated that the activated functional groups of HA were involved in forming the Al-HA complex, which was accompanied by the removal of other groups by co-precipitation. Meanwhile, at pH7, almost no fluorescence quenching occurred, and surface complexation was observed to occur, in which the activated functional groups were absorbed on the amorphous Al(OH) 3 . Two-dimensional FT-IR correlation spectroscopy indicated the sequence of HA structural change during coagulation with aluminum, with IR bands affected in the order of COOH>COO - >NH deformation of amide II>aliphatic hydroxyl COH at pH5, and COO - >aliphatic hydroxyl COH at pH7. This study provides a promising pathway for analysis and insight into the priority of functional groups in the interaction between organic matters and metal coagulants. Copyright © 2017. Published by Elsevier B.V.

Analysing baryon acoustic oscillations in sparse spectroscopic samples via cross-correlation with dense photometry

NASA Astrophysics Data System (ADS)

Patej, A.; Eisenstein, D. J.

2018-07-01

We develop a formalism for measuring the cosmological distance scale from baryon acoustic oscillations (BAO) using the cross-correlation of a sparse redshift survey with a denser photometric sample. This reduces the shot noise that would otherwise affect the autocorrelation of the sparse spectroscopic map. As a proof of principle, we make the first on-sky application of this method to a sparse sample defined as the z > 0.6 tail of the Sloan Digital Sky Survey's (SDSS) BOSS/CMASS sample of galaxies and a dense photometric sample from SDSS DR9. We find a 2.8σ preference for the BAO peak in the cross-correlation at an effective z = 0.64, from which we measure the angular diameter distance DM(z = 0.64) = (2418 ± 73 Mpc)(rs/rs, fid). Accordingly, we expect that using this method to combine sparse spectroscopy with the deep, high-quality imaging that is just now becoming available will enable higher precision BAO measurements than possible with the spectroscopy alone.

Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

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

Alam, Todd M.; Liao, Zuolei; Nyman, May

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO 2(OH) 2] (α-UOH) and hydrated uranyl hydroxide [(UO 2) 4O(OH) 6·5H 2O (metaschoepite). For the metaschoepite material, proton resonances of the μ 2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H– 1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization ofmore » local hydrogen-bond environments in uranyl U 24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

Si-29 NMR spectroscopy of naturally-shocked quartz from Meteor Crater, Arizona: Correlation to Kieffer's classification scheme

NASA Technical Reports Server (NTRS)

Boslough, M. B.; Cygan, R. T.; Kirkpatrick, R. J.

1993-01-01

We have applied solid state Si-29 nuclear magnetic resonance (NMR) spectroscopy to five naturally-shocked Coconino Sandstone samples from Meteor Crater, Arizona, with the goal of examining possible correlations between NMR spectral characteristics and shock level. This work follows our observation of a strong correlation between the width of a Si-29 resonance and peak shock pressure for experimentally shocked quartz powders. The peak width increase is due to the shock-induced formation of amorphous silica, which increases as a function of shock pressure over the range that we studied (7.5 to 22 GPa). The Coconino Sandstone spectra are in excellent agreement with the classification scheme of Kieffer in terms of presence and approximate abundances of quartz, coesite, stishovite, and glass. We also observe a new resonance in two moderately shocked samples that we have tentatively identified with silicon in tetrahedra with one hydroxyl group in a densified form of amorphous silica.

Blood flow measurement of human skeletal muscle during various exercise intensity using diffuse correlation spectroscopy (DCS)

NASA Astrophysics Data System (ADS)

Murakami, Yuya; Ono, Yumie; Ichinose, Masashi

2017-02-01

We studied blood flow dynamics of active skeletal muscle using diffuse correlation spectroscopy (DCS), an emerging optical modality that is suitable for noninvasive quantification of microcirculation level in deep tissue. Seven healthy subjects conducted 0.5 Hz dynamic handgrip exercise for 3 minutes at intensities of 10, 20, 30, and 50 % of maximal voluntary contraction (MVC). DCS could detect the time-dependent increase of the blood flow response of the forearm muscle for continuous exercises, and the increase ratios of the mean blood flow through the exercise periods showed good correlation with the exercise intensities. We also compared blood flow responses detected from DCS with two different photon sampling rates and found that an appropriate photon sampling rates should be selected to follow the wide-ranged increase in the muscle blood flow with dynamic exercise. Our results demonstrate the possibility for utilizing DCS in a field of sports medicine to noninvasively evaluate the dynamics of blood flow in the active muscles.

Simultaneous measurement of deep tissue blood flow and oxygenation using noncontact diffuse correlation spectroscopy flow-oximeter

PubMed Central

Li, Ting; Lin, Yu; Shang, Yu; He, Lian; Huang, Chong; Szabunio, Margaret; Yu, Guoqiang

2013-01-01

We report a novel noncontact diffuse correlation spectroscopy flow-oximeter for simultaneous quantification of relative changes in tissue blood flow (rBF) and oxygenation (Δ[oxygenation]). The noncontact probe was compared against a contact probe in tissue-like phantoms and forearm muscles (n = 10), and the dynamic trends in both rBF and Δ[oxygenation] were found to be highly correlated. However, the magnitudes of Δ[oxygenation] measured by the two probes were significantly different. Monte Carlo simulations and phantom experiments revealed that the arm curvature resulted in a significant underestimation (~−20%) for the noncontact measurements in Δ[oxygenation], but not in rBF. Other factors that may cause the residual discrepancies between the contact and noncontact measurements were discussed, and further comparisons with other established technologies are needed to identify/quantify these factors. Our research paves the way for noncontact and simultaneous monitoring of blood flow and oxygenation in soft and vulnerable tissues without distorting tissue hemodynamics. PMID:23446991

Analysis of human nails by laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Hosseinimakarem, Zahra; Tavassoli, Seyed Hassan

2011-05-01

Laser-induced breakdown spectroscopy (LIBS) is applied to analyze human fingernails using nanosecond laser pulses. Measurements on 45 nail samples are carried out and 14 key species are identified. The elements detected with the present system are: Al, C, Ca, Fe, H, K, Mg, N, Na, O, Si, Sr, Ti as well as CN molecule. Sixty three emission lines have been identified in the spectrum that are dominated by calcium lines. A discriminant function analysis is used to discriminate among different genders and age groups. This analysis demonstrates efficient discrimination among these groups. The mean concentration of each element is compared between different groups. Correlation between concentrations of elements in fingernails is calculated. A strong correlation is found between sodium and potassium while calcium and magnesium levels are inversely correlated. A case report on high levels of sodium and potassium in patients with hyperthyroidism is presented. It is shown that LIBS could be a promising technique for the analysis of nails and therefore identification of health problems.

Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

DOE PAGES

Alam, Todd M.; Liao, Zuolei; Nyman, May; ...

2016-04-27

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO 2(OH) 2] (α-UOH) and hydrated uranyl hydroxide [(UO 2) 4O(OH) 6·5H 2O (metaschoepite). For the metaschoepite material, proton resonances of the μ 2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H– 1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization ofmore » local hydrogen-bond environments in uranyl U 24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

Vibrational correlation between conjugated carbonyl and diazo modes studied by single- and dual-frequency two-dimensional infrared spectroscopy

NASA Astrophysics Data System (ADS)

Maekawa, Hiroaki; Sul, Soohwan; Ge, Nien-Hui

2013-08-01

We have applied infrared three-pulse photon echo and single- and dual-frequency 2D IR spectroscopy to the ester Cdbnd O and diazo Ndbnd N stretching modes in ethyl diazoacetate (EDA), and investigated their vibrational frequency fluctuations and correlation. The two modes exhibit different vibrational dynamics and 2D lineshape, which are well simulated by frequency-frequency correlation functions (FFCFs) with two decaying components. Although the FT IR spectrum shows a single Cdbnd O band, absolute magnitude 2D IR nonrephasing spectrum displays spectral signatures supporting the presence of cis and trans conformations. The cross-peak inclined toward the anti-diagonal in the dual-frequency 2D IR spectrum, indicating that the frequency fluctuations of the two modes are anticorrelated. This behavior is attributed to anticorrelated change in the bond orders when solvent and structural fluctuations causes EDA to adopt a different mixture of the two dominant resonance structures. The effects of cross FFCF on the cross-peak line shape are discussed.

Quantifying Young's moduli of protein fibrils and particles with bimodal force spectroscopy.

PubMed

Gilbert, Jay; Charnley, Mirren; Cheng, Christopher; Reynolds, Nicholas P; Jones, Owen G

2017-10-19

Force spectroscopy is a means of obtaining mechanical information of individual nanometer-scale structures in composite materials, such as protein assemblies for use in consumer films or gels. As a recently developed force spectroscopy technique, bimodal force spectroscopy relates frequency shifts in cantilevers simultaneously excited at multiple frequencies to the elastic properties of the contacted material, yet its utility for quantitative characterization of biopolymer assemblies has been limited. In this study, a linear correlation between experimental frequency shift and Young's modulus of polymer films was used to calibrate bimodal force spectroscopy and quantify Young's modulus of two protein nanostructures: β-lactoglobulin fibrils and zein nanoparticles. Cross-sectional Young's modulus of protein fibrils was determined to be 1.6 GPa while the modulus of zein nanoparticles was determined as 854 MPa. Parallel measurement of β-lactoglobulin fibril by a competing pulsed-force technique found a higher cross-sectional Young's modulus, highlighting the importance of comparative calibration against known standards in both pulsed and bimodal force spectroscopies. These findings demonstrate a successful procedure for measuring mechanical properties of individual protein assemblies with potential use in biological or packaging applications using bimodal force spectroscopy.

Review of optical breast imaging and spectroscopy

NASA Astrophysics Data System (ADS)

Grosenick, Dirk; Rinneberg, Herbert; Cubeddu, Rinaldo; Taroni, Paola

2016-09-01

Diffuse optical imaging and spectroscopy of the female breast is an area of active research. We review the present status of this field and discuss the broad range of methodologies and applications. Starting with a brief overview on breast physiology, the remodeling of vasculature and extracellular matrix caused by solid tumors is highlighted that is relevant for contrast in optical imaging. Then, the various instrumental techniques and the related methods of data analysis and image generation are described and compared including multimodality instrumentation, fluorescence mammography, broadband spectroscopy, and diffuse correlation spectroscopy. We review the clinical results on functional properties of malignant and benign breast lesions compared to host tissue and discuss the various methods to improve contrast between healthy and diseased tissue, such as enhanced spectroscopic information, dynamic variations of functional properties, pharmacokinetics of extrinsic contrast agents, including the enhanced permeability and retention effect. We discuss research on monitoring neoadjuvant chemotherapy and on breast cancer risk assessment as potential clinical applications of optical breast imaging and spectroscopy. Moreover, we consider new experimental approaches, such as photoacoustic imaging and long-wavelength tissue spectroscopy.

[Near infrared spectroscopy study on water content in turbine oil].

PubMed

Chen, Bin; Liu, Ge; Zhang, Xian-Ming

2013-11-01

Near infrared (NIR) spectroscopy combined with successive projections algorithm (SPA) was investigated for determination of water content in turbine oil. Through the 57 samples of different water content in turbine oil scanned applying near infrared (NIR) spectroscopy, with the water content in the turbine oil of 0-0.156%, different pretreatment methods such as the original spectra, first derivative spectra and differential polynomial least squares fitting algorithm Savitzky-Golay (SG), and successive projections algorithm (SPA) were applied for the extraction of effective wavelengths, the correlation coefficient (R) and root mean square error (RMSE) were used as the model evaluation indices, accordingly water content in turbine oil was investigated. The results indicated that the original spectra with different water content in turbine oil were pretreated by the performance of first derivative + SG pretreatments, then the selected effective wavelengths were used as the inputs of least square support vector machine (LS-SVM). A total of 16 variables selected by SPA were employed to construct the model of SPA and least square support vector machine (SPA-LS-SVM). There is 9 as The correlation coefficient was 0.975 9 and the root of mean square error of validation set was 2.655 8 x 10(-3) using the model, and it is feasible to determine the water content in oil using near infrared spectroscopy and SPA-LS-SVM, and an excellent prediction precision was obtained. This study supplied a new and alternative approach to the further application of near infrared spectroscopy in on-line monitoring of contamination such as water content in oil.

aCORN: An experiment to measure the electron-antineutrino correlation coefficient in free neutron decay

DOE PAGES

Collett, B.; Bateman, F.; Bauder, W. K.; ...

2017-08-01

Here, we describe an apparatus used to measure the electron-antineutrino angular correlation coefficient in free neutron decay. This apparatus employs a novel measurement technique in which the angular correlation is converted into a proton time-of-flight asymmetry that is counted directly, avoiding the need for proton spectroscopy. We present details of the method, apparatus, detectors, data acquisition, and data reduction scheme, along with a discussion of the important systematic effects.

aCORN: An experiment to measure the electron-antineutrino correlation coefficient in free neutron decay

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

Collett, B.; Bateman, F.; Bauder, W. K.

Here, we describe an apparatus used to measure the electron-antineutrino angular correlation coefficient in free neutron decay. This apparatus employs a novel measurement technique in which the angular correlation is converted into a proton time-of-flight asymmetry that is counted directly, avoiding the need for proton spectroscopy. We present details of the method, apparatus, detectors, data acquisition, and data reduction scheme, along with a discussion of the important systematic effects.

aCORN: An experiment to measure the electron-antineutrino correlation coefficient in free neutron decay.

PubMed

Collett, B; Bateman, F; Bauder, W K; Byrne, J; Byron, W A; Chen, W; Darius, G; DeAngelis, C; Dewey, M S; Gentile, T R; Hassan, M T; Jones, G L; Komives, A; Laptev, A; Mendenhall, M P; Nico, J S; Noid, G; Park, H; Stephenson, E J; Stern, I; Stockton, K J S; Trull, C; Wietfeldt, F E; Yerozolimsky, B G

2017-08-01

We describe an apparatus used to measure the electron-antineutrino angular correlation coefficient in free neutron decay. The apparatus employs a novel measurement technique in which the angular correlation is converted into a proton time-of-flight asymmetry that is counted directly, avoiding the need for proton spectroscopy. Details of the method, apparatus, detectors, data acquisition, and data reduction scheme are presented, along with a discussion of the important systematic effects.

Correspondence of electroencephalography and near-infrared spectroscopy sensitivities to the cerebral cortex using a high-density layout

PubMed Central

Giacometti, Paolo; Diamond, Solomon G.

2014-01-01

Abstract. This study investigates the correspondence of the cortical sensitivity of electroencephalography (EEG) and near-infrared spectroscopy (NIRS). EEG forward model sensitivity to the cerebral cortex was calculated for 329 EEG electrodes following the 10-5 EEG positioning system using a segmented structural magnetic resonance imaging scan of a human subject. NIRS forward model sensitivity was calculated for the same subject using 156 NIRS source-detector pairs selected from 32 source and 32 detector optodes positioned on the scalp using a subset of the 10-5 EEG positioning system. Sensitivity correlations between colocalized NIRS source-detector pair groups and EEG channels yielded R=0.46±0.08. Groups of NIRS source-detector pairs with maximum correlations to EEG electrode sensitivities are tabulated. The mean correlation between the point spread functions for EEG and NIRS regions of interest (ROI) was R=0.43±0.07. Spherical ROIs with radii of 26 mm yielded the maximum correlation between EEG and NIRS averaged across all cortical mesh nodes. These sensitivity correlations between EEG and NIRS should be taken into account when designing multimodal studies of neurovascular coupling and when using NIRS as a statistical prior for EEG source localization. PMID:25558462

Dual-color two-photon fluorescence correlation spectroscopy

NASA Astrophysics Data System (ADS)

Berland, Keith M.

2001-04-01

Fluorescence correlation spectroscopy (FCS) is rapidly growing in popularity as a research tool in biological and biophysical research. Under favorable conditions, FCS measurements can produce an accurate characterization of the chemical, physical, and kinetic properties of a biological system. However, interpretation of FCS data quickly becomes complicated as the heterogeneity of a molecular system increases, as well as when there is significant non-stationery fluorescence background (e.g. intracellular autofluorescence). Use of multi-parameter correlation measurements is one promising approach that can improve the fidelity of FCS measurements in complex systems. In particular, the use of dual-color fluorescence assays, in which different interacting molecular species are labeled with unique fluorescent indicators, can "tune" the sensitivity of FCS measurements in favor of particular molecular species of interest, while simultaneously minimizing the contribution of other molecular species to the overall fluorescence correlation signal. Here we introduce the combined application of two-photon fluorescence excitation and dual-color cross-correlation analysis for detecting molecular interactions in solution. The use of two-photon excitation is particularly advantageous for dual-color FCS applications due to the uncomplicated optical alignment and the superior capabilities for intracellular applications. The theory of two-photon dual-color FCS is introduced, and initial results quantifying hybridization reactions between three independent single stranded DNA molecules are presented.

Analysis of 2-ethylhexyl-p-methoxycinnamate in sunscreen products by HPLC and Raman spectroscopy.

