Sample records for modulation transfer spectroscopy

  1. Wideband laser locking to an atomic reference with modulation transfer spectroscopy.

    PubMed

    Negnevitsky, V; Turner, L D

    2013-02-11

    We demonstrate that conventional modulated spectroscopy apparatus, used for laser frequency stabilization in many atomic physics laboratories, can be enhanced to provide a wideband lock delivering deep suppression of frequency noise across the acoustic range. Using an acousto-optic modulator driven with an agile oscillator, we show that wideband frequency modulation of the pump laser in modulation transfer spectroscopy produces the unique single lock-point spectrum previously demonstrated with electro-optic phase modulation. We achieve a laser lock with 100 kHz feedback bandwidth, limited by our laser control electronics. This bandwidth is sufficient to reduce frequency noise by 30 dB across the acoustic range and narrows the imputed linewidth by a factor of five.

  2. Laser frequency stabilization by combining modulation transfer and frequency modulation spectroscopy.

    PubMed

    Zi, Fei; Wu, Xuejian; Zhong, Weicheng; Parker, Richard H; Yu, Chenghui; Budker, Simon; Lu, Xuanhui; Müller, Holger

    2017-04-01

    We present a hybrid laser frequency stabilization method combining modulation transfer spectroscopy (MTS) and frequency modulation spectroscopy (FMS) for the cesium D2 transition. In a typical pump-probe setup, the error signal is a combination of the DC-coupled MTS error signal and the AC-coupled FMS error signal. This combines the long-term stability of the former with the high signal-to-noise ratio of the latter. In addition, we enhance the long-term frequency stability with laser intensity stabilization. By measuring the frequency difference between two independent hybrid spectroscopies, we investigate the short-and long-term stability. We find a long-term stability of 7.8 kHz characterized by a standard deviation of the beating frequency drift over the course of 10 h and a short-term stability of 1.9 kHz characterized by an Allan deviation of that at 2 s of integration time.

  3. Mid-infrared wavelength- and frequency-modulation spectroscopy with a pump-modulated singly-resonant optical parametric oscillator

    NASA Astrophysics Data System (ADS)

    Lindsay, I. D.; Groß, P.; Lee, C. J.; Adhimoolam, B.; Boller, K.-J.

    2006-12-01

    We describe the implementation of the wavelength- and frequency-modulation spectroscopy techniques using a singly-resonant optical parametric oscillator (OPO) pumped by a fiber-amplified diode laser. Frequency modulation of the diode laser was transferred to the OPO’s mid-infrared idler output, avoiding the need for external modulation devices. This approach thus provides a means of implementing these important techniques with powerful, widely tunable, mid-infrared sources while retaining the simple, flexible modulation properties of diode lasers.

  4. Bodipy-C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer.

    PubMed

    Guo, Song; Xu, Liang; Xu, Kejing; Zhao, Jianzhang; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

    2015-07-01

    Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives ( B-1 , B-2 and B-3 , which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C 60 was used as the complementary hydrogen bonding module ( C-1 ), in which the C 60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references ( B-1-Me , B-2-Me and B-3-Me ), which are unable to form strong H-bonds with C-1 . Triple H-bonds are formed between each Bodipy antenna ( B-1 , B-2 and B-3 ) and the C 60 module ( C-1 ). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C 60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C 60 module (for assembly B-1·C-1 ), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1 ). Intra-assembly forward-backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet-triplet annihilation upconversion.

  5. Forster Resonance Energy Transfer and Conformational Stability of Proteins: An Advanced Biophysical Module for Physical Chemistry Students

    ERIC Educational Resources Information Center

    Sanchez, Katheryn M.; Schlamadinger, Diana E.; Gable, Jonathan E.; Kim, Judy E.

    2008-01-01

    Protein folding is an exploding area of research in biophysics and physical chemistry. Here, we describe the integration of several techniques, including absorption spectroscopy, fluorescence spectroscopy, and Forster resonance energy transfer (FRET) measurements, to probe important topics in protein folding. Cytochrome c is used as a model…

  6. Modulation Transfer Through Coherence and Its Application to Atomic Frequency Offset Locking

    NASA Astrophysics Data System (ADS)

    Jagatap, B. N.; Ray, Ayan; Kale, Y. B.; Singh, Niharika; Lawande, Q. V.

    We discuss the process of modulation transfer in a coherently prepared three-level atomic medium and its prospective application to atomic frequency offset locking (AFOL). The issue of modulation transfer through coherence is treated in the framework of temporal evolution of dressed atomic system with externally superimposed deterministic flow. This dynamical description of the atom-field system offers distinctive advantage of using a single modulation source to dither passively the coherent phenomenon as probed by an independent laser system under pump-probe configuration. Modulation transfer is demonstrated experimentally using frequency modulation spectroscopy on a subnatural linewidth electromagnetically induced transparency (EIT) and a sub-Doppler linewidth Autler-Townes (AT) resonance in Doppler broadened alkali vapor medium, and AFOL is realized by stabilizing the probe laser on the first/third derivative signals. The stability of AFOL is discussed in terms of the frequency noise power spectral density and Allan variance. Analysis of AFOL schemes is carried out at the backdrop of closed loop active frequency control in a conventional master-slave scheme to point out the contrasting behavior of AFOL schemes based on EIT and AT resonances. This work adds up to the discussion on the subtle link between dressed state spectroscopy and AFOL, which is relevant for developing a master-slave type laser system in the domain of coherent photon-atom interaction.

  7. Laser frequency stabilization and shifting by using modulation transfer spectroscopy

    NASA Astrophysics Data System (ADS)

    Cheng, Bing; Wang, Zhao-Ying; Wu, Bin; Xu, Ao-Peng; Wang, Qi-Yu; Xu, Yun-Fei; Lin, Qiang

    2014-10-01

    The stabilizing and shifting of laser frequency are very important for the interaction between the laser and atoms. The modulation transfer spectroscopy for the 87Rb atom with D2 line transition F = 2 → F' = 3 is used for stabilizing and shifting the frequency of the external cavity grating feedback diode laser. The resonant phase modulator with electro—optical effect is used to generate frequency sideband to lock the laser frequency. In the locking scheme, circularly polarized pump- and probe-beams are used. By optimizing the temperature of the vapor, the pump- and probe-beam intensity, the laser linewidth of 280 kHz is obtained. Furthermore, the magnetic field generated by a solenoid is added into the system. Therefore the system can achieve the frequency locking at any point in a range of hundreds of megahertz frequency shifting with very low power loss.

  8. Investigating the Consistency of Models for Water Splitting Systems by Light and Voltage Modulated Techniques.

    PubMed

    Bertoluzzi, Luca; Bisquert, Juan

    2017-01-05

    The optimization of solar energy conversion devices relies on their accurate and nondestructive characterization. The small voltage perturbation techniques of impedance spectroscopy (IS) have proven to be very powerful to identify the main charge storage modes and charge transfer processes that control device operation. Here we establish the general connection between IS and light modulated techniques such as intensity modulated photocurrent (IMPS) and photovoltage spectroscopies (IMVS) for a general system that converts light to energy. We subsequently show how these techniques are related to the steady-state photocurrent and photovoltage and the external quantum efficiency. Finally, we express the IMPS and IMVS transfer functions in terms of the capacitive and resistive features of a general equivalent circuit of IS for the case of a photoanode used for solar fuel production. We critically discuss how much knowledge can be extracted from the combined use of those three techniques.

  9. Bodipy–C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer† †Electronic supplementary information (ESI) available: Syntheses, structure characterization data, and UV/vis absorption and emission spectra. See DOI: 10.1039/c4sc03865g

    PubMed Central

    Guo, Song; Xu, Liang; Xu, Kejing; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

    2015-01-01

    Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives (B-1, B-2 and B-3, which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C60 was used as the complementary hydrogen bonding module (C-1), in which the C60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references (B-1-Me, B-2-Me and B-3-Me), which are unable to form strong H-bonds with C-1. Triple H-bonds are formed between each Bodipy antenna (B-1, B-2 and B-3) and the C60 module (C-1). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C60 module (for assembly B-1·C-1), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1). Intra-assembly forward–backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet–triplet annihilation upconversion. PMID:29218142

  10. Förster resonance energy transfer studies of luminescent gold nanoparticles functionalized with ruthenium(II) and rhenium(I) complexes: modulation via esterase hydrolysis.

    PubMed

    Leung, Frankie Chi-Ming; Tam, Anthony Yiu-Yan; Au, Vonika Ka-Man; Li, Mei-Jin; Yam, Vivian Wing-Wah

    2014-05-14

    A number of ruthenium(II) and rhenium(I) bipyridine complexes functionalized with lipoic acid moieties have been synthesized and characterized. Functionalization of gold nanoparticles with these chromophoric ruthenium(II) and rhenium(I) complexes has resulted in interesting supramolecular assemblies with Förster resonance energy transfer (FRET) properties that could be modulated via esterase hydrolysis. The luminescence of the metal complex chromophores was turned on upon cleavage of the ester bond linkage by esterase to reduce the efficiency of FRET quenching. The prepared nanoassembly conjugates have been characterized by transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), UV-visible spectroscopy, and emission spectroscopy. The quenching mechanism has also been studied by transient absorption and time-resolved emission decay measurements. The FRET efficiencies were found to vary with the nature of the chromophores and the length of the spacer between the donor (transition metal complexes) and the acceptor (gold nanoparticles).

  11. Frequency stabilization of a 1083 nm fiber laser to {sup 4}He transition lines with optical heterodyne saturation spectroscopies

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

    Gong, W.; Peng, X., E-mail: xiangpeng@pku.edu.cn; Li, W.

    2014-07-15

    Two kinds of optical heterodyne saturation spectroscopies, namely, frequency modulation spectroscopy (FMS) and modulation transfer spectroscopy (MTS), are demonstrated for locking a fiber laser to the transition lines of metastable {sup 4}He atoms around 1083 nm. The servo-loop error signals of FMS and MTS for stabilizing laser frequency are optimized by studying the dependence of the peak-to-peak amplitude and slope on the optical power of pump and probe beams. A comparison of the stabilization performances of FMS/MTS and polarization spectroscopy (PS) is presented, which shows that MTS exhibits relatively superior performance with the least laser frequency fluctuation due to itsmore » flat-background dispersive signal, originated from the four-wave mixing process. The Allan deviation of the stabilized laser frequency is 5.4 × 10{sup −12}@100 s with MTS for data acquired in 1000 s, which is sufficiently applicable for fields like laser cooling, optical pumping, and optical magnetometry.« less

  12. Two-dimensional vibrational-electronic spectroscopy

    NASA Astrophysics Data System (ADS)

    Courtney, Trevor L.; Fox, Zachary W.; Slenkamp, Karla M.; Khalil, Munira

    2015-10-01

    Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE) to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (νCN) and either a ligand-to-metal charge transfer transition ([FeIII(CN)6]3- dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN)5FeIICNRuIII(NH3)5]- dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific νCN modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. The details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.

  13. Two-dimensional vibrational-electronic spectroscopy.

    PubMed

    Courtney, Trevor L; Fox, Zachary W; Slenkamp, Karla M; Khalil, Munira

    2015-10-21

    Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE) to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (νCN) and either a ligand-to-metal charge transfer transition ([Fe(III)(CN)6](3-) dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN)5Fe(II)CNRu(III)(NH3)5](-) dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific νCN modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. The details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.

  14. Two-dimensional vibrational-electronic spectroscopy

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

    Courtney, Trevor L.; Fox, Zachary W.; Slenkamp, Karla M.

    2015-10-21

    Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE)more » to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (ν{sub CN}) and either a ligand-to-metal charge transfer transition ([Fe{sup III}(CN){sub 6}]{sup 3−} dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN){sub 5}Fe{sup II}CNRu{sup III}(NH{sub 3}){sub 5}]{sup −} dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific ν{sub CN} modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. The details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.« less

  15. EX Hydrae in outburst

    NASA Technical Reports Server (NTRS)

    Hellier, C.; Mason, K. O.; Smale, A. P.; Corbet, R. H. D.; O'Donoghue, D.

    1989-01-01

    Photometry and red spectroscopy of the intermediate polar EX Hya in its rare outburst state are presented. Photometry during the declining phase of the July-August 1986 outburst shows the 67-min (spin) modulation to be present with similar characteristics to that in quiescence. In contrast, photometry from near the peak of the 1987 May outburst shows little evidence of the 67-min modulation, while spectroscopy obtained nearly simultaneously is similarly lacking in such evidence, despite its presence in quiescent spectroscopic data. Near the beginning of the May 1987 outburst the H alpha emission line develops a broad, high velocity base component whose velocity is modulated with the orbital cycle. The velocity and phase of the broad base component suggest that it is produced near the magnetosphere of the white dwarf at a point along the projected trajectory of the gas stream from the companion. The feature disappears later in the outburst and is not present during quiescence. It is suggested that the outbursts in EX Hya are caused by an increase in the rate of mass transfer from the companion, and that part of this enhanced mass-transfer stream skims over the top of the accretion disk to strike the magnetosphere directly. The interaction of the stream with the magnetosphere gives rise to the broad-base component observed.

  16. Gate-Variable Mid-Infrared Optical Transitions in a (Bi1-xSbx)2Te3 Topological Insulator.

    PubMed

    Whitney, William S; Brar, Victor W; Ou, Yunbo; Shao, Yinming; Davoyan, Artur R; Basov, D N; He, Ke; Xue, Qi-Kun; Atwater, Harry A

    2017-01-11

    We report mid-infrared spectroscopy measurements of ultrathin, electrostatically gated (Bi 1-x Sb x ) 2 Te 3 topological insulator films in which we observe several percent modulation of transmittance and reflectance as gating shifts the Fermi level. Infrared transmittance measurements of gated films were enabled by use of an epitaxial lift-off method for large-area transfer of topological insulator films from infrared-absorbing SrTiO 3 growth substrates to thermal oxidized silicon substrates. We combine these optical experiments with transport measurements and angle-resolved photoemission spectroscopy to identify the observed spectral modulation as a gate-driven transfer of spectral weight between both bulk and 2D topological surface channels and interband and intraband channels. We develop a model for the complex permittivity of gated (Bi 1-x Sb x ) 2 Te 3 and find a good match to our experimental data. These results open the path for layered topological insulator materials as a new candidate for tunable, ultrathin infrared optics and highlight the possibility of switching topological optoelectronic phenomena between bulk and spin-polarized surface regimes.

  17. An investigation on the photoelectrochemical properties of dye-sensitized solar cells based on graphene-TiO2 composite photoanodes

    NASA Astrophysics Data System (ADS)

    Zhu, Menghua; Li, Xin; Liu, Weiwei; Cui, Ying

    2014-09-01

    The graphene-TiO2 nanocomposite has been prepared by mixing graphene oxide (GO) and tetra-n-butyl titanate (TBT) followed by the facile hydrothermal process when the reduction of GO to reduced graphene oxide (RGO) and the hydrolysis of TBT to TiO2 happen. Characterization of the graphene-TiO2 nanostructures is investigated in detail by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. A dye-sensitized solar cell (DSSC) based on graphene-TiO2 composite photoelectrode exhibits a high energy conversion efficiency of 4.28%, compared with a DSSC based on pure TiO2 photoelectrode (3.11%), accompanied by an increment in both short-circuit photocurrent density and open-circuit voltage. The significant enhancement in performance of DSSC is investigated through intensity-modulated photovoltage spectroscopy, intensity-modulated photocurrent spectroscopy, and electrochemical impedance spectroscopy. It is found that the incorporation of two-dimensional graphene nanosheets in the TiO2 electrodes is the key factor leading to the improved photogenerated electron transfer ability and reduced charge recombination.

  18. Energy level alignment and sub-bandgap charge generation in polymer:fullerene bulk heterojunction solar cells.

    PubMed

    Tsang, Sai-Wing; Chen, Song; So, Franky

    2013-05-07

    Using charge modulated electroabsorption spectroscopy (CMEAS), for the first time, the energy level alignment of a polymer:fullerene bulk heterojunction photovoltaic cell is directly measured. The charge-transfer excitons generated by the sub-bandgap optical pumping are coupled with the modulating electric field and introduce subtle changes in optical absorption in the sub-bandgap region. This minimum required energy for sub-bandgap charge genreation is defined as the effective bandgap. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Photoinduced triplet-triplet energy transfer in a 2-ureido-4(1H)-pyrimidinone-bridged, quadruply hydrogen-bonded ferrocene-fullerene assembly.

    PubMed

    Feng, Ke; Yu, Mao-Lin; Wang, Su-Min; Wang, Ge-Xia; Tung, Chen-Ho; Wu, Li-Zhu

    2013-01-14

    2-Ureido-4(1H)-pyrimidinone-bridged ferrocene-fullerene assembly I is designed and synthesized for elaborating the photoinduced electron-transfer processes in self-complementary quadruply hydrogen-bonded modules. Unexpectedly, steady-state and time-resolved spectroscopy reveal an inefficient electron-transfer process from the ferrocene to the singlet or triplet excited state of the fullerene, although the electron-transfer reactions are thermodynamically feasible. Instead, an effective intra-assembly triplet-triplet energy-transfer process is found to be operative in assembly I with a rate constant of 9.2×10(5) s(-1) and an efficiency of 73% in CH(2)Cl(2) at room temperature. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Collection-efficient, axisymmetric vacuum sublimation module for the purification of solid materials.

    PubMed

    May, Michael; Paul, Elizabeth; Katovic, Vladimir

    2015-11-01

    A vacuum sublimation module of axisymmetric geometry was developed and employed to purify solid-phase materials. The module provides certain practical advantages and it comprises: a metering valve, glass collector, glass lower body, main seal, threaded bushing, and glass internal cartridge (the latter to contain starting material). A complementary process was developed to de-solvate, sublime, weigh, and collect solid chemical materials exemplified by oxalic acid, ferrocene, pentachlorobenzene, chrysene, and urea. The oxalic acid sublimate was analyzed by titration, melting range, Fourier Transform Infrared (FT-IR) Spectroscopy, cyclic voltammetry, and its (aqueous phase) electrolytically generated gas. The analytical data were consistent with a high-purity, anhydrous oxalic acid sublimate. Cyclic voltammograms of 0.11 mol. % oxalic acid in water displayed a 2.1 V window on glassy carbon electrode beyond which electrolytic decomposition occurs. During module testing, fifteen relatively pure materials were sublimed with (energy efficient) passive cooling and the solid-phase recovery averaged 95 mass %. Key module design features include: compact vertical geometry, low-angle conical collector, uniformly compressed main seal, modest power consumption, transparency, glovebox compatibility, cooling options, and preferential conductive heat transfer. To help evaluate the structural (module) heat transfer, vertical temperature profiles along the dynamically evacuated lower body were measured versus electric heater power: for example, an input of 18.6 W generated a temperature 443-K at the bottom. Experimental results and engineering calculations indicate that during sublimation, solid conduction is the primary mode of heat transfer to the starting material.

  1. Transfer and conversion of images based on EIT in atom vapor.

    PubMed

    Cao, Mingtao; Zhang, Liyun; Yu, Ya; Ye, Fengjuan; Wei, Dong; Guo, Wenge; Zhang, Shougang; Gao, Hong; Li, Fuli

    2014-05-01

    Transfer and conversion of images between different wavelengths or polarization has significant applications in optical communication and quantum information processing. We demonstrated the transfer of images based on electromagnetically induced transparency (EIT) in a rubidium vapor cell. In experiments, a 2D image generated by a spatial light modulator is used as a coupling field, and a plane wave served as a signal field. We found that the image carried by coupling field could be transferred to that carried by signal field, and the spatial patterns of transferred image are much better than that of the initial image. It also could be much smaller than that determined by the diffraction limit of the optical system. We also studied the subdiffraction propagation for the transferred image. Our results may have applications in quantum interference lithography and coherent Raman spectroscopy.

  2. J-Refocused Coherence Transfer Spectroscopic Imaging at 7 T in Human Brain

    PubMed Central

    Pan, J.W.; Avdievich, N.; Hetherington, H.P.

    2013-01-01

    Short echo spectroscopy is commonly used to minimize signal modulation due to J-evolution of the cerebral amino acids. However, short echo acquisitions suffer from high sensitivity to macromolecules which make accurate baseline determination difficult. In this report, we describe implementation at 7 T of a double echo J-refocused coherence transfer sequence at echo time (TE) of 34 msec to minimize J-modulation of amino acids while also decreasing interfering macromolecule signals. Simulation of the pulse sequence at 7 T shows excellent resolution of glutamate, glutamine, and N-acetyl aspartate. B1 sufficiency at 7 T for the double echo acquisition is achieved using a transceiver array with radiofrequency (RF) shimming. Using an alternate RF distribution to minimize receiver phase cancellation in the transceiver, accurate phase determination for the coherence transfer is achieved with rapid single scan calibration. This method is demonstrated in spectroscopic imaging mode with n = 5 healthy volunteers resulting in metabolite values consistent with literature and in a patient with epilepsy. PMID:20648684

  3. A Nested Phosphorus and Proton Coil Array for Brain Magnetic Resonance Imaging and Spectroscopy

    PubMed Central

    Brown, Ryan; Lakshmanan, Karthik; Madelin, Guillaume; Parasoglou, Prodromos

    2015-01-01

    A dual-nuclei radiofrequency coil array was constructed for phosphorus and proton magnetic resonance imaging and spectroscopy of the human brain at 7 Tesla. An eight-channel transceive degenerate birdcage phosphorus module was implemented to provide whole-brain coverage and significant sensitivity improvement over a standard dual-tuned loop coil. A nested eight-channel proton module provided adequate sensitivity for anatomical localization without substantially sacrificing performance on the phosphorus module. The developed array enabled phosphorus spectroscopy, a saturation transfer technique to calculate the global creatine kinase forward reaction rate, and single-metabolite whole-brain imaging with 1.4 cm nominal isotropic resolution in 15 min (2.3 cm actual resolution), while additionally enabling 1 mm isotropic proton imaging. This study demonstrates that a multi-channel array can be utilized for phosphorus and proton applications with improved coverage and/or sensitivity over traditional single-channel coils. The efficient multi-channel coil array, time-efficient pulse sequences, and the enhanced signal strength available at ultra-high fields can be combined to allow volumetric assessment of the brain and could provide new insights into the underlying energy metabolism impairment in several neurodegenerative conditions, such as Alzheimer’s and Parkinson’s diseases, as well as mental disorders such as schizophrenia. PMID:26375209

  4. A nested phosphorus and proton coil array for brain magnetic resonance imaging and spectroscopy.

    PubMed

    Brown, Ryan; Lakshmanan, Karthik; Madelin, Guillaume; Parasoglou, Prodromos

    2016-01-01

    A dual-nuclei radiofrequency coil array was constructed for phosphorus and proton magnetic resonance imaging and spectroscopy of the human brain at 7T. An eight-channel transceive degenerate birdcage phosphorus module was implemented to provide whole-brain coverage and significant sensitivity improvement over a standard dual-tuned loop coil. A nested eight-channel proton module provided adequate sensitivity for anatomical localization without substantially sacrificing performance on the phosphorus module. The developed array enabled phosphorus spectroscopy, a saturation transfer technique to calculate the global creatine kinase forward reaction rate, and single-metabolite whole-brain imaging with 1.4cm nominal isotropic resolution in 15min (2.3cm actual resolution), while additionally enabling 1mm isotropic proton imaging. This study demonstrates that a multi-channel array can be utilized for phosphorus and proton applications with improved coverage and/or sensitivity over traditional single-channel coils. The efficient multi-channel coil array, time-efficient pulse sequences, and the enhanced signal strength available at ultra-high fields can be combined to allow volumetric assessment of the brain and could provide new insights into the underlying energy metabolism impairment in several neurodegenerative conditions, such as Alzheimer's and Parkinson's diseases, as well as mental disorders such as schizophrenia. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. Modular Homogeneous Chromophore–Catalyst Assemblies

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

    Mulfort, Karen L.; Utschig, Lisa M.

    2016-05-17

    Photosynthetic reaction center (RC) proteins convert incident solar energy to chemical energy through a network of molecular cofactors which have been evolutionarily tuned to couple efficient light-harvesting, directional electron transfer, and long-lived charge separation with secondary reaction sequences. These molecular cofactors are embedded within a complex protein environment which precisely positions each cofactor in optimal geometries along efficient electron transfer pathways with localized protein environments facilitating sequential and accumulative charge transfer. By contrast, it is difficult to approach a similar level of structural complexity in synthetic architectures for solar energy conversion. However, by using appropriate self-assembly strategies, we anticipate thatmore » molecular modules, which are independently synthesized and optimized for either light-harvesting or redox catalysis, can be organized into spatial arrangements that functionally mimic natural photosynthesis. In this Account, we describe a modular approach to new structural designs for artificial photosynthesis which is largely inspired by photosynthetic RC proteins. We focus on recent work from our lab which uses molecular modules for light-harvesting or proton reduction catalysis in different coordination geometries and different platforms, spanning from discrete supramolecular assemblies to molecule–nanoparticle hybrids to protein-based biohybrids. Molecular modules are particularly amenable to high-resolution characterization of the ground and excited state of each module using a variety of physical techniques; such spectroscopic interrogation helps our understanding of primary artificial photosynthetic mechanisms. In particular, we discuss the use of transient optical spectroscopy, EPR, and X-ray scattering techniques to elucidate dynamic structural behavior and light-induced kinetics and the impact on photocatalytic mechanism. Two different coordination geometries of supramolecular photocatalyst based on the [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) light-harvesting module with cobaloxime-based catalyst module are compared, with progress in stabilizing photoinduced charge separation identified. These same modules embedded in the small electron transfer protein ferredoxin exhibit much longer charge-separation, enabled by stepwise electron transfer through the native [2Fe-2S] cofactor. We anticipate that the use of interchangeable, molecular modules which can interact in different coordination geometries or within entirely different structural platforms will provide important fundamental insights into the effect of environment on parameters such as electron transfer and charge separation, and ultimately drive more efficient designs for artificial photosynthesis.« less

  6. Conjugated polymers nanostructured as smart interfaces for controlling the catalytic properties of enzymes.

    PubMed

    Barbosa, Camila Gouveia; Caseli, Luciano; Péres, Laura Oliveira

    2016-08-15

    The search for new molecular architectures to improve the efficiency of enzymes entrapped in ultrathin films is useful to enhance the effectiveness of biosensors. In this present work, conjugated polymers, based on thiophene and fluorine, were investigated to verify their suitability as matrices for the immobilization of urease. The copolymer poly[(9,9-dioctylfluorene)-co-thiophene], PDOF-co-Th was spread on the air-water interface forming stable Langmuir monolayers as determined by surface pressure-area isotherms, polarization-modulation reflection-absorption infrared spectroscopy (PM-IRRAS), and Brewster angle microscopy (BAM). Urease was incorporated in the floating monolayers being further transferred to solid supports as mixed Langmuir-Blodgett (LB) films. These films were then characterized with transfer ratio, fluorescence spectroscopy, PM-IRRAS and atomic force microscopy, confirming the co-transfer of the enzyme as well as its structuring in β-sheets. The catalytic activity was detected for urease, with a lower reaction rate than that encountered for the homogeneous environment. This was attributed to conformational constraints imposed to the biomacromolecule entrapped in the polymeric matrix. Copyright © 2016 Elsevier Inc. All rights reserved.

  7. The Scope of Direct Alkylation of Gold Surface with Solutions of C1-C4 n-Alkylstannanes.

    PubMed

    Kaletová, Eva; Kohutová, Anna; Hajduch, Jan; Kaleta, Jiří; Bastl, Zdeněk; Pospíšil, Lubomír; Stibor, Ivan; Magnera, Thomas F; Michl, Josef

    2015-09-23

    Treatment of cleaned gold surfaces with dilute tetrahydrofuran or chloroform solutions of tetraalkylstannanes (alkyl = methyl, ethyl, n-propyl, n-butyl) or di-n-butylmethylstannyl tosylate under ambient conditions causes a self-limited growth of disordered monolayers consisting of alkyls and tin oxide. Extensive use of deuterium labeling showed that the alkyls originate from the stannane and not from ambient impurities, and that trialkylstannyl groups are absent in the monolayers, contrary to previous proposals. Methyl groups attached to the Sn atom are not transferred to the surface. Ethyl groups are transferred slowly, and propyl and butyl rapidly. In all cases, tin oxide is codeposited in submonolayer amounts. The monolayers were characterized by ellipsometry, contact angle goniometry, polarization modulated IR reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy with ferrocyanide/ferricyanide, which revealed a very low charge-transfer resistance. The thermal stability of the monolayers and their resistance to solvents are comparable with those of an n-octadecanethiol monolayer. A preliminary examination of the kinetics of monolayer deposition from a THF solution of tetra-n-butylstannane revealed an approximately half-order dependence on the bulk solution concentration of the stannane, hinting that more than one alkyl can be transferred from a single stannane molecule. A detailed structure of the attachment of the alkyl groups is not known, and it is proposed that it involves direct single or multiple bonding of one or more C atoms to one or more Au atoms.

  8. Improved electron transfer and plasmonic effect in dye-sensitized solar cells with bi-functional Nb-doped TiO2/Ag ternary nanostructures.

    PubMed

    Park, Jung Tae; Chi, Won Seok; Jeon, Harim; Kim, Jong Hak

    2014-03-07

    TiO2 nanoparticles are surface-modified via atom transfer radical polymerization (ATRP) with a hydrophilic poly(oxyethylene)methacrylate (POEM), which can coordinate to the Ag precursor, i.e. silver trifluoromethanesulfonate (AgCF3SO3). Following the reduction of Ag ions, a Nb2O5 doping process and calcination at 450 °C, bi-functional Nb-doped TiO2/Ag ternary nanostructures are generated. The resulting nanostructures are characterized by energy-filtering transmission electron microscopy (EF-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. The dye-sensitized solar cell (DSSC) based on the Nb-doped TiO2/Ag nanostructure photoanode with a polymerized ionic liquid (PIL) as the solid polymer electrolyte shows an overall energy conversion efficiency (η) of 6.9%, which is much higher than those of neat TiO2 (4.7%) and Nb-doped TiO2 (5.4%). The enhancement of η is mostly due to the increase of current density, attributed to the improved electron transfer properties including electron injection, collection, and plasmonic effects without the negative effects of charge recombination or problems with corrosion. These properties are supported by intensity modulated photocurrent/voltage spectroscopy (IMPS/IMVS) and incident photon-to-electron conversion efficiency (IPCE) measurements.

  9. Optical impedance spectroscopy with single-mode electro-active-integrated optical waveguides.

    PubMed

    Han, Xue; Mendes, Sergio B

    2014-02-04

    An optical impedance spectroscopy (OIS) technique based on a single-mode electro-active-integrated optical waveguide (EA-IOW) was developed to investigate electron-transfer processes of redox adsorbates. A highly sensitive single-mode EA-IOW device was used to optically follow the time-dependent faradaic current originated from a submonolayer of cytochrome c undergoing redox exchanges driven by a harmonic modulation of the electric potential at several dc bias potentials and at several frequencies. To properly retrieve the faradaic current density from the ac-modulated optical signal, we introduce here a mathematical formalism that (i) accounts for intrinsic changes that invariably occur in the optical baseline of the EA-IOW device during potential modulation and (ii) provides accurate results for the electro-chemical parameters. We are able to optically reconstruct the faradaic current density profile against the dc bias potential in the working electrode, identify the formal potential, and determine the energy-width of the electron-transfer process. In addition, by combining the optically reconstructed faradaic signal with simple electrical measurements of impedance across the whole electrochemical cell and the capacitance of the electric double-layer, we are able to determine the time-constant connected to the redox reaction of the adsorbed protein assembly. For cytochrome c directly immobilized onto the indium tin oxide (ITO) surface, we measured a reaction rate constant of 26.5 s(-1). Finally, we calculate the charge-transfer resistance and pseudocapacitance associated with the electron-transfer process and show that the frequency dependence of the redox reaction of the protein submonolayer follows as expected the electrical equivalent of an RC-series admittance diagram. Above all, we show here that OIS with single-mode EA-IOW's provide strong analytical signals that can be readily monitored even for small surface-densities of species involved in the redox process (e.g., fmol/cm(2), 0.1% of a full protein monolayer). This experimental approach, when combined with the analytical formalism described here, brings additional sensitivity, accuracy, and simplicity to electro-chemical analysis and is expected to become a useful tool in investigations of redox processes.

  10. Immobilization of alcohol dehydrogenase in phospholipid Langmuir-Blodgett films to detect ethanol.

    PubMed

    Caseli, Luciano; Perinotto, Angelo C; Viitala, Tapani; Zucolotto, Valtencir; Oliveira, Osvaldo N

    2009-03-03

    Enzyme immobilization in nanostructured films may be useful for a number of biomimetic systems, particularly if suitable matrixes are identified. Here we show that alcohol dehydrogenase (ADH) has high affinity toward a negatively charged phospholipid, dimyristoylphosphatidic acid (DMPA), which forms a Langmuir monolayer at an air-water interface. Incorporation of ADH into the DMPA monolayer was monitored with surface pressure measurements and polarization-modulation infrared reflection absorption spectroscopy, with the alpha-helices from ADH being mainly oriented parallel to the water surface. ADH remained at the interface even at high surface pressures, thus allowing deposition of Langmuir-Blodgett (LB) films from the DMPA-ADH film. Indeed, interaction with DMPA enhances the transfer of ADH, where the mass transferred onto a solid support increased from 134 ng for ADH on a Gibbs monolayer to 178 ng for an LB film with DMPA. With fluorescence spectroscopy it was possible to confirm that the ADH structure was preserved even after one month of the LB deposition. ADH-containing films deposited onto gold-interdigitated electrodes were employed in a sensor array capable of detecting ethanol at concentrations down to 10 ppb (in volume), using impedance spectroscopy as the method of detection.

  11. Py4CAtS - Python tools for line-by-line modelling of infrared atmospheric radiative transfer

    NASA Astrophysics Data System (ADS)

    Schreier, Franz; García, Sebastián Gimeno

    2013-05-01

    Py4CAtS — Python scripts for Computational ATmospheric Spectroscopy is a Python re-implementation of the Fortran infrared radiative transfer code GARLIC, where compute-intensive code sections utilize the Numeric/Scientific Python modules for highly optimized array-processing. The individual steps of an infrared or microwave radiative transfer computation are implemented in separate scripts to extract lines of relevant molecules in the spectral range of interest, to compute line-by-line cross sections for given pressure(s) and temperature(s), to combine cross sections to absorption coefficients and optical depths, and to integrate along the line-of-sight to transmission and radiance/intensity. The basic design of the package, numerical and computational aspects relevant for optimization, and a sketch of the typical workflow are presented.

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

    de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz

    In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

  13. Influence of convection at outer ceramic surfaces on the characterization of thermoelectric modules by impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Beltrán-Pitarch, Braulio; García-Cañadas, Jorge

    2018-02-01

    Impedance spectroscopy is a useful method for the characterization of thermoelectric (TE) modules. It can determine with high accuracy the module's dimensionless figure of merit (zT) as well as the average TE properties of the module's thermoelements. Interpretation of impedance results requires the use of a theoretical model (equivalent circuit), which provides the desired device parameters after a fitting is performed to the experimental results. Here, we extend the currently available equivalent circuit, only valid for adiabatic conditions, to account for the effect of convection at the outer surface of the module ceramic plates, which is the part of the device where convection is more prominent. This is performed by solving the heat equation in the frequency domain including convection heat losses. As a result, a new element (convection resistance) appears in the developed equivalent circuit, which starts to influence at mid-low frequencies, causing a decrease of the typically observed semicircle in the impedance spectrum. If this effect is not taken into account, an underestimation of the zT occurs when measurements are performed under room conditions. The theoretical model is validated by experimental measurements performed in a commercial module with and without vacuum. Interestingly, the use of the new equivalent circuit allows the determination of the convection heat transfer coefficient (h), if the module's Seebeck coefficient is known, and an impedance measurement in vacuum is performed, opening up the possibility to develop TE modules as h sensors. On the other hand, if h is known, all the properties of the module (zT, ohmic (internal) resistance, average Seebeck coefficient and average thermal conductivity of the thermoelements and thermal conductivity of the ceramics) can be obtained from one impedance measurement in vacuum and another measurement under room conditions.

  14. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe 3Mn-Iodosobenzene Adducts

    DOE PAGES

    de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz; ...

    2017-03-24

    In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

  15. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

    PubMed

    de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

    2017-04-18

    We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 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

  17. Spectroscopic Characterization of YedY: The Role of Sulfur Coordination in a Mo(V) Sulfite Oxidase Family Enzyme Form

    PubMed Central

    Yang, Jing; Rothery, Richard; Sempombe, Joseph

    2011-01-01

    Electronic paramagnetic resonance, electronic absorption, and magnetic circular dichroism spectroscopies have been performed on YedY, a SUOX fold protein with a Mo domain that is remarkably similar to that found in chicken sulfite oxidase, A. thaliana plant sulfite oxidase, and the bacterial sulfite dehydrogenase from S. novella. Low-energy dithiolene→Mo and cysteine thiolate→Mo charge transfer bands have been assigned for the first time in a Mo(V) form of a SUOX fold protein, and the spectroscopic data have been used to interpret the results of bonding calculations. The analysis shows that second coordination sphere effects modulate dithiolene and cysteine sulfur covalency contributions to the Mo bonding scheme. Namely, a more acute Ooxo-Mo-SCys-C dihedral angle results in increased cysteine thiolate S→Mo charge transfer and a high g1 in the EPR spectrum. The spectrosocopic results, coupled with the available structural data, indicate that these second coordination sphere effects may play key roles in modulating the active site redox potential, facilitating hole superexchange pathways for electron transfer regeneration, and affecting the type of reactions catalyzed by sulfite oxidase family enzymes. PMID:19860477

  18. Transient and modulated charge separation at CuInSe2/C60 and CuInSe2/ZnPc hybrid interfaces

    NASA Astrophysics Data System (ADS)

    von Morzé, Natascha; Dittrich, Thomas; Calvet, Wolfram; Lauermann, Iver; Rusu, Marin

    2017-02-01

    Spectral dependent charge transfer and exciton dissociation have been investigated at hybrid interfaces between inorganic polycrystalline CuInSe2 (untreated and Na-conditioned) thin films and organic C60 as well as zinc phthalocyanine (ZnPc) layers by transient and modulated surface photovoltage measurements. The stoichiometry and electronic properties of the bare CuInSe2 surface were characterized by photoelectron spectroscopy which revealed a Cu-poor phase with n-type features. After the deposition of the C60 layer, a strong band bending at the CuInSe2 surface was observed. Evidence for dissociation of excitons followed by charge separation was found at the CuInSe2/ZnPc interface. The Cu-poor layer at the CuInSe2 surface was found to be crucial for transient and modulated charge separation at CuInSe2/organic hybrid interfaces.

  19. Double-modulation spectroscopy of molecular ions - Eliminating the background in velocity-modulation spectroscopy

    NASA Technical Reports Server (NTRS)

    Lan, Guang; Tholl, Hans Dieter; Farley, John W.

    1991-01-01

    Velocity-modulation spectroscopy is an established technique for performing laser absorption spectroscopy of molecular ions in a discharge. However, such experiments are often plagued by a coherent background signal arising from emission from the discharge or from electronic pickup. Fluctuations in the background can obscure the desired signal. A simple technique using amplitude modulation of the laser and two lock-in amplifiers in series to detect the signal is demonstrated. The background and background fluctuations are thereby eliminated, facilitating the detection of molecular ions.

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

    NASA Technical Reports Server (NTRS)

    Chou, Nee-Yin; Sachse, Glen W.

    1987-01-01

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

  1. Carrier and photon dynamics in a topological insulator Bi{sub 2}Te{sub 3}/GaN type II staggered heterostructure

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

    Chaturvedi, P.; Chouksey, S.; Banerjee, D.

    2015-11-09

    We have demonstrated a type-II band-aligned heterostructure between pulsed laser deposited topological insulator bismuth telluride and metal organic-chemical-vapour deposited GaN on a sapphire substrate. The heterostructure shows a large valence band-offset of 3.27 eV as determined from x-ray photoelectron spectroscopy, which is close to the bandgap of GaN (3.4 eV). Further investigation using x-ray diffraction, Raman spectroscopy, and energy-dispersive x-ray spectrum reveals the stoichiometric and material properties of bismuth telluride on GaN. Steady state photon emission from GaN is found to be modulated by the charge transfer process due to diffusion across the junction. The time constant involved with the charge transfermore » process is found to be 0.6 ns by transient absorption spectroscopy. The heterostructure can be used for designing devices with different functionalities and improving the performance of the existing devices on GaN.« less

  2. Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis

    DTIC Science & Technology

    2016-07-08

    AFRL-AFOSR-VA-TR-2016-0244 Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis Jahan Dawlaty UNIVERSITY OF SOUTHERN...TITLE AND SUBTITLE Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis 5a. CONTRACT NUMBER 5b. GRANT NUMBER FA9550...298 Back (Rev. 8/98) DISTRIBUTION A: Distribution approved for public release. Final Report: AFOSR YIP Grant FA9550-13-1-0128: Ultrafast Spectroscopy

  3. 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.

  4. 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.

  5. Modulation Index Adjustment for Recovery of Pure Wavelength Modulation Spectroscopy Second Harmonic Signal Waveforms.

    PubMed

    Wei, Wei; Chang, Jun; Wang, Qiang; Qin, Zengguang

    2017-01-15

    A new technique of modulation index adjustment for pure wavelength modulation spectroscopy second harmonic signal waveforms recovery is presented. As the modulation index is a key parameter in determining the exact form of the signals generated by the technique of wavelength modulation spectroscopy, the method of modulation index adjustment is applied to recover the second harmonic signal with wavelength modulation spectroscopy. By comparing the measured profile with the theoretical profile by calculation, the relationship between the modulation index and average quantities of the scanning wavelength can be obtained. Furthermore, when the relationship is applied in the experimental setup by point-by-point modulation index modification for gas detection, the results show good agreement with the theoretical profile and signal waveform distortion (such as the amplitude modulation effect caused by diode laser) can be suppressed. Besides, the method of modulation index adjustment can be used in many other aspects which involve profile improvement. In practical applications, when the amplitude modulation effect can be neglected and the stability of the detection system is limited by the sampling rate of analog-to-digital, modulation index adjustment can be used to improve detection into softer inflection points and solve the insufficient sampling problem. As a result, measurement stability is improved by 40%.

  6. Modulation Index Adjustment for Recovery of Pure Wavelength Modulation Spectroscopy Second Harmonic Signal Waveforms

    PubMed Central

    Wei, Wei; Chang, Jun; Wang, Qiang; Qin, Zengguang

    2017-01-01

    A new technique of modulation index adjustment for pure wavelength modulation spectroscopy second harmonic signal waveforms recovery is presented. As the modulation index is a key parameter in determining the exact form of the signals generated by the technique of wavelength modulation spectroscopy, the method of modulation index adjustment is applied to recover the second harmonic signal with wavelength modulation spectroscopy. By comparing the measured profile with the theoretical profile by calculation, the relationship between the modulation index and average quantities of the scanning wavelength can be obtained. Furthermore, when the relationship is applied in the experimental setup by point-by-point modulation index modification for gas detection, the results show good agreement with the theoretical profile and signal waveform distortion (such as the amplitude modulation effect caused by diode laser) can be suppressed. Besides, the method of modulation index adjustment can be used in many other aspects which involve profile improvement. In practical applications, when the amplitude modulation effect can be neglected and the stability of the detection system is limited by the sampling rate of analog-to-digital, modulation index adjustment can be used to improve detection into softer inflection points and solve the insufficient sampling problem. As a result, measurement stability is improved by 40%. PMID:28098842

  7. 31P-Magnetization Transfer Magnetic Resonance Spectroscopy Measurements of In Vivo Metabolism

    PubMed Central

    Befroy, Douglas E.; Rothman, Douglas L.; Petersen, Kitt Falk; Shulman, Gerald I.