PubMed

Cheng, J; Li, Y S; L Roberts, R; Walker, G

1997-10-01

The analyses of 2-ethylhexyl-p-methoxycinnamate (EHMC) using HPLC and Raman spectroscopy have been undertaken and compared. EHMC, which is one of the most widely used sunscreen agents in suncare products in the US, exhibits a strong Raman signal. This signal clearly appears in both ethanol solutions of EHMC as well as in commercial sunscreen lotions containing this sun screen agent. A method for the direct detection and analysis of EHMC has been developed using Raman spectroscopy. This was accomplished by correlating the Raman intensities with the HPLC assays for a series of prototype suncare formulations. Based upon this information, it would be possible to employ Raman spectroscopy as an in-process control method in the commercial production of suncare products containing EHMC. The possibility of applying surface-enhanced Raman scattering for trace analysis was discussed.

Enhanced electrical properties in sub-10-nm WO3 nanoflakes prepared via a two-step sol-gel-exfoliation method

PubMed Central

2014-01-01

The morphology and electrical properties of orthorhombic β-WO3 nanoflakes with thickness of ~7 to 9 nm were investigated at the nanoscale with a combination of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), current sensing force spectroscopy atomic force microscopy (CSFS-AFM, or PeakForce TUNA™), Fourier transform infra-red absorption spectroscopy (FTIR), linear sweep voltammetry (LSV) and Raman spectroscopy techniques. CSFS-AFM analysis established good correlation between the topography of the developed nanostructures and various features of WO3 nanoflakes synthesized via a two-step sol-gel-exfoliation method. It was determined that β-WO3 nanoflakes annealed at 550°C possess distinguished and exceptional thickness-dependent properties in comparison with the bulk, micro and nanostructured WO3 synthesized at alternative temperatures. PMID:25221453

The static structure and dynamics of cadmium sulfide nanoparticles within poly(styrene- block-isoprene) diblock copolymer melts

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

Jang, Woo -Sik; Koo, Peter; Bryson, Kyle

Here, the static structure and dynamic behavior of cadmium sulfide nanoparticles suspended in block copolymer matrix are investigated using transmission electron microscopy, small-angle X-ray scattering, and X-ray photon correlation spectroscopy. The transmission electron micro- scopy study shows that cadmium sulfide nanoparticles are preferentially segregated within the polyisoprene domain of a poly(styrene- block-isoprene) diblock copolymer. For the dynamics study, X-ray photon correlation spectroscopy captures the relaxation process of cadmium sulfide nanoparticles. The measured characteristic relaxation time reveals that the observed dynamics are hyperdiffusive. The characteristic velocity and corresponding activation energy, which are hallmarks of a hyperdiffusive system, are determined from themore » relationship between the characteristic relaxation time and the wavevector.« less

The static structure and dynamics of cadmium sulfide nanoparticles within poly(styrene- block-isoprene) diblock copolymer melts

DOE PAGES

Jang, Woo -Sik; Koo, Peter; Bryson, Kyle; ...

2015-12-20

Here, the static structure and dynamic behavior of cadmium sulfide nanoparticles suspended in block copolymer matrix are investigated using transmission electron microscopy, small-angle X-ray scattering, and X-ray photon correlation spectroscopy. The transmission electron micro- scopy study shows that cadmium sulfide nanoparticles are preferentially segregated within the polyisoprene domain of a poly(styrene- block-isoprene) diblock copolymer. For the dynamics study, X-ray photon correlation spectroscopy captures the relaxation process of cadmium sulfide nanoparticles. The measured characteristic relaxation time reveals that the observed dynamics are hyperdiffusive. The characteristic velocity and corresponding activation energy, which are hallmarks of a hyperdiffusive system, are determined from themore » relationship between the characteristic relaxation time and the wavevector.« less

Applications of fluorescence spectroscopy to problems of food safety: detection of fecal contamination and of the presence of central nervous system tissue and diagnosis of neurological disease

NASA Astrophysics Data System (ADS)

Adhikary, Ramkrishna; Bose, Sayantan; Casey, Thomas A.; Gapsch, Al; Rasmussen, Mark A.; Petrich, Jacob W.

2010-02-01

Applications of fluorescence spectroscopy that enable the real-time or rapid detection of fecal contamination on beef carcasses and the presence of central nervous system tissue in meat products are discussed. The former is achieved by employing spectroscopic signatures of chlorophyll metabolites; the latter, by exploiting the characteristic structure and intensity of lipofuscin in central nervous system tissue. The success of these techniques has led us to investigate the possibility of diagnosing scrapie in sheep by obtaining fluorescence spectra of the retina. Crucial to this diagnosis is the ability to obtain baseline correlations of lipofuscin fluorescence with age. A murine model was employed as a proof of principle of this correlation.

Mechanical Anisotropy and Pressure Induced Structural Changes in Piroxicam Crystals Probed by In Situ Indentation and Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Manimunda, Praveena; Hintsala, Eric; Asif, Syed; Mishra, Manish Kumar

2017-01-01

The ability to correlate mechanical and chemical characterization techniques in real time is both lacking and powerful tool for gaining insights into material behavior. This is demonstrated through use of a novel nanoindentation device equipped with Raman spectroscopy to explore the deformation-induced structural changes in piroxicam crystals. Mechanical anisotropy was observed in two major faces ( 0bar{1}1 ) and (011), which are correlated to changes in the interlayer interaction from in situ Raman spectra recorded during indentation. The results of this study demonstrate the considerable potential of an in situ Raman nanoindentation instrument for studying a variety of topics, including stress-induced phase transformation mechanisms, mechanochemistry, and solid state reactivity under mechanical forces that occur in molecular and pharmaceutical solids.

Fluorescence Correlation Spectroscopy to Study Diffusion of Polymer Chains within Layered Hydrogen-Bonded Polymer Films

NASA Astrophysics Data System (ADS)

Pristinski, Denis; Kharlampieva, Evguenia; Sukhishvili, Svetlana

2002-03-01

Fluorescence Correlation Spectroscopy (FCS) has been used to probe molecular motions within polymer multilayers formed by hydrogen-bonding sequential self-assembly. Polyethylene glycol (PEG) molecules were end-labeled with the fluorescent tags, and self-assembled with polymethacrylic acid (PMAA) using layer-by-layer deposition. We have found that molecules included in the top adsorbed layer have significant mobility at the millisecond time scale, probably due to translational diffusion. However, their dynamics deviate from classical Brownian motion with a single diffusion time. Possible reasons for the deviation are discussed. We found that motions were significantly slowed with increasing depth within the PEG/PMAA multilayer. This phenomena occured in a narrow pH range around 4.0 in which intermolecular interactions were relatively weak.

Geomorphic Evidence for Martian Ground Ice and Climate Change

NASA Technical Reports Server (NTRS)

Kanner, L. C.; Allen, C. C.; Bell, M. S.

2004-01-01

Recent results from gamma-ray and neutron spectrometers on Mars Odyssey indicate the presence of a hydrogen-rich layer tens of centimeters thick in the uppermost meter in high latitudes (greater than 60) on Mars. This hydrogen-rich layer correlates to regions of ice stability. Thus, the subsurface hydrogen is thought to be water ice constituting 35 plus or minus 15% by weight near the north and south polar regions. We refine the location of subsurface ice deposits at a less than km scale by combining existing spectroscopy data with surface features indicative of subsurface ice. A positive correlation between spectroscopy data and geomorphic ice indicators has been previously suggested for high latitudes. Here we expand the comparative study to northern mid latitudes (30 degrees N- 65 degrees N).

Quantification of hepatic steatosis with T1-independent, T2-corrected MR imaging with spectral modeling of fat: blinded comparison with MR spectroscopy.

PubMed

Meisamy, Sina; Hines, Catherine D G; Hamilton, Gavin; Sirlin, Claude B; McKenzie, Charles A; Yu, Huanzhou; Brittain, Jean H; Reeder, Scott B

2011-03-01

To prospectively compare an investigational version of a complex-based chemical shift-based fat fraction magnetic resonance (MR) imaging method with MR spectroscopy for the quantification of hepatic steatosis. This study was approved by the institutional review board and was HIPAA compliant. Written informed consent was obtained before all studies. Fifty-five patients (31 women, 24 men; age range, 24-71 years) were prospectively imaged at 1.5 T with quantitative MR imaging and single-voxel MR spectroscopy, each within a single breath hold. The effects of T2 correction, spectral modeling of fat, and magnitude fitting for eddy current correction on fat quantification with MR imaging were investigated by reconstructing fat fraction images from the same source data with different combinations of error correction. Single-voxel T2-corrected MR spectroscopy was used to measure fat fraction and served as the reference standard. All MR spectroscopy data were postprocessed at a separate institution by an MR physicist who was blinded to MR imaging results. Fat fractions measured with MR imaging and MR spectroscopy were compared statistically to determine the correlation (r(2)), and the slope and intercept as measures of agreement between MR imaging and MR spectroscopy fat fraction measurements, to determine whether MR imaging can help quantify fat, and examine the importance of T2 correction, spectral modeling of fat, and eddy current correction. Two-sided t tests (significance level, P = .05) were used to determine whether estimated slopes and intercepts were significantly different from 1.0 and 0.0, respectively. Sensitivity and specificity for the classification of clinically significant steatosis were evaluated. Overall, there was excellent correlation between MR imaging and MR spectroscopy for all reconstruction combinations. However, agreement was only achieved when T2 correction, spectral modeling of fat, and magnitude fitting for eddy current correction were used (r(2) = 0.99; slope ± standard deviation = 1.00 ± 0.01, P = .77; intercept ± standard deviation = 0.2% ± 0.1, P = .19). T1-independent chemical shift-based water-fat separation MR imaging methods can accurately quantify fat over the entire liver, by using MR spectroscopy as the reference standard, when T2 correction, spectral modeling of fat, and eddy current correction methods are used. © RSNA, 2011.

Quantification of Hepatic Steatosis with T1-independent, T2*-corrected MR Imaging with Spectral Modeling of Fat: Blinded Comparison with MR Spectroscopy

PubMed Central

Hines, Catherine D. G.; Hamilton, Gavin; Sirlin, Claude B.; McKenzie, Charles A.; Yu, Huanzhou; Brittain, Jean H.; Reeder, Scott B.

2011-01-01

Purpose: To prospectively compare an investigational version of a complex-based chemical shift–based fat fraction magnetic resonance (MR) imaging method with MR spectroscopy for the quantification of hepatic steatosis. Materials and Methods: This study was approved by the institutional review board and was HIPAA compliant. Written informed consent was obtained before all studies. Fifty-five patients (31 women, 24 men; age range, 24–71 years) were prospectively imaged at 1.5 T with quantitative MR imaging and single-voxel MR spectroscopy, each within a single breath hold. The effects of T2* correction, spectral modeling of fat, and magnitude fitting for eddy current correction on fat quantification with MR imaging were investigated by reconstructing fat fraction images from the same source data with different combinations of error correction. Single-voxel T2-corrected MR spectroscopy was used to measure fat fraction and served as the reference standard. All MR spectroscopy data were postprocessed at a separate institution by an MR physicist who was blinded to MR imaging results. Fat fractions measured with MR imaging and MR spectroscopy were compared statistically to determine the correlation (r2), and the slope and intercept as measures of agreement between MR imaging and MR spectroscopy fat fraction measurements, to determine whether MR imaging can help quantify fat, and examine the importance of T2* correction, spectral modeling of fat, and eddy current correction. Two-sided t tests (significance level, P = .05) were used to determine whether estimated slopes and intercepts were significantly different from 1.0 and 0.0, respectively. Sensitivity and specificity for the classification of clinically significant steatosis were evaluated. Results: Overall, there was excellent correlation between MR imaging and MR spectroscopy for all reconstruction combinations. However, agreement was only achieved when T2* correction, spectral modeling of fat, and magnitude fitting for eddy current correction were used (r2 = 0.99; slope ± standard deviation = 1.00 ± 0.01, P = .77; intercept ± standard deviation = 0.2% ± 0.1, P = .19). Conclusion: T1-independent chemical shift–based water-fat separation MR imaging methods can accurately quantify fat over the entire liver, by using MR spectroscopy as the reference standard, when T2* correction, spectral modeling of fat, and eddy current correction methods are used. © RSNA, 2011 PMID:21248233

Experimental and theoretical study of hydrogen thiocarbonate for heterogeneous reaction of carbonyl sulfide on magnesium oxide.

PubMed

Liu, Yongchun; He, Hong

2009-04-09

In situ diffuse reflectance infrared Fourier transform spectroscopy combined with derivative spectroscopy analysis, two-dimensional correlation spectroscopy analysis, and quantum chemical calculations were used to investigate the infrared absorbance assignment and the molecular structure of hydrogen thiocarbonate on magnesium oxide. The bands at 1283 and 1257 cm(-1), which had the typical characteristic of intermediate, were observed in experiments for the heterogeneous reaction of COS on MgO. On the basis of two-dimensional correlation spectroscopy analysis and quantum chemical calculations, the band at 1283 cm(-1) was assigned to the v(s) band of bridged thiocarbonate which formed on the two neighboring Mg atoms in the (100) face of MgO crystal, and the band at 1257 cm(-1) was the v(s) band of monodentate thiocarbonate on MgO. The v(as)(OCO) band of thiocarbonates was invisible in the experiment due to their weak absorbance and the interruption of surface carbonate. The formation mechanism of thiocarbonates is proposed, which occurred through a nucleophilic attack of preadsorbed COS by surface -OH groups followed by hydrogen atom transfer from the -OH group to the sulfur atom of preadsorbed COS. The activation energy for the intramolecular proton-transfer reaction of bridged thiocarbonate was calculated to be 18.52 kcal x mol(-1) at the B3LYP/6-31+G(d,p) level of theory.

Study of Vis/NIR spectroscopy measurement on acidity of yogurt

NASA Astrophysics Data System (ADS)

He, Yong; Feng, Shuijuan; Wu, Di; Li, Xiaoli

2006-09-01

A fast measurement of pH of yogurt using Vis/NIR-spectroscopy techniques was established in order to measuring the acidity of yogurt rapidly. 27 samples selected separately from five different brands of yogurt were measured by Vis/NIR-spectroscopy. The pH of yogurt on positions scanned by spectrum was measured by a pH meter. The mathematical model between pH and Vis/NIR spectral measurements was established and developed based on partial least squares (PLS) by using Unscramble V9.2. Then 25 unknown samples from 5 different brands were predicted based on the mathematical model. The result shows that The correlation coefficient of pH based on PLS model is more than 0.890, and standard error of calibration (SEC) is 0.037, standard error of prediction (SEP) is 0.043. Through predicting the pH of 25 samples of yogurt from 5 different brands, the correlation coefficient between predictive value and measured value of those samples is more than 0918. The results show the good to excellent prediction performances. The Vis/NIR spectroscopy technique had a significant greater accuracy for determining the value of pH. It was concluded that the VisINIRS measurement technique can be used to measure pH of yogurt fast and accurately, and a new method for the measurement of pH of yogurt was established.

Raman spectroscopy as a tool to understand Kerogen production potential

NASA Astrophysics Data System (ADS)

Khatibi, S.; Ostadhassan, M.; Mohammed, R. A.; Alexeyev, A.

2017-12-01

A lot attention has given to unconventional reservoirs specifically oil shale in North America during the last decades. Understanding Kerogen properties in terms of maturity and production potential are crucial for unconventional reservoir. Since, the amount of hydrocarbon generation is a function of kerogen type and content in the formation, and the magnitude and duration in which heat and pressure were applied. This study presents a non-destructive and fast method to determine Kerogen properties in terms of Rock-Eval parameters by means of Raman Spectroscopy. Samples were gathered from upper and lower Bakken formation, with different maturities at different depth. Raman spectroscopy as a powerful nondestructive analytical tool for molecular reconstruction was employed to find Raman spectra of different samples. In the next step, Rock-Eval was performed for each sample and different measurements were made. Then in an original approach, correlation between Rock-Eval parameters with Raman Spectroscopy results was established to fully understand how kerogen productivity potentials can be reflected on the Raman response. Results showed, maturity related parameters (RO, Tmax), S1 (already generated oil in the rock), S2 (potential hydrocarbon) and OSI (oil saturation index as indication of potential oil flow zones) can be correlated to band separation, D band intensity, G band intensity and G/D intensity, respectively. Proposed method provide a fast nondestructive method to evaluate Kerogen quality even at field without any special sample preparation.

Quantifying the cerebral metabolic rate of oxygen by combining diffuse correlation spectroscopy and time-resolved near-infrared spectroscopy.