    2012-01-01

    Magnetic resonance spectroscopy offers a broad range of noninvasive analytical methods for investigating metabolism in vivo. Of these, the magnetization-transfer (MT) techniques permit the estimation of the unidirectional fluxes associated with metabolic exchange reactions. Phosphorus (31P) MT measurements can be used to examine the bioenergetic reactions of the creatine-kinase system and the ATP synthesis/hydrolysis cycle. Observations from our group and others suggest that the inorganic phosphate (Pi) → ATP flux in skeletal muscle may be modulated by certain conditions, including aging, insulin resistance, and diabetes, and may reflect inherent alterations in mitochondrial metabolism. However, such effects on the Pi → ATP flux are not universally observed under conditions in which mitochondrial function, assessed by other techniques, is impaired, and recent articles have raised concerns about the absolute magnitude of the measured reaction rates. As the application of 31P-MT techniques becomes more widespread, this article reviews the methodology and outlines our experience with its implementation in a variety of models in vivo. Also discussed are potential limitations of the technique, complementary methods for assessing oxidative metabolism, and whether the Pi → ATP flux is a viable biomarker of metabolic function in vivo. PMID:23093656

  8. Electron Transfer Mechanisms of DNA Repair by Photolyase

    NASA Astrophysics Data System (ADS)

    Zhong, Dongping

    2015-04-01

    Photolyase is a flavin photoenzyme that repairs two DNA base damage products induced by ultraviolet (UV) light: cyclobutane pyrimidine dimers and 6-4 photoproducts. With femtosecond spectroscopy and site-directed mutagenesis, investigators have recently made significant advances in our understanding of UV-damaged DNA repair, and the entire enzymatic dynamics can now be mapped out in real time. For dimer repair, six elementary steps have been characterized, including three electron transfer reactions and two bond-breaking processes, and their reaction times have been determined. A unique electron-tunneling pathway was identified, and the critical residues in modulating the repair function at the active site were determined. The dynamic synergy between the elementary reactions for maintaining high repair efficiency was elucidated, and the biological nature of the flavin active state was uncovered. For 6-4 photoproduct repair, a proton-coupled electron transfer repair mechanism has been revealed. The elucidation of electron transfer mechanisms and two repair photocycles is significant and provides a molecular basis for future practical applications, such as in rational drug design for curing skin cancer.

  9. Modeling Current Transfer from PV Modules Based on Meteorological Data

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

    Hacke, Peter; Smith, Ryan; Kurtz, Sarah

    2016-11-21

    Current transferred from the active cell circuit to ground in modules undergoing potential-induced degradation (PID) stress is analyzed with respect to meteorological data. Duration and coulombs transferred as a function of whether the module is wet (from dew or rain) or the extent of uncondensed surface humidity are quantified based on meteorological indicators. With this, functions predicting the mode and rate of coulomb transfer are developed for use in estimating the relative PID stress associated with temperature, moisture, and system voltage in any climate. Current transfer in a framed crystalline silicon module is relatively high when there is no condensedmore » water on the module, whereas current transfer in a thin-film module held by edge clips is not, and displays a greater fraction of coulombs transferred when wet compared to the framed module in the natural environment.« less

  10. Communication: Probing non-equilibrium vibrational relaxation pathways of highly excited C≡N stretching modes following ultrafast back-electron transfer.

    PubMed

    Lynch, Michael S; Slenkamp, Karla M; Khalil, Munira

    2012-06-28

    Fifth-order nonlinear visible-infrared spectroscopy is used to probe coherent and incoherent vibrational energy relaxation dynamics of highly excited vibrational modes indirectly populated via ultrafast photoinduced back-electron transfer in a trinuclear cyano-bridged mixed-valence complex. The flow of excess energy deposited into four C≡N stretching (ν(CN)) modes of the molecule is monitored by performing an IR pump-probe experiment as a function of the photochemical reaction (τ(vis)). Our results provide experimental evidence that the nuclear motions of the molecule are both coherently and incoherently coupled to the electronic charge transfer process. We observe that intramolecular vibrational relaxation dynamics among the highly excited ν(CN) modes change significantly en route to equilibrium. The experiment also measures a 7 cm(-1) shift in the frequency of a ∼57 cm(-1) oscillation reflecting a modulation of the coupling between the probed high-frequency ν(CN) modes for τ(vis) < 500 fs.

  11. Field-modulation spectroscopy of pentacene thin films using field-effect devices: Reconsideration of the excitonic structure

    NASA Astrophysics Data System (ADS)

    Haas, Simon; Matsui, Hiroyuki; Hasegawa, Tatsuo

    2010-10-01

    We report pure electric-field effects on the excitonic absorbance of pentacene thin films as measured by unipolar field-effect devices that allowed us to separate the charge accumulation effects. The field-modulated spectra between 1.8 and 2.6 eV can be well fitted with the first derivative curve of Frenkel exciton absorption and its vibronic progression, and at higher energy a field-induced feature appears at around 2.95 eV. The results are in sharp contrast to the electroabsorption spectra reported by Sebastian in previous studies [Chem. Phys. 61, 125 (1981)10.1016/0301-0104(81)85055-0], and leads us to reconsider the excitonic structure including the location of charge-transfer excitons. Nonlinear π -electronic response is discussed based on second-order electro-optic (Kerr) spectra.

  12. Dual modulation laser line-locking technique for wavelength modulation spectroscopy

    DOEpatents

    Bomse, David S.; Hovde, D. Christian; Silver, Joel A.

    2002-01-01

    Disclosed are a method and apparatus for dual modulation of an optical spectroscopy laser. Demodulation is accomplished in a manner resulting in measurement of absorbance of a gas species, as well as stabilization of laser wavelength and baseline noise reduction.

  13. Wavelength-modulated photocapacitance spectroscopy

    NASA Technical Reports Server (NTRS)

    Kamieniecki, E.; Lagowski, J.; Gatos, H. C.

    1980-01-01

    Derivative deep-level spectroscopy was achieved with wavelength-modulated photocapacitance employing MOS structures and Schottky barriers. The energy position and photoionization characteristics of deep levels of melt-grown GaAs and the Cr level in high-resistivity GaAs were determined. The advantages of this method over existing methods for deep-level spectroscopy are discussed.

  14. Quantum coherent optical phase modulation in an ultrafast transmission electron microscope.

    PubMed

    Feist, Armin; Echternkamp, Katharina E; Schauss, Jakob; Yalunin, Sergey V; Schäfer, Sascha; Ropers, Claus

    2015-05-14

    Coherent manipulation of quantum systems with light is expected to be a cornerstone of future information and communication technology, including quantum computation and cryptography. The transfer of an optical phase onto a quantum wavefunction is a defining aspect of coherent interactions and forms the basis of quantum state preparation, synchronization and metrology. Light-phase-modulated electron states near atoms and molecules are essential for the techniques of attosecond science, including the generation of extreme-ultraviolet pulses and orbital tomography. In contrast, the quantum-coherent phase-modulation of energetic free-electron beams has not been demonstrated, although it promises direct access to ultrafast imaging and spectroscopy with tailored electron pulses on the attosecond scale. Here we demonstrate the coherent quantum state manipulation of free-electron populations in an electron microscope beam. We employ the interaction of ultrashort electron pulses with optical near-fields to induce Rabi oscillations in the populations of electron momentum states, observed as a function of the optical driving field. Excellent agreement with the scaling of an equal-Rabi multilevel quantum ladder is obtained, representing the observation of a light-driven 'quantum walk' coherently reshaping electron density in momentum space. We note that, after the interaction, the optically generated superposition of momentum states evolves into a train of attosecond electron pulses. Our results reveal the potential of quantum control for the precision structuring of electron densities, with possible applications ranging from ultrafast electron spectroscopy and microscopy to accelerator science and free-electron lasers.

  15. Quantum coherent optical phase modulation in an ultrafast transmission electron microscope

    NASA Astrophysics Data System (ADS)

    Feist, Armin; Echternkamp, Katharina E.; Schauss, Jakob; Yalunin, Sergey V.; Schäfer, Sascha; Ropers, Claus

    2015-05-01

    Coherent manipulation of quantum systems with light is expected to be a cornerstone of future information and communication technology, including quantum computation and cryptography. The transfer of an optical phase onto a quantum wavefunction is a defining aspect of coherent interactions and forms the basis of quantum state preparation, synchronization and metrology. Light-phase-modulated electron states near atoms and molecules are essential for the techniques of attosecond science, including the generation of extreme-ultraviolet pulses and orbital tomography. In contrast, the quantum-coherent phase-modulation of energetic free-electron beams has not been demonstrated, although it promises direct access to ultrafast imaging and spectroscopy with tailored electron pulses on the attosecond scale. Here we demonstrate the coherent quantum state manipulation of free-electron populations in an electron microscope beam. We employ the interaction of ultrashort electron pulses with optical near-fields to induce Rabi oscillations in the populations of electron momentum states, observed as a function of the optical driving field. Excellent agreement with the scaling of an equal-Rabi multilevel quantum ladder is obtained, representing the observation of a light-driven `quantum walk' coherently reshaping electron density in momentum space. We note that, after the interaction, the optically generated superposition of momentum states evolves into a train of attosecond electron pulses. Our results reveal the potential of quantum control for the precision structuring of electron densities, with possible applications ranging from ultrafast electron spectroscopy and microscopy to accelerator science and free-electron lasers.

  16. Photoinduced electron transfer pathways in hydrogen-evolving reduced graphene oxide-boosted hybrid nano-bio catalyst.

    PubMed

    Wang, Peng; Dimitrijevic, Nada M; Chang, Angela Y; Schaller, Richard D; Liu, Yuzi; Rajh, Tijana; Rozhkova, Elena A

    2014-08-26

    Photocatalytic production of clean hydrogen fuels using water and sunlight has attracted remarkable attention due to the increasing global energy demand. Natural and synthetic dyes can be utilized to sensitize semiconductors for solar energy transformation using visible light. In this study, reduced graphene oxide (rGO) and a membrane protein bacteriorhodopsin (bR) were employed as building modules to harness visible light by a Pt/TiO2 nanocatalyst. Introduction of the rGO boosts the nano-bio catalyst performance that results in hydrogen production rates of approximately 11.24 mmol of H2 (μmol protein)(-1) h(-1). Photoelectrochemical measurements show a 9-fold increase in photocurrent density when TiO2 electrodes were modified with rGO and bR. Electron paramagnetic resonance and transient absorption spectroscopy demonstrate an interfacial charge transfer from the photoexcited rGO to the semiconductor under visible light.

  17. Catalysis by Methylamine Dehydrogenase and Electron Transfer to Amicyanin and Cytochrome C(551I) from Paracoccus Denitrificans.

    NASA Astrophysics Data System (ADS)

    Brooks, Harold Burns

    1995-01-01

    The quinoprotein methylamine dehydrogenase (MADH), a type I copper protein, amicyanin, and cytochrome c _{55li} form a physiologic ternary complex (Chen et al. (1994) Science 264, 86-90) in which electrons are transferred from tryptophan tryptophylquinone to copper to heme. The reduction of MADH by rm H_3- and rm D_3 -methylamine, the reoxidation of MADH by amicyanin, and the reduction of cytochrome c_{55li } by reduced amicyanin in the presence of MADH have been studied by stopped-flow spectroscopy. When rm CD_3NH_2 was used as a substrate for MADH a deuterium kinetic isotope effect of 17.2 was measured for the hydrogen abstraction step. The maximum deuterium kinetic isotope effect that was measured in steady-state kinetic experiments was 3.0. The temperature dependencies of the rate constants for the reaction of methylamine with MADH were also determined. An iminosemiquinone intermediate for the oxidation of substrate-reduced MADH by amicyanin was detected using stopped-flow spectroscopy, and the presence of the substrate derived nitrogen was confirmed by electron spin echo envelope modulation (ESEEM) spectroscopy. Marcus theory, which was used to analyze the electron transfer reaction between the dithionite-generated redox forms of MADH and amicyanin, gave values of 218 kJ rm mol^{ -1} (2.3 eV) for the reorganizational energy (lambda ) and 11.6 rm cm^{-1} for the coupling rm (H_{AB}). In contrast, the oxidation of substrate-reduced MADH by amicyanin was a gated electron transfer reaction with values for DeltaH* of 76 kJ rm mol^ {-1} and DeltaS* of -41 J rm mol^{ -1} ^circ K^ {-1}. These studies are consistent with the formation of transient unstable intermediates preceeding electron transfer between MADH and amicyanin. Preliminary investigations of the ternary complex of MADH, amicyanin, and cytochrome c_{55li } suggest two distinct cytochrome c _{55li} binding sites on amicyanin. This conclusion is supported by the biphasic nature of the stopped -flow trace, the inhibition of the rm k^ {fast}_{obs} by MADH, and the ionic strength dependence of the two phases. The slow phase had a rate of 3.1 rm s^ {-1} which is consistent with electron transfer between amicyanin and cytochrome c_ {55li} within the ternary complex. The fast phase does not exhibit saturation behavior, must have an electron transfer rate greater than 1000 rm s^{-1}, and likely involves a complex of amicyanin and cytochrome c_{55li } near the hydrophobic patch of amicyanin.

  18. Modulated Raman Spectroscopy for Enhanced Cancer Diagnosis at the Cellular Level

    PubMed Central

    De Luca, Anna Chiara; Dholakia, Kishan; Mazilu, Michael

    2015-01-01

    Raman spectroscopy is emerging as a promising and novel biophotonics tool for non-invasive, real-time diagnosis of tissue and cell abnormalities. However, the presence of a strong fluorescence background is a key issue that can detract from the use of Raman spectroscopy in routine clinical care. The review summarizes the state-of-the-art methods to remove the fluorescence background and explores recent achievements to address this issue obtained with modulated Raman spectroscopy. This innovative approach can be used to extract the Raman spectral component from the fluorescence background and improve the quality of the Raman signal. We describe the potential of modulated Raman spectroscopy as a rapid, inexpensive and accurate clinical tool to detect the presence of bladder cancer cells. Finally, in a broader context, we show how this approach can greatly enhance the sensitivity of integrated Raman spectroscopy and microfluidic systems, opening new prospects for portable higher throughput Raman cell sorting. PMID:26110401

  19. Charge transfer from TiO2 into adsorbed benzene diazonium compounds

    NASA Astrophysics Data System (ADS)

    Merson, A.; Dittrich, Th.; Zidon, Y.; Rappich, J.; Shapira, Yoram

    2004-08-01

    Electron transfer from sol-gel-prepared TiO2 into adsorbed benzene diazonium compounds has been investigated using cyclic voltammetry, x-ray photoelectron spectroscopy, contact potential difference, and surface photovoltage spectroscopy. The results show that the potential of maximum electron transfer depends strongly on the dipole moment of the benzene compound. Two reactive surface sites at which electron transfer occurs have been identified.

  20. Extreme mobility enhancement of two-dimensional electron gases at oxide interfaces by charge-transfer-induced modulation doping

    NASA Astrophysics Data System (ADS)

    Chen, Y. Z.; Trier, F.; Wijnands, T.; Green, R. J.; Gauquelin, N.; Egoavil, R.; Christensen, D. V.; Koster, G.; Huijben, M.; Bovet, N.; Macke, S.; He, F.; Sutarto, R.; Andersen, N. H.; Sulpizio, J. A.; Honig, M.; Prawiroatmodjo, G. E. D. K.; Jespersen, T. S.; Linderoth, S.; Ilani, S.; Verbeeck, J.; van Tendeloo, G.; Rijnders, G.; Sawatzky, G. A.; Pryds, N.

    2015-08-01

    Two-dimensional electron gases (2DEGs) formed at the interface of insulating complex oxides promise the development of all-oxide electronic devices. These 2DEGs involve many-body interactions that give rise to a variety of physical phenomena such as superconductivity, magnetism, tunable metal-insulator transitions and phase separation. Increasing the mobility of the 2DEG, however, remains a major challenge. Here, we show that the electron mobility is enhanced by more than two orders of magnitude by inserting a single-unit-cell insulating layer of polar La1-xSrxMnO3 (x = 0, 1/8, and 1/3) at the interface between disordered LaAlO3 and crystalline SrTiO3 produced at room temperature. Resonant X-ray spectroscopy and transmission electron microscopy show that the manganite layer undergoes unambiguous electronic reconstruction, leading to modulation doping of such atomically engineered complex oxide heterointerfaces. At low temperatures, the modulation-doped 2DEG exhibits Shubnikov-de Haas oscillations and fingerprints of the quantum Hall effect, demonstrating unprecedented high mobility and low electron density.

  1. A characterization of low luminance static and dynamic modulation transfer function curves for P-1, P-43, and P-53 phosphorus

    NASA Astrophysics Data System (ADS)

    Beasley, Howard H.; Martin, John S.; Klymenko, Victor; Harding, Thomas H.; Verona, Robert W.; Rash, Clarence E.

    1995-07-01

    A counterphase modulation technique is used to measure the static and dynamic modulation transfer functions for three phosphorus of current interest to U.S. Army aviation helmet-mounted displays (P-1, P-43, and P-53). A family of modulation transfer curves, one for each temporal frequency, is presented for each phosphorus. The measured MFT curves generally support the supposition that phosphorus persistence is a critical parameter in the ability of a CRT display to accurately reproduce contrast modulation transfer in dynamic environments.

  2. Administering an epoch initiated for remote memory access

    DOEpatents

    Blocksome, Michael A; Miller, Douglas R

    2014-03-18

    Methods, systems, and products are disclosed for administering an epoch initiated for remote memory access that include: initiating, by an origin application messaging module on an origin compute node, one or more data transfers to a target compute node for the epoch; initiating, by the origin application messaging module after initiating the data transfers, a closing stage for the epoch, including rejecting any new data transfers after initiating the closing stage for the epoch; determining, by the origin application messaging module, whether the data transfers have completed; and closing, by the origin application messaging module, the epoch if the data transfers have completed.

  3. Administering an epoch initiated for remote memory access

    DOEpatents

    Blocksome, Michael A; Miller, Douglas R

    2012-10-23

    Methods, systems, and products are disclosed for administering an epoch initiated for remote memory access that include: initiating, by an origin application messaging module on an origin compute node, one or more data transfers to a target compute node for the epoch; initiating, by the origin application messaging module after initiating the data transfers, a closing stage for the epoch, including rejecting any new data transfers after initiating the closing stage for the epoch; determining, by the origin application messaging module, whether the data transfers have completed; and closing, by the origin application messaging module, the epoch if the data transfers have completed.

  4. Administering an epoch initiated for remote memory access

    DOEpatents

    Blocksome, Michael A.; Miller, Douglas R.

    2013-01-01

    Methods, systems, and products are disclosed for administering an epoch initiated for remote memory access that include: initiating, by an origin application messaging module on an origin compute node, one or more data transfers to a target compute node for the epoch; initiating, by the origin application messaging module after initiating the data transfers, a closing stage for the epoch, including rejecting any new data transfers after initiating the closing stage for the epoch; determining, by the origin application messaging module, whether the data transfers have completed; and closing, by the origin application messaging module, the epoch if the data transfers have completed.

  5. Organic doping of rotated double layer graphene

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

    George, Lijin; Jaiswal, Manu, E-mail: manu.jaiswal@iitm.ac.in

    2016-05-06

    Charge transfer techniques have been extensively used as knobs to tune electronic properties of two- dimensional systems, such as, for the modulation of conductivity \\ mobility of single layer graphene and for opening the bandgap in bilayer graphene. The charge injected into the graphene layer shifts the Fermi level away from the minimum density of states point (Dirac point). In this work, we study charge transfer in rotated double-layer graphene achieved by the use of organic dopant, Tetracyanoquinodimethane. Naturally occurring bilayer graphene has a well-defined A-B stacking whereas in rotated double-layer the two graphene layers are randomly stacked with differentmore » rotational angles. This rotation is expected to significantly alter the interlayer interaction. Double-layer samples are prepared using layer-by-layer assembly of chemical vapor deposited single-layer graphene and they are identified by characteristic resonance in the Raman spectrum. The charge transfer and distribution of charges between the two graphene layers is studied using Raman spectroscopy and the results are compared with that for single-layer and A-B stacked bilayer graphene doped under identical conditions.« less

  6. Elucidating the design principles of photosynthetic electron-transfer proteins by site-directed spin labeling EPR spectroscopy.

    PubMed

    Ishara Silva, K; Jagannathan, Bharat; Golbeck, John H; Lakshmi, K V

    2016-05-01

    Site-directed spin labeling electron paramagnetic resonance (SDSL EPR) spectroscopy is a powerful tool to determine solvent accessibility, side-chain dynamics, and inter-spin distances at specific sites in biological macromolecules. This information provides important insights into the structure and dynamics of both natural and designed proteins and protein complexes. Here, we discuss the application of SDSL EPR spectroscopy in probing the charge-transfer cofactors in photosynthetic reaction centers (RC) such as photosystem I (PSI) and the bacterial reaction center (bRC). Photosynthetic RCs are large multi-subunit proteins (molecular weight≥300 kDa) that perform light-driven charge transfer reactions in photosynthesis. These reactions are carried out by cofactors that are paramagnetic in one of their oxidation states. This renders the RCs unsuitable for conventional nuclear magnetic resonance spectroscopy investigations. However, the presence of native paramagnetic centers and the ability to covalently attach site-directed spin labels in RCs makes them ideally suited for the application of SDSL EPR spectroscopy. The paramagnetic centers serve as probes of conformational changes, dynamics of subunit assembly, and the relative motion of cofactors and peptide subunits. In this review, we describe novel applications of SDSL EPR spectroscopy for elucidating the effects of local structure and dynamics on the electron-transfer cofactors of photosynthetic RCs. Because SDSL EPR Spectroscopy is uniquely suited to provide dynamic information on protein motion, it is a particularly useful method in the engineering and analysis of designed electron transfer proteins and protein networks. This article is part of a Special Issue entitled Biodesign for Bioenergetics--the design and engineering of electronic transfer cofactors, proteins and protein networks, edited by Ronald L. Koder and J.L. Ross Anderson. Copyright © 2016. Published by Elsevier B.V.

  7. Chirped laser dispersion spectroscopy using a directly modulated quantum cascade laser

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

    Hangauer, Andreas, E-mail: hangauer@princeton.edu; Nikodem, Michal; Wysocki, Gerard, E-mail: gwysocki@princeton.edu

    2013-11-04

    Chirped laser dispersion spectroscopy (CLaDS) utilizing direct modulation of a quantum cascade laser (QCL) is presented. By controlling the laser bias nearly single- and dual-sideband CLaDS operation can be realized in an extremely simplified optical setup with no external optical modulators. Capability of direct single-sideband modulation is a unique feature of QCLs that exhibit a low linewidth enhancement factor. The developed analytical model shows excellent agreement with the experimental, directly modulated CLaDS spectra. This method overcomes major technical limitations of mid-infrared CLaDS systems by allowing significantly higher modulation frequencies and eliminating optical fringes introduced by external modulators.

  8. Redox Modulation of Flavin and Tyrosine Determines Photoinduced Proton-coupled Electron Transfer and Photoactivation of BLUF Photoreceptors

    PubMed Central

    Mathes, Tilo; van Stokkum, Ivo H. M.; Stierl, Manuela; Kennis, John T. M.

    2012-01-01

    Photoinduced electron transfer in biological systems, especially in proteins, is a highly intriguing matter. Its mechanistic details cannot be addressed by structural data obtained by crystallography alone because this provides only static information on a given redox system. In combination with transient spectroscopy and site-directed manipulation of the protein, however, a dynamic molecular picture of the ET process may be obtained. In BLUF (blue light sensors using FAD) photoreceptors, proton-coupled electron transfer between a tyrosine and the flavin cofactor is the key reaction to switch from a dark-adapted to a light-adapted state, which corresponds to the biological signaling state. Particularly puzzling is the fact that, although the various naturally occurring BLUF domains show little difference in the amino acid composition of the flavin binding pocket, the reaction rates of the forward reaction differ quite largely from a few ps up to several hundred ps. In this study, we modified the redox potential of the flavin/tyrosine redox pair by site-directed mutagenesis close to the flavin C2 carbonyl and fluorination of the tyrosine, respectively. We provide information on how changes in the redox potential of either reaction partner significantly influence photoinduced proton-coupled electron transfer. The altered redox potentials allowed us furthermore to experimentally describe an excited state charge transfer intermediately prior to electron transfer in the BLUF photocycle. Additionally, we show that the electron transfer rate directly correlates with the quantum yield of signaling state formation. PMID:22833672

  9. Revealing the Coulomb interaction strength in a cuprate superconductor

    DOE PAGES

    Yang, S. -L.; Sobota, J. A.; He, Y.; ...

    2017-12-08

    Here, we study optimally doped Bi 2 Sr 2 Ca 0.92 Y 0.08 Cu 2 O 8 + δ (Bi2212) using angle-resolved two-photon photoemission spectroscopy. Three spectral features are resolved near 1.5, 2.7, and 3.6 eV above the Fermi level. By tuning the photon energy, we determine that the 2.7-eV feature arises predominantly from unoccupied states. The 1.5- and 3.6-eV features reflect unoccupied states whose spectral intensities are strongly modulated by the corresponding occupied states. These unoccupied states are thus consistent with the prediction from a cluster perturbation theory based on the single-band Hubbard model. Through this comparison, amore » Coulomb interaction strength U of 2.7 eV is extracted. Our study complements equilibrium photoemission spectroscopy and provides a direct spectroscopic measurement of the unoccupied states in cuprates. The determined Coulomb U indicates that the charge-transfer gap of optimally doped Bi2212 is 1.1 eV.« less

  10. 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.

  11. Note: A simple multi-channel optical system for modulation spectroscopies.

    PubMed

    Solís-Macías, J; Sánchez-López, J D; Castro-García, R; Flores-Camacho, J M; Flores-Rangel, G; Ciou, Jian-Jhih; Chen, Kai-Wei; Chen, Chang-Hsiao; Lastras-Martínez, L F; Balderas-Navarro, R E

    2017-12-01

    Photoreflectance-difference (PR/PRD) and reflectance-difference (RD) spectroscopies employ synchronic detection usually with lock-in amplifiers operating at moderate (200-1000 Hz) and high (50-100 KHz) modulation frequencies, respectively. Here, we report a measurement system for these spectroscopies based on a multichannel CCD spectrometer without a lock-in amplifier. In the proposed scheme, a typical PRD or RD spectrum consists of numerical subtractions between a thousand CCD captures recorded, while a photoelastic modulator is either operating or inhibited. This is advantageous and fits the slow response of CCD detectors to high modulation frequencies. The resulting spectra are processed with Savitzky-Golay filtering and compared well with those measured with conventional scanning systems based on lock-in amplifiers.

  12. Determination of molecular spectroscopic parameters and energy-transfer rates by double-resonance spectroscopy

    NASA Technical Reports Server (NTRS)

    Steinfeld, J. I.; Foy, B.; Hetzler, J.; Flannery, C.; Klaassen, J.; Mizugai, Y.; Coy, S.

    1990-01-01

    The spectroscopy of small to medium-size polyatomic molecules can be extremely complex, especially in higher-lying overtone and combination vibrational levels. The high density of levels also complicates the understanding of inelastic collision processes, which is required to model energy transfer and collision broadening of spectral lines. Both of these problems can be addressed by double-resonance spectroscopy, i.e., time-resolved pump-probe measurements using microwave, infrared, near-infrared, and visible-wavelength sources. Information on excited-state spectroscopy, transition moments, inelastic energy transfer rates and propensity rules, and pressure-broadening parameters may be obtained from such experiments. Examples are given for several species of importance in planetary atmospheres, including ozone, silane, ethane, and ammonia.

  13. Characterization of a commercial software defined radio as high frequency lock-in amplifier for FM spectroscopy.

    PubMed

    Mahnke, Peter

    2018-01-01

    A commercial software defined radio based on a Rafael Micro R820T2 tuner is characterized for the use as a high-frequency lock-in amplifier for frequency modulation spectroscopy. The sensitivity limit of the receiver is 1.6 nV/Hz. Frequency modulation spectroscopy is demonstrated on the 6406.69 cm -1 absorption line of carbon monoxide.

  14. Characterization of a commercial software defined radio as high frequency lock-in amplifier for FM spectroscopy

    NASA Astrophysics Data System (ADS)

    Mahnke, Peter

    2018-01-01

    A commercial software defined radio based on a Rafael Micro R820T2 tuner is characterized for the use as a high-frequency lock-in amplifier for frequency modulation spectroscopy. The sensitivity limit of the receiver is 1.6 nV/√{Hz }. Frequency modulation spectroscopy is demonstrated on the 6406.69 cm-1 absorption line of carbon monoxide.

  15. 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

  16. Signatures of Förster and Dexter transfer processes in coupled nanostructures for linear and two-dimensional coherent optical spectroscopy

    NASA Astrophysics Data System (ADS)

    Specht, Judith F.; Richter, Marten

    2015-03-01

    In this manuscript, we study the impact of the two Coulomb induced resonance energy transfer processes, Förster and Dexter coupling, on the spectral signatures obtained by double quantum coherence spectroscopy. We show that the specific coupling characteristics allow us to identify the underlying excitation transfer mechanism by means of specific signatures in coherent spectroscopy. Therefore, we control the microscopic calculated coupling strength of spin preserving and spin flipping Förster transfer processes by varying the mutual orientation of the two quantum emitters. The calculated spectra reveal the optical selection rules altered by Förster and Dexter coupling between two semiconductor quantum dots. We show that Dexter coupling between bright and dark two-exciton states occurs.

  17. Molecular oxygen detection using frequency modulation diode laser spectroscopy

    NASA Technical Reports Server (NTRS)

    Wang, Liang-Guo; Sachse, Glen

    1990-01-01

    A high-sensitivity spectroscopic measurement of O2 using two-tone frequency modulation spectroscopy with a GaAlAs diode laser is presented. An oxygen sensor based on this technique would be non-intrusive, compact and possess high sensitivity and fast time response.

  18. Metallic transfer between metals in sliding contact examined by auger emission spectroscopy

    NASA Technical Reports Server (NTRS)

    Pepper, S. V.

    1972-01-01

    Metallic transfer between polycrystalline metals in sliding contact was examined. Hemispherical riders of iron, nickel, and cobalt were slid on tungsten, tantalum, niobium, and molybdenum disks in ultrahigh vacuum. Auger emission spectroscopy was used to monitor the elemental composition of the disk surfaces. Iron, nickel, and cobalt transferred to tungsten, whereas only cobalt transferred to tantalum, niobium, and molybdenum. The results of this investigation are discussed in terms of the cohesive energy and strain hardening characteristics of the specimen materials.

  19. Simultaneous quantification of glutamate and glutamine by J-modulated spectroscopy at 3 Tesla.

    PubMed

    Zhang, Yan; Shen, Jun

    2016-09-01

    The echo time (TE) averaged spectrum is the one-dimensional (1D) cross-section of the J-resolved spectrum at J = 0. In multiecho TE-averaged spectroscopy, glutamate (Glu) is differentiated from glutamine (Gln) at 3 Tesla (T). This method, however, almost entirely suppresses Gln resonance lines around 2.35 ppm, leaving Gln undetermined. This study presents a novel method for quantifying both Glu and Gln using multi-echo spectral data. A 1D cross-section of J-resolved spectroscopy at J = 7.5 Hz-referred to as J-modulated spectroscopy-was developed to simultaneously quantify Glu and Gln levels in the human brain. The transverse relaxation times (T2 s) of metabolites were first determined using conventional TE-averaged spectroscopy with different starting echo time and then incorporated into the spectral model for fitting J-modulated data. Simulation and in vivo data showed that the resonance signals of Glu and Gln were clearly separated around 2.35 ppm in J-modulated spectroscopy. In the anterior cingulate cortex, both Glu and Gln levels were found to be significantly higher in gray matter than in white matter in healthy subjects (P < 10(-10) and < 10(-5) , respectively). Gln resonances can be clearly separated from Glu and N-acetyl-aspartate around 2.35 ppm using J-modulated spectroscopy. This method can be used to quantitatively measure Glu and Gln simultaneously at 3T. Magn Reson Med 76:725-732, 2016. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Published 2015. This article is a U.S. Government work and is in the public domain in the USA.

  20. Accumulation effects in modulation spectroscopy with high-repetition-rate pulses: Recursive solution of optical Bloch equations

    NASA Astrophysics Data System (ADS)

    Osipov, Vladimir Al.; Pullerits, Tõnu

    2017-10-01

    Application of the phase-modulated pulsed light for advance spectroscopic measurements is the area of growing interest. The phase modulation of the light causes modulation of the signal. Separation of the spectral components of the modulations allows to distinguish the contributions of various interaction pathways. The lasers with high repetition rate used in such experiments can lead to appearance of the accumulation effects, which become especially pronounced in systems with long-living excited states. Recently it was shown that such accumulation effects can be used to evaluate parameters of the dynamical processes in the material. In this work we demonstrate that the accumulation effects are also important in the quantum characteristics measurements provided by modulation spectroscopy. In particular, we consider a model of quantum two-level system driven by a train of phase-modulated light pulses, organized in analogy with the two-dimensional spectroscopy experiments. We evaluate the harmonics' amplitudes in the fluorescent signal and calculate corrections appearing from the accumulation effects. We show that the corrections can be significant and have to be taken into account at analysis of experimental data.

  1. Spin-Label CW Microwave Power Saturation and Rapid Passage with Triangular Non-Adiabatic Rapid Sweep (NARS) and Adiabatic Rapid Passage (ARP) EPR Spectroscopy

    PubMed Central

    Kittell, Aaron W.; Hyde, James S.

    2015-01-01

    Non-adiabatic rapid passage (NARS) electron paramagnetic resonance (EPR) spectroscopy was introduced by Kittell, A.W., Camenisch, T.G., Ratke, J.J. Sidabras, J.W., Hyde, J.S., 2011 as a general purpose technique to collect the pure absorption response. The technique has been used to improve sensitivity relative to sinusoidal magnetic field modulation, increase the range of inter-spin distances that can be measured under near physiological conditions, and enhance spectral resolution in copper (II) spectra. In the present work, the method is extended to CW microwave power saturation of spin-labeled T4 Lysozyme (T4L). As in the cited papers, rapid triangular sweep of the polarizing magnetic field was superimposed on slow sweep across the spectrum. Adiabatic rapid passage (ARP) effects were encountered in samples undergoing very slow rotational diffusion as the triangular magnetic field sweep rate was increased. The paper reports results of variation of experimental parameters at the interface of adiabatic and non-adiabatic rapid sweep conditions. Comparison of the forward (up) and reverse (down) triangular sweeps is shown to be a good indicator of the presence of rapid passage effects. Spectral turning points can be distinguished from spectral regions between turning points in two ways: differential microwave power saturation and differential passage effects. Oxygen accessibility data are shown under NARS conditions that appear similar to conventional field modulation data. However, the sensitivity is much higher, permitting, in principle, experiments at substantially lower protein concentrations. Spectral displays were obtained that appear sensitive to rotational diffusion in the range of rotational correlation times of 10−3 to 10−7 s in a manner that is analogous to saturation transfer spectroscopy. PMID:25917132

  2. Ultrasensitive detection of atmospheric trace gases using frequency modulation spectroscopy

    NASA Technical Reports Server (NTRS)

    Cooper, David E.

    1986-01-01

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

  3. Laser frequency-offset locking based on the frequency modulation spectroscopy with higher harmonic detection

    NASA Astrophysics Data System (ADS)

    Wang, Anqi; Meng, Zhixin; Feng, Yanying

    2017-10-01

    We design a fiber electro-optic modulator (FEOM)-based laser frequency-offset locking system using frequency modulation spectroscopy (FMS) with the 3F modulation. The modulation signal and the frequency-offset control signal are simultaneously loaded on the FEOM by a mixer in order to suppress the frequency and power jitter caused by internal modulation on the current or piezoelectric ceramic transducer (PZT). It is expected to accomplish a fast locking, a widely tunable frequency-offset, a sensitive and rapid detection of narrow spectral features with the 3F modulation. The laser frequency fluctuation is limited to +/-1MHz and its overlapping Allan deviation is around 10-12 in twenty minutes, which successfully meets the requirements of the cold atom interferometer.

  4. Elimination of residual amplitude modulation in tunable diode laser wavelength modulation spectroscopy using an optical fiber delay line.

    PubMed

    Chakraborty, Arup Lal; Ruxton, Keith; Johnstone, Walter; Lengden, Michael; Duffin, Kevin

    2009-06-08

    A new fiber-optic technique to eliminate residual amplitude modulation in tunable diode laser wavelength modulation spectroscopy is presented. The modulated laser output is split to pass in parallel through the gas measurement cell and an optical fiber delay line, with the modulation frequency / delay chosen to introduce a relative phase shift of pi between them. The two signals are balanced using a variable attenuator and recombined through a fiber coupler. In the absence of gas, the direct laser intensity modulation cancels, thereby eliminating the high background. The presence of gas induces a concentration-dependent imbalance at the coupler's output from which the absolute absorption profile is directly recovered with high accuracy using 1f detection.

  5. Performance of the Versatile Array of Neutron Detectors at Low Energy (VANDLE)

    DOE PAGES

    Peters, W. A.; Ilyushkin, S.; Madurga, M.; ...

    2016-08-26

    The Versatile Array of Neutron Detectors at Low Energy (VANDLE) is a new, highly efficient plastic-scintillator array constructed for decay and transfer reaction experimental setups that require neutron detection. The versatile and modular design allows for customizable experimental setups including beta-delayed neutron spectroscopy and (d,n) transfer reactions in normal and inverse kinematics. The neutron energy and prompt-photon discrimination is determined through the time of flight technique. Fully digital data acquisition electronics and integrated triggering logic enables some VANDLE modules to achieve an intrinsic efficiency over 70% for 300-keV neutrons, measured through two different methods. A custom Geant4 simulation models aspectsmore » of the detector array and the experimental setups to determine efficiency and detector response. Lastly, a low detection threshold, due to the trigger logic and digitizing data acquisition, allowed us to measure the light-yield response curve from elastically scattered carbon nuclei inside the scintillating plastic from incident neutrons with kinetic energies below 2 MeV.« less

  6. Pathways of energy transfer in LHCII revealed by room-temperature 2D electronic spectroscopy.

    PubMed

    Wells, Kym L; Lambrev, Petar H; Zhang, Zhengyang; Garab, Gyözö; Tan, Howe-Siang

    2014-06-21

    We present here the first room-temperature 2D electronic spectroscopy study of energy transfer in the plant light-harvesting complex II, LHCII. Two-dimensional electronic spectroscopy has been used to study energy transfer dynamics in LHCII trimers from the chlorophyll b Qy band to the chlorophyll a Qy band. Observing cross-peak regions corresponding to couplings between different excitonic states reveals partially resolved fine structure at the exciton level that cannot be isolated by pump-probe or linear spectroscopy measurements alone. Global analysis of the data has been performed to identify the pathways and time constants of energy transfer. The measured waiting time (Tw) dependent 2D spectra are found to be composed of 2D decay-associated spectra with three timescales (0.3 ps, 2.3 ps and >20 ps). Direct and multistep cascading pathways from the high-energy chlorophyll b states to the lowest-energy chlorophyll a states have been resolved occurring on time scales of hundreds of femtoseconds to picoseconds.

  7. Controlling data transfers from an origin compute node to a target compute node

    DOEpatents

    Archer, Charles J [Rochester, MN; Blocksome, Michael A [Rochester, MN; Ratterman, Joseph D [Rochester, MN; Smith, Brian E [Rochester, MN

    2011-06-21

    Methods, apparatus, and products are disclosed for controlling data transfers from an origin compute node to a target compute node that include: receiving, by an application messaging module on the target compute node, an indication of a data transfer from an origin compute node to the target compute node; and administering, by the application messaging module on the target compute node, the data transfer using one or more messaging primitives of a system messaging module in dependence upon the indication.

  8. Intracavity Faraday modulation spectroscopy (INFAMOS): A tool for radical detection

    NASA Astrophysics Data System (ADS)

    Gianella, Michele; Pinto, Tomas H. P.; Wu, Xia; Ritchie, Grant A. D.

    2017-08-01

    We present the intra-cavity Faraday modulation spectroscopy technique, whereby optical feedback cavity-enhanced spectroscopy is coupled with Faraday modulation spectroscopy to greatly enhance the interaction path length of a laser beam with a paramagnetic sample in a magnetic field. We describe a first prototype based upon a cw quantum cascade laser targeting a selection of fundamental rovibrational R-branch transitions of nitric oxide (1890 cm-1), consisting of a linear cavity (finesse F =6300 ) and a water-cooled solenoid. We demonstrate a minimum detectable Verdet constant of Vmin=4.7 ×10-14 rad cm-1 G-1 H z-1/2 (at SNR = 1), corresponding to a single-pass rotation angle of 1.6 ×10-10 rad Hz-1/2 and a limit of detection of 0.21 ppbv Hz-1/2 NO.

  9. Fluid Properties Measurements Using Wavelength Modulation Spectroscopy with First Harmonic Detection

    NASA Technical Reports Server (NTRS)

    Silver, Joel A. (Inventor); Chen, Shin-Juh (Inventor)

    2014-01-01

    An apparatus and method for monitoring gas velocity, temperature, and pressure in combustion systems and flow devices, in particular at inlets and isolators of scramjet engines. The invention employs wavelength modulation spectroscopy with first harmonic detection and without the need to scan the full absorption spectra.

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

    PubMed

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

    2012-02-13

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

  11. Molecule-Doped Nickel Oxide: Verified Charge Transfer and Planar Inverted Mixed Cation Perovskite Solar Cell.

    PubMed

    Chen, Wei; Zhou, Yecheng; Wang, Linjing; Wu, Yinghui; Tu, Bao; Yu, Binbin; Liu, Fangzhou; Tam, Ho-Won; Wang, Gan; Djurišić, Aleksandra B; Huang, Li; He, Zhubing

    2018-05-01

    Both conductivity and mobility are essential to charge transfer by carrier transport layers (CTLs) in perovskite solar cells (PSCs). The defects derived from generally used ionic doping method lead to the degradation of carrier mobility and parasite recombinations. In this work, a novel molecular doping of NiO x hole transport layer (HTL) is realized successfully by 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile (F6TCNNQ). Determined by X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy, the Fermi level (E F ) of NiO x HTLs is increased from -4.63 to -5.07 eV and valence band maximum (VBM)-E F declines from 0.58 to 0.29 eV after F6TCNNQ doping. The energy level offset between the VBMs of NiO x and perovskites declines from 0.18 to 0.04 eV. Combining with first-principle calculations, electrostatic force microscopy is applied for the first time to verify direct electron transfer from NiO x to F6TCNNQ. The average power conversion efficiency of CsFAMA mixed cation PSCs is boosted by ≈8% depending on F6TCNNQ-doped NiOx HTLs. Strikingly, the champion cell conversion efficiency of CsFAMA mixed cations and MAPbI 3 -based devices gets to 20.86% and 19.75%, respectively. Different from passivation effect, the results offer an extremely promising molecular doping method for inorganic CTLs in PSCs. This methodology definitely paves a novel way to modulate the doping in hybrid electronics more than perovskite and organic solar cells. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Handling the influence of chemical shift in amplitude-modulated heteronuclear dipolar recoupling solid-state NMR

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

    Basse, Kristoffer; Shankar, Ravi; Bjerring, Morten

    We present a theoretical analysis of the influence of chemical shifts on amplitude-modulated heteronuclear dipolar recoupling experiments in solid-state NMR spectroscopy. The method is demonstrated using the Rotor Echo Short Pulse IRrAdiaTION mediated Cross-Polarization ({sup RESPIRATION}CP) experiment as an example. By going into the pulse sequence rf interaction frame and employing a quintuple-mode operator-based Floquet approach, we describe how chemical shift offset and anisotropic chemical shift affect the efficiency of heteronuclear polarization transfer. In this description, it becomes transparent that the main attribute leading to non-ideal performance is a fictitious field along the rf field axis, which is generated frommore » second-order cross terms arising mainly between chemical shift tensors and themselves. This insight is useful for the development of improved recoupling experiments. We discuss the validity of this approach and present quaternion calculations to determine the effective resonance conditions in a combined rf field and chemical shift offset interaction frame transformation. Based on this, we derive a broad-banded version of the {sup RESPIRATION}CP experiment. The new sequence is experimentally verified using SNNFGAILSS amyloid fibrils where simultaneous {sup 15}N → {sup 13}CO and {sup 15}N → {sup 13}C{sub α} coherence transfer is demonstrated on high-field NMR instrumentation, requiring great offset stability.« less

  13. Proton transfer from imidazole to chloranil studied by FTIR spectroscopy

    NASA Astrophysics Data System (ADS)

    Sharma, Amit

    2018-05-01

    Imidazole is incorporated into many important biological molecules. The most obvious is the amino acid histidine, which has an imidazole side chain. Histidine is present in many proteins and enzymes and plays a vital part in the structure and binding functions of hemoglobin. Therefore it is important to study its proton transfer property. In the present work proton transfer from imidazole to chloranil is investigated by Fourier Transform Infra red Spectroscopy.

  14. Single-molecule interfacial electron transfer dynamics in solar energy conversion

    NASA Astrophysics Data System (ADS)

    Dhital, Bharat

    This dissertation work investigated the parameters affecting the interfacial electron transfer (ET) dynamics in dye-semiconductor nanoparticles (NPs) system by using single-molecule fluorescence spectroscopy and imaging combined with electrochemistry. The influence of the molecule-substrate electronic coupling, the molecular structure, binding geometry on the surface and the molecule-attachment surface chemistry on interfacial charge transfer processes was studied on zinc porphyrin-TiO2 NP systems. The fluorescence blinking measurement on TiO2 NP demonstrated that electronic coupling regulates dynamics of charge transfer processes at the interface depending on the conformation of molecule on the surface. Moreover, semiconductor surface charge induced electronic coupling of molecule which is electrostatically adsorbed on the semiconductor surface also predominantly alters the ET dynamics. Furthermore, interfacial electric field and electron accepting state density dependent ET dynamics has been dissected in zinc porphyrin-TiO2 NP system by observing the single-molecule fluorescence blinking dynamics and fluorescence lifetime with and without applied bias. The significant difference in fluorescence fluctuation and lifetime suggested the modulation of charge transfer dynamics at the interface with external electric field perturbation. Quasi-continuous distribution of fluorescence intensity with applied negative potential was attributed to the faster charge recombination due to reduced density of electron accepting states. The driving force and electron accepting state density ET dependent dynamics has also been probed in zinc porphyrin-TiO2 NP and zinc porphyrin-indium tin oxide (ITO) systems. Study of a molecule adsorbed on two different semiconductors (ITO and TiO2), with large difference in electron densities and distinct driving forces, allows us to observe the changes in rates of back electron transfer process reflected by the suppressed fluorescence blinking of molecule on ITO surface. Finally, the electric field effect on the interface properties has been probed by using surface-enhanced Raman spectroscopy and supported by density functional theory calculations in alizarin-TiO2 system. The perturbation, created by the external potential, has been observed to cause a shift and/or splitting interfacial bond vibrational mode, typical indicator of the coupling energy changes between alizarin and TiO2. Such splitting provides evidence for electric field-dependent electronic coupling changes that have a significant impact on the interfacial electron transfer dynamics.

  15. Description of the docking module ECS for the Apollo-Soyuz Test Project.

    NASA Technical Reports Server (NTRS)

    Guy, W. W.; Jaax, J. R.

    1973-01-01

    The role of the Docking Module ECS (Environmental Control System) to be used on the Apollo-Soyuz Test mission is to provide a means for crewmen to transfer safely between the Apollo and Soyuz vehicles in a shirtsleeve environment. This paper describes the Docking Module ECS and includes the philosophy and rationale used in evaluating and selecting the capabilities that are required to satisfy the Docking Module's airlock function: (1) adjusting the pressure and composition of the atmosphere to effect crew transfer and (2) providing a shirtsleeve environment during transfer operations. An analytical evaluation is given of the environmental parameters (including CO2 level, humidity, and temperature) during a normal transfer timeline.

  16. Adhesion and transfer of PTFE to metals studied by auger emission spectroscopy

    NASA Technical Reports Server (NTRS)

    Pepper, S. V.; Buckley, D. H.

    1972-01-01

    The adhesion and transfer of polytetrafluoroethylene (PTFE) to metals in ultrahigh vacuum has been studied using Auger emission spectroscopy. The transfer was effected both by compressive static contact and by sliding contact. The transfer observed after static contact was independent of the chemical constitution of the substrate. Electron induced desorption of the fluorine in the transferred PTFE showed that the fluorine had no chemical interaction with the metal substrate. The coefficient of friction on metals was independent of the chemical constitution of the substrate. However, sliding PTFE on soft metals such as aluminum, generated wear fragments that lodged in the PTFE and machined the substrate.

  17. Broadband Doppler-limited two-photon and stepwise excitation spectroscopy with laser frequency combs

    NASA Astrophysics Data System (ADS)

    Hipke, Arthur; Meek, Samuel A.; Ideguchi, Takuro; Hänsch, Theodor W.; Picqué, Nathalie

    2014-07-01

    Multiplex two-photon excitation spectroscopy is demonstrated at Doppler-limited resolution. We describe first Fourier-transform two-photon spectroscopy of an atomic sample with two mode-locked laser oscillators in a dual-comb technique. Each transition is uniquely identified by the modulation imparted by the interfering comb excitations. The temporal modulation of the spontaneous two-photon fluorescence is monitored with a single photodetector, and the spectrum of all excited transitions is revealed by a Fourier transform.

  18. Intracavity Faraday modulation spectroscopy (INFAMOS): A tool for radical detection.

    PubMed

    Gianella, Michele; Pinto, Tomas H P; Wu, Xia; Ritchie, Grant A D

    2017-08-07

    We present the intra-cavity Faraday modulation spectroscopy technique, whereby optical feedback cavity-enhanced spectroscopy is coupled with Faraday modulation spectroscopy to greatly enhance the interaction path length of a laser beam with a paramagnetic sample in a magnetic field. We describe a first prototype based upon a cw quantum cascade laser targeting a selection of fundamental rovibrational R-branch transitions of nitric oxide (1890 cm -1 ), consisting of a linear cavity (finesse F=6300) and a water-cooled solenoid. We demonstrate a minimum detectable Verdet constant of V min =4.7×10 -14  rad cm -1  G -1  Hz -1/2 (at SNR = 1), corresponding to a single-pass rotation angle of 1.6×10 -10  rad Hz -1/2 and a limit of detection of 0.21 ppbv Hz -1/2 NO.

  19. Module for multiphoton high-resolution hyperspectral imaging and spectroscopy

    NASA Astrophysics Data System (ADS)

    Zeytunyan, Aram; Baldacchini, Tommaso; Zadoyan, Ruben

    2018-02-01

    We developed a module for dual-output, dual-wavelength lasers that facilitates multiphoton imaging and spectroscopy experiments and enables hyperspectral imaging with spectral resolution up to 5 cm-1. High spectral resolution is achieved by employing spectral focusing. Specifically, two sets of grating pairs are used to control the chirps in each laser beam. In contrast with the approach that uses fixed-length glass rods, grating pairs allow matching the spectral resolution and the linewidths of the Raman lines of interest. To demonstrate the performance of the module, we report the results of spectral focusing CARS and SRS microscopy experiments for various test samples and Raman shifts. The developed module can be used for a variety of multimodal imaging and spectroscopy applications, such as single- and multi-color two-photon fluorescence, second harmonic generation, third harmonic generation, pump-probe, transient absorption, and others.

  20. Rydberg-atom based radio-frequency electrometry using frequency modulation spectroscopy in room temperature vapor cells.

    PubMed

    Kumar, Santosh; Fan, Haoquan; Kübler, Harald; Jahangiri, Akbar J; Shaffer, James P

    2017-04-17

    Rydberg atom-based electrometry enables traceable electric field measurements with high sensitivity over a large frequency range, from gigahertz to terahertz. Such measurements are particularly useful for the calibration of radio frequency and terahertz devices, as well as other applications like near field imaging of electric fields. We utilize frequency modulated spectroscopy with active control of residual amplitude modulation to improve the signal to noise ratio of the optical readout of Rydberg atom-based radio frequency electrometry. Matched filtering of the signal is also implemented. Although we have reached similarly, high sensitivity with other read-out methods, frequency modulated spectroscopy is advantageous because it is well-suited for building a compact, portable sensor. In the current experiment, ∼3 µV cm-1 Hz-1/2 sensitivity is achieved and is found to be photon shot noise limited.

  1. Factors affecting hydrogen-tunneling contribution in hydroxylation reactions promoted by oxoiron(IV) porphyrin π-cation radical complexes.

    PubMed

    Cong, Zhiqi; Kinemuchi, Haruki; Kurahashi, Takuya; Fujii, Hiroshi

    2014-10-06

    Hydrogen atom transfer with a tunneling effect (H-tunneling) has been proposed to be involved in aliphatic hydroxylation reactions catalyzed by cytochrome P450 and synthetic heme complexes as a result of the observation of large hydrogen/deuterium kinetic isotope effects (KIEs). In the present work, we investigate the factors controlling the H-tunneling contribution to the H-transfer process in hydroxylation reaction by examining the kinetics of hydroxylation reactions at the benzylic positions of xanthene and 1,2,3,4-tetrahydronaphthalene by oxoiron(IV) 5,10,15,20-tetramesitylporphyrin π-cation radical complexes ((TMP(+•))Fe(IV)O(L)) under single-turnover conditions. The Arrhenius plots for these hydroxylation reactions of H-isotopomers have upwardly concave profiles. The Arrhenius plots of D-isotopomers, clear isosbestic points, and product analysis rule out the participation of thermally dependent other reaction processes in the concave profiles. These results provide evidence for the involvement of H-tunneling in the rate-limiting H-transfer process. These profiles are simulated using an equation derived from Bell's tunneling model. The temperature dependence of the KIE values (k(H)/k(D)) determined for these reactions indicates that the KIE value increases as the reaction temperature becomes lower, the bond dissociation energy (BDE) of the C-H bond of a substrate becomes higher, and the reactivity of (TMP(+•))Fe(IV)O(L) decreases. In addition, we found correlation of the slope of the ln(k(H)/k(D)) - 1/T plot and the bond strengths of the Fe═O bond of (TMP(+•))Fe(IV)O(L) estimated from resonance Raman spectroscopy. These observations indicate that these factors modulate the extent of the H-tunneling contribution by modulating the ratio of the height and thickness of the reaction barrier.

  2. Fluorescence Spectroscopy in Thermodynamic and Kinetic Analysis of pH-Dependent Membrane Protein Insertion

    PubMed Central

    Ladokhin, Alexey S.

    2016-01-01

    Experimental determination of the free energy stabilizing the structure of membrane proteins in their native lipid environment is undermined by a lack of appropriate methods and suitable model systems. Here, we demonstrate how fluorescence correlation spectroscopy can be used to characterize thermodynamics of pH-triggered bilayer insertion of nonconstitutive membrane proteins (e.g., bacterial toxins, colicins). The experimental design is guided by the appropriate thermodynamic scheme which considers two independent processes: pH-dependent formation of a membrane-competent form and its insertion into the lipid bilayer. Measurements of a model protein annexin B12 under conditions of lipid saturation demonstrate that protonation leading to the formation of the membrane-competent state occurs near membrane interface. Lipid titration experiments demonstrate that the free energy of transfer to the intermediate interfacial state is especially favorable, while the free energy of final insertion is modulated by interplay of hydrophobic and electrostatic interactions on the bilayer interface. The general principles of kinetic measurements along the insertion pathway containing interfacial intermediate are discussed and practical examples emphasizing appropriate fitting and normalization procedures are presented. PMID:21609856

  3. Frequency modulation spectroscopy with a THz quantum-cascade laser.

    PubMed

    Eichholz, R; Richter, H; Wienold, M; Schrottke, L; Hey, R; Grahn, H T; Hübers, H-W

    2013-12-30

    We report on a terahertz spectrometer for high-resolution molecular spectroscopy based on a quantum-cascade laser. High-frequency modulation (up to 50 MHz) of the laser driving current produces a simultaneous modulation of the frequency and amplitude of the laser output. The modulation generates sidebands, which are symmetrically positioned with respect to the laser carrier frequency. The molecular transition is probed by scanning the sidebands across it. In this way, the absorption and the dispersion caused by the molecular transition are measured. The signals are modeled by taking into account the simultaneous modulation of the frequency and amplitude of the laser emission. This allows for the determination of the strength of the frequency as well as amplitude modulation of the laser and of molecular parameters such as pressure broadening.

  4. ULTRAFAST CHEMISTRY: Using Time-Resolved Vibrational Spectroscopy for Interrogation of Structural Dynamics

    NASA Astrophysics Data System (ADS)

    Nibbering, Erik T. J.; Fidder, Henk; Pines, Ehud

    2005-05-01

    Time-resolved infrared (IR) and Raman spectroscopy elucidates molecular structure evolution during ultrafast chemical reactions. Following vibrational marker modes in real time provides direct insight into the structural dynamics, as is evidenced in studies on intramolecular hydrogen transfer, bimolecular proton transfer, electron transfer, hydrogen bonding during solvation dynamics, bond fission in organometallic compounds and heme proteins, cis-trans isomerization in retinal proteins, and transformations in photochromic switch pairs. Femtosecond IR spectroscopy monitors the site-specific interactions in hydrogen bonds. Conversion between excited electronic states can be followed for intramolecular electron transfer by inspection of the fingerprint IR- or Raman-active vibrations in conjunction with quantum chemical calculations. Excess internal vibrational energy, generated either by optical excitation or by internal conversion from the electronic excited state to the ground state, is observable through transient frequency shifts of IR-active vibrations and through nonequilibrium populations as deduced by Raman resonances.

  5. Probing the rate-limiting step for intramolecular transfer of a transcription factor between specific sites on the same DNA molecule by (15)Nz-exchange NMR spectroscopy.

    PubMed

    Ryu, Kyoung-Seok; Tugarinov, Vitali; Clore, G Marius

    2014-10-15

    The kinetics of translocation of the homeodomain transcription factor HoxD9 between specific sites of the same or opposite polarities on the same DNA molecule have been studied by (15)Nz-exchange NMR spectroscopy. We show that exchange occurs by two facilitated diffusion mechanisms: a second-order intermolecular exchange reaction between specific sites located on different DNA molecules without the protein dissociating into free solution that predominates at high concentrations of free DNA, and a first-order intramolecular process involving direct transfer between specific sites located on the same DNA molecule. Control experiments using a mixture of two DNA molecules, each possessing only a single specific site, indicate that transfer between specific sites by full dissociation of HoxD9 into solution followed by reassociation is too slow to measure by z-exchange spectroscopy. Intramolecular transfer with comparable rate constants occurs between sites of the same and opposing polarity, indicating that both rotation-coupled sliding and hopping/flipping (analogous to geminate recombination) occur. The half-life for intramolecular transfer (0.5-1 s) is many orders of magnitude larger than the calculated transfer time (1-100 μs) by sliding, leading us to conclude that the intramolecular transfer rates measured by z-exchange spectroscopy represent the rate-limiting step for a one-base-pair shift from the specific site to the immediately adjacent nonspecific site. At zero concentration of added salt, the intramolecular transfer rate constants between sites of opposing polarity are smaller than those between sites of the same polarity, suggesting that hopping/flipping may become rate-limiting at very low salt concentrations.

  6. Dimensionless figure of merit and its efficiency estimation for transient response of thermoelectric module based on impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Otsuka, Mioko; Hasegawa, Yasuhiro; Arisaka, Taichi; Shinozaki, Ryo; Morita, Hiroyuki

    2017-11-01

    The dimensionless figure of merit and its efficiency for the transient response of a Π-shaped thermoelectric module are estimated according to the theory of impedance spectroscopy. The effective dimensionless figure of merit is described as a function of the product of the characteristic time to reduce the temperature and the representative angular frequency of the module, which is expressed by the thermal diffusivity and the length of the elements used. The characteristic time required for achieving a higher dimensionless figure of merit and efficiency is derived quantitatively for the transient response using the properties of a commercial thermoelectric module.

  7. [Signal analysis and spectrum distortion correction for tunable diode laser absorption spectroscopy system].

    PubMed

    Bao, Wei-Yi; Zhu, Yong; Chen, Jun; Chen, Jun-Qing; Liang, Bo

    2011-04-01

    In the present paper, the signal of a tunable diode laser absorption spectroscopy (TDLAS) trace gas sensing system, which has a wavelength modulation with a wide range of modulation amplitudes, is studied based on Fourier analysis method. Theory explanation of spectrum distortion induced by laser intensity amplitude modulation is given. In order to rectify the spectrum distortion, a method of synchronous amplitude modulation suppression by a variable optical attenuator is proposed. To validate the method, an experimental setup is designed. Absorption spectrum measurement experiments on CO2 gas were carried out. The results show that the residual laser intensity modulation amplitude of the experimental system is reduced to -0.1% of its original value and the spectrum distortion improvement is 92% with the synchronous amplitude modulation suppression. The modulation amplitude of laser intensity can be effectively reduced and the spectrum distortion can be well corrected by using the given correction method and system. By using a variable optical attenuator in the TDLAS (tunable diode laser absorption spectroscopy) system, the dynamic range requirements of photoelectric detector, digital to analog converter, filters and other aspects of the TDLAS system are reduced. This spectrum distortion correction method can be used for online trace gas analyzing in process industry.

  8. Coherent Electron Transfer at the Ag / Graphite Heterojunction Interface

    NASA Astrophysics Data System (ADS)

    Tan, Shijing; Dai, Yanan; Zhang, Shengmin; Liu, Liming; Zhao, Jin; Petek, Hrvoje

    2018-03-01

    Charge transfer in transduction of light to electrical or chemical energy at heterojunctions of metals with semiconductors or semimetals is believed to occur by photogenerated hot electrons in metal undergoing incoherent internal photoemission through the heterojunction interface. Charge transfer, however, can also occur coherently by dipole coupling of electronic bands at the heterojunction interface. Microscopic physical insights into how transfer occurs can be elucidated by following the coherent polarization of the donor and acceptor states on the time scale of electronic dephasing. By time-resolved multiphoton photoemission spectroscopy (MPP), we investigate the coherent electron transfer from an interface state that forms upon chemisorption of Ag nanoclusters onto graphite to a σ symmetry interlayer band of graphite. Multidimensional MPP spectroscopy reveals a resonant two-photon transition, which dephases within 10 fs completing the coherent transfer.

  9. Computational expressions for signals in frequency-modulation spectroscopy.

    PubMed

    Di Rosa, Michael D; Reiten, M T

    2015-06-01

    General expressions for the signals in frequency-modulation spectroscopy (FMS) appear in the literature but are often reduced to simple analytical equations following the assumption of a weak modulation index. This is little help to the experimentalist who wants to predict signals for modulation depths of the order of unity or greater, where strong FMS signals reside. Here, we develop general formulas for FMS signals in the case of an absorber with a Voigt line shape and then link these expressions to an example and existing numerical code for the line shape. The resulting computational recipe is easy to implement and exercised here to show where the larger FMS signals are found over the coordinates of modulation index and modulation frequency. One can also estimate from provided curves the in-phase FMS signal over a wide range of modulation parameters at either the Lorentzian-broadening or Doppler-broadening limit, or anywhere in between by interpolation.

  10. Comparative Study of 28 and 18 Years Field Aged Siemens-Arco M55 Modules in Temperate and Hot-Dry Climates

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

    Chicca, Matthew; Wohlgemuth, John; TamizhMani, GovindaSamy

    The primary objective of this research work is two-fold: (i) determine the degradation rates of Siemens-Arco M55 modules exposed over 18 and 28 years in a hot-dry climate of Arizona and a temperate climate of California, and; (ii) identify the potential modes responsible for these degradation losses. The degradation rates were determined based on the I-V data obtained on exposed modules and on the corresponding control modules which were not exposed in the fields. The degradation modes responsible for these degradations were determined using several nondestructive tests and destructive tests performed on these control and exposed modules. The nondestructive testsmore » included: current-voltage, visual inspection, cell-module quantum efficiency, and module level reflectance spectroscopy. The destructive tests included: transmittance spectroscopy of glass superstrates, and FTIR, DSC and TGA of encapsulant materials.« less

  11. Enantiomeric switching of chiral metamaterial for terahertz polarization modulation employing vertically deformable MEMS spirals

    NASA Astrophysics Data System (ADS)

    Kan, Tetsuo; Isozaki, Akihiro; Kanda, Natsuki; Nemoto, Natsuki; Konishi, Kuniaki; Takahashi, Hidetoshi; Kuwata-Gonokami, Makoto; Matsumoto, Kiyoshi; Shimoyama, Isao

    2015-10-01

    Active modulation of the polarization states of terahertz light is indispensable for polarization-sensitive spectroscopy, having important applications such as non-contact Hall measurements, vibrational circular dichroism measurements and anisotropy imaging. In the terahertz region, the lack of a polarization modulator similar to a photoelastic modulator in the visible range hampers expansion of such spectroscopy. A terahertz chiral metamaterial has a huge optical activity unavailable in nature; nevertheless, its modulation is still challenging. Here we demonstrate a handedness-switchable chiral metamaterial for polarization modulation employing vertically deformable Micro Electro Mechanical Systems. Vertical deformation of a planar spiral by a pneumatic force creates a three-dimensional spiral. Enantiomeric switching is realized by selecting the deformation direction, where the polarity of the optical activity is altered while maintaining the spectral shape. A polarization rotation as high as 28° is experimentally observed, thus providing a practical and compact polarization modulator for the terahertz range.

  12. Enantiomeric switching of chiral metamaterial for terahertz polarization modulation employing vertically deformable MEMS spirals.

    PubMed

    Kan, Tetsuo; Isozaki, Akihiro; Kanda, Natsuki; Nemoto, Natsuki; Konishi, Kuniaki; Takahashi, Hidetoshi; Kuwata-Gonokami, Makoto; Matsumoto, Kiyoshi; Shimoyama, Isao

    2015-10-01

    Active modulation of the polarization states of terahertz light is indispensable for polarization-sensitive spectroscopy, having important applications such as non-contact Hall measurements, vibrational circular dichroism measurements and anisotropy imaging. In the terahertz region, the lack of a polarization modulator similar to a photoelastic modulator in the visible range hampers expansion of such spectroscopy. A terahertz chiral metamaterial has a huge optical activity unavailable in nature; nevertheless, its modulation is still challenging. Here we demonstrate a handedness-switchable chiral metamaterial for polarization modulation employing vertically deformable Micro Electro Mechanical Systems. Vertical deformation of a planar spiral by a pneumatic force creates a three-dimensional spiral. Enantiomeric switching is realized by selecting the deformation direction, where the polarity of the optical activity is altered while maintaining the spectral shape. A polarization rotation as high as 28° is experimentally observed, thus providing a practical and compact polarization modulator for the terahertz range.

  13. Development of Advanced Seed Laser Modules for Lidar and Spectroscopy Applications

    NASA Technical Reports Server (NTRS)

    Prasad, Narasimha S.; Rosiewicz, Alex; Coleman, Steven M.

    2013-01-01

    We report on recent progress made in the development of highly compact, single mode, distributed feedback laser (DFB) seed laser modules for lidar and spectroscopy applications from space based platforms. One of the intended application of this technology is in the NASA's Active Sensing of CO2 Emissions over Nights, Days, and Seasons (ASCENDS) mission. The DFB laser modules operating at 1571 nm and 1262 nm have advanced current and temperature drivers built into them. A combination of temperature and current tuning allows coarse and fine adjustment of the diode wavelengths.

  14. Electrooptic modulation methods for high sensitivity tunable diode laser spectroscopy

    NASA Technical Reports Server (NTRS)

    Glenar, David A.; Jennings, Donald E.; Nadler, Shacher

    1990-01-01

    A CdTe phase modulator and low power RF sources have been used with Pb-salt tunable diode lasers operating near 8 microns to generate optical sidebands for high sensitivity absorption spectroscopy. Sweep averaged, first-derivative sample spectra of CH4 were acquired by wideband phase sensitive detection of the electrooptically (EO) generated carrier-sideband beat signal. EO generated beat signals were also used to frequency lock the TDL to spectral lines. This eliminates low frequency diode jitter, and avoids the excess laser linewidth broadening that accompanies TDL current modulation frequency locking methods.

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

    PubMed Central

    Klein, Alexander; Witzel, Oliver; Ebert, Volker

    2014-01-01

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

  16. Strain-induced modulation of near-field radiative transfer.

    PubMed

    Ghanekar, Alok; Ricci, Matthew; Tian, Yanpei; Gregory, Otto; Zheng, Yi

    2018-06-11

    In this theoretical study, we present a near-field thermal modulator that exhibits change in radiative heat transfer when subjected to mechanical stress/strain. The device has two terminals at different temperatures separated by vacuum: one fixed and one stretchable. The stretchable side contains one-dimensional grating. When subjected to mechanical strain, the effective optical properties of the stretchable side are affected upon deformation of the grating. This results in modulation of surface waves across the interfaces influencing near-field radiative heat transfer. We show that for a separation of 100 nm, it is possible to achieve 25% change in radiative heat transfer for a strain of 10%.

  17. Probing and Exploiting the Interplay between Nuclear and Electronic Motion in Charge Transfer Processes.

    PubMed

    Delor, Milan; Sazanovich, Igor V; Towrie, Michael; Weinstein, Julia A

    2015-04-21

    The Born-Oppenheimer approximation refers to the assumption that the nuclear and electronic wave functions describing a molecular system evolve and can be determined independently. It is now well-known that this approximation often breaks down and that nuclear-electronic (vibronic) coupling contributes greatly to the ultrafast photophysics and photochemistry observed in many systems ranging from simple molecules to biological organisms. In order to probe vibronic coupling in a time-dependent manner, one must use spectroscopic tools capable of correlating the motions of electrons and nuclei on an ultrafast time scale. Recent developments in nonlinear multidimensional electronic and vibrational spectroscopies allow monitoring both electronic and structural factors with unprecedented time and spatial resolution. In this Account, we present recent studies from our group that make use of different variants of frequency-domain transient two-dimensional infrared (T-2DIR) spectroscopy, a pulse sequence combining electronic and vibrational excitations in the form of a UV-visible pump, a narrowband (12 cm(-1)) IR pump, and a broadband (400 cm(-1)) IR probe. In the first example, T-2DIR is used to directly compare vibrational dynamics in the ground and relaxed electronic excited states of Re(Cl)(CO)3(4,4'-diethylester-2,2'-bipyridine) and Ru(4,4'-diethylester-2,2'-bipyridine)2(NCS)2, prototypical charge transfer complexes used in photocatalytic CO2 reduction and electron injection in dye-sensitized solar cells. The experiments show that intramolecular vibrational redistribution (IVR) and vibrational energy transfer (VET) are up to an order of magnitude faster in the triplet charge transfer excited state than in the ground state. These results show the influence of electronic arrangement on vibrational coupling patterns, with direct implications for vibronic coupling mechanisms in charge transfer excited states. In the second example, we show unambiguously that electronic and vibrational movement are coupled in a donor-bridge-acceptor complex based on a Pt(II) trans-acetylide design motif. Time-resolved IR (TRIR) spectroscopy reveals that the rate of electron transfer (ET) is highly dependent on the amount of excess energy localized on the bridge following electronic excitation. Using an adaptation of T-2DIR, we are able to selectively perturb bridge-localized vibrational modes during charge separation, resulting in the donor-acceptor charge separation pathway being completely switched off, with all excess energy redirected toward the formation of a long-lived intraligand triplet state. A series of control experiments reveal that this effect is mode specific: it is only when the high-frequency bridging C≡C stretching mode is pumped that radical changes in photoproduct yields are observed. These experiments therefore suggest that one may perturb electronic movement by stimulating structural motion along the reaction coordinate using IR light. These studies add to a growing body of evidence suggesting that controlling the pathways and efficiency of charge transfer may be achieved through synthetic and perturbative approaches aiming to modulate vibronic coupling. Achieving such control would represent a breakthrough for charge transfer-based applications such as solar energy conversion and molecular electronics.

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

    Argence, B.; Halloin, H.; Jeannin, O.

    We have developed a 532 nm iodine stabilized laser system that may be suitable for the LISA mission (Laser Interferometer Space Antenna) or other future spaceborne missions. This system is based on an externally frequency-doubled Nd:YAG laser source and uses the molecular transfer spectroscopy technique for the frequency stabilization. This technique has been optimized for LISA: compactness (less than 1.1x1.1 m{sup 2}), vacuum compatibility, ease of use and initialization, minimization of the number of active components (acousto-optic modulators are both used for frequency shifting and phase modulating the pump beam). By locking on the a{sub 10} hyperfine component of themore » R(56)32-0 transition, we find an Allan standard deviation ({sigma}) of 3x10{sup -14} at 1 s and {sigma}<2x10{sup -14} for 20 s{<=}{tau}{<=}10{sup 3} s. In terms of linear spectral density, this roughly corresponds to a stability better than 30 Hz/{radical}(Hz) between 10{sup -2} and 1 Hz with a stability decrease close to 1/f below 10 mHz.« less

  19. Quantifying highly efficient incoherent energy transfer in perylene-based multichromophore arrays.

    PubMed

    Webb, James E A; Chen, Kai; Prasad, Shyamal K K; Wojciechowski, Jonathan P; Falber, Alexander; Thordarson, Pall; Hodgkiss, Justin M

    2016-01-21

    Multichromophore perylene arrays were designed and synthesized to have extremely efficient resonance energy transfer. Using broadband ultrafast photoluminescence and transient absorption spectroscopies, transfer timescales of approximately 1 picosecond were resolved, corresponding to efficiencies of up to 99.98%. The broadband measurements also revealed spectra corresponding to incoherent transfer between localized states. Polarization resolved spectroscopy was used to measure the dipolar angles between donor and acceptor chromophores, thereby enabling geometric factors to be fixed when assessing the validity of Förster theory in this regime. Förster theory was found to predict the correct magnitude of transfer rates, with measured ∼2-fold deviations consistent with the breakdown of the point-dipole approximation at close approach. The materials presented, along with the novel methods for quantifying ultrahigh energy transfer efficiencies, will be valuable for applications demanding extremely efficient energy transfer, including fluorescent solar concentrators, optical gain, and photonic logic devices.

  20. Solvent as electron donor: Donor/acceptor electronic coupling is a dynamical variable

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

    Castner, E.W. Jr.; Kennedy, D.; Cave, R.J.

    2000-04-06

    The authors combine analysis of measurements by femtosecond optical spectroscopy, computer simulations, and the generalized Mulliken-Hush (GMH) theory in the study of electron-transfer reactions and electron donor-acceptor interactions. The study focus is on ultrafast photoinduced electron-transfer reactions from aromatic amine solvent donors to excited-state acceptors. The experimental results from femtosecond dynamical measurements fall into three categories: six coumarin acceptors reductively quenched by N,N-dimethylaniline (DMA), eight electron-donating amine solvents reductively quenching coumarin 152 (7-(dimethylamino)-4-(trifluoromethyl)-coumarin), and reductive quenching dynamics of two coumarins by DMA as a function of dilution in the nonreactive solvents toluene and chlorobenzene. Applying a combination of molecular dynamicsmore » trajectories, semiempirical quantum mechanical calculations (of the relevant adiabatic electronic states), and GMH theory to the C152/DMA photoreaction, the authors calculate the electron donor/acceptor interaction parameter H{sub DA} at various time frames, H{sub DA} is strongly modulated by both inner-sphere and outer-sphere nuclear dynamics, leading us to conclude that H{sub DA} must be considered as a dynamical variable.« less

  1. Method and apparatus for time dispersive spectroscopy

    DOEpatents

    Tarver, III, Edward E.; Siems, William F.

    2003-06-17

    Methods and apparatus are described for time dispersive spectroscopy. In particular, a modulated flow of ionized molecules of a sample are introduced into a drift region of an ion spectrometer. The ions are subsequently detected by an ion detector to produce an ion detection signal. The ion detection signal can be modulated to obtain a signal useful in assaying the chemical constituents of the sample.

  2. Method and apparatus for active control of combustion rate through modulation of heat transfer from the combustion chamber wall

    DOEpatents

    Roberts, Jr., Charles E.; Chadwell, Christopher J.

    2004-09-21

    The flame propagation rate resulting from a combustion event in the combustion chamber of an internal combustion engine is controlled by modulation of the heat transfer from the combustion flame to the combustion chamber walls. In one embodiment, heat transfer from the combustion flame to the combustion chamber walls is mechanically modulated by a movable member that is inserted into, or withdrawn from, the combustion chamber thereby changing the shape of the combustion chamber and the combustion chamber wall surface area. In another embodiment, heat transfer from the combustion flame to the combustion chamber walls is modulated by cooling the surface of a portion of the combustion chamber wall that is in close proximity to the area of the combustion chamber where flame speed control is desired.

  3. Final design of a space debris removal system

    NASA Technical Reports Server (NTRS)

    Carlson, Erika; Casali, Steve; Chambers, Don; Geissler, Garner; Lalich, Andrew; Leipold, Manfred; Mach, Richard; Parry, John; Weems, Foley

    1990-01-01

    The objective is the removal of medium sized orbital debris in low Earth orbits. The design incorporates a transfer vehicle and a netting vehicle to capture the medium size debris. The system is based near an operational space station located at 28.5 degrees inclination and 400 km altitude. The system uses ground based tracking to determine the location of a satellite breakup or debris cloud. This data is unloaded to the transfer vehicle, and the transfer vehicle proceeds to rendezvous with the debris at a lower altitude parking orbit. Next, the netting vehicle is deployed, tracks the targeted debris, and captures it. After expending the available nets, the netting vehicle returns to the transfer vehicle for a new netting module and continues to capture more debris in the target area. Once all the netting modules are expended, the transfer vehicle returns to the space station's orbit, where it is resupplied with new netting modules from a space shuttle load. The new modules are launched by the shuttle from the ground, and the expended modules are taken back to Earth for removal of the captured debris, refueling, and repacking of the nets. Once the netting modules are refurbished, they are taken back into orbit for reuse. In a typical mission, the system has the ability to capture 50 pieces of orbital debris. One mission will take about six months. The system is designed to allow for a 30 degree inclination change on the outgoing and incoming trips of the transfer vehicle.

  4. Final design of a space debris removal system

    NASA Astrophysics Data System (ADS)

    Carlson, Erika; Casali, Steve; Chambers, Don; Geissler, Garner; Lalich, Andrew; Leipold, Manfred; Mach, Richard; Parry, John; Weems, Foley

    1990-12-01

    The objective is the removal of medium sized orbital debris in low Earth orbits. The design incorporates a transfer vehicle and a netting vehicle to capture the medium size debris. The system is based near an operational space station located at 28.5 degrees inclination and 400 km altitude. The system uses ground based tracking to determine the location of a satellite breakup or debris cloud. This data is unloaded to the transfer vehicle, and the transfer vehicle proceeds to rendezvous with the debris at a lower altitude parking orbit. Next, the netting vehicle is deployed, tracks the targeted debris, and captures it. After expending the available nets, the netting vehicle returns to the transfer vehicle for a new netting module and continues to capture more debris in the target area. Once all the netting modules are expended, the transfer vehicle returns to the space station's orbit, where it is resupplied with new netting modules from a space shuttle load. The new modules are launched by the shuttle from the ground, and the expended modules are taken back to Earth for removal of the captured debris, refueling, and repacking of the nets. Once the netting modules are refurbished, they are taken back into orbit for reuse. In a typical mission, the system has the ability to capture 50 pieces of orbital debris. One mission will take about six months. The system is designed to allow for a 30 degree inclination change on the outgoing and incoming trips of the transfer vehicle.

  5. Determinants of Ligand Subtype-Selectivity at α1A-Adrenoceptor Revealed Using Saturation Transfer Difference (STD) NMR.

    PubMed

    Yong, Kelvin J; Vaid, Tasneem M; Shilling, Patrick J; Wu, Feng-Jie; Williams, Lisa M; Deluigi, Mattia; Plückthun, Andreas; Bathgate, Ross A D; Gooley, Paul R; Scott, Daniel J

    2018-04-20

    α 1A - and α 1B -adrenoceptors (α 1A -AR and α 1B -AR) are closely related G protein-coupled receptors (GPCRs) that modulate the cardiovascular and nervous systems in response to binding epinephrine and norepinephrine. The GPCR gene superfamily is made up of numerous subfamilies that, like α 1A -AR and α 1B -AR, are activated by the same endogenous agonists but may modulate different physiological processes. A major challenge in GPCR research and drug discovery is determining how compounds interact with receptors at the molecular level, especially to assist in the optimization of drug leads. Nuclear magnetic resonance spectroscopy (NMR) can provide great insight into ligand-binding epitopes, modes, and kinetics. Ideally, ligand-based NMR methods require purified, well-behaved protein samples. The instability of GPCRs upon purification in detergents, however, makes the application of NMR to study ligand binding challenging. Here, stabilized α 1A -AR and α 1B -AR variants were engineered using Cellular High-throughput Encapsulation, Solubilization, and Screening (CHESS), allowing the analysis of ligand binding with Saturation Transfer Difference NMR (STD NMR). STD NMR was used to map the binding epitopes of epinephrine and A-61603 to both receptors, revealing the molecular determinants for the selectivity of A-61603 for α 1A -AR over α 1B -AR. The use of stabilized GPCRs for ligand-observed NMR experiments will lead to a deeper understanding of binding processes and assist structure-based drug design.

  6. Titanium-silicon oxide film structures for polarization-modulated infrared reflection absorption spectroscopy

    PubMed Central

    Dunlop, Iain E.; Zorn, Stefan; Richter, Gunther; Srot, Vesna; Kelsch, Marion; van Aken, Peter A.; Skoda, Maximilian; Gerlach, Alexander; Spatz, Joachim P.; Schreiber, Frank

    2010-01-01

    We present a titanium-silicon oxide film structure that permits polarization modulated infrared reflection absorption spectroscopy on silicon oxide surfaces. The structure consists of a ~6 nm sputtered silicon oxide film on a ~200 nm sputtered titanium film. Characterization using conventional and scanning transmission electron microscopy, electron energy loss spectroscopy, X-ray photoelectron spectroscopy and X-ray reflectometry is presented. We demonstrate the use of this structure to investigate a selectively protein-resistant self-assembled monolayer (SAM) consisting of silane-anchored, biotin-terminated poly(ethylene glycol) (PEG). PEG-associated IR bands were observed. Measurements of protein-characteristic band intensities showed that this SAM adsorbed streptavidin whereas it repelled bovine serum albumin, as had been expected from its structure. PMID:20418963

  7. Identification of another module involved in the horizontal transfer of the Haemophilus genomic island ICEHin1056.

    PubMed

    Juhas, Mario; Dimopoulou, Ioanna; Robinson, Esther; Elamin, Abdel; Harding, Rosalind; Hood, Derek; Crook, Derrick

    2013-09-01

    A significant part of horizontal gene transfer is facilitated by genomic islands. Haemophilus influenzae genomic island ICEHin1056 is an archetype of a genomic island that accounts for pandemic spread of antibiotics resistance. ICEHin1056 has modular structure and harbors modules involved in type IV secretion and integration. Previous studies have shown that ICEHin1056 encodes a functional type IV secretion system; however, other modules have not been characterized yet. Here we show that the module on the 5' extremity of ICEHin1056 consists of 15 genes that are well conserved in a number of related genomic islands. Furthermore by disrupting six genes of the investigated module of ICEHin1056 by site-specific mutagenesis we demonstrate that in addition to type IV secretion system module, the investigated module is also important for the successful conjugal transfer of ICEHin1056 from donor to recipient cells. Copyright © 2013 Elsevier Inc. All rights reserved.

  8. Novel electronic ferroelectricity in an organic charge-order insulator investigated with terahertz-pump optical-probe spectroscopy

    PubMed Central

    Yamakawa, H.; Miyamoto, T.; Morimoto, T.; Yada, H.; Kinoshita, Y.; Sotome, M.; Kida, N.; Yamamoto, K.; Iwano, K.; Matsumoto, Y.; Watanabe, S.; Shimoi, Y.; Suda, M.; Yamamoto, H. M.; Mori, H.; Okamoto, H.

    2016-01-01

    In electronic-type ferroelectrics, where dipole moments produced by the variations of electron configurations are aligned, the polarization is expected to be rapidly controlled by electric fields. Such a feature can be used for high-speed electric-switching and memory devices. Electronic-type ferroelectrics include charge degrees of freedom, so that they are sometimes conductive, complicating dielectric measurements. This makes difficult the exploration of electronic-type ferroelectrics and the understanding of their ferroelectric nature. Here, we show unambiguous evidence for electronic ferroelectricity in the charge-order (CO) phase of a prototypical ET-based molecular compound, α-(ET)2I3 (ET:bis(ethylenedithio)tetrathiafulvalene), using a terahertz pulse as an external electric field. Terahertz-pump second-harmonic-generation(SHG)-probe and optical-reflectivity-probe spectroscopy reveal that the ferroelectric polarization originates from intermolecular charge transfers and is inclined 27° from the horizontal CO stripe. These features are qualitatively reproduced by the density-functional-theory calculation. After sub-picosecond polarization modulation by terahertz fields, prominent oscillations appear in the reflectivity but not in the SHG-probe results, suggesting that the CO is coupled with molecular displacements, while the ferroelectricity is electronic in nature. The results presented here demonstrate that terahertz-pump optical-probe spectroscopy is a powerful tool not only for rapidly controlling polarizations, but also for clarifying the mechanisms of ferroelectricity. PMID:26864779

  9. Novel electronic ferroelectricity in an organic charge-order insulator investigated with terahertz-pump optical-probe spectroscopy.

    PubMed

    Yamakawa, H; Miyamoto, T; Morimoto, T; Yada, H; Kinoshita, Y; Sotome, M; Kida, N; Yamamoto, K; Iwano, K; Matsumoto, Y; Watanabe, S; Shimoi, Y; Suda, M; Yamamoto, H M; Mori, H; Okamoto, H

    2016-02-11

    In electronic-type ferroelectrics, where dipole moments produced by the variations of electron configurations are aligned, the polarization is expected to be rapidly controlled by electric fields. Such a feature can be used for high-speed electric-switching and memory devices. Electronic-type ferroelectrics include charge degrees of freedom, so that they are sometimes conductive, complicating dielectric measurements. This makes difficult the exploration of electronic-type ferroelectrics and the understanding of their ferroelectric nature. Here, we show unambiguous evidence for electronic ferroelectricity in the charge-order (CO) phase of a prototypical ET-based molecular compound, α-(ET)2I3 (ET:bis(ethylenedithio)tetrathiafulvalene), using a terahertz pulse as an external electric field. Terahertz-pump second-harmonic-generation(SHG)-probe and optical-reflectivity-probe spectroscopy reveal that the ferroelectric polarization originates from intermolecular charge transfers and is inclined 27° from the horizontal CO stripe. These features are qualitatively reproduced by the density-functional-theory calculation. After sub-picosecond polarization modulation by terahertz fields, prominent oscillations appear in the reflectivity but not in the SHG-probe results, suggesting that the CO is coupled with molecular displacements, while the ferroelectricity is electronic in nature. The results presented here demonstrate that terahertz-pump optical-probe spectroscopy is a powerful tool not only for rapidly controlling polarizations, but also for clarifying the mechanisms of ferroelectricity.