PubMed

Verdecchia, Kyle; Diop, Mamadou; Lee, Ting-Yim; St Lawrence, Keith

2013-02-01

Preterm infants are highly susceptible to ischemic brain injury; consequently, continuous bedside monitoring to detect ischemia before irreversible damage occurs would improve patient outcome. In addition to monitoring cerebral blood flow (CBF), assessing the cerebral metabolic rate of oxygen (CMRO2) would be beneficial considering that metabolic thresholds can be used to evaluate tissue viability. The purpose of this study was to demonstrate that changes in absolute CMRO2 could be measured by combining diffuse correlation spectroscopy (DCS) with time-resolved near-infrared spectroscopy (TR-NIRS). Absolute CBF was determined using bolus-tracking TR-NIRS to calibrate the DCS measurements. Cerebral venous blood oxygenation (SvO2) was determined by multiwavelength TR-NIRS measurements, the accuracy of which was assessed by directly measuring the oxygenation of sagittal sinus blood. In eight newborn piglets, CMRO2 was manipulated by varying the anesthetics and by injecting sodium cyanide. No significant differences were found between the two sets of SvO2 measurements obtained by TR-NIRS or sagittal sinus blood samples and the corresponding CMRO2 measurements. Bland-Altman analysis showed a mean CMRO2 difference of 0.0268 ± 0.8340 mLO2/100 g/min between the two techniques over a range from 0.3 to 4 mL O2/100 g/min.

In vivo quantification of chromophore concentration using fluorescence differential path length spectroscopy

NASA Astrophysics Data System (ADS)

Kruijt, Bastiaan; Kascakova, Slavka; de Bruijn, Henriette S.; van der Ploeg-van den Heuvel, Angelique; Sterenborg, Henricus J. C. M.; Robinson, Dominic J.; Amelink, Arjen

2009-05-01

We present an optical method based on fluorescence spectroscopy for measuring chromophore concentrations in vivo. Fluorescence differential path length spectroscopy (FPDS) determines chromophore concentration based on the fluorescence intensity corrected for absorption. The concentration of the photosensitizer m-THPC (Foscan®) was studied in vivo in normal rat liver, which is highly vascularized and therefore highly absorbing. Concentration estimates of m-THPC measured by FDPS on the liver are compared with chemical extraction. Twenty-five rats were injected with 0.3 mg/kg m-THPC. In vivo optical concentration measurements were performed on tissue 3, 24, 48, and 96 h after m-THPC administration to yield a 10-fold variation in tissue concentration. After the optical measurements, the liver was harvested for chemical extraction. FDPS showed good correlation with chemical extraction. FDPS also showed a correlation between m-THPC fluorescence and blood volume fraction at the two shortest drug-light intervals. This suggests different compartmental localization of m-THPC for different drug-light intervals that can be resolved using fluorescence spectroscopy. Differences in measured m-THPC concentration between FDPS and chemical extraction are related to the interrogation volume of each technique; ~0.2 mm3 and ~102 mm3, respectively. This indicates intra-animal variation in m-THPC distribution in the liver on the scale of the FDPS sampling volume.

Quantifying the cerebral metabolic rate of oxygen by combining diffuse correlation spectroscopy and time-resolved near-infrared spectroscopy

NASA Astrophysics Data System (ADS)

Verdecchia, Kyle; Diop, Mamadou; Lee, Ting-Yim; St. Lawrence, Keith

2013-02-01

Preterm infants are highly susceptible to ischemic brain injury; consequently, continuous bedside monitoring to detect ischemia before irreversible damage occurs would improve patient outcome. In addition to monitoring cerebral blood flow (CBF), assessing the cerebral metabolic rate of oxygen (CMRO2) would be beneficial considering that metabolic thresholds can be used to evaluate tissue viability. The purpose of this study was to demonstrate that changes in absolute CMRO2 could be measured by combining diffuse correlation spectroscopy (DCS) with time-resolved near-infrared spectroscopy (TR-NIRS). Absolute CBF was determined using bolus-tracking TR-NIRS to calibrate the DCS measurements. Cerebral venous blood oxygenation (SvO2) was determined by multiwavelength TR-NIRS measurements, the accuracy of which was assessed by directly measuring the oxygenation of sagittal sinus blood. In eight newborn piglets, CMRO2 was manipulated by varying the anesthetics and by injecting sodium cyanide. No significant differences were found between the two sets of SvO2 measurements obtained by TR-NIRS or sagittal sinus blood samples and the corresponding CMRO2 measurements. Bland-Altman analysis showed a mean CMRO2 difference of 0.0268±0.8340 mL O2/100 g/min between the two techniques over a range from 0.3 to 4 mL O2/100 g/min.

Correlation of Oxygenated Hemoglobin Concentration and Psychophysical Amount on Speech Recognition

NASA Astrophysics Data System (ADS)

Nozawa, Akio; Ide, Hideto

The subjective understanding on oral language understanding task is quantitatively evaluated by the fluctuation of oxygenated hemoglobin concentration measured by the near-infrared spectroscopy. The English listening comprehension test wihch consists of two difficulty level was executed by 4 subjects during the measurement. A significant correlation was found between the subjective understanding and the fluctuation of oxygenated hemoglobin concentration.

High Frequency Sampling of TTL Pulses on a Raspberry Pi for Diffuse Correlation Spectroscopy Applications.

PubMed

Tivnan, Matthew; Gurjar, Rajan; Wolf, David E; Vishwanath, Karthik

2015-08-12

Diffuse Correlation Spectroscopy (DCS) is a well-established optical technique that has been used for non-invasive measurement of blood flow in tissues. Instrumentation for DCS includes a correlation device that computes the temporal intensity autocorrelation of a coherent laser source after it has undergone diffuse scattering through a turbid medium. Typically, the signal acquisition and its autocorrelation are performed by a correlation board. These boards have dedicated hardware to acquire and compute intensity autocorrelations of rapidly varying input signal and usually are quite expensive. Here we show that a Raspberry Pi minicomputer can acquire and store a rapidly varying time-signal with high fidelity. We show that this signal collected by a Raspberry Pi device can be processed numerically to yield intensity autocorrelations well suited for DCS applications. DCS measurements made using the Raspberry Pi device were compared to those acquired using a commercial hardware autocorrelation board to investigate the stability, performance, and accuracy of the data acquired in controlled experiments. This paper represents a first step toward lowering the instrumentation cost of a DCS system and may offer the potential to make DCS become more widely used in biomedical applications.

High Frequency Sampling of TTL Pulses on a Raspberry Pi for Diffuse Correlation Spectroscopy Applications

PubMed Central

Tivnan, Matthew; Gurjar, Rajan; Wolf, David E.; Vishwanath, Karthik

2015-01-01

Diffuse Correlation Spectroscopy (DCS) is a well-established optical technique that has been used for non-invasive measurement of blood flow in tissues. Instrumentation for DCS includes a correlation device that computes the temporal intensity autocorrelation of a coherent laser source after it has undergone diffuse scattering through a turbid medium. Typically, the signal acquisition and its autocorrelation are performed by a correlation board. These boards have dedicated hardware to acquire and compute intensity autocorrelations of rapidly varying input signal and usually are quite expensive. Here we show that a Raspberry Pi minicomputer can acquire and store a rapidly varying time-signal with high fidelity. We show that this signal collected by a Raspberry Pi device can be processed numerically to yield intensity autocorrelations well suited for DCS applications. DCS measurements made using the Raspberry Pi device were compared to those acquired using a commercial hardware autocorrelation board to investigate the stability, performance, and accuracy of the data acquired in controlled experiments. This paper represents a first step toward lowering the instrumentation cost of a DCS system and may offer the potential to make DCS become more widely used in biomedical applications. PMID:26274961

Position-sensitive scanning fluorescence correlation spectroscopy.

PubMed

Skinner, Joseph P; Chen, Yan; Müller, Joachim D

2005-08-01

Fluorescence correlation spectroscopy (FCS) uses a stationary laser beam to illuminate a small sample volume and analyze the temporal behavior of the fluorescence fluctuations within the stationary observation volume. In contrast, scanning FCS (SFCS) collects the fluorescence signal from a moving observation volume by scanning the laser beam. The fluctuations now contain both temporal and spatial information about the sample. To access the spatial information we synchronize scanning and data acquisition. Synchronization allows us to evaluate correlations for every position along the scanned trajectory. We use a circular scan trajectory in this study. Because the scan radius is constant, the phase angle is sufficient to characterize the position of the beam. We introduce position-sensitive SFCS (PSFCS), where correlations are calculated as a function of lag time and phase. We present the theory of PSFCS and derive expressions for diffusion, diffusion in the presence of flow, and for immobilization. To test PSFCS we compare experimental data with theory. We determine the direction and speed of a flowing dye solution and the position of an immobilized particle. To demonstrate the feasibility of the technique for applications in living cells we present data of enhanced green fluorescent protein measured in the nucleus of COS cells.

Drug-induced parkinsonism in relation to choline-containing compounds measured by 1H-MR spectroscopy in putamen of chronically medicated patients with schizophrenia.

PubMed

Yamasue, Hidenori; Fukui, Tsunehiro; Fukuda, Rin; Kasai, Kiyoto; Iwanami, Akira; Kato, Nobumasa; Kato, Tadafumi

2003-12-01

Extrapyramidal side-effects (EPS), the most frequent and severe side-effects of antipsychotics, sometimes become irreversible and cause severe psychosocial disturbance in patients with schizophrenia. However, the neurobiological basis of EPS has not yet been elucidated. In this study, neurochemical correlates of EPS were examined by 1H-MR spectroscopy (1H-MRS). Sixteen medicated patients with schizophrenia and 15 age-, gender- and parental-socioeconomic-status-matched normal controls were examined using single-voxel 1H-MRS. Absolute concentrations of N-acetyl aspartate (NAA), choline-containing compounds (Cho), creatine/phosphocreatine, myo-inositol, and Glx (glutamate and glutamine) in the left putamen were evaluated. The patient group showed mild EPS and no significant metabolic abnormalities in this region. The more severe drug-induced parkinsonism assessed by the Simpson-Angus Scale, however, significantly correlated with the higher Cho concentration and tended to be correlated with the higher NAA concentration in the patient group. These results suggest a potential of 1H-MRS as a non-invasive monitoring method of neurobiological correlates of EPS associated with neuroleptic treatments in patients with schizophrenia.

Variable Temperature Infrared Spectroscopy Investigation of Benzoic Acid Interactions with Montmorillonite Clay Interlayer Water.

PubMed

Nickels, Tara M; Ingram, Audrey L; Maraoulaite, Dalia K; White, Robert L

2015-07-01

Molecular interactions between benzoic acid and cations and water contained in montmorillonite clay interlayer spaces are characterized by using variable temperature diffuse reflection infrared Fourier transform spectroscopy (VT-DRIFTS). Using sample perturbation and difference spectroscopy, infrared spectral changes resulting from removal of interlayer water and associated changes in local benzoic acid environments are identified. Difference spectra features can be correlated with changes in specific molecular vibrations that are characteristic of benzoic acid molecular orientation. Results suggest that the carboxylic acid functionality of benzoic acid interacts with interlayer cations through a bridging water molecule and that this interaction is affected by the nature of the cation present in the clay interlayer space.

Gap features of layered iron-selenium-tellurium compound below and above the superconducting transition temperature by break-junction spectroscopy combined with STS

NASA Astrophysics Data System (ADS)

Ekino, T.; Sugimoto, A.; Gabovich, A. M.

2018-05-01

We studied correlations between the superconducting gap features of Te-substituted FeSe observed by scanning tunnelling spectroscopy (STS) and break-junction tunnelling spectroscopy (BJTS). At bias voltages outside the superconducting gap-energy range, the broad gap structure exists, which becomes the normal-state gap above the critical temperature, T c. Such behaviour is consistent with the model of the partially gapped density-wave superconductor involving both superconducting gaps and pseudogaps, which has been applied by us earlier to high-Tc cuprates. The similarity suggests that the parent electronic spectrum features should have much in common for these classes of materials.

Correlation ion mobility spectroscopy

DOEpatents

Pfeifer, Kent B [Los Lunas, NM; Rohde, Steven B [Corrales, NM

2008-08-26

Correlation ion mobility spectrometry (CIMS) uses gating modulation and correlation signal processing to improve IMS instrument performance. Closely spaced ion peaks can be resolved by adding discriminating codes to the gate and matched filtering for the received ion current signal, thereby improving sensitivity and resolution of an ion mobility spectrometer. CIMS can be used to improve the signal-to-noise ratio even for transient chemical samples. CIMS is especially advantageous for small geometry IMS drift tubes that can otherwise have poor resolution due to their small size.

Raman correlation spectroscopy: A feasibility study of a new optical correlation technique and development of multi-component nanoparticles using the reprecipitation method

NASA Astrophysics Data System (ADS)

Nishida, Maki

The feasibility of Raman correlation spectroscopy (RCS) is investigated as a new temporal optical fluctuation spectroscopy in this dissertation. RCS analyzes the correlations of the intensity fluctuations of Raman scattering from particles in a suspension that undergo Brownian motion. Because each Raman emission line arises from a specific molecular bond, the RCS method could yield diffusion behavior of specific chemical species within a dispersion. Due to the nature of Raman scattering as a coherent process, RCS could provide similar information as acquired in dynamic light scattering (DLS) and be practical for various applications that requires the chemical specificity in dynamical information. The theoretical development is discussed, and four experimental implementations of this technique are explained. The autocorrelation of the intensity fluctuations from a beta-carotene solution is obtained using the some configurations; however, the difficulty in precise alignment and weak nature of Raman scattering prevented the achievement of high sensitivity and resolution. Possible fluctuations of the phase of Raman scattering could also be affecting the results. A possible explanation of the observed autocorrelation in terms of number fluctuations of particles is also examined to test the feasibility of RCS as a new optical characterization method. In order to investigate the complex systems for which RCS would be useful, strategies for the creation of a multicomponent nanoparticle system are also explored. Using regular solution theory along with the concept of Hansen solubility parameters, an analytical model is developed to predict whether two or more components will form single nanoparticles, and what effect various processing conditions would have. The reprecipitation method was used to demonstrate the formation of the multi-component system of the charge transfer complex perylene:TCNQ (tetracyanoquinodimethane) and the active pharmaceutical ingredient cocrystal of CBZ:NCT (carbamazepine:nicotinamide). The experimental results with various characterization methods including DLS, absorption spectroscopy, powder x-ray diffraction, and SEM imaging, verify formation of the multicomponent cocrystals. The observation of the self-assembly of TCNQ crystals is also discussed.

Weak Long-Range Correlated Motions in a Surface Patch of Ubiquitin Involved in Molecular Recognition

PubMed Central

2011-01-01

Long-range correlated motions in proteins are candidate mechanisms for processes that require information transfer across protein structures, such as allostery and signal transduction. However, the observation of backbone correlations between distant residues has remained elusive, and only local correlations have been revealed using residual dipolar couplings measured by NMR spectroscopy. In this work, we experimentally identified and characterized collective motions spanning four β-strands separated by up to 15 Å in ubiquitin. The observed correlations link molecular recognition sites and result from concerted conformational changes that are in part mediated by the hydrogen-bonding network. PMID:21634390

A forestry GIS-based study on evaluating the potential of imaging spectroscopy in mapping forest land fertility

NASA Astrophysics Data System (ADS)

Mõttus, Matti; Takala, Tuure

2014-12-01

Fertility, or the availability of nutrients and water, controls forest productivity. It affects its carbon sequestration, and thus the forest's effect on climate, as well as its commercial value. Although the availability of nutrients cannot be measured directly using remote sensing methods, fertility alters several vegetation traits detectable from the reflectance spectra of the forest stand, including its pigment content and water stress. However, forest reflectance is also influenced by other factors, such as species composition and stand age. Here, we present a case study demonstrating how data obtained using imaging spectroscopy is correlated with site fertility. The study was carried out in Hyytiälä, Finland, in the southern boreal forest zone. We used a database of state-owned forest stands including basic forestry variables and a site fertility index. To test the suitability of imaging spectroscopy with different spatial and spectral resolutions for site fertility mapping, we performed two airborne acquisitions using different sensor configurations. First, the sensor was flown at a high altitude with high spectral resolution resulting in a pixel size in the order of a tree crown. Next, the same area was flown to provide reflectance data with sub-meter spatial resolution. However, to maintain usable signal-to-noise ratios, several spectral channels inside the sensor were combined, thus reducing spectral resolution. We correlated a number of narrowband vegetation indices (describing canopy biochemical composition, structure, and photosynthetic activity) on site fertility. Overall, site fertility had a significant influence on the vegetation indices but the strength of the correlation depended on dominant species. We found that high spatial resolution data calculated from the spectra of sunlit parts of tree crowns had the strongest correlation with site fertility.

Ensemble and single particle fluorimetric techniques in concerted action to study the diffusion and aggregation of the glycine receptor α3 isoforms in the cell plasma membrane.