  10. White light emitting diode as potential replacement of tungsten-halogen lamp for visible spectroscopy system: a case study in the measurement of mango qualities

    NASA Astrophysics Data System (ADS)

    Chiong, W. L.; Omar, A. F.

    2017-07-01

    Non-destructive technique based on visible (VIS) spectroscopy using light emitting diode (LED) as lighting was used for evaluation of the internal quality of mango fruit. The objective of this study was to investigate feasibility of white LED as lighting in spectroscopic instrumentation to predict the acidity and soluble solids content of intact Sala Mango. The reflectance spectra of the mango samples were obtained and measured in the visible range (400-700 nm) using VIS spectroscopy illuminated under different white LEDs and tungsten-halogen lamp (pro lamp). Regression models were developed by multiple linear regression to establish the relationship between spectra and internal quality. Direct calibration transfer procedure was then applied between master and slave lighting to check on the acidity prediction results after transfer. Determination of mango acidity under white LED lighting was successfully performed through VIS spectroscopy using multiple linear regression but otherwise for soluble solids content. Satisfactory results were obtained for calibration transfer between LEDs with different correlated colour temperature indicated this technique was successfully used in spectroscopy measurement between two similar light sources in prediction of internal quality of mango.

  11. Excited state proton transfer in strongly enhanced GFP (sGFP2).

    PubMed

    van Oort, Bart; ter Veer, Mirelle J T; Groot, Marie Louise; van Stokkum, Ivo H M

    2012-07-07

    Proton transfer is an elementary process in biology. Green fluorescent protein (GFP) has served as an important model system to elucidate the mechanistic details of this reaction, because in GFP proton transfer can be induced by light absorption. We have used pump-dump-probe spectroscopy to study how proton transfer through the 'proton-wire' around the chromophore is affected by a combination of mutations in a modern GFP variety (sGFP2). The results indicate that in H(2)O, after absorption of a photon, a proton is transferred (A* → I*) in 5 ps, and back-transferred from a ground state intermediate (I → A) in 0.3 ns, similar to time constants found with GFPuv, although sGFP2 shows less heterogeneous proton transfer. This suggests that the mutations left the proton-transfer largely unchanged, indicating the robustness of the proton-wire. We used pump-dump-probe spectroscopy in combination with target analysis to probe suitability of the sGFP2 fluorophore for super-resolution microscopy.

  12. Near infrared light induced plasmonic hot hole transfer at a nano-heterointerface.

    PubMed

    Lian, Zichao; Sakamoto, Masanori; Matsunaga, Hironori; Vequizo, Junie Jhon M; Yamakata, Akira; Haruta, Mitsutaka; Kurata, Hiroki; Ota, Wataru; Sato, Tohru; Teranishi, Toshiharu

    2018-06-13

    Localized surface plasmon resonance (LSPR)-induced hot-carrier transfer is a key mechanism for achieving artificial photosynthesis using the whole solar spectrum, even including the infrared (IR) region. In contrast to the explosive development of photocatalysts based on the plasmon-induced hot electron transfer, the hole transfer system is still quite immature regardless of its importance, because the mechanism of plasmon-induced hole transfer has remained unclear. Herein, we elucidate LSPR-induced hot hole transfer in CdS/CuS heterostructured nanocrystals (HNCs) using time-resolved IR (TR-IR) spectroscopy. TR-IR spectroscopy enables the direct observation of carrier in a LSPR-excited CdS/CuS HNC. The spectroscopic results provide insight into the novel hole transfer mechanism, named plasmon-induced transit carrier transfer (PITCT), with high quantum yields (19%) and long-lived charge separations (9.2 μs). As an ultrafast charge recombination is a major drawback of all plasmonic energy conversion systems, we anticipate that PITCT will break the limit of conventional plasmon-induced energy conversion.

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

    NASA Astrophysics Data System (ADS)

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

    2005-01-01

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

  14. Collective Modes and Structural Modulation in Ni-Mn-Ga(Co) Martensite Thin Films Probed by Femtosecond Spectroscopy and Scanning Tunneling Microscopy.

    PubMed

    Schubert, M; Schaefer, H; Mayer, J; Laptev, A; Hettich, M; Merklein, M; He, C; Rummel, C; Ristow, O; Großmann, M; Luo, Y; Gusev, V; Samwer, K; Fonin, M; Dekorsy, T; Demsar, J

    2015-08-14

    The origin of the martensitic transition in the magnetic shape memory alloy Ni-Mn-Ga has been widely discussed. While several studies suggest it is electronically driven, the adaptive martensite model reproduced the peculiar nonharmonic lattice modulation. We used femtosecond spectroscopy to probe the temperature and doping dependence of collective modes, and scanning tunneling microscopy revealed the corresponding static modulations. We show that the martensitic phase can be described by a complex charge-density wave tuned by magnetic ordering and strong electron-lattice coupling.

  15. Collective Modes and Structural Modulation in Ni-Mn-Ga(Co) Martensite Thin Films Probed by Femtosecond Spectroscopy and Scanning Tunneling Microscopy

    NASA Astrophysics Data System (ADS)

    Schubert, M.; Schaefer, H.; Mayer, J.; Laptev, A.; Hettich, M.; Merklein, M.; He, C.; Rummel, C.; Ristow, O.; Großmann, M.; Luo, Y.; Gusev, V.; Samwer, K.; Fonin, M.; Dekorsy, T.; Demsar, J.

    2015-08-01

    The origin of the martensitic transition in the magnetic shape memory alloy Ni-Mn-Ga has been widely discussed. While several studies suggest it is electronically driven, the adaptive martensite model reproduced the peculiar nonharmonic lattice modulation. We used femtosecond spectroscopy to probe the temperature and doping dependence of collective modes, and scanning tunneling microscopy revealed the corresponding static modulations. We show that the martensitic phase can be described by a complex charge-density wave tuned by magnetic ordering and strong electron-lattice coupling.

  16. OrbView-3 Technical Performance Evaluation 2005: Modulation Transfer Function

    NASA Technical Reports Server (NTRS)

    Cole, Aaron

    2007-01-01

    The Technical performance evaluation of OrbView-3 using the Modulation Transfer Function (MTF) is presented. The contents include: 1) MTF Results and Methodology; 2) Radiometric Calibration Methodology; and 3) Relative Radiometric Assessment Results

  17. Triggerable electro-optic amplitude modulator bias stabilizer for integrated optical devices

    DOEpatents

    Conder, A.D.; Haigh, R.E.; Hugenberg, K.F.

    1995-09-26

    An improved Mach-Zehnder integrated optical electro-optic modulator is achieved by application and incorporation of a DC bias box containing a laser synchronized trigger circuit, a DC ramp and hold circuit, a modulator transfer function negative peak detector circuit, and an adjustable delay circuit. The DC bias box ramps the DC bias along the transfer function curve to any desired phase or point of operation at which point the RF modulation takes place. 7 figs.

  18. Triggerable electro-optic amplitude modulator bias stabilizer for integrated optical devices

    DOEpatents

    Conder, Alan D.; Haigh, Ronald E.; Hugenberg, Keith F.

    1995-01-01

    An improved Mach-Zehnder integrated optical electro-optic modulator is achieved by application and incorporation of a DC bias box containing a laser synchronized trigger circuit, a DC ramp and hold circuit, a modulator transfer function negative peak detector circuit, and an adjustable delay circuit. The DC bias box ramps the DC bias along the transfer function curve to any desired phase or point of operation at which point the RF modulation takes place.

  19. Module theoretic zero structures for system matrices

    NASA Technical Reports Server (NTRS)

    Wyman, Bostwick F.; Sain, Michael K.

    1987-01-01

    The coordinate-free module-theoretic treatment of transmission zeros for MIMO transfer functions developed by Wyman and Sain (1981) is generalized to include noncontrollable and nonobservable linear dynamical systems. Rational, finitely-generated-modular, and torsion-divisible interpretations of the Rosenbrock system matrix are presented; Gamma-zero and Omega-zero modules are defined and shown to contain the output-decoupling and input-decoupling zero modules, respectively, as submodules; and the cases of left and right invertible transfer functions are considered.

  20. Preliminary characterization of carbon dioxide transfer in a hollow fiber membrane module as a possible solution for gas-liquid transfer in microgravity conditions

    NASA Astrophysics Data System (ADS)

    Farges, Bérangère; Duchez, David; Dussap, Claude-Gilles; Cornet, Jean-François

    2012-01-01

    In microgravity, one of the major challenge encountered in biological life support systems (BLSS) is the gas-liquid transfer with, for instance, the necessity to provide CO2 (carbon source, pH control) and to recover the evolved O2 in photobioreactors used as atmosphere bioregenerative systems.This paper describes first the development of a system enabling the accurate characterization of the mass transfer limiting step for a PTFE membrane module used as a possible efficient solution to the microgravity gas-liquid transfer. This original technical apparatus, together with a technical assessment of membrane permeability to different gases, is associated with a balance model, determining thus completely the CO2 mass transfer problem between phases. First results are given and discussed for the CO2 mass transfer coefficient kLCO obtained in case of absorption experiments at pH 8 using the hollow fiber membrane module. The consistency of the proposed method, based on a gas and liquid phase balances verifying carbon conservation enables a very accurate determination of the kLCO value as a main limiting step of the whole process. Nevertheless, further experiments are still needed to demonstrate that the proposed method could serve in the future as reference method for mass transfer coefficient determination if using membrane modules for BLSS in reduced or microgravity conditions.

  1. Electronic structure evolution of fullerene on CH 3NH 3PbI 3

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

    Wang, Chenggong; Wang, Congcong; Liu, Xiaoliang

    2015-03-19

    The thickness dependence of fullerene on CH 3NH 3PbI 3 perovskitefilm surface has been investigated by using ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy(XPS), and inverse photoemission spectroscopy (IPES). The lowest unoccupied molecular orbital and highest occupied molecular orbital (HOMO) can be observed directly with IPES and UPS. It is observed that the HOMO level in fullerene shifts to lower binding energy. The XPS results show a strong initial shift of core levels to lower binding energy in the perovskite, which indicates that electrons transfer from the perovskitefilm to fullerene molecules. Further deposition of fullerene forms C 60 solid, accompaniedmore » by the reduction of the electron transfer. As a result, the strongest electron transfer happened at 1/4 monolayer of fullerene.« less

  2. Electronic structure evolution of fullerene on CH{sub 3}NH{sub 3}PbI{sub 3}

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

    Wang, Chenggong; Wang, Congcong; Kauppi, John

    2015-03-16

    The thickness dependence of fullerene on CH{sub 3}NH{sub 3}PbI{sub 3} perovskite film surface has been investigated by using ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy (XPS), and inverse photoemission spectroscopy (IPES). The lowest unoccupied molecular orbital and highest occupied molecular orbital (HOMO) can be observed directly with IPES and UPS. It is observed that the HOMO level in fullerene shifts to lower binding energy. The XPS results show a strong initial shift of core levels to lower binding energy in the perovskite, which indicates that electrons transfer from the perovskite film to fullerene molecules. Further deposition of fullerene forms C{submore » 60} solid, accompanied by the reduction of the electron transfer. The strongest electron transfer happened at 1/4 monolayer of fullerene.« less

  3. Computational expressions for signals in frequency-modulation spectroscopy

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

    Di Rosa, Michael D.; Reiten, M. T.

    2015-05-25

    In this study, general expressions for the signals in frequency-modulation spectroscopy (FMS) appear in the literature but are often reduced to simple analytical equations following the assumption of a weak modulation index. This is little help to the experimentalist who wants to predict signals for modulation depths of the order of unity or greater, where strong FMS signals reside. Here, we develop general formulas for FMS signals in the case of an absorber with a Voigt line shape and then link these expressions to an example and existing numerical code for the line shape. The resulting computational recipe is easymore » to implement and exercised here to show where the larger FMS signals are found over the coordinates of modulation index and modulation frequency. One can also estimate from provided curves the in-phase FMS signal over a wide range of modulation parameters at either the Lorentzian-broadening or Doppler-broadening limit, or anywhere in between by interpolation.« less

  4. New data acquisition system for the focal plane polarimeter of the Grand Raiden spectrometer

    NASA Astrophysics Data System (ADS)

    Tamii, A.; Sakaguchi, H.; Takeda, H.; Yosoi, M.; Akimune, H.; Fujiwara, M.; Ogata, H.; Tanaka, M.; Togawa, H.

    1996-10-01

    This paper describes a new data acquisition system for the focal plane polarimeter of the Grand Raiden spectrometer at the Research Center for Nuclear Physics (RCNP) in Osaka, Japan. Data are acquired by a Creative Electronic Systems (CES) Starburst, which is a CAMAC auxiliary crate controller equipped with a Digital Equipment Corporation (DEC) J11 microprocessor. The data on the Starburst are transferred to a VME single-board computer. A VME reflective memory module broadcasts the data to other systems through a fiber-optic link. A data transfer rate of 2.0 Mbytes/s between VME modules has been achieved by reflective memories. This rate includes the overhead of buffer management. The overall transfer rate, however, is limited by the performance of the Starburst to about 160 Kbytes/s at maximum. In order to further improve the system performance, we developed a new readout module called the Rapid Data Transfer Module (RDTM). RDTM's transfer data from LeCroy PCOS III's or 4298's, and FERA/FERET's directly to CES 8170 High Speed Memories (HSM) in VME crates, the data transfer rate of the RDTM from PCOS III's to the HSM is about 4 Mbytes/s.

  5. Fourier transform infrared difference and time-resolved infrared detection of the electron and proton transfer dynamics in photosynthetic water oxidation.

    PubMed

    Noguchi, Takumi

    2015-01-01

    Photosynthetic water oxidation, which provides the electrons necessary for CO₂ reduction and releases O₂ and protons, is performed at the Mn₄CaO₅ cluster in photosystem II (PSII). In this review, studies that assessed the mechanism of water oxidation using infrared spectroscopy are summarized focusing on electron and proton transfer dynamics. Structural changes in proteins and water molecules between intermediates known as Si states (i=0-3) were detected using flash-induced Fourier transform infrared (FTIR) difference spectroscopy. Electron flow in PSII and proton release from substrate water were monitored using the infrared changes in ferricyanide as an exogenous electron acceptor and Mes buffer as a proton acceptor. Time-resolved infrared (TRIR) spectroscopy provided information on the dynamics of proton-coupled electron transfer during the S-state transitions. In particular, a drastic proton movement during the lag phase (~200μs) before electron transfer in the S3→S0 transition was detected directly by monitoring the infrared absorption of a polarizable proton in a hydrogen bond network. Furthermore, the proton release pathways in the PSII proteins were analyzed by FTIR difference measurements in combination with site-directed mutagenesis, isotopic substitutions, and quantum chemical calculations. Therefore, infrared spectroscopy is a powerful tool for understanding the molecular mechanism of photosynthetic water oxidation. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Novel microfluidic system for online monitoring of biofilm dynamics by electrical impedance spectroscopy and amperometry

    NASA Astrophysics Data System (ADS)

    Bruchmann, Julia; Sachsenheimer, Kai; Schwartz, Thomas; Rapp, Bastian E.

    2016-03-01

    Biofilm formation is ubiquitous in nature where microorganisms attach to surfaces and form highly adapted and protected communities. In technical and industrial systems like drinking water supply, food production or shipping industry biofilms are a major cause of product contamination, biofouling, and biocorrosion. Therefore, understanding of biofilm formation and means of preventing biofilm formation is important to develop novel biofilm treatment strategies. A system allowing directly online detection and monitoring biofilm formation is necessary. However, until today, there are little to none technical systems featuring a non-destructive real-time characterization of biofilm formation in a highthroughput manner. This paper presents such a microfluidic system based on electrical impedance spectroscopy (EIS) and amperomertic current measurement. The sensor consists of four modules, each housing 24 independent electrodes within 12 microfluidic channels. Attached biomass on the electrodes is monitored as increased inhibition in charge transfer by EIS and a change in metabolic activity is measured as change in produced electric current by amperometry. This modular sensor system is highly adaptable and suitable for a broad range of microbiological applications. Among others, biofilm formation processes can be characterized online, biofilm manipulation like inactivation or destabilization can be monitored in real-time and gene expression can be analyzed in parallel. The use of different electrode designs allows effective biofilm studies during all biofilm phases. The whole system was recently extended by an integrated pneumatic microfluidic pump which enables easy handling procedures. Further developments of this pumping module will allow a fully- automated computer-controlled valving and pumping.

  7. Highly Functional TNTs with Superb Photocatalytic, Optical, and Electronic Performance Achieving Record PV Efficiency of 10.1% for 1D-Based DSSCs.

    PubMed

    Qadir, Muhammad Bilal; Li, Yuewen; Sahito, Iftikhar Ali; Arbab, Alvira Ayoub; Sun, Kyung Chul; Mengal, Naveed; Memon, Anam Ali; Jeong, Sung Hoon

    2016-09-01

    Different nanostructures of TiO2 play an important role in the photocatalytic and photoelectronic applications. TiO2 nanotubes (TNTs) have received increasing attention for these applications due to their unique physicochemical properties. Focusing on highly functional TNTs (HF-TNTs) for photocatalytic and photoelectronic applications, this study describes the facile hydrothermal synthesis of HF-TNTs by using commercial and cheaper materials for cost-effective manufacturing. To prove the functionality and applicability, these TNTs are used as scattering structure in dye-sensitized solar cells (DSSCs). Photocatalytic, optical, Brunauer-Emmett-Teller (BET), electrochemical impedance spectrum, incident-photon-to-current efficiency, and intensity-modulated photocurrent spectroscopy/intensity-modulated photovoltage spectroscopy characterizations are proving the functionality of HF-TNTs for DSSCs. HF-TNTs show 50% higher photocatalytic degradation rate and also 68% higher dye loading ability than conventional TNTs (C-TNTs). The DSSCs having HF-TNT and its composite-based multifunctional overlayer show effective light absorption, outstanding light scattering, lower interfacial resistance, longer electron lifetime, rapid electron transfer, and improved diffusion length, and consequently, J SC , quantum efficiency, and record photoconversion efficiency of 10.1% using commercial N-719 dye is achieved, for 1D-based DSSCs. These new and highly functional TNTs will be a concrete fundamental background toward the development of more functional applications in fuel cells, dye-sensitized solar cells, Li-ion batteries, photocatalysis process, ion-exchange/adsorption process, and photoelectrochemical devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. X-ray verification of an optically aligned off-plane grating module

    NASA Astrophysics Data System (ADS)

    Donovan, Benjamin D.; McEntaffer, Randall L.; Tutt, James H.; DeRoo, Casey T.; Allured, Ryan; Gaskin, Jessica A.; Kolodziejczak, Jeffery J.

    2018-01-01

    Off-plane x-ray reflection gratings are theoretically capable of achieving high resolution and high diffraction efficiencies over the soft x-ray bandpass, making them an ideal technology to implement on upcoming x-ray spectroscopy missions. To achieve high effective area, these gratings must be aligned into grating modules. X-ray testing was performed on an aligned grating module to assess the current optical alignment methods. Results indicate that the grating module achieved the desired alignment for an upcoming x-ray spectroscopy suborbital rocket payload with modest effective area and resolving power. These tests have also outlined a pathway towards achieving the stricter alignment tolerances of future x-ray spectrometer payloads, which require improvements in alignment metrology, grating fabrication, and testing techniques.

  9. Correlation among Singlet-Oxygen Quenching, Free-Radical Scavenging, and Excited-State Intramolecular-Proton-Transfer Activities in Hydroxyflavones, Anthocyanidins, and 1-Hydroxyanthraquinones.

    PubMed

    Nagaoka, Shin-Ichi; Bandoh, Yuki; Nagashima, Umpei; Ohara, Keishi

    2017-10-26

    Singlet-oxygen ( 1 O 2 ) quenching, free-radical scavenging, and excited-state intramolecular proton-transfer (ESIPT) activities of hydroxyflavones, anthocyanidins, and 1-hydroxyanthraquinones were studied by means of laser, stopped-flow, and steady-state spectroscopies. In hydroxyflavones and anthocyanidins, the 1 O 2 quenching activity positively correlates to the free-radical scavenging activity. The reason for this correlation can be understood by considering that an early step of each reaction involves electron transfer from the unfused phenyl ring (B-ring), which is singly bonded to the bicyclic chromen or chromenylium moiety (A- and C-rings). Substitution of an electron-donating OH group at B-ring enhances the electron transfer leading to activation of the 1 O 2 quenching and free-radical scavenging. In 3-hydroxyflavones, the OH substitution at B-ring reduces the activity of ESIPT within C-ring, which can be explained in terms of the nodal-plane model. As a result, the 1 O 2 quenching and free-radical scavenging activities negatively correlate to the ESIPT activity. A catechol structure at B-ring is another factor that enhances the free-radical scavenging in hydroxyflavones. In contrast to these hydroxyflavones, 1-hydroxyanthraquinones having an electron-donating OH substituent adjacent to the O-H---O═C moiety susceptible to ESIPT do not show a simple correlation between their 1 O 2 quenching and ESIPT activities, because the OH substitution modulates these reactions.

  10. Spectroscopy and excitation dynamics of the trivalent lanthanides Tm(3+) and Ho(3+) in LiYF4

    NASA Technical Reports Server (NTRS)

    Walsh, Brian M.

    1995-01-01

    A detailed study of the spectroscopy and excitation dynamics Tm3+ and Ho3+ in yttrium lithium fluoride, LiYF4 (YLF), has been done. Absorption spectroscopy is utilized in the Judd-Ofelt theory to determine radiative transition rates of spontaneous emission. Luminescence spectroscopy is studied under cw diode laser excitation at 785nm. The effect of dopant ion concentration and excitation power on the observed luminescence are considered in these measurements. An analysis of these measurements have been used to determine channels of energy transfer between Tm3+ and Ho3+ ions. The temporal response of Tm and Ho in singly and co-doped YLF to pulsed laser excitation with a Ti:Al2O3 laser and a CoMgF2 laser turned to various wavelengths have also been studied. The energy transfer mechanisms of cross relaxation, upconversion, and resonant energy transfer between Tm3+ and Ho3+ ions have been modeled, and the model parameters extracted by a fitting procedure to the measured temporal response curves. Rate equation approaches to modeling are presented that result in predictions of rate constants for energy transfer processes, as well as more conventional approaches to modeling such as the Forster-Dexter models, which give the interaction strengths in terms of microscopic interaction parameters.

  11. Algal polysaccharides as matrices for the immobilization of urease in lipid ultrathin films studied with tensiometry and vibrational spectroscopy: Physical-chemical properties and implications in the enzyme activity.

    PubMed

    de Brito, Audrey Kalinouski; Nordi, Cristina S F; Caseli, Luciano

    2015-11-01

    Currently, many biological substances extracted from algae have received special attention because of their intrinsic characteristics, which can be applied to different areas of biotechnology. Therefore, in the current study, exopolysaccharides (EPS) from the microalgae Cryptomonas tetrapirenoidosa were employed as an aqueous subphase of a monolayer formed by the lipid dioctadecyldimethylammonium bromide (DODAB). The primary objective of this approach was to evaluate whether EPS could serve as a matrix for the immobilization of the enzyme urease to produce biosensors for urea. After DODAB was spread on the EPS solutions, urease was injected into the aqueous subphase, and the surface was submitted to compression using lateral barriers. The monolayers were subsequently characterized by surface pressure-area isotherms and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS). The results indicated that EPS enhanced the adsorption of the enzyme on the lipid monolayer. The mixed films were later transferred to solid supports using the Langmuir-Blodgett (LB) technique and were characterized by transfer ratio, PM-IRRAS, quartz crystal microbalance, and atomic force microscopy. The immobilization of the enzyme on solid supports was fundamental for providing an ideal geometrical accommodation of urease because the interaction of EPS with urease in solution causes a decrease of the relative activity of urease. Therefore, these LB films are promising for the fabrication of future urea biosensors, the architecture of which can be manipulated and enhanced at the molecular level. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Simple, green, and clean removal of a poly(methyl methacrylate) film on chemical vapor deposited graphene

    NASA Astrophysics Data System (ADS)

    Park, J.-H.; Jung, W.; Cho, D.; Seo, J.-T.; Moon, Y.; Woo, S. H.; Lee, C.; Park, C.-Y.; Ahn, J. R.

    2013-10-01

    The clean removal of a poly(methyl methacrylate) (PMMA) film on graphene has been an essential part of the process of transferring chemical vapor deposited graphene to a specific substrate, influencing the quality of the transferred graphene. Here we demonstrate that the clean removal of PMMA can be achieved by a single heat-treatment process without the chemical treatment that was adopted in other methods of PMMA removal. The cleanness of the transferred graphene was confirmed by four-point probe measurements, synchrotron radiation x-ray photoemission spectroscopy, optical images, and Raman spectroscopy.

  13. Ultrafast forward and backward electron transfer dynamics of coumarin 337 in hydrogen-bonded anilines as studied with femtosecond UV-pump/IR-probe spectroscopy.

    PubMed

    Ghosh, Hirendra N; Verma, Sandeep; Nibbering, Erik T J

    2011-02-10

    Femtosecond infrared spectroscopy is used to study both forward and backward electron transfer (ET) dynamics between coumarin 337 (C337) and the aromatic amine solvents aniline (AN), N-methylaniline (MAN), and N,N-dimethylaniline (DMAN), where all the aniline solvents can donate an electron but only AN and MAN can form hydrogen bonds with C337. The formation of a hydrogen bond with AN and MAN is confirmed with steady state FT-IR spectroscopy, where the C═O stretching vibration is a direct marker mode for hydrogen bond formation. Transient IR absorption measurements in all solvents show an absorption band at 2166 cm(-1), which has been attributed to the C≡N stretching vibration of the C337 radical anion formed after ET. Forward electron transfer dynamics is found to be biexponential with time constants τ(ET)(1) = 500 fs, τ(ET)(2) = 7 ps in all solvents. Despite the presence of hydrogen bonds of C337 with the solvents AN and MAN, no effect has been found on the forward electron transfer step. Because of the absence of an H/D isotope effect on the forward electron transfer reaction of C337 in AN, hydrogen bonds are understood to play a minor role in mediating electron transfer. In contrast, direct π-orbital overlap between C337 and the aromatic amine solvents causes ultrafast forward electron transfer dynamics. Backward electron transfer dynamics, in contrast, is dependent on the solvent used. Standard Marcus theory explains the observed backward electron transfer rates.

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

    NASA Astrophysics Data System (ADS)

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

    2018-04-01

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

  15. Multiplexed absorption tomography with calibration-free wavelength modulation spectroscopy

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

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

    2014-04-14

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

  16. OPTICAL INFORMATION PROCESSING: Modulation—spectral analysis of an image transmitted across a distorting medium

    NASA Astrophysics Data System (ADS)

    Zubov, Vladimir A.; Mironova, T. V.

    1998-05-01

    The task of simultaneous determination of the structure and characteristics of a two-dimensional amplitude—phase signal and a two-dimensional complex transfer or instrumental function is considered. The solution is based on determination of four independent intensity distributions of spectral representations of the signal Isr(ωx, ωy) subjected to the action of the transfer function, of the signal Ismr(ωx, ωy which) has experienced additional modulation applied in a certain manner and the action of the transfer function, of the signal Isrn(ωx, ωy) representing the signal Isr(ωx, ωy) with certain additional modulation at the output, and of the signal Ismrn(ωx, ωy) which is the signal Ismr(ωx, ωy) with certain additional modulation at the output. These intensity distributions make it possible to calculate the amplitude and phase components of the image being analysed and of the transfer function. Additional modulations should in some way ensure visualisation of the phase information. A specific type of additional spatial modulation, in the form of linear amplitude, is discussed.

  17. Kononenko uses laptop computer in the SM Transfer Compartment

    NASA Image and Video Library

    2012-03-21

    ISS030-E-161167 (21 March 2012) --- Russian cosmonaut Oleg Kononenko, Expedition 30 flight engineer, uses a computer in the transfer compartment of the International Space Station?s Zvezda Service Module. Russia's Zarya module is visible in the background.

  18. Heat Transfer Processes for the Thermal Energy Balance of Organisms. Physical Processes in Terrestrial and Aquatic Ecosystems, Transport Processes.

    ERIC Educational Resources Information Center

    Stevenson, R. D.

    This module is part of a series designed to be used by life science students for instruction in the application of physical theory to ecosystem operation. Most modules contain computer programs which are built around a particular application of a physical process. This module describes heat transfer processes involved in the exchange of heat…

  19. Impulsive Raman spectroscopy via precision measurement of frequency shift with low energy excitation.

    PubMed

    Raanan, Dekel; Ren, Liqing; Oron, Dan; Silberberg, Yaron

    2018-02-01

    Stimulated Raman scattering (SRS) has recently become useful for chemically selective bioimaging. It is usually measured via modulation transfer from the pump beam to the Stokes beam. Impulsive stimulated Raman spectroscopy, on the other hand, relies on the spectral shift of ultrashort pulses as they propagate in a Raman active sample. This method was considered impractical with low energy pulses since the observed shifts are very small compared to the excitation pulse bandwidth, spanning many terahertz. Here we present a new apparatus, using tools borrowed from the field of precision measurement, for the detection of low-frequency Raman lines via stimulated-Raman-scattering-induced spectral shifts. This method does not require any spectral filtration and is therefore an excellent candidate to resolve low-lying Raman lines (<200  cm -1 ), which are commonly masked by the strong Rayleigh scattering peak. Having the advantage of the high repetition rate of the ultrafast oscillator, we reduce the noise level by implementing a lock-in detection scheme with a wavelength shift sensitivity well below 100 fm. This is demonstrated by the measurement of low-frequency Raman lines of various liquid samples.

  20. Tuning electronic transport via hepta-alanine peptides junction by tryptophan doping.

    PubMed

    Guo, Cunlan; Yu, Xi; Refaely-Abramson, Sivan; Sepunaru, Lior; Bendikov, Tatyana; Pecht, Israel; Kronik, Leeor; Vilan, Ayelet; Sheves, Mordechai; Cahen, David

    2016-09-27

    Charge migration for electron transfer via the polypeptide matrix of proteins is a key process in biological energy conversion and signaling systems. It is sensitive to the sequence of amino acids composing the protein and, therefore, offers a tool for chemical control of charge transport across biomaterial-based devices. We designed a series of linear oligoalanine peptides with a single tryptophan substitution that acts as a "dopant," introducing an energy level closer to the electrodes' Fermi level than that of the alanine homopeptide. We investigated the solid-state electron transport (ETp) across a self-assembled monolayer of these peptides between gold contacts. The single tryptophan "doping" markedly increased the conductance of the peptide chain, especially when its location in the sequence is close to the electrodes. Combining inelastic tunneling spectroscopy, UV photoelectron spectroscopy, electronic structure calculations by advanced density-functional theory, and dc current-voltage analysis, the role of tryptophan in ETp is rationalized by charge tunneling across a heterogeneous energy barrier, via electronic states of alanine and tryptophan, and by relatively efficient direct coupling of tryptophan to a Au electrode. These results reveal a controlled way of modulating the electrical properties of molecular junctions by tailor-made "building block" peptides.

  1. Ultrafast Charge Transfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy

    PubMed Central

    2015-01-01

    The recently developed technique of femtosecond stimulated Raman spectroscopy, and its variant, femtosecond Raman-induced Kerr effect spectroscopy (FRIKES), offer access to ultrafast excited-state dynamics via structurally specific vibrational spectra. We have used FRIKES to study the photoexcitation dynamics of nickel(II) phthalocyanine with eight butoxy substituents, NiPc(OBu)8. NiPc(OBu)8 is reported to have a relatively long-lived ligand-to-metal charge-transfer (LMCT) state, an essential characteristic for efficient electron transfer in photocatalysis. Following photoexcitation, vibrational transitions in the FRIKES spectra, assignable to phthalocyanine ring modes, evolve on the femtosecond to picosecond time scales. Correlation of ring core size with the frequency of the ν10 (asymmetric C–N stretching) mode confirms the identity of the LMCT state, which has a ∼500 ps lifetime, as well as that of a precursor d-d excited state. An even earlier (∼0.2 ps) transient is observed and tentatively assigned to a higher-lying Jahn–Teller-active LMCT state. This study illustrates the power of FRIKES spectroscopy in elucidating ultrafast molecular dynamics. PMID:24841906

  2. Multiple channel data acquisition system

    DOEpatents

    Crawley, H. Bert; Rosenberg, Eli I.; Meyer, W. Thomas; Gorbics, Mark S.; Thomas, William D.; McKay, Roy L.; Homer, Jr., John F.

    1990-05-22

    A multiple channel data acquisition system for the transfer of large amounts of data from a multiplicity of data channels has a plurality of modules which operate in parallel to convert analog signals to digital data and transfer that data to a communications host via a FASTBUS. Each module has a plurality of submodules which include a front end buffer (FEB) connected to input circuitry having an analog to digital converter with cache memory for each of a plurality of channels. The submodules are interfaced with the FASTBUS via a FASTBUS coupler which controls a module bus and a module memory. The system is triggered to effect rapid parallel data samplings which are stored to the cache memories. The cache memories are uploaded to the FEBs during which zero suppression occurs. The data in the FEBs is reformatted and compressed by a local processor during transfer to the module memory. The FASTBUS coupler is used by the communications host to upload the compressed and formatted data from the module memory. The local processor executes programs which are downloaded to the module memory through the FASTBUS coupler.

  3. Multiple channel data acquisition system

    DOEpatents

    Crawley, H.B.; Rosenberg, E.I.; Meyer, W.T.; Gorbics, M.S.; Thomas, W.D.; McKay, R.L.; Homer, J.F. Jr.

    1990-05-22

    A multiple channel data acquisition system for the transfer of large amounts of data from a multiplicity of data channels has a plurality of modules which operate in parallel to convert analog signals to digital data and transfer that data to a communications host via a FASTBUS. Each module has a plurality of submodules which include a front end buffer (FEB) connected to input circuitry having an analog to digital converter with cache memory for each of a plurality of channels. The submodules are interfaced with the FASTBUS via a FASTBUS coupler which controls a module bus and a module memory. The system is triggered to effect rapid parallel data samplings which are stored to the cache memories. The cache memories are uploaded to the FEBs during which zero suppression occurs. The data in the FEBs is reformatted and compressed by a local processor during transfer to the module memory. The FASTBUS coupler is used by the communications host to upload the compressed and formatted data from the module memory. The local processor executes programs which are downloaded to the module memory through the FASTBUS coupler. 25 figs.

  4. High Fidelity Tape Transfer Printing Based On Chemically Induced Adhesive Strength Modulation

    NASA Astrophysics Data System (ADS)

    Sim, Kyoseung; Chen, Song; Li, Yuhang; Kammoun, Mejdi; Peng, Yun; Xu, Minwei; Gao, Yang; Song, Jizhou; Zhang, Yingchun; Ardebili, Haleh; Yu, Cunjiang

    2015-11-01

    Transfer printing, a two-step process (i.e. picking up and printing) for heterogeneous integration, has been widely exploited for the fabrication of functional electronics system. To ensure a reliable process, strong adhesion for picking up and weak or no adhesion for printing are required. However, it is challenging to meet the requirements of switchable stamp adhesion. Here we introduce a simple, high fidelity process, namely tape transfer printing(TTP), enabled by chemically induced dramatic modulation in tape adhesive strength. We describe the working mechanism of the adhesion modulation that governs this process and demonstrate the method by high fidelity tape transfer printing several types of materials and devices, including Si pellets arrays, photodetector arrays, and electromyography (EMG) sensors, from their preparation substrates to various alien substrates. High fidelity tape transfer printing of components onto curvilinear surfaces is also illustrated.

  5. An integrated experimental and theoretical reaction path search: analyses of the multistage reaction of an ionized diethylether dimer involving isomerization, proton transfer, and dissociation.

    PubMed

    Matsuda, Yoshiyuki; Xie, Min; Fujii, Asuka

    2018-05-30

    An ionization-induced multistage reaction of an ionized diethylether (DEE) dimer involving isomerization, proton transfer, and dissociation is investigated by combining infrared (IR) spectroscopy, tandem mass spectrometry, and a theoretical reaction path search. The vertically-ionized DEE dimer isomerizes to a hydrogen-bonded cluster of protonated DEE and the [DEE-H] radical through barrierless intermolecular proton transfer from the CH bond of the ionized moiety. This isomerization process is confirmed by IR spectroscopy and the theoretical reaction path search. The multiple dissociation pathways following the isomerization are analyzed by tandem mass spectrometry. The isomerized cluster dissociates stepwise into a [protonated DEE-acetaldehyde (AA)] cluster, protonated DEE, and protonated AA. The structure of the fragment ion is also analyzed by IR spectroscopy. The reaction map of the multistage processes is revealed through a harmony of these experimental and theoretical methods.

  6. Structure-Activity Relations In Enzymes: An Application Of IR-ATR Modulation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Fringeli, Urs P.; Ahlstrom, Peter; Vincenz, Claudius; Fringeli, Marianna

    1985-12-01

    Relations between structure and specific activity in immobilized acetylcholinesterase (ACNE) have been studied by means of pH- and Ca++-modulation technique combined with attenuated total reflection (ATR) infrared (IR) spectroscopy and enzyme activity measurement. Periodic modulation of pH and Ca++-concentration enabled a periodic on-off switching of about 40% of the total enzyme activity. It was found that about 0.5 to 1% of the amino acids were involved in this process. These 15 to 30 amino acids assumed antiparallel pleated sheet structure in the inhibited state and random and/or helical structure in the activated state.

  7. Field Effect Modulation of Heterogeneous Charge Transfer Kinetics at Back-Gated Two-Dimensional MoS2 Electrodes.

    PubMed

    Wang, Yan; Kim, Chang-Hyun; Yoo, Youngdong; Johns, James E; Frisbie, C Daniel

    2017-12-13

    The ability to improve and to modulate the heterogeneous charge transfer kinetics of two-dimensional (2D) semiconductors, such as MoS 2 , is a major challenge for electrochemical and photoelectrochemical applications of these materials. Here we report a continuous and reversible physical method for modulating the heterogeneous charge transfer kinetics at a monolayer MoS 2 working electrode supported on a SiO 2 /p-Si substrate. The heavily doped p-Si substrate serves as a back gate electrode; application of a gate voltage (V BG ) to p-Si tunes the electron occupation in the MoS 2 conduction band and shifts the conduction band edge position relative to redox species dissolved in electrolyte in contact with the front side of the MoS 2 . The gate modulation of both charge density and energy band alignment impacts charge transfer kinetics as measured by cyclic voltammetry (CV). Specifically, cyclic voltammograms combined with numerical simulations suggest that the standard heterogeneous charge transfer rate constant (k 0 ) for MoS 2 in contact with the ferrocene/ferrocenium (Fc 0/+ ) redox couple can be modulated by over 2 orders of magnitude from 4 × 10 -6 to 1 × 10 -3 cm/s, by varying V BG . In general, the field effect offers the potential to tune the electrochemical properties of 2D semiconductors, opening up new possibilities for fundamental studies of the relationship between charge transfer kinetics and independently controlled electronic band alignment and band occupation.

  8. Is there another major constituent in the atmosphere of Mars?. [radiogenic argon

    NASA Technical Reports Server (NTRS)

    Wood, G. P.

    1974-01-01

    In view of the possible finding of several tens percent of inert gas in the atmosphere of Mars by an instrument on the descent module of the USSR's Mars 6 spacecraft, the likelihood of the correctness of this result was examined. The basis for the well-known fact that the most likely candidate is radiogenic argon is described. It is shown that, for the two important methods of investigating the atmosphere, earth-based CO2 is infrared absorption spectroscopy and S-band occultation, within the estimated 1 standard deviation uncertainties of these methods about 20% argon can be accommodated. Within the estimated 3 standard deviation uncertainties, more than 35% is possible. It is also stated that even with 35% argon the maximum value of heat transfer rate on the Viking 75 entry vehicle does not exceed the design value.

  9. Proton nuclear magnetic resonance studies on the variant-3 neurotoxin from Centruroides sculpturatus Ewing: Sequential assignment of resonances

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

    Nettesheim, D.G.; Klevit, R.E.; Drobny, G.

    1989-02-21

    The authors report the sequential assignment of resonances to specific residues in the proton nuclear magnetic resonance spectrum of the variant-3 neurotoxin from the scorpion Centruroides sculpturatus Ewing (range southwestern U.S.A.). A combination of two-dimensional NMR experiments such as 2D-COSY, 2D-NOESY, and single- and double-RELAY coherence transfer spectroscopy has been employed on samples of the protein dissolved in D{sub 2}O and in H{sub 2}O for assignment purposes. These studies provide a basis for the determination of the solution-phase conformation of this protein and for undertaking detailed structure-function studies of these neurotoxins that modulate the flow of sodium current by bindingmore » to the sodium channels of excitable membranes.« less

  10. Opto-electronic conversion logic behaviour through dynamic modulation of electron/energy transfer states at the TiO2-carbon quantum dot interface.

    PubMed

    Wang, Fang; Zhang, Yonglai; Liu, Yang; Wang, Xuefeng; Shen, Mingrong; Lee, Shuit-Tong; Kang, Zhenhui

    2013-03-07

    Here we show a bias-mediated electron/energy transfer process at the CQDs-TiO(2) interface for the dynamic modulation of opto-electronic properties. Different energy and electron transfer states have been observed in the CQDs-TNTs system due to the up-conversion photoluminescence and the electron donation/acceptance properties of the CQDs decorated on TNTs.

  11. New data acquisition system for the focal plane polarimeter of the Grand Raiden spectrometer

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

    Tamii, A.; Sakaguchi, H.; Takeda, H.

    1996-10-01

    This paper describes a new data acquisition system for the focal plane polarimeter of the Grand Raiden spectrometer at the Research Center for Nuclear Physics (RCNP) in Osaka, Japan. Data are acquired by a Creative Electronic Systems (CES) Starburst, which is a CAMAC auxiliary crate controller equipped with a Digital Equipment Corporation (DEC) J11 microprocessor., The data on the Starburst are transferred to a VME single-board computer. A VME reflective memory module broadcasts the data to other systems through a fiber-optic link. A data transfer rate of 2.0 Mbytes/s between VME modules has been achieved by reflective memories. This ratemore » includes the overhead of buffer management. The overall transfer rate, however, is limited by the performance of the Starburst to about 160 Kbytes/s at maximum. In order to further improve the system performance, the authors developed a new readout module called the Rapid Data Transfer Module (RDTM). RDTM`s transfer data from LeCroy PCOS III`s or 4298`s, and FERA/FERET`s directly to CES 8170 High Speed Memories (HSM) in VME crates. The data transfer rate of the RDTM from PCOS III`s to the HSM is about 4 Mbytes/s.« less

  12. Processing abstract language modulates motor system activity.

    PubMed

    Glenberg, Arthur M; Sato, Marc; Cattaneo, Luigi; Riggio, Lucia; Palumbo, Daniele; Buccino, Giovanni

    2008-06-01

    Embodiment theory proposes that neural systems for perception and action are also engaged during language comprehension. Previous neuroimaging and neurophysiological studies have only been able to demonstrate modulation of action systems during comprehension of concrete language. We provide neurophysiological evidence for modulation of motor system activity during the comprehension of both concrete and abstract language. In Experiment 1, when the described direction of object transfer or information transfer (e.g., away from the reader to another) matched the literal direction of a hand movement used to make a response, speed of responding was faster than when the two directions mismatched (an action-sentence compatibility effect). In Experiment 2, we used single-pulse transcranial magnetic stimulation to study changes in the corticospinal motor pathways to hand muscles while reading the same sentences. Relative to sentences that do not describe transfer, there is greater modulation of activity in the hand muscles when reading sentences describing transfer of both concrete objects and abstract information. These findings are discussed in relation to the human mirror neuron system.