PubMed

Notelaers, Kristof; Smisdom, Nick; Rocha, Susana; Janssen, Daniel; Meier, Jochen C; Rigo, Jean-Michel; Hofkens, Johan; Ameloot, Marcel

2012-12-01

The spatio-temporal membrane behavior of glycine receptors (GlyRs) is known to be of influence on receptor homeostasis and functionality. In this work, an elaborate fluorimetric strategy was applied to study the GlyR α3K and L isoforms. Previously established differential clustering, desensitization and synaptic localization of these isoforms imply that membrane behavior is crucial in determining GlyR α3 physiology. Therefore diffusion and aggregation of homomeric α3 isoform-containing GlyRs were studied in HEK 293 cells. A unique combination of multiple diffraction-limited ensemble average methods and subdiffraction single particle techniques was used in order to achieve an integrated view of receptor properties. Static measurements of aggregation were performed with image correlation spectroscopy (ICS) and, single particle based, direct stochastic optical reconstruction microscopy (dSTORM). Receptor diffusion was measured by means of raster image correlation spectroscopy (RICS), temporal image correlation spectroscopy (TICS), fluorescence recovery after photobleaching (FRAP) and single particle tracking (SPT). The results show a significant difference in diffusion coefficient and cluster size between the isoforms. This reveals a positive correlation between desensitization and diffusion and disproves the notion that receptor aggregation is a universal mechanism for accelerated desensitization. The difference in diffusion coefficient between the clustering GlyR α3L and the non-clustering GlyR α3K cannot be explained by normal diffusion. SPT measurements indicate that the α3L receptors undergo transient trapping and directed motion, while the GlyR α3K displays mild hindered diffusion. These findings are suggestive of differential molecular interaction of the isoforms after incorporation in the membrane. Copyright © 2012 Elsevier B.V. All rights reserved.

In Vivo{sup 1}H Magnetic Resonance Spectroscopy of Lactate in Patients With Stage IV Head and Neck Squamous Cell Carcinoma

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

Le, Quynh-Thu; Koong, Albert; Lieskovsky, Yee Yie

2008-07-15

Purpose: To investigate in vivo{sup 1}H magnetic resonance spectroscopy imaging of lactate for assessing tumor hypoxia in head and neck cancers and to determine its utility in predicting the response and outcomes. Methods and Materials: Volume-localized lactate-edited {sup 1}H magnetic resonance spectroscopy at 1.5 T was performed in vivo on involved neck nodes and control subcutaneous tissues in 36 patients with Stage IV head and neck cancer. The signal intensities (SIs) of lactate, choline, and creatine and the choline/creatine ratio were measured. The tumor partial pressure of oxygen (pO{sub 2}) was obtained in the same lymph node before MRS. Patientsmore » were treated with either two cycles of induction chemotherapy (tirapazamine, cisplatin, 5-fluorouracil) followed by simultaneous chemoradiotherapy or the same regimen without tirapazamine. The lactate SI and the choline/creatine ratio correlated with the tumor pO{sub 2}, nodal response, and locoregional control. Results: The lactate SI was greater for the involved nodes (median, 0.25) than for the subcutaneous tissue (median, 0.04; p = 0.07). No significant correlation was found between the lactate SI and tumor pO{sub 2} (mean, 0.46 {+-} 0.10 for hypoxic nodes [pO{sub 2} {<=}10 mm Hg, n = 15] vs. 0.36 {+-} 0.07 for nonhypoxic nodes [pO{sub 2} >10 mm Hg, n = 21], p = 0.44). A significant correlation was found between the choline/creatine ratios and tumor pO{sub 2} (mean, 2.74 {+-} 0.34 for hypoxic nodes vs. 1.78 {+-} 0.31 for nonhypoxic nodes, p = 0.02). No correlation was found between the lactate SI and the complete nodal response (p = 0.52) or locoregional control rates. Conclusions: The lactate SI did not correlate with tumor pO{sub 2}, treatment response, or locoregional control. Additional research is needed to refine this technique.« less

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.

Application Of Positron Beams For The Characterization Of Nano-scale Pores In Thin Films

NASA Astrophysics Data System (ADS)

Hirata, K.; Ito, K.; Kobayashi, Y.; Suzuki, R.; Ohdaira, T.; Eijt, S. W. H.; Schut, H.; van Veen, A.

2003-08-01

We applied three positron annihilation techniques, positron 3γ-annihilation spectroscopy, positron annihilation lifetime spectroscopy, and angular correlation of annihilation radiation, to the characterization of nano-scale pores in thin films by combining them with variable-energy positron beams. Characterization of pores in thin films is an important part of the research on various thin films of industrial importance. The results of our recent studies on pore characterization of thin films by positron beams will be reported here.

Near Infra-Red Spectroscopy to Reduce Prophylactic Fasciotomies for and Missed Cases of Acute Compartment Syndrome in Soldiers Injured in OEF/OIF

DTIC Science & Technology

2013-10-01

demonstrated that NIRS measurement of hemoglobin oxygen saturation in the tibial compartment provided reliable and sensitive correlation to increases...on 60 healthy participants. Our results indicated that NIRS was able to detect changes in oxygen saturation of muscle with exercise in all 60...Model 41 Introduction 42 Over the last two decades, tissue oxygenation saturation (StO2) measured by near infrared 43 spectroscopy (NIRS) has

Blood proteins analysis by Raman spectroscopy method

NASA Astrophysics Data System (ADS)

Artemyev, D. N.; Bratchenko, I. A.; Khristoforova, Yu. A.; Lykina, A. A.; Myakinin, O. O.; Kuzmina, T. P.; Davydkin, I. L.; Zakharov, V. P.

2016-04-01

This work is devoted to study the possibility of plasma proteins (albumin, globulins) concentration measurement using Raman spectroscopy setup. The blood plasma and whole blood were studied in this research. The obtained Raman spectra showed significant variation of intensities of certain spectral bands 940, 1005, 1330, 1450 and 1650 cm-1 for different protein fractions. Partial least squares regression analysis was used for determination of correlation coefficients. We have shown that the proposed method represents the structure and biochemical composition of major blood proteins.

Quantitative description of yttrium aluminate ceramic composition by means of Er+3 microluminescence spectrum

NASA Astrophysics Data System (ADS)

Videla, F. A.; Tejerina, M. R.; Moreira-Osorio, L.; Conconi, M. S.; Orzi, D. J. O.; Flores, T.; Ponce, L. V.; Bilmes, G. M.; Torchia, G. A.

2018-05-01

The composition of erbium-doped yttrium aluminate ceramics was analyzed by means of confocal luminescence spectroscopy, EDX, and X-ray diffraction. A well-defined linear correlation was found between a proposed estimator computed from the luminescence spectrum and the proportion of ceramic phases coexisting in different samples. This result shows the feasibility of using erbium luminescence spectroscopy to perform a quantitative determination of different phases of yttrium aluminates within a micrometric region in nanograined ceramics.

The study of molecular spectroscopy by ab initio methods

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

1991-01-01

This review illustrates the potential of theory for solving spectroscopic problems. The accuracy of approximate techniques for including electron correlation have been calibrated by comparison with full configuration-interaction calculations. Examples of the application of ab initio calculations to vibrational, rotational, and electronic spectroscopy are given. It is shown that the state-averaged, complete active space self-consistent field, multireference configuration-interaction procedure provides a good approach for treating several electronic states accurately in a common molecular orbital basis.

Elemental profiling of laser cladded multilayer coatings by laser induced breakdown spectroscopy and energy dispersive X-ray spectroscopy

NASA Astrophysics Data System (ADS)

Lednev, V. N.; Sdvizhenskii, P. A.; Filippov, M. N.; Grishin, M. Ya.; Filichkina, V. A.; Stavertiy, A. Ya.; Tretyakov, R. S.; Bunkin, A. F.; Pershin, S. M.

2017-09-01

Multilayer tungsten carbide wear resistant coatings were analyzed by laser induced breakdown spectroscopy (LIBS) and energy dispersive X-ray (EDX) spectroscopy. Coaxial laser cladding technique was utilized to produce tungsten carbide coating deposited on low alloy steel substrate with additional inconel 625 interlayer. EDX and LIBS techniques were used for elemental profiling of major components (Ni, W, C, Fe, etc.) in the coating. A good correlation between EDX and LIBS data was observed while LIBS provided additional information on light element distribution (carbon). A non-uniform distribution of tungsten carbide grains along coating depth was detected by both LIBS and EDX. In contrast, horizontal elemental profiling showed a uniform tungsten carbide particles distribution. Depth elemental profiling by layer-by-layer LIBS analysis was demonstrated to be an effective method for studying tungsten carbide grains distribution in wear resistant coating without any sample preparation.

Quantitative determination of Auramine O by terahertz spectroscopy with 2DCOS-PLSR model

NASA Astrophysics Data System (ADS)

Zhang, Huo; Li, Zhi; Chen, Tao; Qin, Binyi

2017-09-01

Residues of harmful dyes such as Auramine O (AO) in herb and food products threaten the health of people. So, fast and sensitive detection techniques of the residues are needed. As a powerful tool for substance detection, terahertz (THz) spectroscopy was used for the quantitative determination of AO by combining with an improved partial least-squares regression (PLSR) model in this paper. Absorbance of herbal samples with different concentrations was obtained by THz-TDS in the band between 0.2THz and 1.6THz. We applied two-dimensional correlation spectroscopy (2DCOS) to improve the PLSR model. This method highlighted the spectral differences of different concentrations, provided a clear criterion of the input interval selection, and improved the accuracy of detection result. The experimental result indicated that the combination of the THz spectroscopy and 2DCOS-PLSR is an excellent quantitative analysis method.

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.

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.

Complex structural dynamics of nanocatalysts revealed in Operando conditions by correlated imaging and spectroscopy probes

DOE PAGES

Li, Y.; Zakharov, D.; Zhao, S.; ...

2015-06-29

Understanding how heterogeneous catalysts change size, shape and structure during chemical reactions is limited by the paucity of methods for studying catalytic ensembles in working state, that is, in operando conditions. Here by a correlated use of synchrotron X-ray absorption spectroscopy and scanning transmission electron microscopy in operando conditions, we quantitatively describe the complex structural dynamics of supported Pt catalysts exhibited during an exemplary catalytic reaction—ethylene hydrogenation. This work exploits a microfabricated catalytic reactor compatible with both probes. The results demonstrate dynamic transformations of the ensemble of Pt clusters that spans a broad size range throughout changing reaction conditions. Lastly,more » this method is generalizable to quantitative operando studies of complex systems using a wide variety of X-ray and electron-based experimental probes.« less

Orbital-differentiated coherence-incoherence crossover identified by photoemission spectroscopy in LiFeAs

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

Miao, H.; Yin, Z. P.; Wu, S. F.

In the iron-based superconductors (FeSCs), orbital differentiation is an important phenomenon, whereby correlations stronger on the d xy orbital than on the d xz/d yz orbital yield quasi-particles with d xy orbital character having larger mass renormalization and abnormal temperature evolution. However, the physical origin of this orbital di erentiation is debated between the Hund's coupling induced unbinding of spin and orbital degrees of freedom and the Hubbard interaction instigated orbital selective Mott transition. Here we use angle-resolved photoemission spectroscopy to identify an orbital-dependent correlation-induced quasi-particle (QP) anomaly in LiFeAs. Lastly, the excellent agreement between our photoemission measurements and first-principlesmore » many-body theory calculations shows that the orbital-differentiated QP lifetime anomalies in LiFeAs are controlled by the Hund's coupling.« less

Rapid determination of saponification value and polymer content of vegetable and fish oils by terahertz spectroscopy.

PubMed

Jiang, Feng Ling; Ikeda, Ikuo; Ogawa, Yuichi; Endo, Yasushi

2012-01-01

A rapid method for determining the saponification value (SV) and polymer content of vegetable and fish oils using the terahertz (THz) spectroscopy was developed. When the THz absorption spectra for vegetable and fish oils were measured in the range of 20 to 400 cm⁻¹, two peaks were seen at 77 and 328 cm⁻¹. The level of absorbance at 77 cm⁻¹ correlated well with the SV. When the THz absorption spectra of thermally treated high-oleic safflower oils were measured, the absorbance increased with heating time. The polymer content in thermally treated oil correlated with the absorbance at 77 cm⁻¹. These results demonstrate that the THz spectrometry is a suitable non-destructive technique for the rapid determination of the SV and polymer content of vegetable and fish oils.

Enumerating virus-like particles in an optically concentrated suspension by fluorescence correlation spectroscopy.

PubMed

Hu, Yi; Cheng, Xuanhong; Daniel Ou-Yang, H

2013-01-01

Fluorescence correlation spectroscopy (FCS) is one of the most sensitive methods for enumerating low concentration nanoparticles in a suspension. However, biological nanoparticles such as viruses often exist at a concentration much lower than the FCS detection limit. While optically generated trapping potentials are shown to effectively enhance the concentration of nanoparticles, feasibility of FCS for enumerating field-enriched nanoparticles requires understanding of the nanoparticle behavior in the external field. This paper reports an experimental study that combines optical trapping and FCS to examine existing theoretical predictions of particle concentration. Colloidal suspensions of polystyrene (PS) nanospheres and HIV-1 virus-like particles are used as model systems. Optical trapping energies and statistical analysis are used to discuss the applicability of FCS for enumerating nanoparticles in a potential well produced by a force field.

λ-Repressor Oligomerization Kinetics at High Concentrations Using Fluorescence Correlation Spectroscopy in Zero-Mode Waveguides

PubMed Central

Samiee, K. T.; Foquet, M.; Guo, L.; Cox, E. C.; Craighead, H. G.

2005-01-01

Fluorescence correlation spectroscopy (FCS) has demonstrated its utility for measuring transport properties and kinetics at low fluorophore concentrations. In this article, we demonstrate that simple optical nanostructures, known as zero-mode waveguides, can be used to significantly reduce the FCS observation volume. This, in turn, allows FCS to be applied to solutions with significantly higher fluorophore concentrations. We derive an empirical FCS model accounting for one-dimensional diffusion in a finite tube with a simple exponential observation profile. This technique is used to measure the oligomerization of the bacteriophage λ repressor protein at micromolar concentrations. The results agree with previous studies utilizing conventional techniques. Additionally, we demonstrate that the zero-mode waveguides can be used to assay biological activity by measuring changes in diffusion constant as a result of ligand binding. PMID:15613638

Simultaneous characterization of lateral lipid and prothrombin diffusion coefficients by z-scan fluorescence correlation spectroscopy.

PubMed

Stefl, Martin; Kułakowska, Anna; Hof, Martin

2009-08-05

A new (to our knowledge) robust approach for the determination of lateral diffusion coefficients of weakly bound proteins is applied for the phosphatidylserine specific membrane interaction of bovine prothrombin. It is shown that z-scan fluorescence correlation spectroscopy in combination with pulsed interleaved dual excitation allows simultaneous monitoring of the lateral diffusion of labeled protein and phospholipids. Moreover, from the dependencies of the particle numbers on the axial sample positions at different protein concentrations phosphatidylserine-dependent equilibrium dissociation constants are derived confirming literature values. Increasing the amount of membrane-bound prothrombin retards the lateral protein and lipid diffusion, indicating coupling of both processes. The lateral diffusion coefficients of labeled lipids are considerably larger than the simultaneously determined lateral diffusion coefficients of prothrombin, which contradicts findings reported for the isolated N-terminus of prothrombin.

Correlation between skin, bone, and cerebrospinal fluid layer thickness and optical coefficients measured by multidistance frequency-domain near-infrared spectroscopy in term and preterm infants.

PubMed

Demel, Anja; Feilke, Katharina; Wolf, Martin; Poets, Christian F; Franz, Axel R

2014-01-01

Near-infrared spectroscopy (NIRS) is increasingly used in neonatal intensive care. We investigated the impact of skin, bone, and cerebrospinal fluid (CSF) layer thickness in term and preterm infants on absorption-(μa) and/or reduced scattering coefficients (μs') measured by multidistance frequency-domain (FD)-NIRS. Transcranial ultrasound was performed to measure the layer thicknesses. Correlations were only statistically significant for μa at 692 nm with bone thickness and μs' at 834 nm with skin thickness. There is no evidence that skin, bone, or CSF thickness have an important effect on μa and μs'. Layer thicknesses of skin, bone, and CSF in the range studied do not seem to affect cerebral oxygenation measurements by multidistance FD-NIRS significantly.

Orbital-differentiated coherence-incoherence crossover identified by photoemission spectroscopy in LiFeAs

DOE PAGES

Miao, H.; Yin, Z. P.; Wu, S. F.; ...

2016-11-14

In the iron-based superconductors (FeSCs), orbital differentiation is an important phenomenon, whereby correlations stronger on the d xy orbital than on the d xz/d yz orbital yield quasi-particles with d xy orbital character having larger mass renormalization and abnormal temperature evolution. However, the physical origin of this orbital di erentiation is debated between the Hund's coupling induced unbinding of spin and orbital degrees of freedom and the Hubbard interaction instigated orbital selective Mott transition. Here we use angle-resolved photoemission spectroscopy to identify an orbital-dependent correlation-induced quasi-particle (QP) anomaly in LiFeAs. Lastly, the excellent agreement between our photoemission measurements and first-principlesmore » many-body theory calculations shows that the orbital-differentiated QP lifetime anomalies in LiFeAs are controlled by the Hund's coupling.« less

Predicting the ethanol potential of wheat straw using near-infrared spectroscopy and chemometrics: The challenge of inherently intercorrelated response functions

DOE PAGES

Rinnan, Asmund; Bruun, Sander; Lindedam, Jane; ...

2017-02-07

Here, the combination of NIR spectroscopy and chemometrics is a powerful correlation method for predicting the chemical constituents in biological matrices, such as the glucose and xylose content of straw. However, difficulties arise when it comes to predicting enzymatic glucose and xylose release potential, which is matrix dependent. Further complications are caused by xylose and glucose release potential being highly intercorrelated. This study emphasizes the importance of understanding the causal relationship between the model and the constituent of interest. It investigates the possibility of using near-infrared spectroscopy to evaluate the ethanol potential of wheat straw by analyzing more than 1000more » samples from different wheat varieties and growth conditions. During the calibration model development, the prime emphasis was to investigate the correlation structure between the two major quality traits for saccharification of wheat straw: glucose and xylose release. The large sample set enabled a versatile and robust calibration model to be developed, showing that the prediction model for xylose release is based on a causal relationship with the NIR spectral data. In contrast, the prediction of glucose release was found to be highly dependent on the intercorrelation with xylose release. If this correlation is broken, the model performance breaks down. A simple method was devised for avoiding this breakdown and can be applied to any large dataset for investigating the causality or lack of causality of a prediction model.« less

Predicting the ethanol potential of wheat straw using near-infrared spectroscopy and chemometrics: The challenge of inherently intercorrelated response functions

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

Rinnan, Asmund; Bruun, Sander; Lindedam, Jane

Here, the combination of NIR spectroscopy and chemometrics is a powerful correlation method for predicting the chemical constituents in biological matrices, such as the glucose and xylose content of straw. However, difficulties arise when it comes to predicting enzymatic glucose and xylose release potential, which is matrix dependent. Further complications are caused by xylose and glucose release potential being highly intercorrelated. This study emphasizes the importance of understanding the causal relationship between the model and the constituent of interest. It investigates the possibility of using near-infrared spectroscopy to evaluate the ethanol potential of wheat straw by analyzing more than 1000more » samples from different wheat varieties and growth conditions. During the calibration model development, the prime emphasis was to investigate the correlation structure between the two major quality traits for saccharification of wheat straw: glucose and xylose release. The large sample set enabled a versatile and robust calibration model to be developed, showing that the prediction model for xylose release is based on a causal relationship with the NIR spectral data. In contrast, the prediction of glucose release was found to be highly dependent on the intercorrelation with xylose release. If this correlation is broken, the model performance breaks down. A simple method was devised for avoiding this breakdown and can be applied to any large dataset for investigating the causality or lack of causality of a prediction model.« less

Scanning fluorescence correlation spectroscopy techniques to quantify the kinetics of DNA double strand break repair proteins after γ-irradiation and bleomycin treatment

PubMed Central

Abdisalaam, Salim; Davis, Anthony J.; Chen, David J.; Alexandrakis, George

2014-01-01

A common feature of DNA repair proteins is their mobilization in response to DNA damage. The ability to visualizing and quantifying the kinetics of proteins localizing/dissociating from DNA double strand breaks (DSBs) via immunofluorescence or live cell fluorescence microscopy have been powerful tools in allowing insight into the DNA damage response, but these tools have some limitations. For example, a number of well-established DSB repair factors, in particular those required for non-homologous end joining (NHEJ), do not form discrete foci in response to DSBs induced by ionizing radiation (IR) or radiomimetic drugs, including bleomycin, in living cells. In this report, we show that time-dependent kinetics of the NHEJ factors Ku80 and DNA-dependent protein kinase catalytic subunits (DNA–PKcs) in response to IR and bleomycin can be quantified by Number and Brightness analysis and Raster-scan Image Correlation Spectroscopy. Fluorescent-tagged Ku80 and DNA–PKcs quickly mobilized in response to IR and bleomycin treatments consistent with prior reports using laser-generated DSBs. The response was linearly dependent on IR dose, and blocking NHEJ enhanced immobilization of both Ku80 and DNA–PKcs after DNA damage. These findings support the idea of using Number and Brightness and Raster-scan Image Correlation Spectroscopy as methods to monitor kinetics of DSB repair proteins in living cells under conditions mimicking radiation and chemotherapy treatments. PMID:24137007

A Rapid Identification Method for Calamine Using Near-Infrared Spectroscopy Based on Multi-Reference Correlation Coefficient Method and Back Propagation Artificial Neural Network.

PubMed

Sun, Yangbo; Chen, Long; Huang, Bisheng; Chen, Keli

2017-07-01

As a mineral, the traditional Chinese medicine calamine has a similar shape to many other minerals. Investigations of commercially available calamine samples have shown that there are many fake and inferior calamine goods sold on the market. The conventional identification method for calamine is complicated, therefore as a result of the large scale of calamine samples, a rapid identification method is needed. To establish a qualitative model using near-infrared (NIR) spectroscopy for rapid identification of various calamine samples, large quantities of calamine samples including crude products, counterfeits and processed products were collected and correctly identified using the physicochemical and powder X-ray diffraction method. The NIR spectroscopy method was used to analyze these samples by combining the multi-reference correlation coefficient (MRCC) method and the error back propagation artificial neural network algorithm (BP-ANN), so as to realize the qualitative identification of calamine samples. The accuracy rate of the model based on NIR and MRCC methods was 85%; in addition, the model, which took comprehensive multiple factors into consideration, can be used to identify crude calamine products, its counterfeits and processed products. Furthermore, by in-putting the correlation coefficients of multiple references as the spectral feature data of samples into BP-ANN, a BP-ANN model of qualitative identification was established, of which the accuracy rate was increased to 95%. The MRCC method can be used as a NIR-based method in the process of BP-ANN modeling.

Single molecule force spectroscopy at high data acquisition: A Bayesian nonparametric analysis

NASA Astrophysics Data System (ADS)

Sgouralis, Ioannis; Whitmore, Miles; Lapidus, Lisa; Comstock, Matthew J.; Pressé, Steve

2018-03-01

Bayesian nonparametrics (BNPs) are poised to have a deep impact in the analysis of single molecule data as they provide posterior probabilities over entire models consistent with the supplied data, not just model parameters of one preferred model. Thus they provide an elegant and rigorous solution to the difficult problem encountered when selecting an appropriate candidate model. Nevertheless, BNPs' flexibility to learn models and their associated parameters from experimental data is a double-edged sword. Most importantly, BNPs are prone to increasing the complexity of the estimated models due to artifactual features present in time traces. Thus, because of experimental challenges unique to single molecule methods, naive application of available BNP tools is not possible. Here we consider traces with time correlations and, as a specific example, we deal with force spectroscopy traces collected at high acquisition rates. While high acquisition rates are required in order to capture dwells in short-lived molecular states, in this setup, a slow response of the optical trap instrumentation (i.e., trapped beads, ambient fluid, and tethering handles) distorts the molecular signals introducing time correlations into the data that may be misinterpreted as true states by naive BNPs. Our adaptation of BNP tools explicitly takes into consideration these response dynamics, in addition to drift and noise, and makes unsupervised time series analysis of correlated single molecule force spectroscopy measurements possible, even at acquisition rates similar to or below the trap's response times.

[Infrared spectroscopic analysis of Guilin watermelon frost products].

PubMed

Huang, Dong-lan; Chen, Xiao-kang; Xu, Yong-qun; Sun, Su-qin; Zhou, Qun; Lu, Wen-guan

2012-08-01

The objective of the present study is to analyze different products of Guilin watermelon frost by Fourier transform infrared spectroscopy (FTIR), second derivative infrared spectroscopy and two-dimensional correlation spectroscopy (2D-IR) under thermal perturbation. The structural information of the samples indicates that samples from the same factory but of different brands had some dissimilarities in the IR spectra, and the type and content of accessories of them were different compared with conventional IR spectra of samples, peaks at 638 and 616 cm(-1) all arise from anhydrous sodium sulfate in watermelon frost spray and watermelon frost capsule; the characteristic absorption peaks of the sucrose, dextrin or other accessories can be seen clearly in the spectra of watermelon frost throat-clearing buccal tablets, watermelon frost throat tablets and watermelon frost lozenge. And the IR spectra of watermelon frost lozenge is very similar to the IR spectra of sucrose, so it can be easily proved that the content of sucrose in watermelon frost lozenge is high. In the 2D-IR correlation spectra, the samples presented the differences in the position, number and relative intensity of autopeaks and correlation peak clusters. Consequently, the macroscopical fingerprint characters of FTIR, second derivative infrared spectra and 2D-IR spectra can not only provide the information about main chemical constituents in medical materials, but also analyze and identify the type and content of accessories in Guilin watermelon frost. In conclusion, the multi-steps IR macro-fingerprint method is rapid, effective, visual and accurate for pharmaceutical research.

Superheavy-element spectroscopy: Correlations along element 115 decay chains

NASA Astrophysics Data System (ADS)

Rudolph, D.; Forsberg, U.; Sarmiento, L. G.; Golubev, P.; Fahlander, C.

2016-05-01

Following a brief summary of the region of the heaviest atomic nuclei yet created in the laboratory, data on more than hundred α-decay chains associated with the production of element 115 are combined to investigate time and energy correlations along the observed decay chains. Several of these are analysed using a new method for statistical assessments of lifetimes in sets of decay chains.

MRI, volumetry, 1H spectroscopy, and cerebropetal blood flowmetry in childhood idiopathic anatomic megalencephaly.

PubMed

Koudijs, Suzanne M; van der Grond, Jeroen; Hoogendoorn, Mechteld L C; Hulshoff Pol, Hilleke E; Schnack, Hugo G; Witkamp, Theo D; Gooskens, Rob H J M; van Nieuwenhuizen, Onno; Braun, Kees P J

2006-08-01

To evaluate cerebral abnormalities in childhood idiopathic anatomic megalencephaly (MC) by means of different magnetic resonance (MR) modalities. MRI, volumetry, spectroscopy, and cerebropetal blood flowmetry were performed in six children with idiopathic anatomic MC, and seven volunteers. MRI revealed an increased ventricular system in five of six patients. A thalamic hamartoma was found in one patient and a Chiari I malformation was found in two. Volumetric analysis showed a disproportional increase of ventricular volume but normal subarachnoid cerebrospinal fluid (CSF) volume. Supratentorial volume was disproportionally increased compared to cerebellar volume. Intracranial volume correlated significantly with skull circumference. MR spectroscopy (MRS) N-acetyl aspartate/choline (NAA/Cho) peak ratios in WM were significantly higher in patients than in controls. Choline/creatine (Cho/Cr) peak ratios in WM were significantly lower in patients. Cortical gray matter (GM) MRS ratios were unaltered. Cerebropetal flow was increased in MC, possibly related to increased brain volume. This study reveals associated developmental anomalies for idiopathic anatomic MC. A relative ventriculomegaly was found, which should not be misinterpreted as true hydrocephalus. In contrast to metabolic MC, MRS showed no severe disturbances. Total intracranial volume is correlated to skull circumference and cerebropetal blood flow.

Structural characterization of sulfated steroids that activate mouse pheromone-sensing neurons.

PubMed

Hsu, Fong-Fu; Nodari, Francesco; Kao, Lung-Fa; Fu, Xiaoyan; Holekamp, Terrence F; Turk, John; Holy, Timothy E

2008-12-30

In many species, social behavior is organized via chemical signaling. While many of these signals have been identified for insects, the chemical identity of these social cues (often called pheromones) for mammals is largely unknown. We recently isolated these chemical cues that caused firing in the pheromone-sensing neurons of the vomeronasal organ from female mouse urine [Nodari, F., et al. (2008) J. Neurosci. 28, 6407-6418]. Here, we report their structural characterization. Mass spectrometric approaches, including tandem quadrupole, multiple-stage linear ion trap, high-resolution mass spectrometry, and H-D exchange followed by ESI mass spectrometry, along with (1)H and (13)C nuclear magnetic resonance spectroscopy, including two-dimensional correlation spectroscopy, total correlation spectroscopy, heteronuclear multiple-quantum coherence, and NOE, were used to identify two sulfated steroids, 4-pregnene-11beta,20,21-triol-3-one 21-sulfate (I) (the configuration at C20 was not deduced) and 4-pregnene-11beta,21-diol-3,20-dione 21-sulfate (II), whose presence is sex-specific. The identification of this novel class of mammalian social signaling compounds suggests that steroid hormones, upon conjugation, assume a new biological role, conveying information about the organism's identity and physiological state.

Raman Spectroscopy of DNA Packaging in Individual Human Sperm Cells distinguishes Normal from Abnormal Cells

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

Huser, T; Orme, C; Hollars, C

Healthy human males produce sperm cells of which about 25-40% have abnormal head shapes. Increases in the percentage of sperm exhibiting aberrant sperm head morphologies have been correlated with male infertility, and biochemical studies of pooled sperm have suggested that sperm with abnormal shape may contain DNA that has not been properly repackaged by protamine during spermatid development. We have used micro-Raman spectroscopy to obtain Raman spectra from individual human sperm cells and examined how differences in the Raman spectra of sperm chromatin correlate with cell shape. We show that Raman spectra of individual sperm cells contain vibrational marker modesmore » that can be used to assess the efficiency of DNA-packaging for each cell. Raman spectra obtained from sperm cells with normal shape provide evidence that DNA in these sperm is very efficiently packaged. We find, however, that the relative protein content per cell and DNA packaging efficiencies are distributed over a relatively wide range for sperm cells with both normal and abnormal shape. These findings indicate that single cell Raman spectroscopy should be a valuable tool in assessing the quality of sperm cells for in-vitro fertilization.« less

Identification of green pigments from fragments of Roman mural paintings of three Roman sites from north of Germania Superior

NASA Astrophysics Data System (ADS)

Debastiani, Rafaela; Simon, Rolf; Goettlicher, Joerg; Heissler, Stefan; Steininger, Ralph; Batchelor, David; Fiederle, Michael; Baumbach, Tilo

2016-10-01

Roman mural green pigment painting fragments from three Roman sites in the north of the Roman province Germania Superior: Koblenz Stadtwald Remstecken (KOSR), Weißenthurm " Am guten Mann" (WEIS) and Mendig Lungenkärchen (MELU), dating from second and third centuries AD were analyzed. The experiments were performed nondestructively using synchrotron-based scanning macro-X-ray fluorescence (SR-MA-XRF), synchrotron-based scanning micro-X-ray fluorescence (SR-μ-XRF), synchrotron-based X-ray diffraction (SR-XRD) and Raman spectroscopy. Correlation between SR-MA-XRF, SR-μ-XRF elemental map distributions and optical images of scanned areas was mainly found for the elements Ca, Fe and K. With XRF, Fe and K were identified correlated with green pigment, but in samples from two sites, Mendig Lungenkärchen and Weißenthurm " Am guten Mann", also Cu was detected in minor concentration. The results of SR-XRD and Raman spectroscopy were limited to one sample from Weißenthurm " Am guten Mann". In this sample, green earth and calcium carbonate were identified by SR-XRD and, additionally, malachite by Raman spectroscopy.

Differentiation of the root of Cultivated Ginseng, Mountain Cultivated Ginseng and Mountain Wild Ginseng using FT-IR and two-dimensional correlation IR spectroscopy

NASA Astrophysics Data System (ADS)

Liu, Dan; Li, Yong-Guo; Xu, Hong; Sun, Su-Qin; Wang, Zheng-Tao

2008-07-01

Ginseng is one of the most widely used herbal medicines. Based on the grown environments and the cultivate method, three kinds of ginseng, Cultivated Ginseng (CG), Mountain Cultivated Ginseng (MCG) and Mountain Wild Ginseng (MWG) are classified. A novel and scientific-oriented method was developed and established to discriminate and identify three kinds of ginseng using Fourier transform infrared spectroscopy (FT-IR), secondary derivative IR spectra and two-dimensional correlation infrared spectroscopy (2D-IR). The findings indicated that the relative contents of starch in the CG were more than that in MCG and MWG, while the relative contents of calcium oxalate and lipids in MWG were more than that in CG and MCG, and the relative contents of fatty acid in MCG were more than that in CG and MWG. The hierarchical cluster analysis was applied to data analysis of MWG, CG and MWG, which could be classified successfully. The results demonstrated the macroscopic IR fingerprint method, including FT-IR, secondary derivative IR and 2D-IR, can be applied to discriminate different ginsengs rapidly, effectively and non-destructively.

Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

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

Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.

A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlatemore » with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. It was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.« less

Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

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

Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.

A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlatemore » with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. Moreover, it was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.« less

Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

DOE PAGES

Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.; ...

2015-10-14

A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlatemore » with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. Moreover, it was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.« less

Prediction of ethanol in bottled Chinese rice wine by NIR spectroscopy

NASA Astrophysics Data System (ADS)

Ying, Yibin; Yu, Haiyan; Pan, Xingxiang; Lin, Tao

2006-10-01

To evaluate the applicability of non-invasive visible and near infrared (VIS-NIR) spectroscopy for determining ethanol concentration of Chinese rice wine in square brown glass bottle, transmission spectra of 100 bottled Chinese rice wine samples were collected in the spectral range of 350-1200 nm. Statistical equations were established between the reference data and VIS-NIR spectra by partial least squares (PLS) regression method. Performance of three kinds of mathematical treatment of spectra (original spectra, first derivative spectra and second derivative spectra) were also discussed. The PLS models of original spectra turned out better results, with higher correlation coefficient in calibration (R cal) of 0.89, lower root mean standard error of calibration (RMSEC) of 0.165, and lower root mean standard error of cross validation (RMSECV) of 0.179. Using original spectra, PLS models for ethanol concentration prediction were developed. The R cal and the correlation coefficient in validation (R val) were 0.928 and 0.875, respectively; and the RMSEC and the root mean standard error of validation (RMSEP) were 0.135 (%, v v -1) and 0.177 (%, v v -1), respectively. The results demonstrated that VIS-NIR spectroscopy could be used to predict ethanol concentration in bottled Chinese rice wine.