  13. Temporal modulation transfer functions in auditory receptor fibres of the locust ( Locusta migratoria L.).

    PubMed

    Prinz, P; Ronacher, B

    2002-08-01

    The temporal resolution of auditory receptors of locusts was investigated by applying noise stimuli with sinusoidal amplitude modulations and by computing temporal modulation transfer functions. These transfer functions showed mostly bandpass characteristics, which are rarely found in other species at the level of receptors. From the upper cut-off frequencies of the modulation transfer functions the minimum integration times were calculated. Minimum integration times showed no significant correlation to the receptor spike rates but depended strongly on the body temperature. At 20 degrees C the average minimum integration time was 1.7 ms, dropping to 0.95 ms at 30 degrees C. The values found in this study correspond well to the range of minimum integration times found in birds and mammals. Gap detection is another standard paradigm to investigate temporal resolution. In locusts and other grasshoppers application of this paradigm yielded values of the minimum detectable gap widths that are approximately twice as large than the minimum integration times reported here.

  14. Development of broad bandwidth nonlinear spectroscopies for characterization of electronic states in materials systems

    NASA Astrophysics Data System (ADS)

    Mehlenbacher, Randy D.

    Carbon nanotubes are an interesting class of materials with many exceptional properties that make them appealing for optoelectronic devices. Their optical properties, particularly when cast in thin films, are not well understood. In this thesis, I describe the development of spectroscopic techniques for measuring energy and charge transport processes in thin films of semiconducting carbon nanotubes. Using transient absorption spectroscopy, I observe energy transport on two time scales in these films, with 20% of nanotubes transferring energy to smaller bandgap nanotubes within 300 fs. After 3 ps, 70% of the photoexcitation resides on small bandgap nanotubes. To study the complete landscape of energy transport in thin films of carbon nanotubes, I developed two dimensional white light spectroscopy (2D-WL). In 2D-WL spectroscopy, a broadband, white light supercontinuum is used to both excite and probe the sample. This technique has a bandwidth spanning > 500-1500 nm, a far broader bandwidth than previously reported in 2D electronic spectra. I take advantage of this large bandwidth to study the interactions and evolution of S1 and S2 excitons in a thin film of carbon nanotubes. I find that energy transfers between S1 excitons on a 2 ps time scale and occurs by a non-Forster energy transfer mechanism. In contrast, the energy in the S2 states redistributes on an ultrafast time scale, <100 fs, and undergoes autoionization producing free electrons and holes. I use 2D-WL spectroscopy to study the electronic states in thin films of bare, semiconducting carbon nanotubes. In these films, energy transfer occurs in <100 fs between bare carbon nanotubes and this energy transfer is between parallel nanotubes. By taking advantage of the laser pulse polarization for each interaction, I resolve otherwise difficult to observe couplings between electronic states. To facilitate data interpretation, the orientational response for isotropic two dimensional samples to polarized electric fields is developed. Using polarization control 2D-WL spectroscopy, I measure the coupling between nanotube S1 transitions and radial breathing modes. The doped tubes form trions with transition dipoles that are not parallel to the S1 transition and energy transfer from the S1 exciton to the trion occurs within 1 ps.

  15. Origin of the 900 cm{sup −1} broad double-hump OH vibrational feature of strongly hydrogen-bonded carboxylic acids

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

    Van Hoozen, Brian L.; Petersen, Poul B.

    2015-03-14

    Medium and strong hydrogen bonds are common in biological systems. Here, they provide structural support and can act as proton transfer relays to drive electron and/or energy transfer. Infrared spectroscopy is a sensitive probe of molecular structure and hydrogen bond strength but strongly hydrogen-bonded structures often exhibit very broad and complex vibrational bands. As an example, strong hydrogen bonds between carboxylic acids and nitrogen-containing aromatic bases commonly display a 900 cm{sup −1} broad feature with a remarkable double-hump structure. Although previous studies have assigned this feature to the OH, the exact origin of the shape and width of this unusualmore » feature is not well understood. In this study, we present ab initio calculations of the contributions of the OH stretch and bend vibrational modes to the vibrational spectrum of strongly hydrogen-bonded heterodimers of carboxylic acids and nitrogen-containing aromatic bases, taking the 7-azaindole—acetic acid and pyridine—acetic acid dimers as examples. Our calculations take into account coupling between the OH stretch and bend modes as well as how both of these modes are affected by lower frequency dimer stretch modes, which modulate the distance between the monomers. Our calculations reproduce the broadness and the double-hump structure of the OH vibrational feature. Where the spectral broadness is primarily caused by the dimer stretch modes strongly modulating the frequency of the OH stretch mode, the double-hump structure results from a Fermi resonance between the out of the plane OH bend and the OH stretch modes.« less

  16. Simultaneous backward data transmission and power harvesting in an ultrasonic transcutaneous energy transfer link employing acoustically dependent electric impedance modulation.

    PubMed

    Ozeri, Shaul; Shmilovitz, Doron

    2014-09-01

    The advancement and miniaturization of body implanted medical devices pose several challenges to Ultrasonic Transcutaneous Energy Transfer (UTET), such as the need to reduce the size of the piezoelectric resonator, and the need to maximize the UTET link power-transfer efficiency. Accordingly, the same piezoelectric resonator that is used for energy harvesting at the body implant, may also be used for ultrasonic backward data transfer, for instance, through impedance modulation. This paper presents physical considerations and design guidelines of the body implanted transducer of a UTET link with impedance modulation for a backward data transfer. The acoustic matching design procedure was based on the 2×2 transfer matrix chain analysis, in addition to the Krimholtz Leedom and Matthaei KLM transmission line model. The UTET power transfer was carried out at a frequency of 765 kHz, continuous wave (CW) mode. The backward data transfer was attained by inserting a 9% load resistance variation around its matched value (550 Ohm), resulting in a 12% increase in the acoustic reflection coefficient. A backward data transmission rate of 1200 bits/s was experimentally demonstrated using amplitude shift keying, simultaneously with an acoustic power transfer of 20 mW to the implant. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. A Refined Model for the TSG-6 Link Module in Complex with Hyaluronan

    PubMed Central

    Higman, Victoria A.; Briggs, David C.; Mahoney, David J.; Blundell, Charles D.; Sattelle, Benedict M.; Dyer, Douglas P.; Green, Dixy E.; DeAngelis, Paul L.; Almond, Andrew; Milner, Caroline M.; Day, Anthony J.

    2014-01-01

    Tumor necrosis factor-stimulated gene-6 (TSG-6) is an inflammation-associated hyaluronan (HA)-binding protein that contributes to remodeling of HA-rich extracellular matrices during inflammatory processes and ovulation. The HA-binding domain of TSG-6 consists solely of a Link module, making it a prototypical member of the superfamily of proteins that interacts with this high molecular weight polysaccharide composed of repeating disaccharides of d-glucuronic acid and N-acetyl-d-glucosamine (GlcNAc). Previously we modeled a complex of the TSG-6 Link module in association with an HA octasaccharide based on the structure of the domain in its HA-bound conformation. Here we have generated a refined model for a HA/Link module complex using novel restraints identified from NMR spectroscopy of the protein in the presence of 10 distinct HA oligosaccharides (from 4- to 8-mers); the model was then tested using unique sugar reagents, i.e. chondroitin/HA hybrid oligomers and an octasaccharide in which a single sugar ring was 13C-labeled. The HA chain was found to make more extensive contacts with the TSG-6 surface than thought previously, such that a d-glucuronic acid ring makes stacking and ionic interactions with a histidine and lysine, respectively. Importantly, this causes the HA to bend around two faces of the Link module (resembling the way that HA binds to CD44), potentially providing a mechanism for how TSG-6 can reorganize HA during inflammation. However, the HA-binding site defined here may not play a role in TSG-6-mediated transfer of heavy chains from inter-α-inhibitor onto HA, a process known to be essential for ovulation. PMID:24403066

  18. Transit Spectroscopy of Extrasolar Planet HD209458b: The Radiative Transfer Model

    NASA Astrophysics Data System (ADS)

    Rojo, P.; Harrington, J.; Dermody, J.; Zeehandelaar, D.; Deming, D.; Wiedemann, G.; Seager, S.; Iro, N.; Fortney, J. J.; Burrows, A.

    2004-11-01

    We have developed a new code that calculates the modulation of a star's spectrum as a planet transits. We are applying this model to data from the VLT, Palomar, Keck, and IRTF to search for water on HD209458b, the transiting planet with the brightest primary. Observations of HD209458b's stellar spectrum modulation have yielded the first detections of exoplanetary sodium (Charbonneau et al. 2001), hydrogen, oxygen and carbon (Vidal-Madjar et al. 2003, 2004). Molecules, however, have still avoided detection. Water is predicted to be abundant at all plausible temperatures, but the modulation for most of the observable features is <0.04%. By simultaneously fitting for many excited water features while avoiding telluric water lines, we can significantly increase our signal. Our model predicts the modulation given line data, system geometry, and thermal and abundance profiles for any transiting planet. We will use this code to compare the observed modulation for HD209458b with that predicted by different planetary theories, do calculations for specific instruments with different resolutions and wavelength ranges, and constrain the abundances of detected species. We find that integrating the extinction over altitude produces significantly better results than assuming that the planet is an opaque disk whose radius is the altitude of optical depth unity. The latter is a widely used simplification. Our work will allow us to establish or place strong limits on the water abundance in HD209458b's atmosphere. Even a non-detection will be important, as it will require significant modifications to existing theory and/or will justify the need for better space-based instruments. This work was supported by NASA grant NAG5-13154.

  19. Polyaniline decorated Bi2MoO6 nanosheets with effective interfacial charge transfer as photocatalysts and optical limiters.

    PubMed

    Zhao, Wei; Li, Cheng; Wang, Aijian; Lv, Cuncai; Zhu, Weihua; Dou, Shengping; Wang, Qian; Zhong, Qin

    2017-11-01

    Polyaniline (PANI)-decorated Bi 2 MoO 6 nanosheets (BMO/PANI) were prepared by a facile solvothermal method. Different characterization techniques, including X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, diffuse reflectance ultraviolet-visible spectroscopy, photoluminescence spectroscopy, electrochemical impedance spectroscopy, photocurrent spectroscopy, and nanosecond time-resolved emission studies, have been employed to investigate the structure, optical and electrical properties of the BMO/PANI composites. The wide absorption of the samples in the visible light region makes them suitable for nonlinear transmission and photocatalytic activity studies. The associated photocatalytic activity and optical nonlinearities for the BMO/PANI composites are shown to be dependent on the PANI loadings. The rational mechanisms responsible for deteriorating pollutants and improving optical nonlinearities were also proposed, which could be mainly attributed to the efficient interfacial charge transfer and the interfacial electronic interactions between PANI and Bi 2 MoO 6 . The photoluminescence spectroscopy, electrochemical impedance spectroscopy, and photocurrent spectroscopy studies confirmed that the interface charge separation efficiency was greatly improved by coupling Bi 2 MoO 6 with PANI. The tuning of photocatalysis and nonlinear optical behaviors with variation in the content of PANI provides an easy way to attain tunable properties, which are exceedingly required in optoelectronics applications.

  20. Diiodobodipy-styrylbodipy Dyads: Preparation and Study of the Intersystem Crossing and Fluorescence Resonance Energy Transfer.

    PubMed

    Wang, Zhijia; Xie, Yun; Xu, Kejing; Zhao, Jianzhang; Glusac, Ksenija D

    2015-07-02

    2,6-Diiodobodipy-styrylbodipy dyads were prepared to study the competing intersystem crossing (ISC) and the fluorescence-resonance-energy-transfer (FRET), and its effect on the photophysical property of the dyads. In the dyads, 2,6-diiodobodipy moiety was used as singlet energy donor and the spin converter for triplet state formation, whereas the styrylbodipy was used as singlet and triplet energy acceptors, thus the competition between the ISC and FRET processes is established. The photophysical properties were studied with steady-state UV-vis absorption and fluorescence spectroscopy, electrochemical characterization, and femto/nanosecond time-resolved transient absorption spectroscopies. FRET was confirmed with steady state fluorescence quenching and fluorescence excitation spectra and ultrafast transient absorption spectroscopy (kFRET = 5.0 × 10(10) s(-1)). The singlet oxygen quantum yield (ΦΔ = 0.19) of the dyad was reduced as compared with that of the reference spin converter (2,6-diiodobodipy, ΦΔ = 0.85), thus the ISC was substantially inhibited by FRET. Photoinduced intramolecular electron transfer (ET) was studied by electrochemical data and fluorescence quenching. Intermolecular triplet energy transfer was studied with nanosecond transient absorption spectroscopy as an efficient (ΦTTET = 92%) and fast process (kTTET = 5.2 × 10(4) s(-1)). These results are useful for designing organic triplet photosensitizers and for the study of the photophysical properties.

  1. Solar Energy: Heat Transfer.

    ERIC Educational Resources Information Center

    Knapp, Henry H., III

    This module on heat transfer is one of six in a series intended for use as supplements to currently available materials on solar energy and energy conservation. Together with the recommended texts and references (sources are identified), these modules provide an effective introduction to energy conservation and solar energy technologies. The…

  2. SAFETY AND EFFICIENCY OF MODULATING PARACELLULAR PERMEABILITY TO ENHANCE AIRWAY EPITHELIAL GENE TRANSFER IN VIVO

    EPA Science Inventory


    ABSTRACT

    We evaluated the safety of agents that enhance gene transfer by modulating paracellular permeability. Lactate dehydrogenase (LDH) and cytokine release were measured in polarized primary human airway epithelial (HAE) cells after luminal application of vehicle, ...

  3. Bayesian Atmospheric Radiative Transfer (BART) Code and Application to WASP-43b

    NASA Astrophysics Data System (ADS)

    Blecic, Jasmina; Harrington, Joseph; Cubillos, Patricio; Bowman, Oliver; Rojo, Patricio; Stemm, Madison; Lust, Nathaniel B.; Challener, Ryan; Foster, Austin James; Foster, Andrew S.; Blumenthal, Sarah D.; Bruce, Dylan

    2016-01-01

    We present a new open-source Bayesian radiative-transfer framework, Bayesian Atmospheric Radiative Transfer (BART, https://github.com/exosports/BART), and its application to WASP-43b. BART initializes a model for the atmospheric retrieval calculation, generates thousands of theoretical model spectra using parametrized pressure and temperature profiles and line-by-line radiative-transfer calculation, and employs a statistical package to compare the models with the observations. It consists of three self-sufficient modules available to the community under the reproducible-research license, the Thermochemical Equilibrium Abundances module (TEA, https://github.com/dzesmin/TEA, Blecic et al. 2015}, the radiative-transfer module (Transit, https://github.com/exosports/transit), and the Multi-core Markov-chain Monte Carlo statistical module (MCcubed, https://github.com/pcubillos/MCcubed, Cubillos et al. 2015). We applied BART on all available WASP-43b secondary eclipse data from the space- and ground-based observations constraining the temperature-pressure profile and molecular abundances of the dayside atmosphere of WASP-43b. This work was supported by NASA Planetary Atmospheres grant NNX12AI69G and NASA Astrophysics Data Analysis Program grant NNX13AF38G. JB holds a NASA Earth and Space Science Fellowship.

  4. Fourier transfer Raman spectroscopy of pyridine adsorbed onto Y-zeolites

    NASA Astrophysics Data System (ADS)

    Ferwerda, R.; van der Maas, John H.

    1994-01-01

    FT near-infrared excited Raman spectroscopy is used to get a better insight in the adsorption of pyridine onto NaxHyY zeolites. It appears that five different adsorption sites can be monitored; `physisorbed,' OH bonded, Lewis and two distinct Bronsted sites. Comparison to infrared spectroscopy reveals better understanding of the vibrational spectra.

  5. Characterization of Infrared Properties of Layered Semiconductors.

    DTIC Science & Technology

    1987-02-20

    candidate -10- V. PUBLICATIONS INCLUDED WITH REPORT 1) R. Braunstein, R. K . Kim, D. Matthews, and M. Braunstein: "Derivative Absorption Spectroscopy of...34Wavelength Modulation Spectra of a-Ag0.7Zn0 .3 Near the Optical Absorption Edge," Phys. Stat. Sol.(b) 131, 659 (1983). 5) R. K . Kim and R. Braunstein...34Infrared Wavelength Modulation Spectroscopy of Some Optical Material," Appl. Optics 23(8), 1166 (1984). 6) C.E. Jones, K . James, J. Merz, R. Braunstein, M

  6. Simultaneous transfer of optical frequency and time over 306 km long-haul optical fibre link

    NASA Astrophysics Data System (ADS)

    Hucl, Vaclav; Cizek, Martin; Pravdova, Lenka; Rerucha, Simon; Hrabina, Jan; Mikel, Bretislav; Smotlacha, Vladimir; Vojtech, Josef; Lazar, Josef; Cip, Ondrej

    2016-12-01

    Optical fibre links for distributing optical frequencies and time stamps were researched and experimentally tested in the past fifteen years. They have been used mainly for stability comparison of experimental optical clocks. But recent development puts demands on a technology transfer from laboratory experiments to the real industry. The remote calibration of interrogators of Fibre Bragg Grating strain sensory networks is one of important examples. The first step of the adoption the time and frequency broadcasting should be the drop-out free long-term operation of this technology between research laboratories connected via long-haul fibre links. We present a 306 km long-haul optical fibre link between the cities of Prague and Brno in the Czech Republic where a coherent transfer of stable optical frequency and a stable time signal has been firstly demonstrated. The link between ISI CAS Brno and CESNET Prague uses an internet communication fibre where a window of 1540-1546 nm is dedicated for the coherent transfer and 1PPS signal. The link is equipped with 6 bidirectional EDFA amplifiers. The optical frequency standard based on the highly-coherent laser Koheras Adjustik working at 1540.5 nm and stabilized with a saturation absorption spectroscopy technique was used for the coherent wave transfer. The suppression of the Doppler shift induced by the optical fibre was based on an accoustooptical modulator with a servo-loop including a fast PID controller processing the beat-note frequency given by mixing of the Adjustik laser (Brno) and the reflected frequency of this laser from the far end of 306 km long-haul fibre link (Prague). We verified the Doppler shift suppression for the coherent wave with a measuring method analysing the transport delay of the 1PPS signal.

  7. Structural instability and electronic localization in the 2:1 salts: The case of the Fabre and the (DMtTTF){2}CIO{4}salts

    NASA Astrophysics Data System (ADS)

    Ravy, S.; Foury-Leylekian, P.; Le Bolloc'h, D.; Pouget, J.-P.; Fabre, J. M.; Prado, R. J.; Lagarde, P.

    2004-04-01

    The charge ordering observed in the (TMTTF){2}X family has been studied by X-ray absorption spectroscopy. XANES measurements at the Sulfur K-edge show no evidence of charge disproportionation larger than 0.5 e, and EXAFS at the Phosphorus K-edge indicate no displacements of the PF{6} anion larger than 0.05 Å. The difficulty to observe a structural signature of this charge ordering is due to the triclinic symmetry of these salts. By contrast, in the monoclinic charge transfer salt (DMtTTF){2}ClO{4}, a screw axis symmetry constrains the molecular stacks to be uniform. In this real 1/4-filled system, charge localization is observed at about 150 K. We show that around this temperature an incommensurate modulation of reduced wave vector (0.58,0,-0.275) is stabilized. The transition is strongly hysteretic, but no long range order is established. We suggest that this modulation, which has the 4k{F} periodicity in the chain direction, stabilizes a local antiferroelectric state similar to the one previously observed in (TMTTF){2}SCN. Key words. Charge ordering, Structural phase transition.

  8. Extension of wavelength-modulation spectroscopy to large modulation depth for diode laser absorption measurements in high-pressure gases

    NASA Astrophysics Data System (ADS)

    Li, Hejie; Rieker, Gregory B.; Liu, Xiang; Jeffries, Jay B.; Hanson, Ronald K.

    2006-02-01

    Tunable diode laser absorption measurements at high pressures by use of wavelength-modulation spectroscopy (WMS) require large modulation depths for optimum detection of molecular absorption spectra blended by collisional broadening or dense spacing of the rovibrational transitions. Diode lasers have a large and nonlinear intensity modulation when the wavelength is modulated over a large range by injection-current tuning. In addition to this intensity modulation, other laser performance parameters are measured, including the phase shift between the frequency modulation and the intensity modulation. Following published theory, these parameters are incorporated into an improved model of the WMS signal. The influence of these nonideal laser effects is investigated by means of wavelength-scanned WMS measurements as a function of bath gas pressure on rovibrational transitions of water vapor near 1388 nm. Lock-in detection of the magnitude of the 2f signal is performed to remove the dependence on detection phase. We find good agreement between measurements and the improved model developed for the 2f component of the WMS signal. The effects of the nonideal performance parameters of commercial diode lasers are especially important away from the line center of discrete spectra, and these contributions become more pronounced for 2f signals with the large modulation depths needed for WMS at elevated pressures.

  9. Strategic modulation of the photonic properties of conjugated organometallic Pt-Ir polymers exhibiting hybrid CT-excited states.

    PubMed

    Soliman, Ahmed M; Zysman-Colman, Eli; Harvey, Pierre D

    2015-04-01

    Polymer 6, ([trans-Pt(PBu3 )2 (C≡C)2 ]-[Ir(dFMeppy)2 (N^N)](PF6 ))n , (([Pt]-[Ir](PF6 ))n ; N^N = 5,5'-disubstituted-2,2'-bipyridyl; dFMeppy = 2-(2,4-difluoro-phenyl)-5-methylpyridine) is prepared along with model compounds. These complexes are investigated by absorption and emission spectroscopy and their photophysical and electrochemical properties are measured and compared with their corresponding non fluorinated complexes. Density functional theory (DFT) and time-dependent DFT computations corroborate the nature of the excited state as being a hybrid between the metal-to-ligand charge transfer ((1,3) MLCT) for the trans-Pt(PBu3 )2 (C≡CAr)2 unit, [Pt] and the metal-to-ligand/ligand-to-ligand' charge transfer ((1,3) ML'CT/LL'CT) for [Ir] with L = dFMeppy. Overall, the fluorination of the phenylpyridine group expectedly does not change the nature of the excited state but desirably induces a small blue shift of the absorption and emission bands along a slight decrease in emission quantum yields and lifetimes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Remotely Exploring Deeper-Into-Matter by Non-Contact Detection of Audible Transients Excited by Laser Radiation

    PubMed Central

    Moros, Javier; Gaona, Inmaculada; Laserna, J. Javier

    2017-01-01

    An acoustic spectroscopic approach to detect contents within different packaging, with substantially wider applicability than other currently available subsurface spectroscopies, is presented. A frequency-doubled Nd:YAG (neodymium-doped yttrium aluminum garnet) pulsed laser (13 ns pulse length) operated at 1 Hz was used to generate the sound field of a two-component system at a distance of 50 cm. The acoustic emission was captured using a unidirectional microphone and analyzed in the frequency domain. The focused laser pulse hitting the system, with intensity above that necessary to ablate the irradiated surface, transferred an impulsive force which led the structure to vibrate. Acoustic airborne transients were directly radiated by the vibrating elastic structure of the outer component that excited the surrounding air in contact with. However, under boundary conditions, sound field is modulated by the inner component that modified the dynamical integrity of the system. Thus, the resulting frequency spectra are useful indicators of the concealed content that influences the contributions originating from the wall of the container. High-quality acoustic spectra could be recorded from a gas (air), liquid (water), and solid (sand) placed inside opaque chemical-resistant polypropylene and stainless steel sample containers. Discussion about effects of laser excitation energy and sampling position on the acoustic emission events is reported. Acoustic spectroscopy may complement the other subsurface alternative spectroscopies, severely limited by their inherent optical requirements for numerous detection scenarios. PMID:29261126

  11. Accurate formulas for interaction force and energy in frequency modulation force spectroscopy

    NASA Astrophysics Data System (ADS)

    Sader, John E.; Jarvis, Suzanne P.

    2004-03-01

    Frequency modulation atomic force microscopy utilizes the change in resonant frequency of a cantilever to detect variations in the interaction force between cantilever tip and sample. While a simple relation exists enabling the frequency shift to be determined for a given force law, the required complementary inverse relation does not exist for arbitrary oscillation amplitudes of the cantilever. In this letter we address this problem and present simple yet accurate formulas that enable the interaction force and energy to be determined directly from the measured frequency shift. These formulas are valid for any oscillation amplitude and interaction force, and are therefore of widespread applicability in frequency modulation dynamic force spectroscopy.

  12. Preface: phys. stat. sol. (a) 202/7

    NASA Astrophysics Data System (ADS)

    Pollak, Fred H.; Misiewicz, Jan; Sitarek, Piotr

    2005-05-01

    We have recently observed a growing interest in using the powerful technique of optical modulation spectroscopy. These applications are related mostly to the characterization of low dimensional semiconductor structures and devices based on them.The International Workshop on Modulation Spectroscopy of Semiconductor Structures (MS3) at the beginning of July 2004 gathered in Wrocaw (in the southwest part of Poland) almost 40 participants, half of them from abroad. The 8 invited and 16 contributed talks were presented by the leaders of research teams from the USA, Japan, Taiwan, Canada, Germany, France, the Netherlands, Sweden, Ireland, Russia, Lithuania and Poland. Part of the MS3 workshop was held at the Laboratory of Advanced Optical Spectroscopy, Institute of Physics, Wrocaw University of Technology, where discussions on technical matter of the modulation spectroscopy were carried out in a relaxing atmosphere over a cup of coffee.The topics of the MS3 workshop included: advantages of photoreflectance, electroreflectance, contactless electroreflectance, thermoreflectance, differential reflectance and wavelength-modulated surface photovoltage spectroscopy. The applications of the above methods to investigate transistor, diode and laser structures including VCSELs, low dimensional structures of both wings of the spectrum, i.e. wide band gap materials like GaN, AlGaN, ZnO and low band gap materials such as GaInN(Sb)As, InAs, InSb, and FeSi2 were demonstrated.It is our great pleasure to publish the most interesting of the MS3 workshop presentations in this issue of physica status solidi (a).The organizers acknowledge Wrocaw University of Technology, the Center of Exellence CEPHONA from the Institute of Electron Technology in Warsaw and the Polish Committee for Scientific Research for financial support of the workshop.

  13. Readout Electronics for the Central Drift Chamber of the Belle-II Detector

    NASA Astrophysics Data System (ADS)

    Uchida, Tomohisa; Taniguchi, Takashi; Ikeno, Masahiro; Iwasaki, Yoshihito; Saito, Masatoshi; Shimazaki, Shoichi; Tanaka, Manobu M.; Taniguchi, Nanae; Uno, Shoji

    2015-08-01

    We have developed readout electronics for the central drift chamber (CDC) of the Belle-II detector. The space near the endplate of the CDC for installation of the electronics was limited by the detector structure. Due to the large amounts of data generated by the CDC, a high-speed data link, with a greater than one gigabit transfer rate, was required to transfer the data to a back-end computer. A new readout module was required to satisfy these requirements. This module processes 48 signals from the CDC, converts them to digital data and transfers it directly to the computer. All functions that transfer digital data via the high speed link were implemented on the single module. We have measured its electrical characteristics and confirmed that the results satisfy the requirements of the Belle-II experiment.

  14. Quantitative Detection of Pharmaceuticals Using a Combination of Paper Microfluidics and Wavelength Modulated Raman Spectroscopy

    PubMed Central

    Craig, Derek; Mazilu, Michael; Dholakia, Kishan

    2015-01-01

    Raman spectroscopy has proven to be an indispensable technique for the identification of various types of analytes due to the fingerprint vibration spectrum obtained. Paper microfluidics has also emerged as a low cost, easy to fabricate and portable approach for point of care testing. However, due to inherent background fluorescence, combining Raman spectroscopy with paper microfluidics is to date an unmet challenge in the absence of using surface enhanced mechanisms. We describe the first use of wavelength modulated Raman spectroscopy (WMRS) for analysis on a paper microfluidics platform. This study demonstrates the ability to suppress the background fluorescence of the paper using WMRS and the subsequent implementation of this technique for pharmaceutical analysis. The results of this study demonstrate that it is possible to discriminate between both paracetamol and ibuprofen, whilst, also being able to detect the presence of each analyte quantitatively at nanomolar concentrations. PMID:25938464

  15. NASA Tech Briefs, January 2009

    NASA Technical Reports Server (NTRS)

    2009-01-01

    Tech Briefs are short announcements of innovations originating from research and development activities of the National Aeronautics and Space Administration. They emphasize information considered likely to be transferable across industrial, regional, or disciplinary lines and are issued to encourage commercial application. Topics covered include: The Radio Frequency Health Node Wireless Sensor System; Effects of Temperature on Polymer/Carbon Chemical Sensors; Small CO2 Sensors Operate at Lower Temperature; Tele-Supervised Adaptive Ocean Sensor Fleet; Synthesis of Submillimeter Radiation for Spectroscopy; 100-GHz Phase Switch/Mixer Containing a Slot-Line Transition; Generating Ka-Band Signals Using an X-Band Vector Modulator; SiC Optically Modulated Field-Effect Transistor; Submillimeter-Wave Amplifier Module with Integrated Waveguide Transitions; Metrology System for a Large, Somewhat Flexible Telescope; Economical Implementation of a Filter Engine in an FPGA; Improved Joining of Metal Components to Composite Structures; Machined Titanium Heat-Pipe Wick Structure; Gadolinia-Doped Ceria Cathodes for Electrolysis of CO2; Utilizing Ocean Thermal Energy in a Submarine Robot; Fuel-Cell Power Systems Incorporating Mg-Based H2 Generators; Alternative OTEC Scheme for a Submarine Robot; Sensitive, Rapid Detection of Bacterial Spores; Adenosine Monophosphate-Based Detection of Bacterial Spores; Silicon Microleaks for Inlets of Mass Spectrometers; CGH Figure Testing of Aspherical Mirrors in Cold Vacuums; Series-Coupled Pairs of Silica Microresonators; Precise Stabilization of the Optical Frequency of WGMRs; Formation Flying of Components of a Large Space Telescope; Laser Metrology Heterodyne Phase-Locked Loop; Spatial Modulation Improves Performance in CTIS; High-Performance Algorithm for Solving the Diagnosis Problem; Truncation Depth Rule-of-Thumb for Convolutional Codes; Efficient Method for Optimizing Placement of Sensors.

  16. Flexible lock-in detection system based on synchronized computer plug-in boards applied in sensitive gas spectroscopy

    NASA Astrophysics Data System (ADS)

    Andersson, Mats; Persson, Linda; Svensson, Tomas; Svanberg, Sune

    2007-11-01

    We present a flexible and compact, digital, lock-in detection system and its use in high-resolution tunable diode laser spectroscopy. The system involves coherent sampling, and is based on the synchronization of two data acquisition cards running on a single standard computer. A software-controlled arbitrary waveform generator is used for laser modulation, and a four-channel analog/digital board records detector signals. Gas spectroscopy is performed in the wavelength modulation regime. The coherently detected signal is averaged a selected number of times before it is stored or analyzed by software-based, lock-in techniques. Multiple harmonics of the modulation signal (1f, 2f, 3f, 4f, etc.) are available in each single data set. The sensitivity is of the order of 10-5, being limited by interference fringes in the measurement setup. The capabilities of the system are demonstrated by measurements of molecular oxygen in ambient air, as well as dispersed gas in scattering materials, such as plants and human tissue.

  17. Flexible lock-in detection system based on synchronized computer plug-in boards applied in sensitive gas spectroscopy.

    PubMed

    Andersson, Mats; Persson, Linda; Svensson, Tomas; Svanberg, Sune

    2007-11-01

    We present a flexible and compact, digital, lock-in detection system and its use in high-resolution tunable diode laser spectroscopy. The system involves coherent sampling, and is based on the synchronization of two data acquisition cards running on a single standard computer. A software-controlled arbitrary waveform generator is used for laser modulation, and a four-channel analog/digital board records detector signals. Gas spectroscopy is performed in the wavelength modulation regime. The coherently detected signal is averaged a selected number of times before it is stored or analyzed by software-based, lock-in techniques. Multiple harmonics of the modulation signal (1f, 2f, 3f, 4f, etc.) are available in each single data set. The sensitivity is of the order of 10(-5), being limited by interference fringes in the measurement setup. The capabilities of the system are demonstrated by measurements of molecular oxygen in ambient air, as well as dispersed gas in scattering materials, such as plants and human tissue.

  18. Characterization of self assembly layers of octadecanephosphonic acid by polarisation modulation FT-IRRA spectroscopy mapping

    NASA Astrophysics Data System (ADS)

    Steiner, G.; Sablinskas, V.; Savchuk, O.; Bariseviciute, R.; Jähne, E.; Adler, H. J.; Salzer, R.

    2003-12-01

    Self assembly layers were studied by a polarization modulation FT-spectroscopy mapping technique. The optical lay out is based on polarization modulation FT infrared reflection absorption spectroscopy (PM-FT-IRRAS). Here we report for the first time on a PM-FT-IRRAS mapping instrument. Octadecanephosphonic acid adsorbed on a patterned aluminum/gold surface was investigated. The nature of chemical bonding at particular surface areas was evaluated by principal component analysis. The most prominent features of the PM-FT-IRRA spectra are the P-O and PO stretching vibrations. It is shown that octadecanephosphonic acid is adsorbed both on Al 2O 3 and on Au. Moreover, PM-FT-IRRAS maps reveal areas of non-equivalent structural features. Lateral dimensions of these areas are in the micrometer range. Such non-equivalencies may control the inhibition potential of SAMs on ignoble metals, hence become crucial to the quality of products as biosensors or microelectronic components.

  19. Neutron transport analysis for nuclear reactor design

    DOEpatents

    Vujic, Jasmina L.

    1993-01-01

    Replacing regular mesh-dependent ray tracing modules in a collision/transfer probability (CTP) code with a ray tracing module based upon combinatorial geometry of a modified geometrical module (GMC) provides a general geometry transfer theory code in two dimensions (2D) for analyzing nuclear reactor design and control. The primary modification of the GMC module involves generation of a fixed inner frame and a rotating outer frame, where the inner frame contains all reactor regions of interest, e.g., part of a reactor assembly, an assembly, or several assemblies, and the outer frame, with a set of parallel equidistant rays (lines) attached to it, rotates around the inner frame. The modified GMC module allows for determining for each parallel ray (line), the intersections with zone boundaries, the path length between the intersections, the total number of zones on a track, the zone and medium numbers, and the intersections with the outer surface, which parameters may be used in the CTP code to calculate collision/transfer probability and cross-section values.

  20. Neutron transport analysis for nuclear reactor design

    DOEpatents

    Vujic, J.L.

    1993-11-30

    Replacing regular mesh-dependent ray tracing modules in a collision/transfer probability (CTP) code with a ray tracing module based upon combinatorial geometry of a modified geometrical module (GMC) provides a general geometry transfer theory code in two dimensions (2D) for analyzing nuclear reactor design and control. The primary modification of the GMC module involves generation of a fixed inner frame and a rotating outer frame, where the inner frame contains all reactor regions of interest, e.g., part of a reactor assembly, an assembly, or several assemblies, and the outer frame, with a set of parallel equidistant rays (lines) attached to it, rotates around the inner frame. The modified GMC module allows for determining for each parallel ray (line), the intersections with zone boundaries, the path length between the intersections, the total number of zones on a track, the zone and medium numbers, and the intersections with the outer surface, which parameters may be used in the CTP code to calculate collision/transfer probability and cross-section values. 28 figures.

  1. Nonadiabatic effect on the quantum heat flux control.

    PubMed

    Uchiyama, Chikako

    2014-05-01

    We provide a general formula of quantum transfer that includes the nonadiabatic effect under periodic environmental modulation by using full counting statistics in Hilbert-Schmidt space. Applying the formula to an anharmonic junction model that interacts with two bosonic environments within the Markovian approximation, we find that the quantum transfer is divided into the adiabatic (dynamical and geometrical phases) and nonadiabatic contributions. This extension shows the dependence of quantum transfer on the initial condition of the anharmonic junction just before the modulation, as well as the characteristic environmental parameters such as interaction strength and cut-off frequency of spectral density. We show that the nonadiabatic contribution represents the reminiscent effect of past modulation including the transition from the initial condition of the anharmonic junction to a steady state determined by the very beginning of the modulation. This enables us to tune the frequency range of modulation, whereby we can obtain the quantum flux corresponding to the geometrical phase by setting the initial condition of the anharmonic junction.

  2. Performance characteristics of a thermal energy storage module - A transient PCM/forced convection conjugate analysis

    NASA Technical Reports Server (NTRS)

    Cao, Y.; Faghri, A.

    1991-01-01

    The performance of a thermal energy storage module is simulated numerically. The change of phase of the phase-change material (PCM) and the transient forced convective heat transfer for the transfer fluid with low Prandtl numbers are solved simultaneously as a conjugate problem. A parametric study and a system optimization are conducted. The numerical results show that module geometry is crucial to the design of a space-based thermal energy storage system.

  3. The Air Force Manufacturing Technology (MANTECH): Technology transfer methodology as exemplified by the radar transmit/receive module program

    NASA Technical Reports Server (NTRS)

    Houpt, Tracy; Ridgely, Margaret

    1991-01-01

    The Air Force Manufacturing Technology program is involved with the improvement of radar transmit/receive modules for use in active phased array radars for advanced fighter aircraft. Improvements in all areas of manufacture and test of these modules resulting in order of magnitude improvements in the cost of and the rate of production are addressed, as well as the ongoing transfer of this technology to the Navy.

  4. A compact frequency stabilized telecom laser diode for space applications

    NASA Astrophysics Data System (ADS)

    Philippe, C.; Holleville, D.; Le Targat, R.; Wolf, P.; Leveque, T.; Le Goff, R.; Martaud, E.; Acef, O.

    2017-09-01

    We report on a Telecom laser diode (LD) frequency stabilization to a narrow iodine hyperfine line in the green range, after frequency tripling process using fibered nonlinear waveguide PPLN crystals. We have generated up to 300 mW optical power in the green range ( 514 nm) from 800 mW of infrared power ( 1542 nm), corresponding to a nonlinear conversion efficiency h = P3?/P? 36%. Less than 10 mW of the generated green power are used for Doppler-free spectroscopy of 127I2 molecular iodine, and -therefore- for the frequency stabilization purpose. The frequency tripling optical setup is very compact (< 5 l), fully fibered, and could operate over the full C-band of the Telecom range (1530 nm - 1565 nm). Several thousands of hyperfine iodine lines may thus be interrogated in the 510 nm - 521 nm range. We build up an optical bench used at first in free space configuration, using the well-known modulation transfer spectroscopy technique (MTS), in order to test the potential of this new frequency standard based on the couple "1.5 ?m laser / iodine molecule". We have already demonstrated a preliminary frequency stability of 4.8 x 10-14 ? -1/2 with a minimum value of 6 x 10-15 reached after 50 s of integration time, conferred to a laser diode operating at 1542.1 nm. We focus now our efforts to expand the frequency stability to a longer integration time in order to meet requirements of many space experiments, such earth gravity missions, inters satellites links or space to ground communications. Furthermore, we investigate the potential of a new approach based on frequency modulation technique (FM), associated to a 3rd harmonic detection of iodine lines to increase the compactness of the optical setup.

  5. Study of the interaction of lactoferricin B with phospholipid monolayers and bilayers.

    PubMed

    Arseneault, Marjolaine; Bédard, Sarah; Boulet-Audet, Maxime; Pézolet, Michel

    2010-03-02

    Bovine lactoferricin (LfcinB) is an antimicrobial peptide obtained from the pepsin cleavage of lactoferrin. The activity of LfcinB has been extensively studied on diverse pathogens, but its mechanism of action still has to be elucidated. Because of its nonspecificity, its mode of action is assumed to be related to interactions with membranes. In this study, the interaction of LfcinB with a negatively charged monolayer of dipalmitoylphosphatidylglycerol has been investigated as a function of the surface pressure of the lipid film using in situ Brewster angle and polarization modulation infrared reflection absorption spectroscopy and on transferred monolayers by atomic force microscopy and polarized attenuated total reflection infrared spectroscopy. The data show clearly that LfcinB forms stable films at the air-water interface. They also reveal that the interaction of LfcinB with the lipid monolayer is modulated by the surface pressure. At low surface pressure, LfcinB inserts within the lipid film with its long molecular axis oriented mainly parallel to the acyl chains, while at high surface pressure, LfcinB is adsorbed under the lipid film, the hairpin being preferentially aligned parallel to the plane of the interface. The threshold for which the behavior changes is 20 mN/m. At this critical surface pressure, LfcinB interacts with the monolayer to form discoidal lipid-peptide assemblies. This structure may actually represent the mechanism of action of this peptide. The results obtained on monolayers are correlated by fluorescent probe release measurements of dye-containing vesicles made of lipids in different phases and support the important role of the lipid fluidity and packing on the activity of LfcinB.

  6. UCEPR: Ultrafast localized CEST-spectroscopy with PRESS in phantoms and in vivo.

    PubMed

    Liu, Zheng; Dimitrov, Ivan E; Lenkinski, Robert E; Hajibeigi, Asghar; Vinogradov, Elena

    2016-05-01

    Chemical exchange saturation transfer (CEST) is a contrast mechanism enhancing low-concentration molecules through saturation transfer from their exchangeable protons to bulk water. Often many scans are acquired to form a Z-spectrum, making the CEST method time-consuming. Here, an ultrafast localized CEST-spectroscopy with PRESS (UCEPR) is proposed to obtain the entire Z-spectrum of a voxel using only two scans, significantly accelerating CEST. The approach combines ultrafast nonlocalized CEST spectroscopy with localization using PRESS. A field gradient is applied concurrently with the saturation pulse producing simultaneous saturation of all Z-spectrum frequencies that are also spatially encoded. A readout gradient during data acquisition resolves the spatial dependence of the CEST responses into frequency. UCEPR was tested on a 3T scanner both in phantoms and in vivo. In phantoms, a fast Z-spectroscopy acquisition of multiple pH-variant iopamidol samples was achieved with four- to seven-fold acceleration as compared to the conventional CEST methods. In vivo, amide proton transfer (APT) in white matter of healthy human brain was measured rapidly in 48 s and with high frequency resolution (≤ 0.2 ppm). Compared with conventional CEST methods, UCEPR has the advantage of rapidly acquiring high-resolution Z-spectra. Potential in vivo applications include ultrafast localized Z-spectroscopy, quantitative, or dynamic CEST studies. © 2015 Wiley Periodicals, Inc.

  7. Gas Phase Molecular Spectroscopy: Electronic Spectroscopy of Combustion Intermediates, Chlorine Azide kinetics, and Rovibrational Energy Transfer in Acetylene

    NASA Astrophysics Data System (ADS)

    Freel, Keith A.

    This dissertation is composed of three sections. The first deals with the electronic spectroscopy of combustion intermediates that are related to the formation of polycyclic aromatic hydrocarbons. Absorption spectra for phenyl, phenoxy, benzyl, and phenyl peroxy radicals were recorded using the technique of cavity ring-down spectroscopy. When possible, molecular constants, vibrational frequencies, and excited state lifetimes for these radicals were derived from these data. The results were supported by theoretical predictions. The second section presents a study of electron attachment to chlorine azide (ClN3) using a flowing-afterglow Langmuir-probe apparatus. Electron attachment rates were measured to be 3.5x10-8 and 4.5x10-8 cm3s-1 at 298 and 400 K respectively. The reactions of ClN3 with eighteen cations and seventeen anions were characterized. Rate constants were measured using a selected ion flow tube. The ionization energy (>9.6eV), proton affinity (713+/-41 kJ mol-1), and electron affinity (2.48+/-0.2 eV) for ClN 3 were determined from these data. The third section demonstrates the use of double resonance spectroscopy to observe state-selected rovibrational energy transfer from the first overtone asymmetric stretch of acetylene. The total population removal rate constants from various rotational levels of the (1,0,1,00,00) vibrational state were determined to be in the range of (9-17) x 10 -10 cm3s-1. Rotational energy transfer accounted for approximately 90% of the total removal rate from each state. Therefore, the upper limit of vibrational energy transfer from the (1,0,1,0 0,00) state was 10%.

  8. Insights into the enhanced photoelectrochemical performance of hydrothermally controlled hematite nanostructures for proficient solar water oxidation.

    PubMed

    Park, Jin Woo; Subramanian, Arunprabaharan; Mahadik, Mahadeo A; Lee, Su Yong; Choi, Sun Hee; Jang, Jum Suk

    2018-03-28

    In this paper, we focus on the controlled growth mechanism of α-Fe 2 O 3 nanostructures via the hydrothermal method. The field emission scanning electron microscopy (FESEM) results reveal that at a lower hydrothermal time, the initial nucleation involves the formation of short and thin β-FeOOH nanorods. The subsequent increase in the hydrothermal time leads β-FeOOH to form thicker and longer nanorods. However, high-temperature quenching (HTQ) at 800 °C for 10 min causes the conversion of akaganeite to the hematite phase and activation of hematite by Sn 4+ diffusion from a FTO substrate. Sn 4+ diffusion from the FTO substrate to the hematite nanostructure was elaborated by X-ray photoelectron spectroscopy (XPS). An α-Fe 2 O 3 nanorod photoanode prepared by a hydrothermal reaction for 3 h and HTQ exhibits the highest photocurrent density of 1.04 mA cm -2 . The excellent photoelectrochemical performance could be ascribed to the synergistic effect of the optimum growth of α-Fe 2 O 3 nanorod arrays and Sn 4+ diffusion. Intensity modulated photovoltage spectroscopy (IMVS) studies revealed that the α-Fe 2 O 3 photoanodes prepared at 3 h and HTQ exhibited a long electron lifetime (132.69 ms), and contribute to the enhanced PEC performance. The results confirmed that the controlled growth of the β-FeOOH nanorods, as well as Sn 4+ diffusion, played a key role in charge transfer during the photoelectrochemical application. The charge transfer mechanisms in α-Fe 2 O 3 nanostructure photoanodes prepared at different hydrothermal times and high-temperature quenching are also investigated.

  9. Realization of pure frequency modulation of DFB laser via combined optical and electrical tuning.

    PubMed

    Tian, Chao; Chen, I-Chun Anderson; Park, Seong-Wook; Martini, Rainer

    2013-04-08

    In this paper we present a novel approach to convert AM signal into FM signal in semiconductor lasers via off resonance optical pumping and report on experimental results obtained with a commercial DFB laser. Aside of demonstrating discrete and fast frequency modulation, we achieve pure frequency modulation through combination with electrical modulation suppressing the associated amplitude modulation, which is detrimental to application such as spectroscopy and communication.

  10. Static magnetic Faraday rotation spectroscopy combined with a differential scheme for OH detection

    NASA Astrophysics Data System (ADS)

    Zhao, Weixiong; Deng, Lunhua; Qian, Xiaodong; Fang, Bo; Gai, Yanbo; Chen, Weidong; Gao, Xiaoming; Zhang, Weijun

    2015-04-01

    The hydroxyl (OH) radical plays a critical role in atmospheric chemistry due to its high reactivity with volatile organic compounds (VOCs) and other trace gaseous species. Because of its very short life time and very low concentration in the atmosphere, interference-free high sensitivity in-situ OH monitoring by laser spectroscopy represents a real challenge. Faraday rotation spectroscopy (FRS) relies on the particular magneto-optic effect observed for paramagnetic species, which makes it capable of enhancing the detection sensitivity and mitigation of spectral interferences from diamagnetic species in the atmosphere. When an AC magnetic field is used, the Zeeman splitting of the molecular absorption line (and thus the magnetic circular birefringence) is modulated. This provides an 'internal modulation' of the sample, which permits to suppress the external noise like interference fringes. An alternative FRS detection scheme is to use a static magnetic field (DC-field) associated with laser wavelength modulation to effectively modulate the Zeeman splitting of the absorption lines. In the DC field case, wavelength modulation of the laser frequency can provide excellent performance compared to most of the sensing systems based on direct absorption and wavelength modulation spectroscopy. The dimension of the DC solenoid is not limited by the resonant frequency of the RLC circuit, which makes large dimension solenoid coil achievable and the absorption base length could be further increased. By employing a combination of the environmental photochemical reactor or smog chamber with multipass absorption cell, one can lower the minimum detection limit for high accuracy atmospheric chemistry studies. In this paper, we report on the development of a DC field based FRS in conjunction with a balanced detection scheme for OH radical detection at 2.8 μm and the construction of OH chemistry research platform which combined a large dimension superconducting magnetic coil with the multipass cell and photochemical reactor chamber for real time in-situ measurement of OH radical concentration in the chamber.

  11. Tissue Characterization with Quantitative High-Resolution Magic Angle Spinning Chemical Exchange Saturation Transfer Z-Spectroscopy.

    PubMed

    Zhou, Iris Yuwen; Fuss, Taylor L; Igarashi, Takahiro; Jiang, Weiping; Zhou, Xin; Cheng, Leo L; Sun, Phillip Zhe

    2016-11-01

    Chemical exchange saturation transfer (CEST) provides sensitive magnetic resonance (MR) contrast for probing dilute compounds via exchangeable protons, serving as an emerging molecular imaging methodology. CEST Z-spectrum is often acquired by sweeping radiofrequency saturation around bulk water resonance, offset by offset, to detect CEST effects at characteristic chemical shift offsets, which requires prolonged acquisition time. Herein, combining high-resolution magic angle spinning (HRMAS) with concurrent application of gradient and rf saturation to achieve fast Z-spectral acquisition, we demonstrated the feasibility of fast quantitative HRMAS CEST Z-spectroscopy. The concept was validated with phantoms, which showed excellent agreement with results obtained from conventional HRMAS MR spectroscopy (MRS). We further utilized the HRMAS Z-spectroscopy for fast ex vivo quantification of ischemic injury with rodent brain tissues after ischemic stroke. This method allows rapid and quantitative CEST characterization of biological tissues and shows potential for a host of biomedical applications.

  12. Transfer doping of single isolated nanodiamonds, studied by scanning probe microscopy techniques.

    PubMed

    Bolker, Asaf; Saguy, Cecile; Kalish, Rafi

    2014-09-26

    The transfer doping of diamond surfaces has been applied in various novel two-dimensional electronic devices. Its extension to nanodiamonds (ND) is essential for ND-based applications in many fields. In particular, understanding the influence of the crystallite size on transfer doping is desirable. Here, we report the results of a detailed study of the electronic energetic band structure of single, isolated transfer-doped nanodiamonds with nanometric resolution using a combination of scanning tunneling spectroscopy and Kelvin force microscopy measurements. The results show how the band gap, the valence band maximum, the electron affinity and the work function all depend on the ND's size and nanoparticle surface properties. The present analysis, which combines information from both scanning tunneling spectroscopy and Kelvin force microscopy, should be applicable to any nanoparticle or surface that can be measured with scanning probe techniques.

  13. Visible spectroscopy calibration transfer model in determining pH of Sala mangoes

    NASA Astrophysics Data System (ADS)

    Yahaya, O. K. M.; MatJafri, M. Z.; Aziz, A. A.; Omar, A. F.

    2015-05-01

    The purpose of this study is to compare the efficiency of calibration transfer procedures between three spectrometers involving two Ocean Optics Inc. spectrometers, namely, QE65000 and Jaz, and also, ASD FieldSpec 3 in measuring the pH of Sala mango by visible reflectance spectroscopy. This study evaluates the ability of these spectrometers in measuring the pH of Sala mango by applying similar calibration algorithms through direct calibration transfer. This visible reflectance spectroscopy technique defines a spectrometer as a master instrument and another spectrometer as a slave. The multiple linear regression (MLR) of calibration model generated using the QE65000 spectrometer is transferred to the Jaz spectrometer and vice versa for Set 1. The same technique is applied for Set 2 with QE65000 spectrometer is transferred to the FieldSpec3 spectrometer and vice versa. For Set 1, the result showed that the QE65000 spectrometer established a calibration model with higher accuracy than that of the Jaz spectrometer. In addition, the calibration model developed on Jaz spectrometer successfully predicted the pH of Sala mango, which was measured using QE65000 spectrometer, with a root means square error of prediction RMSEP = 0.092 pH and coefficients of determination R2 = 0.892. Moreover, the best prediction result is obtained for Set 2 when the calibration model developed on QE65000 spectrometer is successfully transferred to FieldSpec 3 with R2 = 0.839 and RMSEP = 0.16 pH.

  14. Versatile Desktop Experiment Module (DEMo) on Heat Transfer

    ERIC Educational Resources Information Center

    Minerick, Adrienne R.

    2010-01-01

    This paper outlines a new Desktop Experiment Module (DEMo) engineered for a chemical engineering junior-level Heat Transfer course. This new DEMo learning tool is versatile, fairly inexpensive, and portable such that it can be positioned on student desks throughout a classroom. The DEMo system can illustrate conduction of various materials,…

  15. Charge transfer from an adsorbed ruthenium-based photosensitizer through an ultra-thin aluminium oxide layer and into a metallic substrate

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

    Gibson, Andrew J.; Temperton, Robert H.; Handrup, Karsten

    2014-06-21

    The interaction of the dye molecule N3 (cis-bis(isothiocyanato)bis(2,2-bipyridyl-4,4′-dicarbo-xylato) -ruthenium(II)) with the ultra-thin oxide layer on a AlNi(110) substrate, has been studied using synchrotron radiation based photoelectron spectroscopy, resonant photoemission spectroscopy, and near edge X-ray absorption fine structure spectroscopy. Calibrated X-ray absorption and valence band spectra of the monolayer and multilayer coverages reveal that charge transfer is possible from the molecule to the AlNi(110) substrate via tunnelling through the ultra-thin oxide layer and into the conduction band edge of the substrate. This charge transfer mechanism is possible from the LUMO+2 and 3 in the excited state but not from the LUMO,more » therefore enabling core-hole clock analysis, which gives an upper limit of 6.0 ± 2.5 fs for the transfer time. This indicates that ultra-thin oxide layers are a viable material for use in dye-sensitized solar cells, which may lead to reduced recombination effects and improved efficiencies of future devices.« less

  16. Precision Saturated Absorption Spectroscopy of H3+

    NASA Astrophysics Data System (ADS)

    Guan, Yu-chan; Liao, Yi-Chieh; Chang, Yung-Hsiang; Peng, Jin-Long; Shy, Jow-Tsong

    2016-06-01

    In our previous work on the Lamb dips of the νb{2} fundamental band of H3+, the saturated absorption spectrum was obtained by the third-derivative spectroscopy using frequency modulation [1]. However, the frequency modulation also causes error in absolute frequency determination. To solve this problem, we have built an offset-locking system to lock the OPO pump frequency to an iodine-stabilized Nd:YAG laser. With this modification, we are able to scan the OPO idler frequency precisely and obtain the profile of the Lamb dips. Double modulation (amplitude modulation of the idler power and concentration modulation of the ion) is employed to subtract the interference fringes of the signal and increase the signal-to-noise ratio effectively. To Determine the absolute frequency of the idler wave, the pump wave is offset locked on the R(56) 32-0 a10 hyperfine component of 127I2, and the signal wave is locked on a GPS disciplined fiber optical frequency comb (OFC). All references and lock systems have absolute frequency accuracy better than 10 kHz. Here, we demonstrate its performance by measuring one transition of methane and sixteen transitions of H3+. This instrument could pave the way for the high-resolution spectroscopy of a variety of molecular ions. [1] H.-C. Chen, C.-Y. Hsiao, J.-L. Peng, T. Amano, and J.-T. Shy, Phys. Rev. Lett. 109, 263002 (2012).

  17. Direct observation of multistep energy transfer in LHCII with fifth-order 3D electronic spectroscopy.

    PubMed

    Zhang, Zhengyang; Lambrev, Petar H; Wells, Kym L; Garab, Győző; Tan, Howe-Siang

    2015-07-31

    During photosynthesis, sunlight is efficiently captured by light-harvesting complexes, and the excitation energy is then funneled towards the reaction centre. These photosynthetic excitation energy transfer (EET) pathways are complex and proceed in a multistep fashion. Ultrafast two-dimensional electronic spectroscopy (2DES) is an important tool to study EET processes in photosynthetic complexes. However, the multistep EET processes can only be indirectly inferred by correlating different cross peaks from a series of 2DES spectra. Here we directly observe multistep EET processes in LHCII using ultrafast fifth-order three-dimensional electronic spectroscopy (3DES). We measure cross peaks in 3DES spectra of LHCII that directly indicate energy transfer from excitons in the chlorophyll b (Chl b) manifold to the low-energy level chlorophyll a (Chl a) via mid-level Chl a energy states. This new spectroscopic technique allows scientists to move a step towards mapping the complete complex EET processes in photosynthetic systems.

  18. High-Power DFB Diode Laser-Based CO-QEPAS Sensor: Optimization and Performance.

    PubMed

    Ma, Yufei; Tong, Yao; He, Ying; Yu, Xin; Tittel, Frank K

    2018-01-04

    A highly sensitive carbon monoxide (CO) trace gas sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) was demonstrated. A high-power distributed feedback (DFB), continuous wave (CW) 2.33 μm diode laser with an 8.8 mW output power was used as the QEPAS excitation source. By optimizing the modulation depth and adding an optimum micro-resonator, compared to a bare quartz tuning fork (QTF), a 10-fold enhancement of the CO-QEPAS signal amplitude was achieved. When water vapor acting as a vibrational transfer catalyst was added to the target gas, the signal was further increased by a factor of ~7. A minimum detection limit (MDL) of 11.2 ppm and a calculated normalized noise equivalent absorption (NNEA) coefficient of 1.8 × 10 -5 cm -1 W/√Hz were obtained for the reported CO-QEPAS sensor.

  19. High-Power DFB Diode Laser-Based CO-QEPAS Sensor: Optimization and Performance

    PubMed Central

    Ma, Yufei; Tong, Yao; He, Ying; Yu, Xin

    2018-01-01

    A highly sensitive carbon monoxide (CO) trace gas sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) was demonstrated. A high-power distributed feedback (DFB), continuous wave (CW) 2.33 μm diode laser with an 8.8 mW output power was used as the QEPAS excitation source. By optimizing the modulation depth and adding an optimum micro-resonator, compared to a bare quartz tuning fork (QTF), a 10-fold enhancement of the CO-QEPAS signal amplitude was achieved. When water vapor acting as a vibrational transfer catalyst was added to the target gas, the signal was further increased by a factor of ~7. A minimum detection limit (MDL) of 11.2 ppm and a calculated normalized noise equivalent absorption (NNEA) coefficient of 1.8 × 10−5 cm−1W/√Hz were obtained for the reported CO-QEPAS sensor. PMID:29300310

  20. Efficiencies of state and velocity-changing collisions of superthermal CN A(2)Pi with He, Ar, N(2) and O(2).

    PubMed

    Alagappan, Azhagammai; Ballingall, Iain; Costen, Matthew L; McKendrick, Kenneth G; Paterson, Grant

    2007-02-14

    Polarized laser photolysis of ICN is combined with saturated optical pumping to prepare state-selected CN Alpha(2)Pi (nu' = 4, J = 0.5, F(2), f) with a well-defined anisotropic superthermal speed distribution. The collisional evolution of the prepared state is observed by Doppler-resolved Frequency Modulated (FM) spectroscopy via stimulated emission on the CN Alpha(2)Pi-Chi(2)Sigma(+) (4,2) band. The phenomenological rate constants for removal of the prepared state in collisions with He, Ar, N(2) and O(2) are reported. The observed collision cross-sections are consistent with attractive forces contributing significantly for all the colliders with the exception of He. The collisional evolution of the prepared velocity distribution demonstrates that no significant back-transfer into the prepared level occurs, and that any elastic scattering is strongly in the forward hemisphere.

  1. Wannier-Stark localization of a strongly coupled asymmetric double-well GaAs/AlAs superlattice

    NASA Astrophysics Data System (ADS)

    Kawashima, Kenji; Matsumoto, Takeshi; Arima, Kiyotoku; Ohsumi, Takahiro; Nogami, Takamitsu; Satoh, Kazuo; Fujiwara, Kenzo

    2000-06-01

    A novel new type of superlattice (SL) structure which consists of strongly coupled asymmetric double-well (ADW) in one period have been investigated to introduce a new degree of freedom for the device funtionality. The GaAs/A1As ADS-SL contained in a p-i-n diode structure was grown by molecular beam epitaxy, and the electroabsorption properties were measured by low temperature photocurrent spectroscopy. It is found that the introduction of the confinement potential asymmetry with respect to electric field will lead to the selectivity of spatially indirect Stark-ladder transitions associated with two different types of the localized hole states, thus providing a new way of modulating the oscillator strengths. Assignment of the possible optical transitions from the miniband to the Stark-ladder regimes as a function of field strength is elucidated in detail by transfer matrix calculations.

  2. Structure-reactivity relationships in the hydrogenation of carbon dioxide with ruthenium complexes bearing pyridinylazolato ligands.

    PubMed

    Muller, Keven; Sun, Yu; Heimermann, Andreas; Menges, Fabian; Niedner-Schatteburg, Gereon; van Wüllen, Christoph; Thiel, Werner R

    2013-06-10

    Pyridinylazolato (N-N') ruthenium(II) complexes of the type [(N-N')RuCl(PMe3)3] have been obtained in high yields by treating the corresponding functionalised azolylpyridines with [RuCl2 (PMe3)4] in the presence of a base. (15)N NMR spectroscopy was used to elucidate the electronic influence of the substituents attached to the azolyl ring. The findings are in agreement with slight differences in the bond lengths of the ruthenium complexes. Furthermore, the electronic nature of the azolate moiety modulates the catalytic activity of the ruthenium complexes in the hydrogenation of carbon dioxide under supercritical conditions and in the transfer hydrogenation of acetophenone. DFT calculations were performed to shed light on the mechanism of the hydrogenation of carbon dioxide and to clarify the impact of the electronic nature of the pyridinylazolate ligands. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Ultrafast dynamics of multi-exciton state coupled to coherent vibration in zinc chlorin aggregates for artificial photosynthesis.

    PubMed

    Shi, Tongchao; Liu, Zhengzheng; Miyatake, Tomohiro; Tamiaki, Hitoshi; Kobayashi, Takayoshi; Zhang, Zeyu; Du, Juan; Leng, Yuxin

    2017-11-27

    Ultrafast vibronic dynamics induced by the interaction of the Frenkel exciton with the coherent molecular vibrations in a layer-structured zinc chlorin aggregates prepared for artificial photosynthesis have been studied by 7.1 fs real-time vibrational spectroscopy with multi-spectrum detection. The fast decay of 100 ± 5fs is ascribed to the relaxation from the higher multi-exciton state (MES) to the one-exciton state, and the slow one of 863 ± 70fs is assigned to the relaxation from Q-exciton state to the dark nonfluorescent charge-transfer (CT) state, respectively. In addition, the wavelength dependences of the exciton-vibration coupling strength are found to follow the zeroth derivative of the transient absorption spectra of the exciton. It could be explained in term of the transition dipole moment modulated by dynamic intensity borrowing between the B transition and the Q transition through the vibronic interactions.

  4. Multilayer porous structures of HVPE and MOCVD grown GaN for photonic applications

    NASA Astrophysics Data System (ADS)

    Braniste, T.; Ciers, Joachim; Monaico, Ed.; Martin, D.; Carlin, J.-F.; Ursaki, V. V.; Sergentu, V. V.; Tiginyanu, I. M.; Grandjean, N.

    2017-02-01

    In this paper we report on a comparative study of electrochemical processes for the preparation of multilayer porous structures in hydride vapor phase epitaxy (HVPE) and metal organic chemical vapor phase deposition (MOCVD) grown GaN. It was found that in HVPE-grown GaN, multilayer porous structures are obtained due to self-organization processes leading to a fine modulation of doping during the crystal growth. However, these processes are not totally under control. Multilayer porous structures with a controlled design have been produced by optimizing the technological process of electrochemical etching in MOCVD-grown samples, consisting of five pairs of thin layers with alternating-doping profiles. The samples have been characterized by SEM imaging, photoluminescence spectroscopy, and micro-reflectivity measurements, accompanied by transfer matrix analysis and simulations by a method developed for the calculation of optical reflection spectra. We demonstrate the applicability of the produced structures for the design of Bragg reflectors.

  5. Excitation transfer and trapping kinetics in plant photosystem I probed by two-dimensional electronic spectroscopy.

    PubMed

    Akhtar, Parveen; Zhang, Cheng; Liu, Zhengtang; Tan, Howe-Siang; Lambrev, Petar H

    2018-03-01

    Photosystem I is a robust and highly efficient biological solar engine. Its capacity to utilize virtually every absorbed photon's energy in a photochemical reaction generates great interest in the kinetics and mechanisms of excitation energy transfer and charge separation. In this work, we have employed room-temperature coherent two-dimensional electronic spectroscopy and time-resolved fluorescence spectroscopy to follow exciton equilibration and excitation trapping in intact Photosystem I complexes as well as core complexes isolated from Pisum sativum. We performed two-dimensional electronic spectroscopy measurements with low excitation pulse energies to record excited-state kinetics free from singlet-singlet annihilation. Global lifetime analysis resolved energy transfer and trapping lifetimes closely matches the time-correlated single-photon counting data. Exciton energy equilibration in the core antenna occurred on a timescale of 0.5 ps. We further observed spectral equilibration component in the core complex with a 3-4 ps lifetime between the bulk Chl states and a state absorbing at 700 nm. Trapping in the core complex occurred with a 20 ps lifetime, which in the supercomplex split into two lifetimes, 16 ps and 67-75 ps. The experimental data could be modelled with two alternative models resulting in equally good fits-a transfer-to-trap-limited model and a trap-limited model. However, the former model is only possible if the 3-4 ps component is ascribed to equilibration with a "red" core antenna pool absorbing at 700 nm. Conversely, if these low-energy states are identified with the P 700 reaction centre, the transfer-to-trap-model is ruled out in favour of a trap-limited model.

  6. Thermal Management of Vehicle Electronic Payloads Using Nanofluids and Thermoelectric Devices--Modeling and Analysis (PREPRINT)

    DTIC Science & Technology

    2011-03-01

    Transfer Engineering, Vol. 30, No. 14, pp. 1136-1150. Chang, Y.W., Chang, C.C., Ke, M.T. and Chen, S.L. (2009) ’ Thermoelectric air-cooling module for...2005) ’An assessment of module cooling enhancement with thermoelectric coolers’, Journal of Heat Transfer-Transactions of the Asme, Vol. 127, No. 1, pp...nanoparticle out outer loop p nanoparticle TEC thermoelectric module w water UNCLASSIFIED UNCLASSIFIED Page 23 of 28 Tables Table 1

  7. Amide Proton Transfer Imaging Allows Detection of Glioma Grades and Tumor Proliferation: Comparison with Ki-67 Expression and Proton MR Spectroscopy Imaging.

    PubMed

    Su, C; Liu, C; Zhao, L; Jiang, J; Zhang, J; Li, S; Zhu, W; Wang, J

    2017-09-01

    Prognosis in glioma depends strongly on tumor grade and proliferation. In this prospective study of patients with untreated primary cerebral gliomas, we investigated whether amide proton transfer-weighted imaging could reveal tumor proliferation and reliably distinguish low-grade from high-grade gliomas compared with Ki-67 expression and proton MR spectroscopy imaging. This study included 42 patients with low-grade ( n = 28) or high-grade ( n = 14) glioma, all of whom underwent conventional MR imaging, proton MR spectroscopy imaging, and amide proton transfer-weighted imaging on the same 3T scanner within 2 weeks before surgery. We assessed metabolites of choline and N -acetylaspartate from proton MR spectroscopy imaging and the asymmetric magnetization transfer ratio at 3.5 ppm from amide proton transfer-weighted imaging and compared them with histopathologic grade and immunohistochemical expression of the proliferation marker Ki-67 in the resected specimens. The asymmetric magnetization transfer ratio at 3.5 ppm values measured by different readers showed good concordance and were significantly higher in high-grade gliomas than in low-grade gliomas (3.61% ± 0.155 versus 2.64% ± 0.185, P = .0016), with sensitivity and specificity values of 92.9% and 71.4%, respectively, at a cutoff value of 2.93%. The asymmetric magnetization transfer ratio at 3.5 ppm values correlated with tumor grade ( r = 0.506, P = .0006) and Ki-67 labeling index ( r = 0.502, P = .002). For all patients, the asymmetric magnetization transfer ratio at 3.5 ppm correlated positively with choline ( r = 0.43, P = .009) and choline/ N -acetylaspartate ratio ( r = 0.42, P = .01) and negatively with N -acetylaspartate ( r = -0.455, P = .005). These correlations held for patients with low-grade gliomas versus those with high-grade gliomas, but the correlation coefficients were higher in high-grade gliomas (choline: r = 0.547, P = .053; N -acetylaspartate: r = -0.644, P = .017; choline/ N -acetylaspartate: r = 0.583, P = .036). The asymmetric magnetization transfer ratio at 3.5 ppm may serve as a potential biomarker not only for assessing proliferation, but also for predicting histopathologic grades in gliomas. © 2017 by American Journal of Neuroradiology.

  8. Electron-transfer mediator for a NAD-glucose dehydrogenase-based glucose sensor.

    PubMed

    Kim, Dong-Min; Kim, Min-yeong; Reddy, Sanapalli S; Cho, Jaegeol; Cho, Chul-ho; Jung, Suntae; Shim, Yoon-Bo

    2013-12-03

    A new electron-transfer mediator, 5-[2,5-di (thiophen-2-yl)-1H-pyrrol-1-yl]-1,10-phenanthroline iron(III) chloride (FePhenTPy) oriented to the nicotinamide adenine dinucleotide-dependent-glucose dehydrogenase (NAD-GDH) system was synthesized through a Paal-Knorr condensation reaction. The structure of the mediator was confirmed by Fourier-transform infrared spectroscopy, proton and carbon nucler magnetic resonance spectroscopy, and mass spectroscopy, and its electron-transfer characteristic for a glucose sensor was investigated using voltammetry and impedance spectroscopy. A disposable amperometric glucose sensor with NAD-GDH was constructed with FePhenTPy as an electron-transfer mediator on a screen printed carbon electrode (SPCE) and its performance was evaluated, where the addition of reduces graphene oxide (RGO) to the mediator showed the enhanced sensor performance. The experimental parameters to affect the analytical performance and the stability of the proposed glucose sensor were optimized, and the sensor exhibited a dynamic range between 30 mg/dL and 600 mg/dL with the detection limit of 12.02 ± 0.6 mg/dL. In the real sample experiments, the interference effects by acetaminophen, ascorbic acid, dopamine, uric acid, caffeine, and other monosaccharides (fructose, lactose, mannose, and xylose) were completely avoided through coating the sensor surface with the Nafion film containing lead(IV) acetate. The reliability of proposed glucose sensor was evaluated by the determination of glucose in artificial blood and human whole blood samples.

  9. Genetic Modulation of Training and Transfer in Older Adults: BDNF Val66Met Polymorphism is Associated with Wider Useful Field of View

    PubMed Central

    Colzato, Lorenza S.; van Muijden, Jesse; Band, Guido P. H.; Hommel, Bernhard

    2011-01-01

    Western society has an increasing proportion of older adults. Increasing age is associated with a general decrease in the control over task-relevant mental processes. In the present study we investigated the possibility that successful transfer of game-based cognitive improvements to untrained tasks in elderly people is modulated by preexisting neuro-developmental factors as genetic variability related to levels of the brain-derived neurotrophic factor (BDNF), an important neuromodulator underlying cognitive processes. We trained participants, genotyped for the BDNF Val66Met polymorphism, on cognitive tasks developed to improve dynamic attention. Pre-training (baseline) and post-training measures of attentional processes (divided and selective attention) were acquired by means of the useful field of view task. As expected, Val/Val homozygous individuals showed larger beneficial transfer effects than Met/-carriers. Our findings support the idea that genetic predisposition modulates transfer effects. PMID:21909331

  10. Wireless power using magnetic resonance coupling for neural sensing applications

    NASA Astrophysics Data System (ADS)

    Yoon, Hargsoon; Kim, Hyunjung; Choi, Sang H.; Sanford, Larry D.; Geddis, Demetris; Lee, Kunik; Kim, Jaehwan; Song, Kyo D.

    2012-04-01

    Various wireless power transfer systems based on electromagnetic coupling have been investigated and applied in many biomedical applications including functional electrical stimulation systems and physiological sensing in humans and animals. By integrating wireless power transfer modules with wireless communication devices, electronic systems can deliver data and control system operation in untethered freely-moving conditions without requiring access through the skin, a potential source of infection. In this presentation, we will discuss a wireless power transfer module using magnetic resonance coupling that is specifically designed for neural sensing systems and in-vivo animal models. This research presents simple experimental set-ups and circuit models of magnetic resonance coupling modules and discusses advantages and concerns involved in positioning and sizing of source and receiver coils compared to conventional inductive coupling devices. Furthermore, the potential concern of tissue heating in the brain during operation of the wireless power transfer systems will also be addressed.

  11. Activations in gray and white matter are modulated by uni-manual responses during within and inter-hemispheric transfer: effects of response hand and right-handedness.

    PubMed

    Diwadkar, Vaibhav A; Bellani, Marcella; Chowdury, Asadur; Savazzi, Silvia; Perlini, Cinzia; Marinelli, Veronica; Zoccatelli, Giada; Alessandrini, Franco; Ciceri, Elisa; Rambaldelli, Gianluca; Ruggieri, Mirella; Carlo Altamura, A; Marzi, Carlo A; Brambilla, Paolo

    2017-08-14

    Because the visual cortices are contra-laterally organized, inter-hemispheric transfer tasks have been used to behaviorally probe how information briefly presented to one hemisphere of the visual cortex is integrated with responses resulting from the ipsi- or contra-lateral motor cortex. By forcing rapid information exchange across diverse regions, these tasks robustly activate not only gray matter regions, but also white matter tracts. It is likely that the response hand itself (dominant or non-dominant) modulates gray and white matter activations during within and inter-hemispheric transfer. Yet the role of uni-manual responses and/or right hand dominance in modulating brain activations during such basic tasks is unclear. Here we investigated how uni-manual responses with either hand modulated activations during a basic visuo-motor task (the established Poffenberger paradigm) alternating between inter- and within-hemispheric transfer conditions. In a large sample of strongly right-handed adults (n = 49), we used a factorial combination of transfer condition [Inter vs. Within] and response hand [Dominant(Right) vs. Non-Dominant (Left)] to discover fMRI-based activations in gray matter, and in narrowly defined white matter tracts. These tracts were identified using a priori probabilistic white matter atlases. Uni-manual responses with the right hand strongly modulated activations in gray matter, and notably in white matter. Furthermore, when responding with the left hand, activations during inter-hemispheric transfer were strongly predicted by the degree of right-hand dominance, with increased right-handedness predicting decreased fMRI activation. Finally, increasing age within the middle-aged sample was associated with a decrease in activations. These results provide novel evidence of complex relationships between uni-manual responses in right-handed subjects, and activations during within- and inter-hemispheric transfer suggest that the organization of the motor system exerts sophisticated functional effects. Moreover, our evidence of activation in white matter tracts is consistent with prior studies, confirming fMRI-detectable white matter activations which are systematically modulated by experimental condition.

  12. Dynamics of charge-transfer excitons in type-II semiconductor heterostructures

    NASA Astrophysics Data System (ADS)

    Stein, M.; Lammers, C.; Richter, P.-H.; Fuchs, C.; Stolz, W.; Koch, M.; Vänskä, O.; Weseloh, M. J.; Kira, M.; Koch, S. W.

    2018-03-01

    The formation, decay, and coherence properties of charge-transfer excitons in semiconductor heterostructures are investigated by applying four-wave-mixing and terahertz spectroscopy in combination with a predictive microscopic theory. A charge-transfer process is identified where the optically induced coherences decay directly into a charge-transfer electron-hole plasma and exciton states. It is shown that charge-transfer excitons are more sensitive to the fermionic electron-hole substructure than regular excitons.

  13. Development of multichannel analyzer using sound card ADC for nuclear spectroscopy system

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

    Ibrahim, Maslina Mohd; Yussup, Nolida; Lombigit, Lojius

    This paper describes the development of Multi-Channel Analyzer (MCA) using sound card analogue to digital converter (ADC) for nuclear spectroscopy system. The system was divided into a hardware module and a software module. Hardware module consist of detector NaI (Tl) 2” by 2”, Pulse Shaping Amplifier (PSA) and a build in ADC chip from readily available in any computers’ sound system. The software module is divided into two parts which are a pre-processing of raw digital input and the development of the MCA software. Band-pass filter and baseline stabilization and correction were implemented for the pre-processing. For the MCA development,more » the pulse height analysis method was used to process the signal before displaying it using histogram technique. The development and tested result for using the sound card as an MCA are discussed.« less

  14. Pressure modulation algorithm to separate cerebral hemodynamic signals from extracerebral artifacts.

    PubMed

    Baker, Wesley B; Parthasarathy, Ashwin B; Ko, Tiffany S; Busch, David R; Abramson, Kenneth; Tzeng, Shih-Yu; Mesquita, Rickson C; Durduran, Turgut; Greenberg, Joel H; Kung, David K; Yodh, Arjun G

    2015-07-01

    We introduce and validate a pressure measurement paradigm that reduces extracerebral contamination from superficial tissues in optical monitoring of cerebral blood flow with diffuse correlation spectroscopy (DCS). The scheme determines subject-specific contributions of extracerebral and cerebral tissues to the DCS signal by utilizing probe pressure modulation to induce variations in extracerebral blood flow. For analysis, the head is modeled as a two-layer medium and is probed with long and short source-detector separations. Then a combination of pressure modulation and a modified Beer-Lambert law for flow enables experimenters to linearly relate differential DCS signals to cerebral and extracerebral blood flow variation without a priori anatomical information. We demonstrate the algorithm's ability to isolate cerebral blood flow during a finger-tapping task and during graded scalp ischemia in healthy adults. Finally, we adapt the pressure modulation algorithm to ameliorate extracerebral contamination in monitoring of cerebral blood oxygenation and blood volume by near-infrared spectroscopy.

  15. Broadband pump-probe spectroscopy at 20-MHz modulation frequency.

    PubMed

    Preda, Fabrizio; Kumar, Vikas; Crisafi, Francesco; Figueroa Del Valle, Diana Gisell; Cerullo, Giulio; Polli, Dario

    2016-07-01

    We introduce an innovative high-sensitivity broadband pump-probe spectroscopy system, based on Fourier-transform detection, operating at 20-MHz modulation frequency. A common-mode interferometer employing birefringent wedges creates two phase-locked delayed replicas of the broadband probe pulse, interfering at a single photodetector. A single-channel lock-in amplifier demodulates the interferogram, whose Fourier transform provides the differential transmission spectrum. Our approach combines broad spectral coverage with high sensitivity, due to high-frequency modulation and detection. We demonstrate its performances by measuring two-dimensional differential transmission maps of a carbon nanotubes sample, simultaneously acquiring the signal over the entire 950-1350 nm range with 2.7·10-6  rms noise over 1.5 s integration time.

  16. In Site Analysis of a High Temperature Cure Reaction in Real Time Using Modulated Fiber-Optic FT-Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Cooper, John; Aust, Jeffrey F.; Wise, Kent L.; Jensen, Brian J.

    1999-01-01

    The vibrational spectrum of a high temperature (330 C) polymerization reaction was successfully monitored in real time using a modulated fiber-optic FT-Raman spectrometer. A phenylethynyl terminated monomer was cured, and spectral evidence for two different reaction products was acquired. The products are a conjugated polyene chain and a cyclized trimer. This is the first report describing the use of FT-Raman spectroscopy to monitor a high temperature (greater than 250 C) reaction in real time.

  17. In Situ Analysis of a High-Temperature Cure Reaction in Real Time Using Modulated Fiber-Optic FT-Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Aust, Jeffrey F.; Cooper, John B.; Wise, Kent L.; Jensen, Brian J.

    1999-01-01

    The vibrational spectrum of a high-temperature (330 C) polymerization reaction was successfully monitored in real time with the use of a modulated fiber-optic Fourier transform (FT)-Raman spectrometer. A phenylethynyl-terminated monomer was cured, and spectral evidence for two different reaction products was acquired. The products are a conjugated polyene chain and a cyclized trimer. This is the first report describing the use of FT-Raman spectroscopy to monitor a high temperature (greater than 250 C) reaction in real time.

  18. Probing energy transfer events in the light harvesting complex 2 (LH2) of Rhodobacter sphaeroides with two-dimensional spectroscopy.

    PubMed

    Fidler, Andrew F; Singh, Ved P; Long, Phillip D; Dahlberg, Peter D; Engel, Gregory S

    2013-10-21

    Excitation energy transfer events in the photosynthetic light harvesting complex 2 (LH2) of Rhodobacter sphaeroides are investigated with polarization controlled two-dimensional electronic spectroscopy. A spectrally broadened pulse allows simultaneous measurement of the energy transfer within and between the two absorption bands at 800 nm and 850 nm. The phased all-parallel polarization two-dimensional spectra resolve the initial events of energy transfer by separating the intra-band and inter-band relaxation processes across the two-dimensional map. The internal dynamics of the 800 nm region of the spectra are resolved as a cross peak that grows in on an ultrafast time scale, reflecting energy transfer between higher lying excitations of the B850 chromophores into the B800 states. We utilize a polarization sequence designed to highlight the initial excited state dynamics which uncovers an ultrafast transfer component between the two bands that was not observed in the all-parallel polarization data. We attribute the ultrafast transfer component to energy transfer from higher energy exciton states to lower energy states of the strongly coupled B850 chromophores. Connecting the spectroscopic signature to the molecular structure, we reveal multiple relaxation pathways including a cyclic transfer of energy between the two rings of the complex.

  19. Development of 24GHz Rectenna for Receiving and Rectifying Modulated Waves

    NASA Astrophysics Data System (ADS)

    Shinohara, Naoki; Hatano, Ken

    2014-11-01

    In this paper, we show experimental results of RF-DC conversion with modulated 24GHz waves. We have already developed class-F MMIC rectenna with resonators for higher harmonics at no modulated 24GHz microwave for RF energy transfer. Dimensions of the MMIC rectifying circuit is 1 mm × 3 mm on GaAs. Maximum RF-DC conversion efficiency is measured 47.9% for a 210 mW microwave input of 24 GHz with a 120 Ω load. The class-F rectenna is based on a single shunt full-wave rectifier. For future application of a simultaneous energy and information transfer system or an energy harvesting from broadcasting waves, input microwave will be modulated. In this paper, we show an experimental result of RF-DC conversion of the class-F rectenna with 24GHz waves modulated by 16QAM as 1st modulation and OFDM as 2nd modulation.

  20. The Power Transistor: A Module on Heat Transfer. Tech Physics Series.

    ERIC Educational Resources Information Center

    Technical Education Research Center, Cambridge, MA.

    This module is intended to provide an understanding of the principles related to heat transfer. The objectives are designed to enable the learner to select and install a device for measuring the temperature of a power transistor, determine power ratings, measure the transient response for a power level and its final equilibrium temperature. Other…

  1. Optimization of identity operation in NMR spectroscopy via genetic algorithm: Application to the TEDOR experiment

    NASA Astrophysics Data System (ADS)

    Manu, V. S.; Veglia, Gianluigi

    2016-12-01

    Identity operation in the form of π pulses is widely used in NMR spectroscopy. For an isolated single spin system, a sequence of even number of π pulses performs an identity operation, leaving the spin state essentially unaltered. For multi-spin systems, trains of π pulses with appropriate phases and time delays modulate the spin Hamiltonian to perform operations such as decoupling and recoupling. However, experimental imperfections often jeopardize the outcome, leading to severe losses in sensitivity. Here, we demonstrate that a newly designed Genetic Algorithm (GA) is able to optimize a train of π pulses, resulting in a robust identity operation. As proof-of-concept, we optimized the recoupling sequence in the transferred-echo double-resonance (TEDOR) pulse sequence, a key experiment in biological magic angle spinning (MAS) solid-state NMR for measuring multiple carbon-nitrogen distances. The GA modified TEDOR (GMO-TEDOR) experiment with improved recoupling efficiency results in a net gain of sensitivity up to 28% as tested on a uniformly 13C, 15N labeled microcrystalline ubiquitin sample. The robust identity operation achieved via GA paves the way for the optimization of several other pulse sequences used for both solid- and liquid-state NMR used for decoupling, recoupling, and relaxation experiments.

  2. An electrochemical and photophysical study of a covalently linked inorganic-organic dyad.

    PubMed

    Kahnt, Axel; Heiniger, Leo-Philipp; Liu, Shi-Xia; Tu, Xiaoyan; Zheng, Zhiping; Hauser, Andreas; Decurtins, Silvio; Guldi, Dirk M

    2010-02-22

    A molecular donor-acceptor dyad comprising a hexarhenium cluster core, [Re(6)(mu(3)-Se)(8)](2+), and a fullerene moiety which are covalently linked through a pyridine ligand was synthesized and fully characterized. The electrochemical and photophysical properties are reported. The detailed study includes cyclic voltammetry, steady-state absorption and fluorescence spectroscopy, radiation chemistry and transient absorption spectroscopy. A light-induced electron transfer between the inorganic cluster moiety and the fullerene can be excluded. However, a light-induced energy transfer from the rhenium cluster to the fullerene is proposed.

  3. [Interaction between strychnine and bovine serum albumin].

    PubMed

    Zhao, Jin; Wang, Zhi; Wu, Qiu-hua; Yang, Xiu-min; Wang, Chun; Hu, Yan-xue

    2006-07-01

    To study the interaction between strychnine and bovine serum albumin. Fluorescence spectroscopy and ultraviolet spectroscopy were used. The static quenching and the non-radiation energy transfer are the two main reasons to leading the fluorescence quenching of BSA. The apparent combining constants (K(A)) between strychnine and BSA are 3.72 x 10(3) at 27 degrees C, 4.27 x 10(3) at 37 degrees C, 4.47 x 10(3) at 47 degrees C and the combining sites are 1.01 +/- 0.03. The combining distance (r = 3.795 nm) and energy transfer efficiency (E = 0.0338) are obtained by Förster's non-radiation energy transfer mechanism. The interaction between strychnine and BSA was driven mainly by hydrophobic force.