Profiling planktonic biomass using element-specific, multicomponent nuclear magnetic resonance spectroscopy.

PubMed

Komatsu, Takanori; Kobayashi, Toshiya; Hatanaka, Minoru; Kikuchi, Jun

2015-06-02

Planktonic metabolism plays crucial roles in Earth's elemental cycles. Chemical speciation as well as elemental stoichiometry is important for advancing our understanding of planktonic roles in biogeochemical cycles. In this study, a multicomponent solid-state nuclear magnetic resonance (NMR) approach is proposed for chemical speciation of cellular components, using several advanced NMR techniques. Measurements by ssNMR were performed on (13)C and (15)N-labeled Euglena gracilis, a flagellated protist. 3D dipolar-assisted rotational resonance, double-cross-polarization (1)H-(13)C correlation spectroscopy, and (1)H-(13)C solid-state heteronuclear single quantum correlation spectroscopy successively allowed characterization of cellular components. These techniques were then applied to E. gracilis cultured in high and low ammonium media to demonstrate the power of this method for profiling and comparing cellular components. Cellular NMR spectra indicated that ammonium induced both paramylon degradation and amination. Arginine was stored as a nitrogen reserve and ammonium replaced by arginine catabolism via the arginine dihydrolase pathway. (15)N and (31)P cellular ssNMR indicated arginine and polyphosphate accumulation in E. gracilis, respectively. This chemical speciation technique will contribute to environmental research by providing detailed information on environmental chemical properties.

Quantitative Phase Composition of TiO 2-Coated Nanoporous-Au Monoliths by X-ray Absorption Spectroscopy and Correlations to Catalytic

DOE PAGES

Bagge-Hansen, Michael; Wichmann, Andre; Wittstock, Arne; ...

2014-02-03

Porous titania/metal composite materials have many potential applications in the fields of green catalysis, energy harvesting, and storage in which both the overall morphology of the nanoporous host material and the crystallographic phase of the titania (TiO 2) guest determine the material’s performance. New insights into the structure–function relationships of these materials were obtained by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy that, for example, provides quantitative crystallographic phase composition from ultrathin, nanostructured titania films, including sensitivity to amorphous components. We demonstrate that crystallographic phase, morphology, and catalytic activity of TiO 2-functionalized nanoporous gold (np-Au) can be controlled by amore » simple annealing procedure (T < 1300 K). The material was prepared by atomic layer deposition of ~2 nm thick TiO 2 on millimeter-sized samples of np-Au (40–50 nm mean ligament size) and catalytically investigated with respect to aerobic CO oxidation. Moreover, the annealing-induced changes in catalytic activity are correlated with concurrent morphology and phase changes as provided by cross-sectional scanning electron microscopy, transmission electron microscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy.« less

1H-MR spectroscopy metabolite levels correlate with executive function in vascular cognitive impairment

PubMed Central

Gasparovic, Charles; Prestopnik, Jillian; Thompson, Jeffrey; Taheri, Saeid; Huisa, Branko; Schrader, Ronald; Adair, John C; Rosenberg, Gary A

2013-01-01

Background White matter hyperintensities (WMHs) are associated with vascular cognitive impairment (VCI) but fail to correlate with neuropsychological measures. As proton MR spectroscopy (1H-MRS) can identify ischaemic tissue, we hypothesised that MRS detectable brain metabolites would be superior to WMHs in predicting performance on neuropsychological tests. Methods 60 patients with suspected VCI underwent clinical, neuropsychological, MRI and CSF studies. They were diagnosed as having subcortical ischaemic vascular disease (SIVD), multiple infarcts, mixed dementia and leukoaraiosis. We measured brain metabolites in a white matter region above the lateral ventricles with 1H-MRS and WMH volume in this region and throughout the brain. Results We found a significant correlation between both total creatine (Cr) and N-acetylaspartyl compounds (NAA) and standardised neuropsychological test scores. Cr levels in white matter correlated significantly with executive function (p=0.001), attention (p=0.03) and overall T score (p=0.007). When lesion volume was added as a covariate, NAA also showed a significant correlation with executive function (p=0.003) and overall T score (p=0.015). Furthermore, while metabolite levels also correlated with total white matter lesion volume, adjusting the Cr levels for lesion volume did not diminish the strength of the association between Cr levels and neuropsychological scores. The lowest metabolite levels and neuropsychological scores were found in the SIVD group. Finally, lesion volume alone did not correlate significantly with any neuropsychological test score. Conclusion These results suggest that estimates of neurometabolite levels provide additional and useful information concerning cognitive function in VCI not obtainable by measurements of lesion load. PMID:23418212

1H magnetic resonance spectroscopy evidence for occipital involvement in treatment-naive paediatric obsessive-compulsive disorder.

PubMed

Ljungberg, Maria; Nilsson, Marie K L; Melin, Karin; Jönsson, Lars; Carlsson, Arvid; Carlsson, Åsa; Forssell-Aronsson, Eva; Ivarsson, Tord; Carlsson, Maria; Starck, Göran

2017-06-01

Obsessive-compulsive disorder (OCD) is a chronic psychiatric disorder leading to considerable distress and disability. Therapies are effective in a majority of paediatric patients, however, many only get partial response. It is therefore important to study the underlying pathophysiology of the disorder. 1H magnetic resonance spectroscopy (MRS) was used to study the concentration of brain metabolites in four different locations (cingulate gyrus and sulcus, occipital cortex, thalamus and right caudate nucleus). Treatment-naive children and adolescents with OCD (13 subjects) were compared with a group of healthy age- and gender-matched subjects (11 subjects). Multivariate analyses were performed on the concentration values. No separation between controls and patients was found. However, a correlation between metabolite concentrations and symptom severity as measured with the Children's Yale-Brown Obsessive-Compulsive Scale (CY-BOCS) was found. Strongest was the correlation with the CY-BOCS obsession subscore and aspartate and choline in the caudate nucleus (positively correlated with obsessions), lipids at 2 and 0.9 ppm in thalamus, and occipital glutamate+glutamine, N-acetylaspartate and myo-inosytol (negatively correlated with obsessions). The observed correlations between 1H MRS and CY-BOCS in treatment-naive patients further supports an occipital involvement in OCD. The results are consistent with our previous study on adult OCD patients. The 1H MRS data were not supportive of a separation between the patient and control groups.

Orientational Dynamics of a Functionalized Alkyl Planar Monolayer Probed by Polarization-Selective Angle-Resolved Infrared Pump-Probe Spectroscopy.

PubMed

Nishida, Jun; Yan, Chang; Fayer, Michael D

2016-10-12

Polarization-selective angle-resolved infrared pump-probe spectroscopy was developed and used to study the orientational dynamics of a planar alkylsiloxane monolayer functionalized with a rhenium metal carbonyl headgroup on an SiO 2 surface. The technique, together with a time-averaged infrared linear dichroism measurement, characterized picosecond orientational relaxation of the headgroup occurring at the monolayer-air interface by employing several sets of incident angles of the infrared pulses relative to the sample surface. By application of this method and using a recently developed theory, it was possible to extract both the out-of-plane and "mainly"-in-plane orientational correlation functions in a model-independent manner. The observed correlation functions were compared with theoretically derived correlation functions based on several dynamical models. The out-of-plane correlation function reveals the highly restricted out-of-plane motions of the head groups and also suggests that the angular distribution of the transition dipole moments is bimodal. The mainly-in-plane correlation function, for the sample studied here with the strongly restricted out-of-plane motions, essentially arises from the purely in-plane dynamics. In contrast to the out-of-plane dynamics, significant in-plane motions occurring over various time scales were observed including an inertial motion, a restricted wobbling motion of ∼3 ps, and complete randomization occurring in ∼25 ps.

Fluorescence Correlation Spectroscopy and Nonlinear Stochastic Reaction-Diffusion

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

Del Razo, Mauricio; Pan, Wenxiao; Qian, Hong

2014-05-30

The currently existing theory of fluorescence correlation spectroscopy (FCS) is based on the linear fluctuation theory originally developed by Einstein, Onsager, Lax, and others as a phenomenological approach to equilibrium fluctuations in bulk solutions. For mesoscopic reaction-diffusion systems with nonlinear chemical reactions among a small number of molecules, a situation often encountered in single-cell biochemistry, it is expected that FCS time correlation functions of a reaction-diffusion system can deviate from the classic results of Elson and Magde [Biopolymers (1974) 13:1-27]. We first discuss this nonlinear effect for reaction systems without diffusion. For nonlinear stochastic reaction-diffusion systems there are no closedmore » solutions; therefore, stochastic Monte-Carlo simulations are carried out. We show that the deviation is small for a simple bimolecular reaction; the most significant deviations occur when the number of molecules is small and of the same order. Extending Delbrück-Gillespie’s theory for stochastic nonlinear reactions with rapidly stirring to reaction-diffusion systems provides a mesoscopic model for chemical and biochemical reactions at nanometric and mesoscopic level such as a single biological cell.« less

Evidence for Weakly Correlated Oxygen Holes in the Highest-Tc Cuprate Superconductor HgBa2 Ca2 Cu3 O8 +δ

NASA Astrophysics Data System (ADS)

Chainani, A.; Sicot, M.; Fagot-Revurat, Y.; Vasseur, G.; Granet, J.; Kierren, B.; Moreau, L.; Oura, M.; Yamamoto, A.; Tokura, Y.; Malterre, D.

2017-08-01

We study the electronic structure of HgBa2 Ca2 Cu3 O8 +δ (Hg1223; Tc=134 K ) using photoemission spectroscopy (PES) and x -ray absorption spectroscopy (XAS). Resonant valence band PES across the O K edge and Cu L edge identifies correlation satellites originating in O 2 p and Cu 3 d two-hole final states, respectively. Analyses using the experimental O 2 p and Cu 3 d partial density of states show quantitatively different on-site Coulomb energy for the Cu site (Ud d=6.5 ±0.5 eV ) and O site (Up p=1.0 ±0.5 eV ). Cu2 O7 -cluster calculations with nonlocal screening explain the Cu 2 p core level PES and Cu L -edge XAS spectra, confirm the Ud d and Up p values, and provide evidence for the Zhang-Rice singlet state in Hg1223. In contrast to other hole-doped cuprates and 3 d -transition metal oxides, the present results indicate weakly correlated oxygen holes in Hg1223.

Rapid identification of Chinese Sauce liquor from different fermentation positions with FT-IR spectroscopy

NASA Astrophysics Data System (ADS)

Li, Changwen; Wei, Jiping; Zhou, Qun; Sun, Suqin

2008-07-01

FT-IR and two-dimensional correlation spectroscopy (2D-IR) technology were applied to discriminate Chinese Sauce liquor from different fermentation positions (top, middle and bottom of fermentation cellar) for the first time. The liquors at top, middle and bottom of fermentation cellar, possessed the characteristic peaks at 1731 cm -1, 1733 cm -1 and 1602 cm -1, respectively. In the 2D correlation infrared spectra, the differences were amplified. A strong auto-peak at 1725 cm -1 showed in the 2D spectra of the Top Liquor, which indicated that the liquor might contain some ester compounds. Different from Top Liquor, three auto-peaks at 1695, 1590 and 1480 cm -1 were identified in 2D spectra of Middle Liquor, which were the characteristic absorption of acid, lactate. In 2D spectra of Bottom Liquor, two auto-peaks at 1570 and 1485 cm -1 indicated that lactate was the major component. As a result, FT-IR and 2D-IR correlation spectra technology provided a rapid and effective method for the quality analysis of the Sauce liquor.

IRX– β RELATION OF STAR-FORMING REGIONS IN NGC 628 BASED ON INTEGRAL FIELD SPECTROSCOPY

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

Ye, Chengyun; Lian, Jianhui; Hu, Ning

2016-08-01

It has been found that the infrared-to-ultraviolet luminosity ratio (IRX) and ultraviolet spectral slope ( β ) have a tight correlation in starburst galaxies, while in normal galaxies the relation is deviated and has a much larger scatter. Star formation regions are much simpler in both morphology and physical properties than galaxies, so their photometric and spectroscopic properties are more easily and accurately determined. We have used the integral field spectroscopy and multiband photometric images to study the IRX– β relation of H ii regions in a nearby galaxy, NGC 628. There are obvious correlations between the D{sub n} (4000),more » stellar population age, star formation rate, especially H α equivalent width EW(H α), and deviation distance d {sub p} from the starburst IRX– β relation. However, there is little correlation between the Balmer decrement, metallicity, and d {sub p}. It is much more complicated than expected, so that we cannot introduce a single second parameter to describe the scatter and deviation of the H ii region IRX– β relation.« less

In situ fluorescence spectroscopy correlates ionomer degradation to reactive oxygen species generation in an operating fuel cell.

PubMed

Prabhakaran, Venkateshkumar; Arges, Christopher G; Ramani, Vijay

2013-11-21

The rate of generation of reactive oxygen species (ROS) within the polymer electrolyte membrane (PEM) of an operating proton exchange member fuel cell (PEMFC) was monitored using in situ fluorescence spectroscopy. A modified barrier layer was introduced between the PEM and the electrocatalyst layer to eliminate metal-dye interactions and fluorescence resonance energy transfer (FRET) effects during measurements. Standard fuel cell operating parameters (temperature, relative humidity, and electrode potential) were systematically varied to evaluate their influence on the rate of ROS generation during PEMFC operation. Independently, the macroscopic rate of PEM degradation was measured by monitoring the fluoride ion emission rate (FER) in the effluent stream at each operating condition. The ROS generation reaction rate constant (estimated from the in situ fluorescence experiments) correlated perfectly with the measured FER across all conditions, demonstrating unequivocally for the first time that a direct correlation exists between in situ ROS generation and PEM macroscopic degradation. The activation energy for ROS generation within the PEM was estimated to be 12.5 kJ mol(-1).

Weak-coupling superconductivity in a strongly correlated iron pnictide

PubMed Central

Charnukha, A.; Post, K. W.; Thirupathaiah, S.; Pröpper, D.; Wurmehl, S.; Roslova, M.; Morozov, I.; Büchner, B.; Yaresko, A. N.; Boris, A. V.; Borisenko, S. V.; Basov, D. N.

2016-01-01

Iron-based superconductors have been found to exhibit an intimate interplay of orbital, spin, and lattice degrees of freedom, dramatically affecting their low-energy electronic properties, including superconductivity. Albeit the precise pairing mechanism remains unidentified, several candidate interactions have been suggested to mediate the superconducting pairing, both in the orbital and in the spin channel. Here, we employ optical spectroscopy (OS), angle-resolved photoemission spectroscopy (ARPES), ab initio band-structure, and Eliashberg calculations to show that nearly optimally doped NaFe0.978Co0.022As exhibits some of the strongest orbitally selective electronic correlations in the family of iron pnictides. Unexpectedly, we find that the mass enhancement of itinerant charge carriers in the strongly correlated band is dramatically reduced near the Γ point and attribute this effect to orbital mixing induced by pronounced spin-orbit coupling. Embracing the true band structure allows us to describe all low-energy electronic properties obtained in our experiments with remarkable consistency and demonstrate that superconductivity in this material is rather weak and mediated by spin fluctuations. PMID:26729630

Validation of diffuse correlation spectroscopy sensitivity to nicotinamide-induced blood flow elevation in the murine hindlimb using the fluorescent microsphere technique

NASA Astrophysics Data System (ADS)

Proctor, Ashley R.; Ramirez, Gabriel A.; Han, Songfeng; Liu, Ziping; Bubel, Tracy M.; Choe, Regine

2018-03-01

Nicotinamide has been shown to affect blood flow in both tumor and normal tissues, including skeletal muscle. Intraperitoneal injection of nicotinamide was used as a simple intervention to test the sensitivity of noninvasive diffuse correlation spectroscopy (DCS) to changes in blood flow in the murine left quadriceps femoris skeletal muscle. DCS was then compared with the gold-standard fluorescent microsphere (FM) technique for validation. The nicotinamide dose-response experiment showed that relative blood flow measured by DCS increased following treatment with 500- and 1000-mg / kg nicotinamide. The DCS and FM technique comparison showed that blood flow index measured by DCS was correlated with FM counts quantified by image analysis. The results of this study show that DCS is sensitive to nicotinamide-induced blood flow elevation in the murine left quadriceps femoris. Additionally, the results of the comparison were consistent with similar studies in higher-order animal models, suggesting that mouse models can be effectively employed to investigate the utility of DCS for various blood flow measurement applications.

Comparison of local adipose tissue content and SRS-derived NIRS muscle oxygenation measurements in 90 individuals.