  4. Transfer doping of single isolated nanodiamonds, studied by scanning probe microscopy techniques

    NASA Astrophysics Data System (ADS)

    Bolker, Asaf; Saguy, Cecile; Kalish, Rafi

    2014-09-01

    The transfer doping of diamond surfaces has been applied in various novel two-dimensional electronic devices. Its extension to nanodiamonds (ND) is essential for ND-based applications in many fields. In particular, understanding the influence of the crystallite size on transfer doping is desirable. Here, we report the results of a detailed study of the electronic energetic band structure of single, isolated transfer-doped nanodiamonds with nanometric resolution using a combination of scanning tunneling spectroscopy and Kelvin force microscopy measurements. The results show how the band gap, the valence band maximum, the electron affinity and the work function all depend on the ND’s size and nanoparticle surface properties. The present analysis, which combines information from both scanning tunneling spectroscopy and Kelvin force microscopy, should be applicable to any nanoparticle or surface that can be measured with scanning probe techniques.

  5. 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.

  6. FTIR Study of the Photoactivation Process of Xenopus (6-4) Photolyase†

    PubMed Central

    Yamada, Daichi; Zhang, Yu; Iwata, Tatsuya; Hitomi, Kenichi; Getzoff, Elizabeth D.; Kandori, Hideki

    2012-01-01

    Photolyases (PHRs) are blue-light activated DNA repair enzymes that maintain genetic integrity by reverting UV-induced photoproducts into normal bases. The FAD chromophore of PHRs has four different redox states: oxidized (FADox), anion radical (FAD•−), neutral radical (FADH•) and fully reduced (FADH−). We combined difference Fourier-transform infrared (FTIR) spectroscopy with UV-visible spectroscopy to study the detailed photoactivation process of Xenopus (6-4) PHR. Two photons produce the enzymatically active, fully reduced PHR from oxidized FAD: FADox is converted to semiquinone via light-induced one-electron and one-proton transfers, and then to FADH− by light-induced one-electron transfer. We successfully trapped FAD•− at 200 K, where electron transfer occurs, but proton transfer does not. UV-visible spectroscopy following 450-nm illumination of FADox at 277 K defined the FADH•/FADH− mixture and allowed calculation of difference FTIR spectra among the four redox states. The absence of a characteristic C=O stretching vibration indicated that the proton donor is not a protonated carboxylic acid. Structural changes in Trp and Tyr are suggested from UV-visible and FTIR analysis of FAD•− at 200 K. Spectral analysis of amide-I vibrations revealed structural perturbation of the protein’s β-sheet during initial electron transfer (FAD•− formation), transient increase in α-helicity during proton transfer (FADH• formation) and reversion to the initial amide-I signal following subsequent electron transfer (FADH− formation). Consequently, in (6-4) PHR, unlike cryptochrome-DASH, formation of enzymatically active FADH− did not perturb α-helicity. Protein structural changes in the photoactivation of (6-4) PHR are discussed on the basis of the present FTIR observations. PMID:22747528

  7. Ring resonant cavities for spectroscopy

    DOEpatents

    Zare, R.N.; Martin, J.; Paldus, B.A.; Xie, J.

    1999-06-15

    Ring-shaped resonant cavities for spectroscopy allow a reduction in optical feedback to the light source, and provide information on the interaction of both s- and p-polarized light with samples. A laser light source is locked to a single cavity mode. An intracavity acousto-optic modulator may be used to couple light into the cavity. The cavity geometry is particularly useful for Cavity Ring-Down Spectroscopy (CRDS). 6 figs.

  8. Ring resonant cavities for spectroscopy

    DOEpatents

    Zare, Richard N.; Martin, Juergen; Paldus, Barbara A.; Xie, Jinchun

    1999-01-01

    Ring-shaped resonant cavities for spectroscopy allow a reduction in optical feedback to the light source, and provide information on the interaction of both s- and p-polarized light with samples. A laser light source is locked to a single cavity mode. An intracavity acousto-optic modulator may be used to couple light into the cavity. The cavity geometry is particularly useful for Cavity Ring-Down Spectroscopy (CRDS).

  9. Measurements of the rate constant of HOsub2 + NOsub2 + Nsub2 --> HOsub2NOsub2 + Nsub2 using near-infrared wavelength-modulation spectroscopy and UV-visible absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Christensen, L. E.; Okumura, M.; Sander, S. P.; Friedl, R. R.; Miller, C. E.; Sloan, J. J.

    2004-01-01

    Rate coefficients for the reaction HO(sub 2)+ NO(sub 2) + N(sub 2) --> HO(sub 2)NO(sub 2) + N(sub 2) (reaction 1) were measured using simultaneous near-IR and UV spectroscopy from 220 to 298 K and from 45 to 200 Torr.

  10. Horizontal modular dry irradiated fuel storage system

    DOEpatents

    Fischer, Larry E.; McInnes, Ian D.; Massey, John V.

    1988-01-01

    A horizontal, modular, dry, irradiated fuel storage system (10) includes a thin-walled canister (12) for containing irradiated fuel assemblies (20), which canister (12) can be positioned in a transfer cask (14) and transported in a horizontal manner from a fuel storage pool (18), to an intermediate-term storage facility. The storage system (10) includes a plurality of dry storage modules (26) which accept the canister (12) from the transfer cask (14) and provide for appropriate shielding about the canister (12). Each module (26) also provides for air cooling of the canister (12) to remove the decay heat of the irradiated fuel assemblies (20). The modules (26) can be interlocked so that each module (26) gains additional shielding from the next adjacent module (26). Hydraulic rams (30) are provided for inserting and removing the canisters (12) from the modules (26).

  11. ULTRAVIOLET SPECTROSCOPY OF PQ Gem AND V405 Aur FROM THE HST AND IUE SATELLITES

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

    Sanad, M. R., E-mail: mrsanad1@yahoo.com

    Ultraviolet spectra of two intermediate polars (IPs), PQ Gem and V405 Aur, observed with Hubble Space Telescope (HST) Space Telescope Imaging Spectrograph and Faint Object Spectrograph and International Ultraviolet Explorer (IUE) satellites were analyzed during the period between 1994–2000. We estimated the reddening of the two systems from the 2200 Å feature. Six spectra of the two systems revealing modulations of line fluxes at different times are presented. PQ Gem and V405 Aur are featured by spectral lines in different ionization states. This paper focuses on the third ionized carbon emission line at 1550 Å and the first ionized heliummore » emission line at 1640 Å produced in the optically thin outer region of the accretion curtain for the two systems by calculating spectral line fluxes. From HST and IUE data, we deduced ultraviolet luminosities and ultraviolet accretion rates for the two binary stars. The average temperature of the accretion streams for PQ Gem and V405 Aur are ∼4500 K and 4100 K, respectively. The results reveal that there are modulations in fluxes of spectral lines, ultraviolet luminosities, and ultraviolet accretion rates with time for both systems. These modulations are referred to the changes of both density and temperature as a result of the variations of mass transfer rate from the secondary star to the primary star. The current results are consistent with an accretion curtain model for IPs.« less

  12. Efficient modulation of optical and electrical properties of X-shaped thermally activated delayed fluorescence emitters by substitution.

    PubMed

    Fan, Jianzhong; Wang, Xin; Lin, Lili; Wang, Chuankui

    2016-08-01

    A series of X-shaped thermally activated delayed fluorescence (TADF) emitters are systematically studied by first-principles calculations. Effects of the cyano group adding to the acceptor unit and the hydroxyl group adding to the donor part on the optical and electrical properties are analyzed. It is found that both kinds of groups can efficiently increase the emission wavelength to realize full-color emission. Although they play different roles in modulating the energy level of frontier orbitals, the S-T energy gap, the reorganization energy and transfer integral for different molecules, they can efficiently increase the charge transfer rate and reduce the difference of electron transfer rate and hole transfer rate. These results indicate that these designed strategies are efficient to achieve balanced charge transfer rates and modulate emission colors. By analyzing the energy matching between the TADF emitters and three kinds of hosts, the emission spectra of the 3,5-bis(N-carbazolyl)benzene (mcp) and the absorption spectra of most TADF emitters have a large overlap, which provides helpful information in application of these TADF molecules.

  13. Optical Emission Spectroscopy of a 150kW DC Arc Torch: A Comparison of Transferred vs. Non-Transferred Modes

    NASA Astrophysics Data System (ADS)

    Counts, D. A.; Giuliani, J. L.; Peterson, S. H.; Han, Q. Y.; Sartwell, B. D.

    1997-04-01

    DC arc torches are proposed or in use for solid waste remediation at several sites. However, there is no consensus on the optimal mode of operation: transferred or non-transferred arc. As part of a project to investigate plasma treatment of shipboard waste, we have been investigating both modes at atmospheric pressure. This paper reports on the use of visible optical emission spectroscopy to determine the electron temperature, T_e, in the arc discharge for both the transferred and non transferred mode. In each case three industrial gases are compared, nitrogen, air and oxygen, at different flow rates and currents. Te is determined from the Balmer line ratio, wherein 5% hydrogen gas is added to the working gas in the torch flow. Variation of the emission with torch height and across the arc radius will be discussed. Recently, free arcs have shown evidence of non-LTE behavior in the arc mantle. Comparison of arc emission spectra as a function of radius for the transferred vs. non-transferred modes will be reported. Calorimetry results for the chamber walls, exhaust, and waste crucible will be correlated with the spectral results. This work was supported by the Office of Naval Research.

  14. Optimisation of wavelength modulated Raman spectroscopy: towards high throughput cell screening.

    PubMed

    Praveen, Bavishna B; Mazilu, Michael; Marchington, Robert F; Herrington, C Simon; Riches, Andrew; Dholakia, Kishan

    2013-01-01

    In the field of biomedicine, Raman spectroscopy is a powerful technique to discriminate between normal and cancerous cells. However the strong background signal from the sample and the instrumentation affects the efficiency of this discrimination technique. Wavelength Modulated Raman spectroscopy (WMRS) may suppress the background from the Raman spectra. In this study we demonstrate a systematic approach for optimizing the various parameters of WMRS to achieve a reduction in the acquisition time for potential applications such as higher throughput cell screening. The Signal to Noise Ratio (SNR) of the Raman bands depends on the modulation amplitude, time constant and total acquisition time. It was observed that the sampling rate does not influence the signal to noise ratio of the Raman bands if three or more wavelengths are sampled. With these optimised WMRS parameters, we increased the throughput in the binary classification of normal human urothelial cells and bladder cancer cells by reducing the total acquisition time to 6 s which is significantly lower in comparison to previous acquisition times required for the discrimination between similar cell types.

  15. Method and apparatus of highly linear optical modulation

    DOEpatents

    DeRose, Christopher; Watts, Michael R.

    2016-05-03

    In a new optical intensity modulator, a nonlinear change in refractive index is used to balance the nonlinearities in the optical transfer function in a way that leads to highly linear optical intensity modulation.

  16. Charge density wave modulation and gap measurements in CeTe 3

    DOE PAGES

    Ralevic, U.; Lazarevic, N.; Baum, A.; ...

    2016-10-14

    Here, we present a study of charge density wave (CDW) ordering in CeTe 3 at room temperature using a scanning tunneling microscope and Raman spectroscopy. Two characteristic CDW ordering wave vectors obtained from the Fourier analysis are assessed to be |c* – q|=4.19nm –1 and |q|=10.26nm –1 where |c*|=2π/c is the reciprocal lattice vector. The scanning tunneling spectroscopy measurements, along with inelastic light (Raman) scattering measurements, show a CDW gap Δ max of approximately 0.37 eV. In addition to the CDW modulation, we observe an organization of the Te sheet atoms in an array of alternating V- and N-shaped groupsmore » along the CDW modulation, as predicted in the literature.« less

  17. Bragg stack-functionalized counter electrode for solid-state dye-sensitized solar cells.

    PubMed

    Park, Jung Tae; Prosser, Jacob H; Kim, Dong Jun; Kim, Jong Hak; Lee, Daeyeon

    2013-05-01

    A highly reflective counter electrode is prepared through the deposition of alternating layers of organized mesoporous TiO(2) (om-TiO(2)) and colloidal SiO(2) (col-SiO(2)) nanoparticles. We present the effects of introducing this counter electrode into dye-sensitized solar cells (DSSCs) for maximizing light harvesting properties. The om-TiO(2) layers with a high refractive index are prepared by using an atomic transfer radical polymerization and a sol-gel process, in which a polyvinyl chloride-g-poly(oxyethylene) methacrylate graft copolymer is used as a structure-directing agent. The col-SiO(2) layers with a low refractive index are prepared by spin-coating commercially available silica nanoparticles. The properties of the Bragg stack (BS)-functionalized counter electrode in DSSCs are analyzed by using a variety of techniques, including spectroscopic ellipsometry, SEM, UV/Vis spectroscopy, incident photon-to-electron conversion efficiency, electrochemical impedance spectroscopy, and intensity modulated photocurrent/voltage spectroscopy measurements, to understand the critical factors contributing to the cell performance. When incorporated into DSSCs that are used in conjunction with a polymerized ionic liquid as the solid electrolyte, the energy conversion efficiency of this solid-state DSSC (ssDSSC) approaches 6.6 %, which is one of the highest of the reported N719 dye-based ssDSSCs. Detailed optical and electrochemical analyses of the device performance show that this assembly yields enhanced light harvesting without the negative effects of charge recombination or electrolyte penetration, which thus, presents new possibilities for effective light management. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Steering Charge Kinetics of Tin Niobate Photocatalysts: Key Roles of Phase Structure and Electronic Structure

    NASA Astrophysics Data System (ADS)

    Huang, Shushu; Wang, Chunyan; Sun, Hao; Wang, Xiaojing; Su, Yiguo

    2018-05-01

    Tin niobate photocatalysts with the phase structures of froodite (SnNb2O6) and pyrochlore (Sn2Nb2O7) were obtained by a facile solvothermal method in order to explore the impact of phase structure and electronic structure on the charge kinetics and photocatalytic performance. By employing tin niobate as a model compound, the effects of phase structure over electronic structure, photocatalytic activity toward methyl orange solution and hydrogen evolution were systematically investigated. It is found that the variation of phase structure from SnNb2O6 to Sn2Nb2O7 accompanied with modulation of particle size and band edge potentials that has great consequences on photocatalytic performance. In combination with the electrochemical impedance spectroscopy (EIS), transient photocurrent responses, transient absorption spectroscopy (TAS), and the analysis of the charge-carrier dynamics suggested that variation of electronic structure has great impacts on the charge separation and transfer rate of tin niobate photocatalysts and the subsequent photocatalytic performance. Moreover, the results of the X-ray photoelectron spectroscopy (XPS) indicated that the existent of Sn4+ species in Sn2Nb2O7 could result in a decrease in photocatalytic activity. Photocatalytic test demonstrated that the SnNb2O6 (froodite) catalyst possesses a higher photocatalytic activity toward MO degradation and H2 evolution compared with the sample of Sn2Nb2O7 (pyrochlore). On the basis of spin resonance measurement and trapping experiment, it is expected that photogenerated holes, O2 -•, and OH• active species dominate the photodegradation of methyl orange.

  19. Steering Charge Kinetics of Tin Niobate Photocatalysts: Key Roles of Phase Structure and Electronic Structure.

    PubMed

    Huang, Shushu; Wang, Chunyan; Sun, Hao; Wang, Xiaojing; Su, Yiguo

    2018-05-23

    Tin niobate photocatalysts with the phase structures of froodite (SnNb 2 O 6 ) and pyrochlore (Sn 2 Nb 2 O 7 ) were obtained by a facile solvothermal method in order to explore the impact of phase structure and electronic structure on the charge kinetics and photocatalytic performance. By employing tin niobate as a model compound, the effects of phase structure over electronic structure, photocatalytic activity toward methyl orange solution and hydrogen evolution were systematically investigated. It is found that the variation of phase structure from SnNb 2 O 6 to Sn 2 Nb 2 O 7 accompanied with modulation of particle size and band edge potentials that has great consequences on photocatalytic performance. In combination with the electrochemical impedance spectroscopy (EIS), transient photocurrent responses, transient absorption spectroscopy (TAS), and the analysis of the charge-carrier dynamics suggested that variation of electronic structure has great impacts on the charge separation and transfer rate of tin niobate photocatalysts and the subsequent photocatalytic performance. Moreover, the results of the X-ray photoelectron spectroscopy (XPS) indicated that the existent of Sn 4+ species in Sn 2 Nb 2 O 7 could result in a decrease in photocatalytic activity. Photocatalytic test demonstrated that the SnNb 2 O 6 (froodite) catalyst possesses a higher photocatalytic activity toward MO degradation and H 2 evolution compared with the sample of Sn 2 Nb 2 O 7 (pyrochlore). On the basis of spin resonance measurement and trapping experiment, it is expected that photogenerated holes, O 2 -• , and OH • active species dominate the photodegradation of methyl orange.

  20. Mechanism to support generic collective communication across a variety of programming models

    DOEpatents

    Almasi, Gheorghe [Ardsley, NY; Dozsa, Gabor [Ardsley, NY; Kumar, Sameer [White Plains, NY

    2011-07-19

    A system and method for supporting collective communications on a plurality of processors that use different parallel programming paradigms, in one aspect, may comprise a schedule defining one or more tasks in a collective operation, an executor that executes the task, a multisend module to perform one or more data transfer functions associated with the tasks, and a connection manager that controls one or more connections and identifies an available connection. The multisend module uses the available connection in performing the one or more data transfer functions. A plurality of processors that use different parallel programming paradigms can use a common implementation of the schedule module, the executor module, the connection manager and the multisend module via a language adaptor specific to a parallel programming paradigm implemented on a processor.

  1. Comparison of Cf-252 thin-film sources prepared by evaporation or self-transfer

    DOE PAGES

    Algutifan, Noor J.; Sherman, Steven R.; Alexander, Charles W.

    2014-11-29

    Californium-252 (Z = 98) is valued as a potent neutron source due to its spontaneous fission decay path. Thin film sources containing Cf-252 were prepared by two techniques: evaporation and self-transfer. The sources were analyzed by alpha and gamma spectroscopy. Results indicate that self-transfer sources exhibit less alpha energy straggling and energy loss than evaporative sources. Fission fragments may also self-transfer, and sources made by self-transfer may need some decay time to reach radioactive equilibrium.

  2. Transfer of graphene onto Pt/Glass substrate for transparent and large area graphene film using low temperature water bath

    NASA Astrophysics Data System (ADS)

    Aziz, Tengku Norazman Tengku Abd; Rosli, Aimi Bazilah; Yusoff, Marmeezee Mohd; Herman, Sukreen Hana; Zulkifli, Zurita

    2018-05-01

    This paper demonstrates the transfer of graphene at low temperature using water bath. Graphene in water solution (highly opaque) was transferred onto Platinum/Glass (Pt/Glass) substrate and the technique involves no additional chemicals. We obtained high transparency and large area of graphene film that is free of contaminants. The transferred graphene is characterized using FESEM, Raman spectroscopy and I-V measurements. This transfer method enables us to transfer graphene onto ZnO thin film for memristive devices.

  3. Wavelength modulation spectroscopy--digital detection of gas absorption harmonics based on Fourier analysis.

    PubMed

    Mei, Liang; Svanberg, Sune

    2015-03-20

    This work presents a detailed study of the theoretical aspects of the Fourier analysis method, which has been utilized for gas absorption harmonic detection in wavelength modulation spectroscopy (WMS). The lock-in detection of the harmonic signal is accomplished by studying the phase term of the inverse Fourier transform of the Fourier spectrum that corresponds to the harmonic signal. The mathematics and the corresponding simulation results are given for each procedure when applying the Fourier analysis method. The present work provides a detailed view of the WMS technique when applying the Fourier analysis method.

  4. In Vivo Assessment of Neurotransmitters and Modulators with Magnetic Resonance Spectroscopy: Application to Schizophrenia

    PubMed Central

    Wijtenburg, S. Andrea; Yang, Shaolin; Fischer, Bernard A.; Rowland, Laura M.

    2015-01-01

    In vivo measurement of neurotransmitters and modulators is now feasible with advanced proton magnetic resonance spectroscopy (1H-MRS) techniques. This review provides a basic tutorial of MRS, describes the methods available to measure brain glutamate, glutamine, γ-aminobutyric acid, glutathione, N-acetylaspartylglutamate, glycine, and serine at magnetic field strengths of 3Tesla or higher, and summarizes the neurochemical findings in schizophrenia. Overall, 1H-MRS holds great promise for producing biomarkers that can serve as treatment targets, prediction of disease onset, or illness exacerbation in schizophrenia and other brain diseases. PMID:25614132

  5. Comprehensive Analysis of Interstellar Iso-PROPYL Cyanide up to 480 GHZ

    NASA Astrophysics Data System (ADS)

    Kolesniková, Lucie; Alonso, E. R.; Cabezas, Carlos; Mata, Santiago; Alonso, José L.

    2016-06-01

    Iso-propyl cyanide, also known as iso-butyronitrile, is a branched alkyl molecule recently detected in the interstellar medium. A combination of Stark-modulated microwave spectroscopy and frequency-modulated millimeter and submillimeter wave spectroscopy was used to analyze its rotational spectrum from 26 to 480 GHz. Spectral assignments and analysis include transitions from the ground state, eight excited vibrational states and 13C isotopologues. Results of this work should facilitate astronomers further observations of iso-propyl cyanide in the interstellar medium. A. Belloche, R. T. Garrod, H. S. P. Müller, K. M. Menten, Science, 2014, 345, 1584

  6. Combining UV photodissociation action spectroscopy with electron transfer dissociation for structure analysis of gas-phase peptide cation-radicals.

    PubMed

    Shaffer, Christopher J; Pepin, Robert; Tureček, František

    2015-12-01

    We report the first example of using ultraviolet (UV) photodissociation action spectroscopy for the investigation of gas-phase peptide cation-radicals produced by electron transfer dissociation. z-Type fragment ions (●) Gly-Gly-Lys(+), coordinated to 18-crown-6-ether (CE), are generated, selected by mass and photodissociated in the 200-400 nm region. The UVPD action spectra indicate the presence of valence-bond isomers differing in the position of the Cα radical defect, (α-Gly)-Gly-Lys(+) (CE), Gly-(α-Gly)-Lys(+) (CE) and Gly-Gly-(α-Lys(+))(CE). The isomers are readily distinguishable by UV absorption spectra obtained by time-dependent density functional theory (TD-DFT) calculations. In contrast, conformational isomers of these radical types are calculated to have similar UV spectra. UV photodissociation action spectroscopy represents a new tool for the investigation of transient intermediates of ion-electron reactions. Specifically, z-type cation radicals are shown to undergo spontaneous hydrogen atom migrations upon electron transfer dissociation. Copyright © 2015 John Wiley & Sons, Ltd.

  7. Method for calibration-free scanned-wavelength modulation spectroscopy for gas sensing

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

    Hanson, Ronald K.; Jeffries, Jay B.; Sun, Kai

    A method of calibration-free scanned-wavelength modulation spectroscopy (WMS) absorption sensing is provided by obtaining absorption lineshape measurements of a gas sample on a sensor using 1f-normalized WMS-2f where an injection current to an injection current-tunable diode laser (TDL) is modulated at a frequency f, where a wavelength modulation and an intensity modulation of the TDL are simultaneously generated, extracting using a numerical lock-in program and a low-pass filter appropriate band-width WMS-nf (n=1, 2, . . . ) signals, where the WMS-nf signals are harmonics of the f, determining a physical property of the gas sample according to ratios of themore » WMS-nf signals, determining the zero-absorption background using scanned-wavelength WMS, and determining non-absorption losses using at least two of the harmonics, where a need for a non-absorption baseline measurement is removed from measurements in environments where collision broadening has blended transition linewidths, where calibration free WMS measurements without knowledge of the transition linewidth is enabled.« less

  8. A compact 7-cell Si-drift detector module for high-count rate X-ray spectroscopy.

    PubMed

    Hansen, K; Reckleben, C; Diehl, I; Klär, H

    2008-05-01

    A new Si-drift detector module for fast X-ray spectroscopy experiments was developed and realized. The Peltier-cooled module comprises a sensor with 7 × 7-mm 2 active area, an integrated circuit for amplification, shaping and detection, storage, and derandomized readout of signal pulses in parallel, and amplifiers for line driving. The compactness and hexagonal shape of the module with a wrench size of 16mm allow very short distances to the specimen and multi-module arrangements. The power dissipation is 186mW. At a shaper peaking time of 190 ns and an integration time of 450 ns an electronic rms noise of ~11 electrons was achieved. When operated at 7 °C, FWHM line widths around 260 and 460 eV (Cu-K α ) were obtained at low rates and at sum-count rates of 1.7 MHz, respectively. The peak shift is below 1% for a broad range of count rates. At 1.7-MHz sum-count rate the throughput loss amounts to 30%.

  9. Thermal equilibrium control by frequent bang-bang modulation.

    PubMed

    Yang, Cheng-Xi; Wang, Xiang-Bin

    2010-05-01

    In this paper, we investigate the non-Markovian heat transfer between a weakly damped harmonic oscillator (system) and a thermal bath. When the system is initially in a thermal state and not correlated with the environment, the mean energy of the system always first increases, then oscillates, and finally reaches equilibrium with the bath, no matter what the initial temperature of the system is. Moreover, the heat transfer between the system and the bath can be controlled by fast bang-bang modulation. This modulation does work on the system, and temporarily inverts the direction of heat flow. In this case, the common sense that heat always transfers from hot to cold does not hold any more. At the long time scale, a new dynamic equilibrium is established between the system and the bath. At this equilibrium, the energy of the system can be either higher or lower than its normal equilibrium value. A comprehensive analysis of the relationship between the dynamic equilibrium and the parameters of the modulation as well as the environment is presented.

  10. Ferroelectric Polarization-Modulated Interfacial Fine Structures Involving Two-Dimensional Electron Gases in Pb(Zr,Ti)O3/LaAlO3/SrTiO3 Heterostructures.

    PubMed

    Wang, Shuangbao; Bai, Yuhang; Xie, Lin; Li, Chen; Key, Julian D; Wu, Di; Wang, Peng; Pan, Xiaoqing

    2018-01-10

    Interfacial fine structures of bare LaAlO 3 /SrTiO 3 (LAO/STO) heterostructures are compared with those of LAO/STO heterostructures capped with upward-polarized Pb(Zr 0.1 ,Ti 0.9 )O 3 (PZT up ) or downward-polarized Pb(Zr 0.5 ,Ti 0.5 )O 3 (PZT down ) overlayers by aberration-corrected scanning transmission electron microscopy experiments. By combining the acquired electron energy-loss spectroscopy mapping, we are able to directly observe electron transfer from Ti 4+ to Ti 3+ and ionic displacements at the interface of bare LAO/STO and PZT down /LAO/STO heterostructure unit cell by unit cell. No evidence of Ti 3+ is observed at the interface of the PZT up /LAO/STO samples. Furthermore, the confinement of the two-dimensional electron gas (2DEG) at the interface is determined by atomic-column spatial resolution. Compared with the bare LAO/STO interface, the 2DEG density at the LAO/STO interface is enhanced or depressed by the PZT down or PZT up overlayer, respectively. Our microscopy studies shed light on the mechanism of ferroelectric modulation of interfacial transport at polar/nonpolar oxide heterointerfaces, which may facilitate applications of these materials as nonvolatile memory.

  11. Two-dimensional spectroscopy: An approach to distinguish Förster and Dexter transfer processes in coupled nanostructures

    NASA Astrophysics Data System (ADS)

    Specht, Judith F.; Knorr, Andreas; Richter, Marten

    2015-04-01

    The linear and two-dimensional coherent optical spectra of Coulomb-coupled quantum emitters are discussed with respect to the underlying coupling processes. We present a theoretical analysis of the two different resonance energy transfer mechanisms between coupled nanostructures: Förster and Dexter interaction. Our investigation shows that the features visible in optical spectra of coupled quantum dots can be traced back to the nature of the underlying coupling mechanism (Förster or Dexter). Therefore, we discuss how the excitation transfer pathways can be controlled by choosing particular laser polarizations and mutual orientations of the quantum emitters in coherent two-dimensional spectroscopy. In this context, we analyze to what extent the delocalized double-excitonic states are bound to the optical selection rules of the uncoupled system.

  12. Forster resonance energy transfer in the system of human serum albumin-xanthene dyes

    NASA Astrophysics Data System (ADS)

    Kochubey, V. I.; Pravdin, A. B.; Melnikov, A. G.; Konstantinova, I.; Alonova, I. V.

    2016-04-01

    The processes of interaction of fluorescent probes: eosin and erythrosine with human serum albumin (HSA) were studied by the methods of absorption and fluorescence spectroscopy. Extinction coefficients of probes were determined. Critical transfer radius and the energy transfer efficiency were defined by fluorescence quenching of HSA. Analysis of the excitation spectra of HSA revealed that the energy transfer process is carried out mainly between tryptophanyl and probes.

  13. Graphene assisted effective hole-extraction on In2O3:H/CH3NH3PbI3 interface: Studied by modulated surface spectroscopy

    NASA Astrophysics Data System (ADS)

    Vinoth Kumar, Sri Hari Bharath; Muydinov, Ruslan; Kol'tsova, Tat‘yana; Erfurt, Darja; Steigert, Alexander; Tolochko, Oleg; Szyszka, Bernd

    2018-01-01

    Charge separation in CH3NH3PbI3 (MAPbI3) films deposited on a hydrogen doped indium oxide (In2O3:H) photoelectrode was investigated by modulated surface photovoltage (SPV) spectroscopy in a fixed capacitor arrangement. It was found that In2O3:H reproducibly extracts photogenerated-holes from MAPbI3 films. The oxygen-plasma treatment of the In2O3:H surface is suggested to be a reason for this phenomenon. Introducing graphene interlayer increased charge separation nearly 6 times as compared to that on the In2O3:H/MAPbI3 interface. Furthermore, it is confirmed by SPV spectroscopy that the defects of the MAPbI3 interface are passivated by graphene.

  14. Surface initiated atom transfer radical polymerization grafting of sodium styrene sulfonate from titanium and silicon substrates.

    PubMed

    Foster, Rami N; Keefe, Andrew J; Jiang, Shaoyi; Castner, David G

    2013-11-01

    This study investigates the grafting of poly-sodium styrene sulfonate (pNaSS) from trichlorosilane/10-undecen-1-yl 2-bromo-2-methylpropionate functionalized Si and Ti substrates by atom transfer radical polymerization (ATRP). The composition, molecular structure, thickness, and topography of the grafted pNaSS films were characterized with x-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), variable angle spectroscopic ellipsometry (VASE), and atomic force microscopy (AFM), respectively. XPS and ToF-SIMS results were consistent with the successful grafting of a thick and uniform pNaSS film on both substrates. VASE and AFM scratch tests showed the films were between 25 and 49 nm thick on Si, and between 13 and 35 nm thick on Ti. AFM determined root-mean-square roughness values were ∼2 nm on both Si and Ti substrates. Therefore, ATRP grafting is capable of producing relatively smooth, thick, and chemically homogeneous pNaSS films on Si and Ti substrates. These films will be used in subsequent studies to test the hypothesis that pNaSS-grafted Ti implants preferentially adsorb certain plasma proteins in an orientation and conformation that modulates the foreign body response and promotes formation of new bone.

  15. Surface initiated atom transfer radical polymerization grafting of sodium styrene sulfonate from titanium and silicon substrates

    PubMed Central

    Foster, Rami N.; Keefe, Andrew J.; Jiang, Shaoyi; Castner, David G.

    2013-01-01

    This study investigates the grafting of poly-sodium styrene sulfonate (pNaSS) from trichlorosilane/10-undecen-1-yl 2-bromo-2-methylpropionate functionalized Si and Ti substrates by atom transfer radical polymerization (ATRP). The composition, molecular structure, thickness, and topography of the grafted pNaSS films were characterized with x-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), variable angle spectroscopic ellipsometry (VASE), and atomic force microscopy (AFM), respectively. XPS and ToF-SIMS results were consistent with the successful grafting of a thick and uniform pNaSS film on both substrates. VASE and AFM scratch tests showed the films were between 25 and 49 nm thick on Si, and between 13 and 35 nm thick on Ti. AFM determined root-mean-square roughness values were ∼2 nm on both Si and Ti substrates. Therefore, ATRP grafting is capable of producing relatively smooth, thick, and chemically homogeneous pNaSS films on Si and Ti substrates. These films will be used in subsequent studies to test the hypothesis that pNaSS-grafted Ti implants preferentially adsorb certain plasma proteins in an orientation and conformation that modulates the foreign body response and promotes formation of new bone. PMID:24482558

  16. Modulation Transfer Function (MTF) measurement techniques for lenses and linear detector arrays

    NASA Technical Reports Server (NTRS)

    Schnabel, J. J., Jr.; Kaishoven, J. E., Jr.; Tom, D.

    1984-01-01

    Application is the determination of the Modulation Transfer Function (MTF) for linear detector arrays. A system set up requires knowledge of the MTF of the imaging lens. Procedure for this measurement is described for standard optical lab equipment. Given this information, various possible approaches to MTF measurement for linear arrays is described. The knife edge method is then described in detail.

  17. Direct observation of back energy transfer in blue phosphorescent materials for organic light emitting diodes by time-resolved optical waveguide spectroscopy.

    PubMed

    Hirayama, H; Sugawara, Y; Miyashita, Y; Mitsuishi, M; Miyashita, T

    2013-02-25

    We demonstrate a high-sensitive transient absorption technique for detection of excited states in an organic thin film by time-resolved optical waveguide spectroscopy. By using a laser beam as a probe light, we detect small change in the transient absorbance which is equivalent to 10 -7 absorbance unit in a conventional method. This technique was applied to organic thin films of blue phosphorescent materials for organic light emitting diodes. We directly observed the back energy transfer from emitting guest molecules to conductive host molecules.

  18. Apollo Spacecraft 012 Command/Service Module being moved to Operations bldg

    NASA Technical Reports Server (NTRS)

    1967-01-01

    Transfer of Apollo Spacecraft 012 Command/Service Module for mating to the Saturn Lunar Module Adapter No. 05 in the Manned Spacecraft Operations bldg. S/C 012 will be flown on the Apollo/Saturn 204 mission.

  19. Light adaptation of the unicellular red alga, Cyanidioschyzon merolae, probed by time-resolved fluorescence spectroscopy.

    PubMed

    Ueno, Yoshifumi; Aikawa, Shimpei; Kondo, Akihiko; Akimoto, Seiji

    2015-08-01

    Photosynthetic organisms change the quantity and/or quality of their pigment-protein complexes and the interactions among these complexes in response to light conditions. In the present study, we analyzed light adaptation of the unicellular red alga Cyanidioschyzon merolae, whose pigment composition is similar to that of cyanobacteria because its phycobilisomes (PBS) lack phycoerythrin. C. merolae were grown under different light qualities, and their responses were measured by steady-state absorption, steady-state fluorescence, and picosecond time-resolved fluorescence spectroscopies. Cells were cultivated under four monochromatic light-emitting diodes (blue, green, yellow, and red), and changes in pigment composition and energy transfer were observed. Cells grown under blue and green light increased their relative phycocyanin levels compared with cells cultured under white light. Energy-transfer processes to photosystem I (PSI) were sensitive to yellow and red light. The contribution of direct energy transfer from PBS to PSI increased only under yellow light, while red light induced a reduction in energy transfer from photosystem II to PSI and an increase in energy transfer from light-harvesting chlorophyll protein complex I to PSI. Differences in pigment composition, growth, and energy transfer under different light qualities are discussed.

  20. Temporal modulation transfer functions in cochlear implantees using a method that limits overall loudness cues

    PubMed Central

    Fraser, Matthew; McKay, Colette M.

    2012-01-01

    Temporal modulation transfer functions (TMTFs) were measured for six users of cochlear implants, using different carrier rates and levels. Unlike most previous studies investigating modulation detection, the experimental design limited potential effects of overall loudness cues. Psychometric functions (percent correct discrimination of modulated from unmodulated stimuli versus modulation depth) were obtained. For each modulation depth, each modulated stimulus was loudness balanced to the unmodulated reference stimulus, and level jitter was applied in the discrimination task. The loudness-balance data showed that the modulated stimuli were louder than the unmodulated reference stimuli with the same average current, thus confirming the need to limit loudness cues when measuring modulation detection. TMTFs measured in this way had a low-pass characteristic, with a cut-off frequency (at comfortably loud levels) similar to that for normal-hearing listeners. A reduction in level caused degradation in modulation detection efficiency and a lower-cut-off frequency (i.e. poorer temporal resolution). An increase in carrier rate also led to a degradation in modulation detection efficiency, but only at lower levels or higher modulation frequencies. When detection thresholds were expressed as a proportion of dynamic range, there was no effect of carrier rate for the lowest modulation frequency (50 Hz) at either level. PMID:22146425

  1. Electron density modulation of NiCo2S4 nanowires by nitrogen incorporation for highly efficient hydrogen evolution catalysis.

    PubMed

    Wu, Yishang; Liu, Xiaojing; Han, Dongdong; Song, Xianyin; Shi, Lei; Song, Yao; Niu, Shuwen; Xie, Yufang; Cai, Jinyan; Wu, Shaoyang; Kang, Jian; Zhou, Jianbin; Chen, Zhiyan; Zheng, Xusheng; Xiao, Xiangheng; Wang, Gongming

    2018-04-12

    Metal sulfides for hydrogen evolution catalysis typically suffer from unfavorable hydrogen desorption properties due to the strong interaction between the adsorbed H and the intensely electronegative sulfur. Here, we demonstrate a general strategy to improve the hydrogen evolution catalysis of metal sulfides by modulating the surface electron densities. The N modulated NiCo 2 S 4 nanowire arrays exhibit an overpotential of 41 mV at 10 mA cm -2 and a Tafel slope of 37 mV dec -1 , which are very close to the performance of the benchmark Pt/C in alkaline condition. X-ray photoelectron spectroscopy, synchrotron-based X-ray absorption spectroscopy, and density functional theory studies consistently confirm the surface electron densities of NiCo 2 S 4 have been effectively manipulated by N doping. The capability to modulate the electron densities of the catalytic sites could provide valuable insights for the rational design of highly efficient catalysts for hydrogen evolution and beyond.

  2. Pressure modulation algorithm to separate cerebral hemodynamic signals from extracerebral artifacts

    PubMed Central

    Baker, Wesley B.; Parthasarathy, Ashwin B.; Ko, Tiffany S.; Busch, David R.; Abramson, Kenneth; Tzeng, Shih-Yu; Mesquita, Rickson C.; Durduran, Turgut; Greenberg, Joel H.; Kung, David K.; Yodh, Arjun G.

    2015-01-01

    Abstract. We introduce and validate a pressure measurement paradigm that reduces extracerebral contamination from superficial tissues in optical monitoring of cerebral blood flow with diffuse correlation spectroscopy (DCS). The scheme determines subject-specific contributions of extracerebral and cerebral tissues to the DCS signal by utilizing probe pressure modulation to induce variations in extracerebral blood flow. For analysis, the head is modeled as a two-layer medium and is probed with long and short source-detector separations. Then a combination of pressure modulation and a modified Beer-Lambert law for flow enables experimenters to linearly relate differential DCS signals to cerebral and extracerebral blood flow variation without a priori anatomical information. We demonstrate the algorithm’s ability to isolate cerebral blood flow during a finger-tapping task and during graded scalp ischemia in healthy adults. Finally, we adapt the pressure modulation algorithm to ameliorate extracerebral contamination in monitoring of cerebral blood oxygenation and blood volume by near-infrared spectroscopy. PMID:26301255

  3. Transfer of monolayer TMD WS2 and Raman study of substrate effects

    PubMed Central

    Mlack, Jerome T.; Masih Das, Paul; Danda, Gopinath; Chou, Yung-Chien; Naylor, Carl H.; Lin, Zhong; López, Néstor Perea; Zhang, Tianyi; Terrones, Mauricio; Johnson, A. T. Charlie; Drndić, Marija

    2017-01-01

    A facile transfer process for transition metal dichalcogenide WS2 flakes is reported and the effect of the underlying substrate on the flake properties is investigated using Raman spectroscopy. The flakes are transferred from their growth substrate using polymethyl methacrylate (PMMA) and a wet etch to allow the user to transfer the flakes to a final substrate using a microscope and micromanipulator combined with semi-transparent Kapton tape. The substrates used range from insulators such as industry standard high-k dielectric HfO2 and “green polymer” parylene-C, to conducting chemical vapor deposition (CVD) grown graphene. Raman spectroscopy is used first to confirm the material quality of the transferred flakes to the substrates and subsequently to analyze and separate the effects arising from material transfer from those arising from interactions with the substrate. We observe changes in the Raman spectra associated with the interactions between the substrates in the flakes. These interactions affect both in-plane and out-of-plane modes in different ways depending on their sources, for example strain or surface charge. These changes vary with final substrate, with the strongest effects being observed for WS2 transferred onto graphene and HfO2, demonstrating the importance of understanding substrate interaction for fabrication of future devices. PMID:28220852

  4. The role of defects in Fe(II) – goethite electron transfer

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

    Andrade de Notini, Luiza; Latta, Drew; Neumann, Anke

    Despite accumulating experimental evidence for Fe(II)-Fe(III) oxide electron transfer, computational chemical calculations suggest that oxidation of sorbed Fe(II) is not energetically feasible unless defects are present. Here we used isotope specific 57Fe Mössbauer spectroscopy to investigate whether Fe(II)-goethite electron transfer is influenced by defects. Specifically, we heated the mineral to try to anneal the goethite surface and ground goethite to try to create defects. We found that heating goethite results in less oxidation of sorbed Fe(II) by goethite. When goethite was re-ground after heating, electron transfer was partially restored. X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) ofmore » heated and ground goethite confirm that heating and grinding alter the surface structure of the goethite. We propose that the heating process annealed the surface and decreased the number of sites where electron transfer could occur. Our experimental findings suggest that surface defects play an important role in Fe(II)-goethite electron transfer as suggested by computational calculations. Our finding that defects influence heterogeneous Fe(II)-goethite electron transfer has important implications for Fe(II) driven recrystallization of Fe oxides, as well as X and Y.« less

  5. Purely wavelength- and amplitude-modulated quartz-enhanced photoacoustic spectroscopy.

    PubMed

    Patimisco, Pietro; Sampaolo, Angelo; Bidaux, Yves; Bismuto, Alfredo; Scott, Marshall; Jiang, James; Muller, Antoine; Faist, Jerome; Tittel, Frank K; Spagnolo, Vincenzo

    2016-11-14

    We report here on a quartz-enhanced photoacoustic (QEPAS) sensor employing a quantum cascade laser (QCL) structure capable of operating in a pure amplitude or wavelength modulation configuration. The QCL structure is composed of three electrically independent sections: Gain, Phase (PS) and Master Oscillator (MO). Selective current pumping of these three sections allows obtaining laser wavelength tuning without changes in the optical power, and power modulation without emission wavelength shifts. A pure QEPAS amplitude modulation condition is obtained by modulating the PS current, while pure wavelength modulation is achieved by modulating simultaneously the MO and PS QCL sections and slowly scanning the DC current level injected in the PS section.

  6. Correlation transfer and diffusion of ultrasound-modulated multiply scattered light.

    PubMed

    Sakadzić, Sava; Wang, Lihong V

    2006-04-28

    We develop a temporal correlation transfer equation (CTE) and a temporal correlation diffusion equation (CDE) for ultrasound-modulated multiply scattered light. These equations can be applied to an optically scattering medium with embedded optically scattering and absorbing objects to calculate the power spectrum of light modulated by a nonuniform ultrasound field. We present an analytical solution based on the CDE and Monte Carlo simulation results for light modulated by a cylinder of ultrasound in an optically scattering slab. We further validate with experimental measurements the numerical calculations for an actual ultrasound field. The CTE and CDE are valid for moderate ultrasound pressures and on a length scale comparable with the optical transport mean-free path. These equations should be applicable to a wide spectrum of conditions for ultrasound-modulated optical tomography of soft biological tissues.