PubMed

Cooper, Chris E; Penfold, Stacey-Marie; Elwell, Clare E; Angus, Caroline

2010-01-01

Adipose content in the region over the vastus lateralis muscle was measured in a young (21.1 +/- 3.1 years old, mean +/- SD) population of males (n = 62) and females (n = 28). Three techniques were used: skinfold thickness, ultrasound and near infrared spectroscopy. All techniques closely correlated with each other and all showed a significantly larger adipose content in females and a limited overlap with the range of values in males. Spatially resolved near infrared spectroscopy (SRS-NIRS) was then used to measure the tissue oxygenation index (TOI) at the same site. A source-detector separation of 4 cm was used to allow for significant light penetration into muscle tissue. TOI at rest was significantly higher in the female (65.3 +/- 7.0, mean +/- SD) than the male (61.9 +/- 5.1, mean +/- SD) group. There was a strong positive correlation between adipose content and TOI in male subjects. However, no correlation was seen in the female group. The possible optical and physiological explanations for these results are discussed.

Viscosity-dependent diffusion of fluorescent particles using fluorescence correlation spectroscopy.

PubMed

Jung, Chanbae; Lee, Jaeran; Kang, Manil; Kim, Sok Won

2014-11-01

Fluorescent particles show the variety characteristics by the interaction with other particles and solvent. In order to investigate the relationship between the dynamic properties of fluorescent particles and solvent viscosity, particle diffusion in various solvents was evaluated using a fluorescence correlation spectroscopy. Upon analyzing the correlation functions of AF-647, Q-dot, and beads with different viscosity values, the diffusion time of all particles was observed to increase with increasing solvent viscosity, and the ratio of diffusion time to solvent viscosity, τ D /η, showed a linear dependence on particle size. The particle diffusion coefficients calculated from the diffusion time decreased with increasing solvent viscosity. Further, the hydrodynamic radii of AF-647, Q-dot, and beads were 0.98 ± 0.1 nm, 64.8 ± 3.23 nm, and 89.8 ± 4.91 nm, respectively, revealing a linear dependence on τ D /η, which suggests that the hydrodynamic radius of a particle strongly depends on both the physical size of the particle and solvent viscosity.

TDPAC and β-NMR applications in chemistry and biochemistry

NASA Astrophysics Data System (ADS)

Jancso, Attila; Correia, Joao G.; Gottberg, Alexander; Schell, Juliana; Stachura, Monika; Szunyogh, Dániel; Pallada, Stavroula; Lupascu, Doru C.; Kowalska, Magdalena; Hemmingsen, Lars

2017-06-01

Time differential perturbed angular correlation (TDPAC) of γ-rays spectroscopy has been applied in chemistry and biochemistry for decades. Herein we aim to present a comprehensive review of chemical and biochemical applications of TDPAC spectroscopy conducted at ISOLDE over the past 15 years, including elucidation of metal site structure and dynamics in proteins and model systems. β-NMR spectroscopy is well established in nuclear physics, solid state physics, and materials science, but only a limited number of applications in chemistry have appeared. Current endeavors at ISOLDE advancing applications of β-NMR towards chemistry and biochemistry are presented, including the first experiment on 31Mg2+ in an ionic liquid solution. Both techniques require the production of radioisotopes combined with advanced spectroscopic instrumentation present at ISOLDE.

Facile method for liquid-exfoliated graphene size prediction by UV-visible spectroscopy

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

Ismail, Zulhelmi, E-mail: helmie83@hotmail.com; Yusoh, Kamal, E-mail: kamal@ump.edu.my

2016-07-19

In this work, an application of UV spectroscopy for facile prediction of liquid –exfoliated graphene size is discussed. Dynamic light scattering method was used to estimate the graphene flake size ( whilst UV spectroscopy measurement was carried out for extinction coefficient value (ε) determination. It was found that the value of (ε) decreased gradually as the graphene size was further reduced after intense sonication time (7h). This observation showed the influence of sonication time on electronic structure of graphene. A mathematical equation was derived from log-log graph for correlation between () and (ε) value. Both values can be expressed inmore » a single equation as ( = (3.4 × 10{sup −2}) ε{sup 1.2}).« less

Dispersion of carbon nanotubes in melt compounded polypropylene based composites investigated by THz spectroscopy.

PubMed

Casini, R; Papari, G; Andreone, A; Marrazzo, D; Patti, A; Russo, P

2015-07-13

We investigate the use of Terahertz (THz) Time Domain Spectroscopy (TDS) as a tool for the measurement of the index dispersion of multi-walled carbon nanotubes (MWCNT) in polypropylene (PP) based composites. Samples containing 0.5% by volume concentration of non-functionalized and functionalized carbon nanotubes are prepared by melt compounding technology. Results indicate that the THz response of the investigated nanocomposites is strongly dependent on the kind of nanotube functionalization, which in turn impacts on the level of dispersion inside the polymer matrix. We show that specific dielectric parameters such as the refractive index and the absorption coefficient measured by THz spectroscopy can be both correlated to the index of dispersion as estimated using conventional optical microscopy.

Momentum-resolved spectroscopy of a Fermi liquid

PubMed Central

Doggen, Elmer V. H.; Kinnunen, Jami J.

2015-01-01

We consider a recent momentum-resolved radio-frequency spectroscopy experiment, in which Fermi liquid properties of a strongly interacting atomic Fermi gas were studied. Here we show that by extending the Brueckner-Goldstone model, we can formulate a theory that goes beyond basic mean-field theories and that can be used for studying spectroscopies of dilute atomic gases in the strongly interacting regime. The model hosts well-defined quasiparticles and works across a wide range of temperatures and interaction strengths. The theory provides excellent qualitative agreement with the experiment. Comparing the predictions of the present theory with the mean-field Bardeen-Cooper-Schrieffer theory yields insights into the role of pair correlations, Tan's contact, and the Hartree mean-field energy shift. PMID:25941948

Detection of the presence of Chlamydia trachomatis bacteria using diffusing wave spectroscopy with a small number of scatterers

NASA Astrophysics Data System (ADS)

Ulyanov, Sergey; Ulianova, Onega; Filonova, Nadezhda; Moiseeva, Yulia; Zaitsev, Sergey; Saltykov, Yury; Polyanina, Tatiana; Lyapina, Anna; Kalduzova, Irina; Larionova, Olga; Utz, Sergey; Feodorova, Valentina

2018-04-01

Theory of diffusing wave spectroscopy has been firstly adapted to the problem of rapid detection of Chlamydia trachomatis bacteria in blood samples of Chlamydia patients. Formula for correlation function of temporal fluctuations of speckle intensity is derived for the case of small number of scattering events. Dependence of bandwidth of spectrum on average number of scatterers is analyzed. Set-up for detection of the presence of C. trachomatis cells in aqueous suspension is designed. Good agreement between theoretical results and experimental data is shown. Possibility of detection of the presence of C. trachomatis cells in probing volume using diffusing wave spectroscopy with a small number of scatterers is successfully demonstrated for the first time.

VCSEL-based oxygen spectroscopy for structural analysis of pharmaceutical solids

NASA Astrophysics Data System (ADS)

Svensson, T.; Andersson, M.; Rippe, L.; Svanberg, S.; Andersson-Engels, S.; Johansson, J.; Folestad, S.

2008-02-01

We present a minimalistic and flexible single-beam instrumentation based on sensitive tunable diode laser absorption spectroscopy (TDLAS) and its use in structural analysis of highly scattering pharmaceutical solids. By utilising a vertical cavity surface emitting laser (VCSEL) for sensing of molecular oxygen dispersed in tablets, we address structural properties such as porosity. Experiments involve working with unknown path lengths, severe backscattering and diffuse light. These unusual experimental conditions has led to the use of the term gas in scattering media absorption spectroscopy (GASMAS). By employing fully digital wavelength modulation spectroscopy and coherent sampling, system sensitivity in ambient air experiments reaches the 10-7 range. Oxygen absorption exhibited by our tablets, being influenced by both sample porosity and scattering, was in the range 8×10-5 to 2×10-3, and corresponds to 2-50 mm of path length through ambient air (Leq). The day-to-day reproducibility was on average 1.8% (0.3 mm Leq), being limited by mechanical positioning. This is the first time sub-millimetre sensitivity is reached in GASMAS. We also demonstrate measurements on gas transport on a 1-s time scale. By employing pulsed illumination and time-correlated single-photon counting, we reveal that GASMAS exhibits excellent correlation with time-domain photon migration. In addition, we introduce an optical measure of porosity by relating oxygen absorption to average photon time-of-flight. Finally, the simplicity, robustness and low cost of this novel TDLAS instrumentation provide industrial potential.

Characterization of lipid oxidation process of beef during repeated freeze-thaw by electron spin resonance technology and Raman spectroscopy.

PubMed

Chen, Qingmin; Xie, Yunfei; Xi, Jinzhong; Guo, Yahui; Qian, He; Cheng, Yuliang; Chen, Yi; Yao, Weirong

2018-03-15

In this study, electron spin resonance (ESR) and Raman spectroscopy were applied to characterize lipid oxidation of beef during repeated freeze-thaw (RFT). Besides the conventional indexes including peroxide values (PV), thiobarbituric acid-reactive substances (TBARS) and acid values (AV) were evaluated, the radical and molecular structure changes were also measured by ESR and Raman spectroscopy. The results showed that PV, TBARS and AV were increased (P<0.05) after RFT. This suggested that lipid oxidation was occurred during RFT. With the increase of radical signal intensity, lower oxidation stability was presented by ESR. Raman intensity of ν(CC) stretching region (1655cm -1 ) was decreased during RFT. Furthermore, lower Raman intensity ratio of I 1655 /I 1442 , I 1655 /I 1745 that determine total unsaturation was also observed. Significant correlations (p<0.01) were obtained among conventional methods, ESR and Raman spectroscopy. Our result has proved that ESR and Raman spectroscopy showed great potential in characterizing lipid oxidation process of beef during RFT. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fluorescence spectroscopy for the detection of potentially malignant disorders of the oral cavity: analysis of 30 cases

NASA Astrophysics Data System (ADS)

Francisco, A. L. N.; Correr, W. R.; Azevedo, L. H.; Galletta, V. K.; Pinto, C. A. L.; Kowalski, L. P.; Kurachi, C.

2014-01-01

Oral cancer is a major health problem worldwide and although early diagnosis of potentially malignant and malignant diseases is associated with better treatment results, a large number of cancers are initially misdiagnosed, with unfortunate consequences for long-term survival. Fluorescence spectroscopy is a noninvasive modality of diagnostic approach using induced fluorescence emission in tumors that can improve diagnostic accuracy. The objective of this study was to determine the ability to discriminate between normal oral mucosa and potentially malignant disorders by fluorescence spectroscopy. Fluorescence investigation under 408 and 532 nm excitation wavelengths was performed on 60 subjects, 30 with potentially malignant disorders and 30 volunteers with normal mucosa. Data was analyzed to correlate fluorescence patterns with clinical and histopathological diagnostics. Fluorescence spectroscopy used as a point measurement technique resulted in a great variety of spectral information. In a qualitative analysis of the fluorescence spectral characteristics of each type of injury evaluated, it was possible to discriminate between normal and abnormal oral mucosa. The results show the potential use of fluorescence spectroscopy for an improved discrimination of oral disorders.

Communication: Two-dimensional gas-phase coherent anti-Stokes Raman spectroscopy (2D-CARS): Simultaneous planar imaging and multiplex spectroscopy in a single laser shot

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

Bohlin, Alexis; Kliewer, Christopher J.

2013-01-01

Coherent anti-Stokes Raman spectroscopy (CARS) has been widely used as a powerful tool for chemical sensing, molecular dynamics measurements, and rovibrational spectroscopy since its development over 30 years ago, finding use in fields of study as diverse as combustion diagnostics, cell biology, plasma physics, and the standoff detection of explosives. The capability for acquiring resolved CARS spectra in multiple spatial dimensions within a single laser shot has been a long-standing goal for the study of dynamical processes, but has proven elusive because of both phase-matching and detection considerations. Here, by combining new phase matching and detection schemes with the highmore » efficiency of femtosecond excitation of Raman coherences, we introduce a technique for single-shot two-dimensional (2D) spatial measurements of gas phase CARS spectra. We demonstrate a spectrometer enabling both 2D plane imaging and spectroscopy simultaneously, and present the instantaneous measurement of 15, 000 spatially correlated rotational CARS spectra in N 2 and air over a 2D field of 40 mm 2.« less

Two-Dimensional Resonance Raman Signatures of Vibronic Coherence Transfer in Chemical Reactions.

PubMed

Guo, Zhenkun; Molesky, Brian P; Cheshire, Thomas P; Moran, Andrew M

2017-11-02

Two-dimensional resonance Raman (2DRR) spectroscopy has been developed for studies of photochemical reaction mechanisms and structural heterogeneity in condensed phase systems. 2DRR spectroscopy is motivated by knowledge of non-equilibrium effects that cannot be detected with traditional resonance Raman spectroscopy. For example, 2DRR spectra may reveal correlated distributions of reactant and product geometries in systems that undergo chemical reactions on the femtosecond time scale. Structural heterogeneity in an ensemble may also be reflected in the 2D spectroscopic line shapes of both reactive and non-reactive systems. In this chapter, these capabilities of 2DRR spectroscopy are discussed in the context of recent applications to the photodissociation reactions of triiodide. We show that signatures of "vibronic coherence transfer" in the photodissociation process can be targeted with particular 2DRR pulse sequences. Key differences between the signal generation mechanisms for 2DRR and off-resonant 2D Raman spectroscopy techniques are also addressed. Overall, recent experimental developments and applications of the 2DRR method suggest that it will be a valuable tool for elucidating ultrafast chemical reaction mechanisms.

Correlations between near-infrared spectroscopy, perfusion index, and cardiac outputs in extremely preterm infants in the first 72 h of life.

PubMed

Janaillac, Marie; Beausoleil, Thierry P; Barrington, Keith J; Raboisson, Marie-Josée; Karam, Oliver; Dehaes, Mathieu; Lapointe, Anie

2018-04-01

Haemodynamic assessment during the transitional period in preterm infants is challenging. We aimed to describe the relationships between cerebral regional tissue oxygen saturation (CrSO 2 ), perfusion index (PI), echocardiographic, and clinical parameters in extremely preterm infants in their first 72 h of life. Twenty newborns born at < 28 weeks of gestation were continuously monitored with CrSO 2 and preductal PI. Cardiac output was measured at H6, H24, H48, and H72. The median gestational age and birth weight were 25.0 weeks (24-26) and 750 g (655-920), respectively. CrSO 2 and preductal PI had r values < 0.35 with blood gases, lactates, haemoglobin, and mean blood pressure. Cardiac output significantly increased over the 72 h of the study period. Fifteen patients had at least one episode of low left and/or right ventricular output (RVO), during which there was a strong correlation between CrSO 2 and superior vena cava (SVC) flow (at H6 (r = 0.74) and H24 (r = 0.86)) and between PI and RVO (at H6 (r = 0.68) and H24 (r = 0.92)). Five patients had low SVC flow (≤ 40 mL/kg/min) at H6, during which PI was strongly correlated with RVO (r = 0.98). CrSO 2 and preductal PI are strongly correlated with cardiac output during low cardiac output states. What is Known: • Perfusion index and near-infrared spectroscopy are non-invasive tools to evaluate haemodynamics in preterm infants. • Pre- and postductal perfusion indexes strongly correlate with left ventricular output in term infants, and near-infrared spectroscopy has been validated to assess cerebral oxygenation in term and preterm infants. What is New: • Cerebral regional tissue oxygen saturation and preductal perfusion index were strongly correlated with cardiac output during low cardiac output states. • The strength of the correlation between cerebral regional tissue oxygen saturation, preductal perfusion index, and cardiac output varied in the first 72 h of life, reflecting the complexity of the transitional physiology.

Characterizing chlorine oxidation of dissolved organic matter and disinfection by-product formation with fluorescence spectroscopy and parallel factor analysis

NASA Astrophysics Data System (ADS)

Beggs, Katherine M. H.; Summers, R. Scott; McKnight, Diane M.

2009-12-01

Relationships between chlorine demand and disinfection by-product (DBP) formation during chlorination and fluorescence of dissolved organic matter (DOM) were developed. Fluorescence excitation and emission (EEM) spectroscopy was employed, and parameters including fluorescence index, redox index, and overall fluorescence intensity (OFI) were correlated to chlorine demand and DBP formation. The EEMs were also analyzed using a well established global parallel factor analysis (PARAFAC) model which resolves the fluorescence signal into 13 components, including quinone-like and protein-like components. Over an 8-day chlorination period the OFI and sum of the 13 PARAFAC loadings decreased by more than 70%. The remaining identified quinone-like compounds within the DOM were shifted to a more oxidized state. Quinone fluorescence was strongly correlated to both reduced fluorescence intensity and to chlorine demand which indicates that fluorescence may be used to track the chlorine oxidation of DOM. Quinone fluorescence was also correlated strongly with both classes of regulated DBPs: total trihalomethanes and haloacetic acids. Quinone-like components were found to be strongly correlated to overall, short-term, and long-term specific DBP formation. The results of this study show that fluorescence is a useful tool in tracking both DOM oxidation and DBP formation during chlorination.

Anterior Insula GABA Levels Correlate with Emotional Aspects of Empathy: A Proton Magnetic Resonance Spectroscopy Study

PubMed Central

Dong, Fang; Chen, Luguang; Zheng, Li; Guo, Xiuyan; Li, Jianqi

2014-01-01

Background: Empathy is a multidimensional construct referring to the capacity to understand and share the emotional and affective states of another person. Cerebral γ-aminobutyric acid (GABA)-ergic levels are associated with a variety of neurological and psychiatric disorders. However, the role of the GABA system in different dimensions of empathy has not been investigated. Materials and Methods: Thirty-two right-handed healthy volunteers took part in this study. We used proton magnetic resonance spectroscopy to determine GABA concentrations in the anterior insula (AI) and the anterior cingulate cortex (ACC) and to examine the relationship between the GABA concentrations and the subcomponents of empathy evaluated by the Interpersonal Reactivity Index (IRI). Result: Pearson correlation analyses (two-tailed) showed that AI GABA was significantly associated with the empathy concern score (r = 0.584, p<0.05) and the personal distress score (r = 0.538, p<0.05) but not significantly associated with other empathy subscales. No significant correlation was found between ACC GABA and empathy subscores. Conclusion: Left AI GABA was positively correlated with the emotional aspects of empathy. These preliminary findings call into question whether AI GABA alterations might predict empathy dysfunction in major psychiatric disorders such as autism and schizophrenia, which have been described as deficits in emotional empathic abilities. PMID:25419976

Gas detection by correlation spectroscopy employing a multimode diode laser.

PubMed

Lou, Xiutao; Somesfalean, Gabriel; Zhang, Zhiguo

2008-05-01

A gas sensor based on the gas-correlation technique has been developed using a multimode diode laser (MDL) in a dual-beam detection scheme. Measurement of CO(2) mixed with CO as an interfering gas is successfully demonstrated using a 1570 nm tunable MDL. Despite overlapping absorption spectra and occasional mode hops, the interfering signals can be effectively excluded by a statistical procedure including correlation analysis and outlier identification. The gas concentration is retrieved from several pair-correlated signals by a linear-regression scheme, yielding a reliable and accurate measurement. This demonstrates the utility of the unsophisticated MDLs as novel light sources for gas detection applications.

[A comparative analysis of the informative value of anti-AChR-antibody radioimmunoassay and laser correlation spectroscopy in myasthenia gravis].

PubMed

Alchinova, I B; Yakovenko, E N; Sidnev, D V; Dedaev, S Yu; Sanadze, A G; Karganov, M Yu

An aim of the study was to compare informative value of traditional approach (anti-AChR antibody radioimmunoassay) and evaluation of metabolic shifts by laser correlation spectroscopy in myasthenia gravis. The search for the relationship between the disease severity in 77 patients, 12-80 years and the distribution pattern of subfraction serum components revealed three informative zones: 6-15, 27-67, and 127-223 nm. In patients without disturbances of vital functions, the contribution of the first zone particles into light scatter increases and that of the third zone particles decreases. Considerable differences attaining the level of statistical significance in zones 6 and 20 nm were revealed in the spectra of serum from patients with myasthenia gravis of the same severity with and without thymoma. This opens prospects for dynamic monitoring of the efficiency of therapy.

Theory of point contact spectroscopy in correlated materials

DOE PAGES

Lee, Wei-Cheng; Park, Wan Kyu; Arham, Hamood Z.; ...

2015-01-05

Here, we developed a microscopic theory for the point-contact conductance between a metallic electrode and a strongly correlated material using the nonequilibrium Schwinger-Kadanoff-Baym-Keldysh formalism. We explicitly show that, in the classical limit, contact size shorter than the scattering length of the system, the microscopic model can be reduced to an effective model with transfer matrix elements that conserve in-plane momentum. We found that the conductance dI/dV is proportional to the effective density of states, that is, the integrated single-particle spectral function A(ω = eV) over the whole Brillouin zone. From this conclusion, we are able to establish the conditions undermore » which a non-Fermi liquid metal exhibits a zero-bias peak in the conductance. Lastly, this finding is discussed in the context of recent point-contact spectroscopy on the iron pnictides and chalcogenides, which has exhibited a zero-bias conductance peak.« less

Optical Antenna-Based Fluorescence Correlation Spectroscopy to Probe the Nanoscale Dynamics of Biological Membranes.

PubMed

Winkler, Pamina M; Regmi, Raju; Flauraud, Valentin; Brugger, Jürgen; Rigneault, Hervé; Wenger, Jérôme; García-Parajo, María F

2018-01-04

The plasma membrane of living cells is compartmentalized at multiple spatial scales ranging from the nano- to the mesoscale. This nonrandom organization is crucial for a large number of cellular functions. At the nanoscale, cell membranes organize into dynamic nanoassemblies enriched by cholesterol, sphingolipids, and certain types of proteins. Investigating these nanoassemblies known as lipid rafts is of paramount interest in fundamental cell biology. However, this goal requires simultaneous nanometer spatial precision and microsecond temporal resolution, which is beyond the reach of common microscopes. Optical antennas based on metallic nanostructures efficiently enhance and confine light into nanometer dimensions, breaching the diffraction limit of light. In this Perspective, we discuss recent progress combining optical antennas with fluorescence correlation spectroscopy (FCS) to monitor microsecond dynamics at nanoscale spatial dimensions. These new developments offer numerous opportunities to investigate lipid and protein dynamics in both mimetic and native biological membranes.

Serial proton MR spectroscopy and diffusion tensor imaging in infantile Balo's concentric sclerosis.

PubMed

Dreha-Kulaczewski, Steffi F; Helms, Gunther; Dechent, Peter; Hofer, Sabine; Gärtner, Jutta; Frahm, Jens

2009-02-01

Proton magnetic resonance spectroscopy (MRS) and diffusion tensor imaging (DTI) yield different parameters for characterizing the evolution of a demyelinating white matter disease. The purpose was to elucidate biochemical and microstructural changes in Balo's concentric sclerosis lesions and to correlate the findings with the clinical course. Localized short-echo time MRS and DTI were performed over 6 years in a left occipital lesion of a female patient (age at onset 13.8 years) with Balo's concentric sclerosis. A right homonym hemianopsia persisted. Metabolite patterns were in line with initial active demyelination followed by gliosis and partial recovery of neuroaxonal metabolites. Fractional anisotropy and mean diffusivity of tissue water remained severely altered. Fiber tracking confirmed a disruption in the geniculo-calcarine tract as well as involvement of the corpus callosum. MRS and DTI depict complementary parameters, but DTI seems to correlate better with clinical symptoms.

Characterization of humic acids by two-dimensional correlation fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Nakashima, K.; Xing, Shaoyong; Gong, Yongkuan; Miyajima, Toru

2008-07-01

We have investigated interaction between humic acids and heavy metal ions by fluorescence spectroscopy. The humic acids examined are Aldrich humic acid (AHA) and Dando humic acid (DHA), and heavy metal ions are Cu 2+ and Pb 2+. The binding constants between the humic acids and the heavy metal ions are obtained by a conventional fluorescence quenching technique. The two prominent bands in the fluorescence spectra of the humic acids give different binding constants, implying that the two bands are originated from different fluorescent species in the matrices of the humic acids. This was confirmed by two-dimensional correlation analysis based on the quenching perturbation on the fluorescence spectra. Two prominent cross peaks corresponding to the two fluorescence bands are obtained in the asynchronous maps, indicating that the two fluorescence bands belong to different species. The order of the response of the two fluorescence bands to the quenching perturbation is also elucidated based on Noda's rule.

Multi-excitonic emission from Stranski-Krastanov GaN/AlN quantum dots inside a nanoscale tip

NASA Astrophysics Data System (ADS)

Mancini, L.; Moyon, F.; Houard, J.; Blum, I.; Lefebvre, W.; Vurpillot, F.; Das, A.; Monroy, E.; Rigutti, L.

2017-12-01

Single-dot time-resolved micro-photoluminescence spectroscopy and correlated electron tomography (ET) have been performed on self-assembled GaN/AlN quantum dots isolated within a field-emission nanoscale tip by focused ion beam (FIB). Despite the effect of the FIB, the system conserves the capability of emitting light through multi-excitonic complexes. The optical spectroscopy data have then been correlated with the electronic structure and lifetime parameters that could be extracted using the structural parameters obtained by ET via a 6 band k.p model. A biexciton-exciton cascade could be identified and thoroughly analysed. The biexciton-exciton states exhibit a non-negligible polarization component along the [0001] polar crystal axis, indicating a significant valence band mixing, while the relationship between exciton energy and biexciton binding energy is consistent with a hybrid character of the biexciton.

A novel diarylheptanoid-bearing sesquiterpene moiety from the rhizomes of Alpinia officinarum.

PubMed

Wei, Na; Zhou, Zhonglin; Wei, Qing; Wang, Yong; Jiang, Jun; Zhang, Junqing; Wu, Lixiang; Dai, Shuiping; Li, Youbin

2016-10-01

A new diarylheptanoid analogue-bearing sesquiterpene moiety, named Alpinisin A, was isolated from the rhizomes of Alpinia officinarum Hance. The new structure was determined by various spectroscopic techniques (1)H-nuclear magnetic resonance ((1)H NMR), (13)C-attached proton test ((13)C-APT), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond correlation (HMBC), (1)H-(1)H correlation spectroscopy ((1)H-(1)HCOSY), nuclear overhauser effect spectroscopy (NOESY) and high resolution electrospray ionization mass spectrometry (HR-ESI-MS). The compound was tested for cytotoxic activity in vitro against human tumour cell lines (gastric carcinoma cell -7901 (SGC-7901), Michigan Cancer Foundation-7 (MCF-7) and Caski), which showed significant inhibitory effects with IC50 levels of 11.42, 15.14 and 14.78 μM, respectively. The novel chemical structure characterised with a diarylheptanoid linked to a chain-like sesquiterpenoid should be highlighted.

Measuring the diffusion coefficient of ganglioside on cell membrane by fluorescence correlation spectroscopy

NASA Astrophysics Data System (ADS)

Dong, Shiqing; You, Minghai; Chen, Jianling; Zhou, Jie; Xie, Shusen; Yang, Hongqin

2017-06-01

The fluidity of proteins and lipids on cell membrane plays an important role in cell’s physiological functions. Fluorescence correlation spectroscopy (FCS) is an effective technique to detect the rapid dynamic behaviors of proteins and/or lipids in living cells. In this study, we used the rhodamine6G solution to optimize the FCS system. And, cholera toxin B subunit (CT-B) was used to label ganglioside on living Hela cell membranes. The diffusion time and coefficients of ganglioside can be obtained through fitting the autocorrelation curve based on the model of two-dimensional cell membrane. The results showed that the diffusion coefficients of ganglioside distributed within a wide range. It revealed the lateral diffusion of lipids on cell membrane was inhomogeneous, which was due to different microstructures of cytoplasmic membrane. The study provides a helpful method for further studying the dynamic characteristics of proteins and lipids molecules on living cell membrane.

Optical characterization of poly(methyl methacrylate) implanted with low energy ions

NASA Astrophysics Data System (ADS)

Gupta, Renu; Kumar, Vijay; Goyal, Parveen Kumar; Kumar, Shyam

2012-12-01

The samples of poly(methyl methacrylate) (PMMA) were subjected to 100 keV N+ and Ar+ ion implantation up to a maximum fluence of 2 × 1016 ions/cm2. The effect of ion implantation on the optical energy gap and the refractive index has been studied through UV-visible spectroscopy. The results clearly indicate a decrease in the values of optical energy gap and an increase in the values of refractive index as an effect of ion implantation corresponding to both of the ions. It has also been observed that the changes induced by the implanted ions are more pronounced for N+ ions in comparison to Ar+ ions. This variation has been correlated with the calculated ranges of these ions in PMMA polymer using Stopping and Range of Ions in Matter (SRIM) code. Finally, an attempt has been made to correlate all the observed changes with the induced structural changes as revealed through Raman spectroscopy.

Fluorescence correlation spectroscopy directly monitors coalescence during nanoparticle preparation.

PubMed

Schaeffel, David; Staff, Roland Hinrich; Butt, Hans-Juergen; Landfester, Katharina; Crespy, Daniel; Koynov, Kaloian

2012-11-14

Dual color fluorescence cross-correlation spectroscopy (DC FCCS) experiments were conducted to study the coalescence and aggregation during the formation of nanoparticles. To assess the generality of the method, three completely different processes were selected to prepare the nanoparticles. Polymeric nanoparticles were formed either by solvent evaporation from emulsion nanodroplets of polymer solutions or by miniemulsion polymerization. Inorganic nanocapsules were formed by polycondensation of alkoxysilanes at the interface of nanodroplets. In all cases, DC FCCS provided fast and unambiguous information about the occurrence of coalescence and thus a deeper insight into the mechanism of nanoparticle formation. In particular, it was found that coalescence played a minor role for the emulsion-solvent evaporation process and the miniemulsion polymerization, whereas substantial coalescence was detected during the formation of the inorganic nanocapsules. These findings demonstrate that DC FCCS is a powerful tool for monitoring nanoparticles genesis.

Confined detection volume of fluorescence correlation spectroscopy by bare fiber probes.

PubMed

Lu, Guowei; Lei, Franck H; Angiboust, Jean-François; Manfait, Michel

2010-04-01

A fiber-tip-based near-field fluorescence correlation spectroscopy (FCS) has been developed for confining the detection volume to sub-diffraction-limited dimensions. This near-field FCS is based on near-field illumination by coupling a scanning near-field optical microscope (SNOM) to a conventional confocal FCS. Single-molecule FCS analysis at 100 nM Rhodamine 6G has been achieved by using bare chemically etched, tapered fiber tips. The detection volume under control of the SNOM system has been reduced over one order of magnitude compared to that of the conventional confocal FCS. Related factors influencing the near-field FCS performance are investigated and discussed in detail. In this proof-of-principle study, the preliminary experimental results suggest that the fiber-tip-based near-field FCS might be a good alternative to realize localized analysis at the single-molecule level.

Understanding the interactions of CO 2 with doped and undoped SrTiO 3

DOE PAGES

Wu, Qiyuan; Cen, Jiajie; Goodman, Kenneth R.; ...

2016-06-17

SrTiO 3 and doped SrTiO 3 have a wide range of applications in different fields. For example, Rh-doped SrTiO 3 has been shown to have photocatalytic activity for both hydrogen production and CO 2 conversion. In this study, both undoped and Rh-doped SrTiO 3 were synthesized by hydrothermal and polymerizable complex methods. Different characterizations techniques including X-ray photoelectron spectroscopy (XPS), XRD, Raman, and UV/Vis spectroscopy were utilized to establish correlations between the preparation methods and the electronic/structural properties of Rh-doped SrTiO 3. The presence of dopants and oxygen vacancies substantially influenced the CO 2 interactions with the surface, as revealedmore » by the in situ infrared spectroscopic study. As a result, the presence of distinctly different adsorption sites was correlated to oxygen vacancies and oxidation states of Ti and Rh.« less

Construction and Application of a Terahertz Scanning Near-Field Microscope for Study of Correlated Electron Materials at Cryogenic Temperatures and Nanometer Length Scales

NASA Astrophysics Data System (ADS)

Stinson, Harry Theodore, III

This dissertation describes the design and construction of the world's first cryogenic apertureless near-field microscope designed for terahertz sources and detectors. I first provide motivation for the creation of this instrument in the context of spectroscopy of correlated electron materials, and background information on the two techniques that the instrument combines, scanning near-field optical microscopy and terahertz time-domain spectroscopy. I then detail key components of the instrument design, including proof-of-principle results obtained at room and cryogenic temperatures. Following this, I discuss an imaging experiment performed with this instrument on vanadium dioxide, an insulator-metal transition material, which sheds new light on the nature of the phase transition and provides support for a new model Hamiltonian for the system. Finally, I discuss a theoretical proposal for the study of cuprate superconductors using this instrument.

Comparison of nanoparticle diffusion using fluorescence correlation spectroscopy and differential dynamic microscopy within concentrated polymer solutions

NASA Astrophysics Data System (ADS)

Shokeen, Namita; Issa, Christopher; Mukhopadhyay, Ashis

2017-12-01

We studied the diffusion of nanoparticles (NPs) within aqueous entangled solutions of polyethylene oxide (PEO) by using two different optical techniques. Fluorescence correlation spectroscopy, a method widely used to investigate nanoparticle dynamics in polymer solution, was used to measure the long-time diffusion coefficient (D) of 25 nm radius particles within high molecular weight, Mw = 600 kg/mol PEO in water solutions. Differential dynamic microscopy (DDM) was used to determine the wave-vector dependent dynamics of NPs within the same polymer solutions. Our results showed good agreement between the two methods, including demonstration of normal diffusion and almost identical diffusion coefficients obtained by both techniques. The research extends the scope of DDM to study the dynamics and rheological properties of soft matter at a nanoscale. The measured diffusion coefficients followed a scaling theory, which can be explained by the coupling between polymer dynamics and NP motion.