  7. Measurements of ocean wave spectra and modulation transfer function with the airborne two frequency scatterometer

    NASA Technical Reports Server (NTRS)

    Weissman, D. E.; Johnson, J. W.

    1984-01-01

    The directional spectrum and the microwave modulation transfer function of ocean waves can be measured with the airborne two frequency scatterometer technique. Similar to tower based observations, the aircraft measurements of the Modulation Transfer Function (MTF) show that it is strongly affected by both wind speed and sea state. Also detected are small differences in the magnitudes of the MTF between downwind and upwind radar look directions, and variations with ocean wavenumber. The MTF inferred from the two frequency radar is larger than that measured using single frequency, wave orbital velocity techniques such as tower based radars or ROWS measurements from low altitude aircraft. Possible reasons for this are discussed. The ability to measure the ocean directional spectrum with the two frequency scatterometer, with supporting MTF data, is demonstrated.

  8. Measurements of ocean wave spectra and modulation transfer function with the airborne two-frequency scatterometer

    NASA Technical Reports Server (NTRS)

    Weissman, D. E.; Johnson, J. W.

    1986-01-01

    The directional spectrum and the microwave modulation transfer function of ocean waves can be measured with the airborne two frequency scatterometer technique. Similar to tower based observations, the aircraft measurements of the Modulation Transfer Function (MTF) show that it is strongly affected by both wind speed and sea state. Also detected are small differences in the magnitudes of the MTF between downwind and upwind radar look directions, and variations with ocean wavenumber. The MTF inferred from the two frequency radar is larger than that measured using single frequency, wave orbital velocity techniques such as tower based radars or ROWS measurements from low altitude aircraft. Possible reasons for this are discussed. The ability to measure the ocean directional spectrum with the two frequency scatterometer, with supporting MTF data, is demonstrated.

  9. Communication: Coherences observed in vivo in photosynthetic bacteria using two-dimensional electronic spectroscopy

    NASA Astrophysics Data System (ADS)

    Dahlberg, Peter D.; Norris, Graham J.; Wang, Cheng; Viswanathan, Subha; Singh, Ved P.; Engel, Gregory S.

    2015-09-01

    Energy transfer through large disordered antenna networks in photosynthetic organisms can occur with a quantum efficiency of nearly 100%. This energy transfer is facilitated by the electronic structure of the photosynthetic antennae as well as interactions between electronic states and the surrounding environment. Coherences in time-domain spectroscopy provide a fine probe of how a system interacts with its surroundings. In two-dimensional electronic spectroscopy, coherences can appear on both the ground and excited state surfaces revealing detailed information regarding electronic structure, system-bath coupling, energy transfer, and energetic coupling in complex chemical systems. Numerous studies have revealed coherences in isolated photosynthetic pigment-protein complexes, but these coherences have not been observed in vivo due to the small amplitude of these signals and the intense scatter from whole cells. Here, we present data acquired using ultrafast video-acquisition gradient-assisted photon echo spectroscopy to observe quantum beating signals from coherences in vivo. Experiments were conducted on isolated light harvesting complex II (LH2) from Rhodobacter sphaeroides, whole cells of R. sphaeroides, and whole cells of R. sphaeroides grown in 30% deuterated media. A vibronic coherence was observed following laser excitation at ambient temperature between the B850 and the B850∗ states of LH2 in each of the 3 samples with a lifetime of ˜40-60 fs.

  10. Millwright Apprenticeship. Related Training Modules. 10.1-10.5 Combustion.

    ERIC Educational Resources Information Center

    Lane Community Coll., Eugene, OR.

    This packet, part of the instructional materials for the Oregon apprenticeship program for millwright training, contains five modules covering combustion. The modules provide information on the following topics: the combustion process, types of fuel, air and fuel gases, heat transfer, and combustion in wood. Each module consists of a goal,…

  11. Stationary Engineers Apprenticeship. Related Training Modules. 16.1-16.5 Combustion.

    ERIC Educational Resources Information Center

    Lane Community Coll., Eugene, OR.

    This learning module, one in a series of 20 related training modules for apprentice stationary engineers, deals with combustion. Addressed in the individual instructional packages included in the module are the following topics: the combustion process, types of fuel, air and flue gases, heat transfer during combustion, and wood combustion. Each…

  12. Reusable module for the storage, transportation, and supply of multiple propellants in a space environment

    NASA Technical Reports Server (NTRS)

    Mazanek, Daniel D. (Inventor); Mankins, John C. (Inventor)

    2004-01-01

    A space module has an outer structure designed for traveling in space, a docking mechanism for facilitating a docking operation therewith in space, a first storage system storing a first propellant that burns as a result of a chemical reaction therein, a second storage system storing a second propellant that burns as a result of electrical energy being added thereto, and a bi-directional transfer interface coupled to each of the first and second storage systems to transfer the first and second propellants into and out thereof. The space module can be part of a propellant supply architecture that includes at least two of the space modules placed in an orbit in space.

  13. Electromagnetic behavior of spatial terahertz wave modulators based on reconfigurable micromirror gratings in Littrow configuration.

    PubMed

    Kappa, Jan; Schmitt, Klemens M; Rahm, Marco

    2017-08-21

    Efficient, high speed spatial modulators with predictable performance are a key element in any coded aperture terahertz imaging system. For spectroscopy, the modulators must also provide a broad modulation frequency range. In this study, we numerically analyze the electromagnetic behavior of a dynamically reconfigurable spatial terahertz wave modulator based on a micromirror grating in Littrow configuration. We show that such a modulator can modulate terahertz radiation over a wide frequency range from 1.7 THz to beyond 3 THz at a modulation depth of more than 0.6. As a specific example, we numerically simulated coded aperture imaging of an object with binary transmissive properties and successfully reconstructed the image.

  14. Orbit Transfer Systems with Emphasis on Shuttle Applications, 1986-1991

    NASA Technical Reports Server (NTRS)

    1977-01-01

    A systems study is presented for a transportation system which will follow the interim upper stage and spinning solid upper stage. Included are concepts, concept comparisons, trends, parametric data, etc. associated with the future system. Relevant technical and programmatic information is developed. This information is intended to focus future activity to identify attractive options and to summarize the major issues associated with the future development of the system. To establish a common basis for identifying current transportation concepts, an orbit transfer vehicle (OTV) is defined as a propulsive (velocity producing) rocket or stage. When used with a crew transfer module, a manned sortie module or other payloads, the combination becomes an orbit transfer system (OTS). Standardization of OTV's and OTS's is required.

  15. Spectroscopy of charge transfer states in Mg1 - x Ni x O

    NASA Astrophysics Data System (ADS)

    Churmanov, V. N.; Sokolov, V. I.; Pustovarov, V. A.; Gruzdev, N. B.; Mironova-Ulmane, N.

    2016-10-01

    Photoluminescence and photoluminescence excitation spectra of solid solution Mg1- x Ni x O ( x = 0.008) have been analyzed. The contributions of charge transfer electronic states and nonradiative Auger relaxation to the formation of the photoluminescence spectrum are discussed.

  16. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

    PubMed

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

    2016-10-24

    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

    PubMed Central

    Canton, Sophie E.; Kjær, Kasper S.; Vankó, György; van Driel, Tim B.; Adachi, Shin-ichi; Bordage, Amélie; Bressler, Christian; Chabera, Pavel; Christensen, Morten; Dohn, Asmus O.; Galler, Andreas; Gawelda, Wojciech; Gosztola, David; Haldrup, Kristoffer; Harlang, Tobias; Liu, Yizhu; Møller, Klaus B.; Németh, Zoltán; Nozawa, Shunsuke; Pápai, Mátyás; Sato, Tokushi; Sato, Takahiro; Suarez-Alcantara, Karina; Togashi, Tadashi; Tono, Kensuke; Uhlig, Jens; Vithanage, Dimali A.; Wärnmark, Kenneth; Yabashi, Makina; Zhang, Jianxin; Sundström, Villy; Nielsen, Martin M.

    2015-01-01

    Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances. Experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined. PMID:25727920

  18. Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

    DOE PAGES

    Canton, Sophie E.; Kjær, Kasper S.; Vankó, György; ...

    2015-03-02

    Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances.more » Thus experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.« less

  19. Photo-dynamics of roseoflavin and riboflavin in aqueous and organic solvents

    NASA Astrophysics Data System (ADS)

    Zirak, P.; Penzkofer, A.; Mathes, T.; Hegemann, P.

    2009-03-01

    Roseoflavin (8-dimethylamino-8-demethyl- D-riboflavin) and riboflavin in aqueous and organic solvents are studied by optical absorption spectroscopy, fluorescence spectroscopy, and fluorescence decay kinetics. Solvent polarity dependent absorption shifts are observed. The fluorescence quantum yields are solvent dependent. For roseoflavin the fluorescence decay shows a bi-exponential dependence (ps to sub-ps time constant, and 100 ps to a few ns time constant). The roseoflavin photo-dynamics is explained in terms of fast intra-molecular charge transfer (diabatic electron transfer) from the dimethylamino electron donor group to the pteridin carbonyl electron acceptor followed by intra-molecular charge recombination. The fast fluorescence component is due to direct locally-excited-state emission, and the slow fluorescence component is due to delayed locally-excited-state emission and charge transfer state emission. The fluorescence decay of riboflavin is mono-exponential. The S 1-state potential energy surface is determined by vibronic relaxation and solvation dynamics due to excited-state dipole moment changes (adiabatic optical electron transfer).

  20. Sulfur K-edge X-ray absorption spectroscopy and density functional theory calculations on monooxo Mo(IV) and bisoxo Mo(VI) bis-dithiolenes: insights into the mechanism of oxo transfer in sulfite oxidase and its relation to the mechanism of DMSO reductase.

    PubMed

    Ha, Yang; Tenderholt, Adam L; Holm, Richard H; Hedman, Britt; Hodgson, Keith O; Solomon, Edward I

    2014-06-25

    Sulfur K-edge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations have been used to determine the electronic structures of two complexes [Mo(IV)O(bdt)2](2-) and [Mo(VI)O2(bdt)2](2-) (bdt = benzene-1,2-dithiolate(2-)) that relate to the reduced and oxidized forms of sulfite oxidase (SO). These are compared with those of previously studied dimethyl sulfoxide reductase (DMSOr) models. DFT calculations supported by the data are extended to evaluate the reaction coordinate for oxo transfer to a phosphite ester substrate. Three possible transition states are found with the one at lowest energy, stabilized by a P-S interaction, in good agreement with experimental kinetics data. Comparison of both oxo transfer reactions shows that in DMSOr, where the oxo is transferred from the substrate to the metal ion, the oxo transfer induces electron transfer, while in SO, where the oxo transfer is from the metal site to the substrate, the electron transfer initiates oxo transfer. This difference in reactivity is related to the difference in frontier molecular orbitals (FMO) of the metal-oxo and substrate-oxo bonds. Finally, these experimentally related calculations are extended to oxo transfer by sulfite oxidase. The presence of only one dithiolene at the enzyme active site selectively activates the equatorial oxo for transfer, and allows facile structural reorganization during turnover.

  1. Does the pressure dependence of kinetic isotope effects report usefully on dynamics in enzyme H-transfer reactions?

    PubMed

    Hoeven, Robin; Heyes, Derren J; Hay, Sam; Scrutton, Nigel S

    2015-08-01

    The temperature dependence of kinetic isotope effects (KIEs) has emerged as the main experimental probe of enzymatic H-transfer by quantum tunnelling. Implicit in the interpretation is a presumed role for dynamic coupling of H-transfer chemistry to the protein environment, the so-called 'promoting motions/vibrations hypothesis'. This idea remains contentious, and others have questioned the importance and/or existence of promoting motions/vibrations. New experimental methods of addressing this problem are emerging, including use of mass-modulated enzymes and time-resolved spectroscopy. The pressure dependence of KIEs has been considered as a potential probe of quantum tunnelling reactions, because semi-classical KIEs, which are defined by differences in zero-point vibrational energy, are relatively insensitive to kbar changes in pressure. Reported combined pressure and temperature (p-T) dependence studies of H-transfer reactions are, however, limited. Here, we extend and review the available p-T studies that have utilized well-defined experimental systems in which quantum mechanical tunnelling is established. These include flavoproteins, quinoproteins, light-activated enzymes and chemical model systems. We show that there is no clear general trend between the p-T dependencies of the KIEs in these systems. Given the complex nature of p-T studies, we conclude that computational simulations using determined (e.g. X-ray) structures are also needed alongside experimental measurements of reaction rates/KIEs to guide the interpretation of p-T effects. In providing new insight into H-transfer/environmental coupling, combined approaches that unite both atomistic understanding with experimental rate measurements will require careful evaluation on a case-by-case basis. Although individually informative, we conclude that p-T studies do not provide the more generalized insight that has come from studies of the temperature dependence of KIEs. © 2015 The Authors. FEBS Journal published by John Wiley & Sons Ltd on behalf of FEBS.

  2. Advanced space system analysis software. Technical, user, and programmer guide

    NASA Technical Reports Server (NTRS)

    Farrell, C. E.; Zimbelman, H. F.

    1981-01-01

    The LASS computer program provides a tool for interactive preliminary and conceptual design of LSS. Eight program modules were developed, including four automated model geometry generators, an associated mass properties module, an appendage synthesizer module, an rf analysis module, and an orbital transfer analysis module. The existing rigid body controls analysis module was modified to permit analysis of effects of solar pressure on orbital performance. A description of each module, user instructions, and programmer information are included.

  3. Electron Tunneling in Lithium Ammonia Solutions Probed by Frequency-Dependent Electron-Spin Relaxation Studies

    PubMed Central

    Maeda, Kiminori; Lodge, Matthew T.J.; Harmer, Jeffrey; Freed, Jack H.; Edwards, Peter P.

    2012-01-01

    Electron transfer or quantum tunneling dynamics for excess or solvated electrons in dilute lithium-ammonia solutions have been studied by pulse electron paramagnetic resonance (EPR) spectroscopy at both X- (9.7 GHz) and W-band (94 GHz) frequencies. The electron spin-lattice (T1) and spin-spin (T2) relaxation data indicate an extremely fast transfer or quantum tunneling rate of the solvated electron in these solutions which serves to modulate the hyperfine (Fermi-contact) interaction with nitrogen nuclei in the solvation shells of ammonia molecules surrounding the localized, solvated electron. The donor and acceptor states of the solvated electron in these solutions are the initial and final electron solvation sites found before, and after, the transfer or tunneling process. To interpret and model our electron spin relaxation data from the two observation EPR frequencies requires a consideration of a multi-exponential correlation function. The electron transfer or tunneling process that we monitor through the correlation time of the nitrogen Fermi-contact interaction has a time scale of (1–10)×10−12 s over a temperature range 230–290K in our most dilute solution of lithium in ammonia. Two types of electron-solvent interaction mechanisms are proposed to account for our experimental findings. The dominant electron spin relaxation mechanism results from an electron tunneling process characterized by a variable donor-acceptor distance or range (consistent with such a rapidly fluctuating liquid structure) in which the solvent shell that ultimately accepts the transferring electron is formed from random, thermal fluctuations of the liquid structure in, and around, a natural hole or Bjerrum-like defect vacancy in the liquid. Following transfer and capture of the tunneling electron, further solvent-cage relaxation with a timescale of ca. 10−13 s results in a minor contribution to the electron spin relaxation times. This investigation illustrates the great potential of multi-frequency EPR measurements to interrogate the microscopic nature and dynamics of ultra fast electron transfer or quantum-tunneling processes in liquids. Our results also impact on the universal issue of the role of a host solvent (or host matrix, e.g. a semiconductor) in mediating long-range electron transfer processes and we discuss the implications of our results with a range of other materials and systems exhibiting the phenomenon of electron transfer. PMID:22568866

  4. Measurement of Oxygen A Band Line Parameters by Using Modulation Spectroscopy with Higher Harmonic Detection

    NASA Technical Reports Server (NTRS)

    Dharamsi, Amin

    1999-01-01

    Wavelength modulation spectroscopy is used to demonstrate that extremely weak absorption lines can be measured even when these lines suffer from interference from the wings of adjacent stronger lines. It is shown that the use of detection at several harmonics allows such interference to be examined clearly and conveniently. The results of experimental measurements on a weak magnetic dipole driven, spin-forbidden line in the oxygen A band, which experiences interference from the wings of a pair of adjacent lines towards the blue and red regions of line center, are presented. A comparison of the experimental results to theory is given.

  5. 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.

  6. Surface emitting ring quantum cascade lasers for chemical sensing

    NASA Astrophysics Data System (ADS)

    Szedlak, Rolf; Hayden, Jakob; Martín-Mateos, Pedro; Holzbauer, Martin; Harrer, Andreas; Schwarz, Benedikt; Hinkov, Borislav; MacFarland, Donald; Zederbauer, Tobias; Detz, Hermann; Andrews, Aaron Maxwell; Schrenk, Werner; Acedo, Pablo; Lendl, Bernhard; Strasser, Gottfried

    2018-01-01

    We review recent advances in chemical sensing applications based on surface emitting ring quantum cascade lasers (QCLs). Such lasers can be implemented in monolithically integrated on-chip laser/detector devices forming compact gas sensors, which are based on direct absorption spectroscopy according to the Beer-Lambert law. Furthermore, we present experimental results on radio frequency modulation up to 150 MHz of surface emitting ring QCLs. This technique provides detailed insight into the modulation characteristics of such lasers. The gained knowledge facilitates the utilization of ring QCLs in combination with spectroscopic techniques, such as heterodyne phase-sensitive dispersion spectroscopy for gas detection and analysis.

  7. Combining CFD simulations with blockoriented heatflow-network model for prediction of photovoltaic energy-production

    NASA Astrophysics Data System (ADS)

    Haber, I. E.; Farkas, I.

    2011-01-01

    The exterior factors which influencing the working circumstances of photovoltaic modules are the irradiation, the optical air layer (Air Mass - AM), the irradiation angle, the environmental temperature and the cooling effect of the wind. The efficiency of photovoltaic (PV) devices is inversely proportional to the cell temperature and therefore the mounting of the PV modules can have a big affect on the cooling, due to wind flow-around and naturally convection. The construction of the modules could be described by a heatflow-network model, and that can define the equation which determines the cells temperature. An equation like this can be solved as a block oriented model with hybrid-analogue simulator such as Matlab-Simulink. In view of the flow field and the heat transfer, witch was calculated numerically, the heat transfer coefficients can be determined. Five inflow rates were set up for both pitched and flat roof cases, to let the trend of the heat transfer coefficient know, while these functions can be used for the Matlab/Simulink model. To model the free convection flows, the Boussinesq-approximation were used, integrated into the Navier-Stokes equations and the energy equation. It has been found that under a constant solar heat gain, the air velocity around the modules and behind the pitched-roof mounted module is increasing, proportionately to the wind velocities, and as result the heat transfer coefficient increases linearly, and can be described by a function in both cases. To the block based model the meteorological parameters and the results of the CFD simulations as single functions were attached. The final aim was to make a model that could be used for planning photovoltaic systems, and define their accurate performance for better sizing of an array of modules.

  8. Time-resolved energy transfer in DNA sequence detection using water-soluble conjugated polymers: the role of electrostatic and hydrophobic interactions.

    PubMed

    Xu, Qing-Hua; Gaylord, Brent S; Wang, Shu; Bazan, Guillermo C; Moses, Daniel; Heeger, Alan J

    2004-08-10

    We have investigated the energy transfer processes in DNA sequence detection by using cationic conjugated polymers and peptide nucleic acid (PNA) probes with ultrafast pump-dump-emission spectroscopy. Pump-dump-emission spectroscopy provides femtosecond temporal resolution and high sensitivity and avoids interference from the solvent response. The energy transfer from donor (the conjugated polymer) to acceptor (a fluorescent molecule attached to a PNA terminus) has been time resolved. The results indicate that both electrostatic and hydrophobic interactions contribute to the formation of cationic conjugated polymers/PNA-C/DNA complexes. The two interactions result in two different binding conformations. This picture is supported by the average donor-acceptor separations as estimated from time-resolved and steady-state measurements. Electrostatic interactions dominate at low concentrations and in mixed solvents.

  9. Time-resolved energy transfer in DNA sequence detection using water-soluble conjugated polymers: The role of electrostatic and hydrophobic interactions

    PubMed Central

    Xu, Qing-Hua; Gaylord, Brent S.; Wang, Shu; Bazan, Guillermo C.; Moses, Daniel; Heeger, Alan J.

    2004-01-01

    We have investigated the energy transfer processes in DNA sequence detection by using cationic conjugated polymers and peptide nucleic acid (PNA) probes with ultrafast pump-dump-emission spectroscopy. Pump-dump-emission spectroscopy provides femtosecond temporal resolution and high sensitivity and avoids interference from the solvent response. The energy transfer from donor (the conjugated polymer) to acceptor (a fluorescent molecule attached to a PNA terminus) has been time resolved. The results indicate that both electrostatic and hydrophobic interactions contribute to the formation of cationic conjugated polymers/PNA-C/DNA complexes. The two interactions result in two different binding conformations. This picture is supported by the average donor–acceptor separations as estimated from time-resolved and steady-state measurements. Electrostatic interactions dominate at low concentrations and in mixed solvents. PMID:15282375

  10. Synaptic convergence regulates synchronization-dependent spike transfer in feedforward neural networks.

    PubMed

    Sailamul, Pachaya; Jang, Jaeson; Paik, Se-Bum

    2017-12-01

    Correlated neural activities such as synchronizations can significantly alter the characteristics of spike transfer between neural layers. However, it is not clear how this synchronization-dependent spike transfer can be affected by the structure of convergent feedforward wiring. To address this question, we implemented computer simulations of model neural networks: a source and a target layer connected with different types of convergent wiring rules. In the Gaussian-Gaussian (GG) model, both the connection probability and the strength are given as Gaussian distribution as a function of spatial distance. In the Uniform-Constant (UC) and Uniform-Exponential (UE) models, the connection probability density is a uniform constant within a certain range, but the connection strength is set as a constant value or an exponentially decaying function, respectively. Then we examined how the spike transfer function is modulated under these conditions, while static or synchronized input patterns were introduced to simulate different levels of feedforward spike synchronization. We observed that the synchronization-dependent modulation of the transfer function appeared noticeably different for each convergence condition. The modulation of the spike transfer function was largest in the UC model, and smallest in the UE model. Our analysis showed that this difference was induced by the different spike weight distributions that was generated from convergent synapses in each model. Our results suggest that, the structure of the feedforward convergence is a crucial factor for correlation-dependent spike control, thus must be considered important to understand the mechanism of information transfer in the brain.

  11. Nonphotochemical Hole-Burning Studies of Energy Transfer Dynamics in Antenna Complexes of Photosynthetic Bacteria

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

    Matsuzaki, Satoshi

    2001-01-01

    This thesis contains the candidate's original work on excitonic structure and energy transfer dynamics of two bacterial antenna complexes as studied using spectral hole-burning spectroscopy. The general introduction is divided into two chapters (1 and 2). Chapter 1 provides background material on photosynthesis and bacterial antenna complexes with emphasis on the two bacterial antenna systems related to the thesis research. Chapter 2 reviews the underlying principles and mechanism of persistent nonphotochemical hole-burning (NPHB) spectroscopy. Relevant energy transfer theories are also discussed. Chapters 3 and 4 are papers by the candidate that have been published. Chapter 3 describes the application ofmore » NPHB spectroscopy to the Fenna-Matthews-Olson (FMO) complex from the green sulfur bacterium Prosthecochloris aestuarii; emphasis is on determination of the low energy vibrational structure that is important for understanding the energy transfer process associated within three lowest energy Q y-states of the complex. The results are compared with those obtained earlier on the FMO complex from Chlorobium tepidum. In Chapter 4, the energy transfer dynamics of the B800 molecules of intact LH2 and B800-deficient LH2 complexes of the purple bacterium Rhodopseudomonas acidophila are compared. New insights on the additional decay channel of the B800 ring of bacteriochlorophyll a (BChl a) molecules are provided. General conclusions are given in Chapter 5. A version of the hole spectrum simulation program written by the candidate for the FMO complex study (Chapter 3) is included as an appendix. The references for each chapter are given at the end of each chapter.« less

  12. Calibration-free wavelength-modulation spectroscopy based on a swiftly determined wavelength-modulation frequency response function of a DFB laser.

    PubMed

    Zhao, Gang; Tan, Wei; Hou, Jiajia; Qiu, Xiaodong; Ma, Weiguang; Li, Zhixin; Dong, Lei; Zhang, Lei; Yin, Wangbao; Xiao, Liantuan; Axner, Ove; Jia, Suotang

    2016-01-25

    A methodology for calibration-free wavelength modulation spectroscopy (CF-WMS) that is based upon an extensive empirical description of the wavelength-modulation frequency response (WMFR) of DFB laser is presented. An assessment of the WMFR of a DFB laser by the use of an etalon confirms that it consists of two parts: a 1st harmonic component with an amplitude that is linear with the sweep and a nonlinear 2nd harmonic component with a constant amplitude. Simulations show that, among the various factors that affect the line shape of a background-subtracted peak-normalized 2f signal, such as concentration, phase shifts between intensity modulation and frequency modulation, and WMFR, only the last factor has a decisive impact. Based on this and to avoid the impractical use of an etalon, a novel method to pre-determine the parameters of the WMFR by fitting to a background-subtracted peak-normalized 2f signal has been developed. The accuracy of the new scheme to determine the WMFR is demonstrated and compared with that of conventional methods in CF-WMS by detection of trace acetylene. The results show that the new method provides a four times smaller fitting error than the conventional methods and retrieves concentration more accurately.

  13. Quantum cascade laser-based multipass absorption system for hydrogen peroxide detection

    NASA Astrophysics Data System (ADS)

    Cao, Yingchun; Sanchez, Nancy P.; Jiang, Wenzhe; Ren, Wei; Lewicki, Rafal; Jiang, Dongfang; Griffin, Robert J.; Tittel, Frank K.

    2015-01-01

    Hydrogen peroxide (H2O2) is a relevant molecular trace gas species, that is related to the oxidative capacity of the atmosphere, the production of radical species such as OH, the generation of sulfate aerosol via oxidation of S(IV) to S(VI), and the formation of acid rain. The detection of atmospheric H2O2 involves specific challenges due to its high reactivity and low concentration (ppbv to sub-ppbv level). Traditional methods for measuring atmospheric H2O2 concentration are often based on wet-chemistry methods that require a transfer from the gas- to liquid-phase for a subsequent determination by techniques such as fluorescence spectroscopy, which can lead to problems such as sampling artifacts and interference by other atmospheric constituents. A quartz-enhanced photoacoustic spectroscopy-based system for the measurement of atmospheric H2O2 with a detection limit of 75 ppb for 1-s integration time was previously reported. In this paper, an updated H2O2 detection system based on long-optical-path-length absorption spectroscopy by using a distributed feedback quantum cascade laser (DFB-QCL) will be described. A 7.73-μm CW-DFB-QCL and a thermoelectrically cooled infrared detector, optimized for a wavelength of 8 μm, are employed for theH2O2 sensor system. A commercial astigmatic Herriott multi-pass cell with an effective optical path-length of 76 m is utilized for the reported QCL multipass absorption system. Wavelength modulation spectroscopy (WMS) with second harmonic detection is used for enhancing the signal-to-noise-ratio. A minimum detection limit of 13.4 ppb is achieved with a 2 s sampling time. Based on an Allan-Werle deviation analysis the minimum detection limit can be improved to 1.5 ppb when using an averaging time of 300 s.

  14. Investigating molecule-semiconductor interfaces with nonlinear spectroscopies

    NASA Astrophysics Data System (ADS)

    Giokas, Paul George

    Knowledge of electronic structures and transport mechanisms at molecule-semiconductor interfaces is motivated by their ubiquity in photoelectrochemical cells. In this dissertation, optical spectroscopies are used uncover the influence of electronic coupling, coherent vibrational motion, and molecular geometry, and other factors on dynamics initiated by light absorption at such interfaces. These are explored for a family of ruthenium bipyridyl chromophores bound to titanium dioxide. Transient absorption measurements show molecular singlet state electron injection in 100 fs or less. Resonance Raman intensity analysis suggests the electronic excitations possess very little charge transfer character. The connections drawn in this work between molecular structure and photophysical behavior contribute to the general understanding of photoelectrochemical cells. Knowledge of binding geometry in nanocrystalline films is challenged by heterogeneity of semiconductor surfaces. Polarized resonance Raman spectroscopy is used to characterize the ruthenium chromophore family on single crystal titanium dioxide . Chromophores display a broad distribution of molecular geometries at the interface, with increased variation in binding angle due to the presence of a methylene bridge, as well as additional phosphonate anchors. This result implies multiple binding configurations for chromophores which incorporate multiple phosphonate ligands, and indicates the need for careful consideration when developing surface-assembled chromophore-catalyst cells. Electron transfer transitions occurring on the 100 fs time scale challenge conventional second-order approximations made when modeling these reactions. A fourth-order perturbative model which includes the relationship between coincident electron transfer and nuclear relaxation processes is presented. Insights provided by the model are illustrated for a two-level donor molecule. The presented fourth-order rate formula constitutes a rigorous and intuitive framework for understanding sub-picosecond photoinduced electron transfer dynamics. Charge transfer systems fit by this model include catechol-sensitized titanium dioxide nanoparticles and a closely-related molecular complex. These systems exhibit vibrational coherence coincident with back-electron transfer in the first picosecond after excitation, which suggests that intramolecular nuclear motion strongly influences the electronic transfer process and plays an important role in the dynamics of interfacial systems following light absorption.

  15. Evidence for protein conformational change at a Au(110)/protein interface

    NASA Astrophysics Data System (ADS)

    Messiha, H. L.; Smith, C. I.; Scrutton, N. S.; Weightman, P.

    2008-07-01

    Evidence is presented that reflection anisotropy spectroscopy (RAS) can provide real-time measurements of conformational change in proteins induced by electron transfer reactions. A bacterial electron transferring flavoprotein (ETF) has been modified so as to adsorb on an Au(110) electrode and enable reversible electron transfer to the protein cofactor in the absence of mediators. Reversible changes are observed in the RAS of this protein that are interpreted as arising from conformational changes accompanying the transfer of electrons.

  16. Beneficial effects of amino acid-functionalized graphene nanosheets incorporated in the photoanode material of dye-sensitized solar cells: A practical and theoretical study

    NASA Astrophysics Data System (ADS)

    Taki, Mahmood; Rezaei, Behzad; Fani, Najmeh; Borandeh, Sedigheh; Abdolmaleki, Amir; Ensafi, Ali A.

    2017-05-01

    In this research, covalently functionalized graphene oxide (GO) with some biocompatible amino acids were incorporated to the TiO2 film and employed as the photoanodes of dye-sensitized solar cells (DSSCs). Electrochemical analysis of the amino acids-functionalized graphene oxide (AFGs) confirmed that the attached amino acids could be acted as a reducing agent of the GO. The photovoltaic performance of the assembled DSSCs under illumination of simulated AM 1.5 sunlight (100 mW cm-2) showed an enhancement of about 4.1 and 1.8 fold for the solar cell assembled with the tyrosine-functionalized GO in relation to the control solar cells constructed with GO-TiO2 composite and blank TiO2 film, respectively. These results were in accordance with electron life time and transport time resulted from the open circuit voltage decay (OCVD), electrochemical impedance spectroscopy (EIS) and intensity modulated photocurrent spectroscopy (IMPS) analysis. The density functional theory (DFT) calculations exhibited a proper spacial arrangement for the tyrosine-GO structure that could improve electron transfer between the adjucent GO sheets. Density of electronic states (DOS) exhibited a gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels for the simulated AFG structures. This effect could facilitate the light adsorption process in near-IR region.

  17. Altered phospholipid metabolism in schizophrenia: a phosphorus 31 nuclear magnetic resonance spectroscopy study.

    PubMed

    Weber-Fahr, Wolfgang; Englisch, Susanne; Esser, Andrea; Tunc-Skarka, Nuran; Meyer-Lindenberg, Andreas; Ende, Gabriele; Zink, Mathias

    2013-12-30

    Phospholipid (PL) metabolism is investigated by in vivo 31P magnetic resonance spectroscopy (MRS). Inconsistent alterations of phosphocholine (PC), phosphoethanolamine (PE), glycerophosphocholine (GPC) and glycerophosphoethanolamine (GPE) have been described in schizophrenia, which might be overcome by specific editing techniques. The selective refocused insensitive nuclei-enhanced polarization transfer (RINEPT) technique was applied in a cross-sectional study involving 11 schizophrenia spectrum disorder patients (SZP) on stable antipsychotic monotherapy and 15 matched control subjects. Metabolite signals were found to be modulated by cerebrospinal fluid (CSF) content and gray matter/brain matter ratio. Corrected metabolite concentrations of PC, GPC and PE differed between patients and controls in both subcortical and cortical regions, whereas antipsychotic medication exerted only small effects. Significant correlations were found between the severity of clinical symptoms and the assessed signals. In particular, psychotic symptoms correlated with PC levels in the cerebral cortex, depression with PC levels in the cerebellum and executive functioning with GPC in the insular and temporal cortices. In conclusion, after controlling for age and tissue composition, this investigation revealed alterations of metabolite levels in SZP and correlations with clinical properties. RINEPT 31P MRS should also be applied to at-risk-mental-state patients as well as drug-naïve and chronically treated schizophrenic patients in order to enhance the understanding of longitudinal alterations of PL metabolism in schizophrenia. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  18. Quantifying internal friction in unfolded and intrinsically disordered proteins with single-molecule spectroscopy

    PubMed Central

    Soranno, Andrea; Buchli, Brigitte; Nettels, Daniel; Cheng, Ryan R.; Müller-Späth, Sonja; Pfeil, Shawn H.; Hoffmann, Armin; Lipman, Everett A.; Makarov, Dmitrii E.; Schuler, Benjamin

    2012-01-01

    Internal friction, which reflects the “roughness” of the energy landscape, plays an important role for proteins by modulating the dynamics of their folding and other conformational changes. However, the experimental quantification of internal friction and its contribution to folding dynamics has remained challenging. Here we use the combination of single-molecule Förster resonance energy transfer, nanosecond fluorescence correlation spectroscopy, and microfluidic mixing to determine the reconfiguration times of unfolded proteins and investigate the mechanisms of internal friction contributing to their dynamics. Using concepts from polymer dynamics, we determine internal friction with three complementary, largely independent, and consistent approaches as an additive contribution to the reconfiguration time of the unfolded state. We find that the magnitude of internal friction correlates with the compactness of the unfolded protein: its contribution dominates the reconfiguration time of approximately 100 ns of the compact unfolded state of a small cold shock protein under native conditions, but decreases for more expanded chains, and approaches zero both at high denaturant concentrations and in intrinsically disordered proteins that are expanded due to intramolecular charge repulsion. Our results suggest that internal friction in the unfolded state will be particularly relevant for the kinetics of proteins that fold in the microsecond range or faster. The low internal friction in expanded intrinsically disordered proteins may have implications for the dynamics of their interactions with cellular binding partners. PMID:22492978

  19. Quantifying internal friction in unfolded and intrinsically disordered proteins with single-molecule spectroscopy.

    PubMed

    Soranno, Andrea; Buchli, Brigitte; Nettels, Daniel; Cheng, Ryan R; Müller-Späth, Sonja; Pfeil, Shawn H; Hoffmann, Armin; Lipman, Everett A; Makarov, Dmitrii E; Schuler, Benjamin

    2012-10-30

    Internal friction, which reflects the "roughness" of the energy landscape, plays an important role for proteins by modulating the dynamics of their folding and other conformational changes. However, the experimental quantification of internal friction and its contribution to folding dynamics has remained challenging. Here we use the combination of single-molecule Förster resonance energy transfer, nanosecond fluorescence correlation spectroscopy, and microfluidic mixing to determine the reconfiguration times of unfolded proteins and investigate the mechanisms of internal friction contributing to their dynamics. Using concepts from polymer dynamics, we determine internal friction with three complementary, largely independent, and consistent approaches as an additive contribution to the reconfiguration time of the unfolded state. We find that the magnitude of internal friction correlates with the compactness of the unfolded protein: its contribution dominates the reconfiguration time of approximately 100 ns of the compact unfolded state of a small cold shock protein under native conditions, but decreases for more expanded chains, and approaches zero both at high denaturant concentrations and in intrinsically disordered proteins that are expanded due to intramolecular charge repulsion. Our results suggest that internal friction in the unfolded state will be particularly relevant for the kinetics of proteins that fold in the microsecond range or faster. The low internal friction in expanded intrinsically disordered proteins may have implications for the dynamics of their interactions with cellular binding partners.

  20. IDeF-X ECLAIRs: A CMOS ASIC for the Readout of CdTe and CdZnTe Detectors for High Resolution Spectroscopy

    NASA Astrophysics Data System (ADS)

    Gevin, Olivier; Baron, Pascal; Coppolani, Xavier; Daly, FranÇois; Delagnes, Eric; Limousin, Olivier; Lugiez, Francis; Meuris, Aline; Pinsard, FrÉdÉric; Renaud, Diana

    2009-08-01

    The very last member of the IDeF-X ASIC family is presented: IDeF-X ECLAIRs is a 32-channel front end ASIC designed for the readout of Cadmium Telluride (CdTe) and Cadmium Zinc Telluride (CdZnTe) Detectors. Thanks to its noise performance (Equivalent Noise Charge floor of 33 e- rms) and to its radiation hardened design (Single Event Latchup Linear Energy Transfer threshold of 56 MeV.cm2.mg-1), the chip is well suited for soft X-rays energy discrimination and high energy resolution, ldquospace proof,rdquo hard X-ray spectroscopy. We measured an energy low threshold of less than 4 keV with a 10 pF input capacitor and a minimal reachable sensitivity of the Equivalent Noise Charge (ENC) to input capacitance of less than 7 e-/pF obtained with a 6 mus peak time. IDeF-X ECLAIRs will be used for the readout of 6400 CdTe Schottky monopixel detectors of the 2D coded mask imaging telescope ECLAIRs aboard the SVOM satellite. IDeF-X ECLAIRs (or IDeF-X V2) has also been designed for the readout of a pixelated CdTe detector in the miniature spectro-imager prototype Caliste 256 that is currently foreseen for the high energy detector module of the Simbol-X mission.

  1. Cross-linked polyimides for integrated optics

    NASA Astrophysics Data System (ADS)

    Singer, Kenneth D.; Kowalczyk, Tony C.; Nguyen, Hung D.; Beuhler, Allyson J.; Wargowski, David A.

    1997-01-01

    We have investigated a promising class of polyimide materials for both passive and active electro-optic devices, namely crosslinkable polyimides. These fluorinated polyimides are soluble in the imidized form and are both thermally and photo-crosslinkable leading to easy processability into waveguide structures and the possibility of stable electro-optic properties. We have fabricated channel and slab waveguides and investigated the mechanism of optical propagation loss using photothermal deflection spectroscopy and waveguide loss spectroscopy, and found the losses to arise from residual absorption due to the formation of charge transfer states. The absorption is inhibited by fluorination leading to propagation losses as low as 0.3 dB/cm in the near infrared. Because of the ability to photocrosslink, channel waveguides are fabricated using a simple wet-etch process. Channel waveguides so formed are observed to have no excess loss over slab structures. Solubility followed by thermal cross-linking allows the formation of multilayer structures. We have produced electro-optic polymers by doping with the nonlinear optical chromophores, DCM and DADC; and a process of concurrent poling and thermal crosslinking. Multilayer structures have been investigated and poling fields optimized in the active layer by doping the cladding with an anti-static agent. The high glass-transition temperature and cross-linking leads to very stable electro-optic properties. We are currently building electro-optic modulators based on these materials. Progress and results in this area also are reported.

  2. A SiC MOSFET Based Inverter for Wireless Power Transfer Applications

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

    Onar, Omer C; Chinthavali, Madhu Sudhan; Campbell, Steven L

    2014-01-01

    In a wireless power transfer (WPT) system, efficiency of the power conversion stages is crucial so that the WPT technology can compete with the conventional conductive charging systems. Since there are 5 or 6 power conversion stages, each stage needs to be as efficient as possible. SiC inverters are crucial in this case; they can handle high frequency operation and they can operate at relatively higher temperatures resulting in reduces cost and size for the cooling components. This study presents the detailed power module design, development, and fabrication of a SiC inverter. The proposed inverter has been tested at threemore » center frequencies that are considered for the WPT standardization. Performance of the inverter at the same target power transfer level is analyzed along with the other system components. In addition, another SiC inverter has been built in authors laboratory by using the ORNL designed and developed SiC modules. It is shown that the inverter with ORNL packaged SiC modules performs simular to that of the inverter having commercially available SiC modules.« less

  3. Modulation transfer function cascade model for a sampled IR imaging system.

    PubMed

    de Luca, L; Cardone, G

    1991-05-01

    The performance of the infrared scanning radiometer (IRSR) is strongly stressed in convective heat transfer applications where high spatial frequencies in the signal that describes the thermal image are present. The need to characterize more deeply the system spatial resolution has led to the formulation of a cascade model for the evaluation of the actual modulation transfer function of a sampled IR imaging system. The model can yield both the aliasing band and the averaged modulation response for a general sampling subsystem. For a line scan imaging system, which is the case of a typical IRSR, a rule of thumb that states whether the combined sampling-imaging system is either imaging-dependent or sampling-dependent is proposed. The model is tested by comparing it with other noncascade models as well as by ad hoc measurements performed on a commercial digitized IRSR.

  4. [Design and Implementation of a Novel Networked Sleep Monitoring System].

    PubMed

    Tian, Yu; Yan, Zhuangzhi; Tao, Jia'an

    2015-03-01

    To meet the need of cost-effective multi-biosignal monitoring devices nowadays, we designed a system based on super low power MCU. It can collect, record and transfer several signals including ECG, Oxygen saturation, thoracic and abdominal wall expansion, oronasal airflow signal. The data files can be stored on a flash chip and transferred to a computer by a USB module. In addition, the sensing data can be sent wirelessly in real time. Considering that long term work of wireless module consumes much energy, we present a low-power optimization method based on delay constraint. Lower energy consumption comes at the cost of little delay. Experimental results show that it can effectively decrease the energy consumption without changing wireless module and transfer protocol. Besides, our system is powered by two dry batteries and can work at least 8 hours throughout a whole night.

  5. SAFSIM theory manual: A computer program for the engineering simulation of flow systems

    NASA Astrophysics Data System (ADS)

    Dobranich, Dean

    1993-12-01

    SAFSIM (System Analysis Flow SIMulator) is a FORTRAN computer program for simulating the integrated performance of complex flow systems. SAFSIM provides sufficient versatility to allow the engineering simulation of almost any system, from a backyard sprinkler system to a clustered nuclear reactor propulsion system. In addition to versatility, speed and robustness are primary SAFSIM development goals. SAFSIM contains three basic physics modules: (1) a fluid mechanics module with flow network capability; (2) a structure heat transfer module with multiple convection and radiation exchange surface capability; and (3) a point reactor dynamics module with reactivity feedback and decay heat capability. Any or all of the physics modules can be implemented, as the problem dictates. SAFSIM can be used for compressible and incompressible, single-phase, multicomponent flow systems. Both the fluid mechanics and structure heat transfer modules employ a one-dimensional finite element modeling approach. This document contains a description of the theory incorporated in SAFSIM, including the governing equations, the numerical methods, and the overall system solution strategies.

  6. Potassium-intercalated H2Pc films: Alkali-induced electronic and geometrical modifications

    NASA Astrophysics Data System (ADS)

    Nilson, K.; Åhlund, J.; Shariati, M.-N.; Schiessling, J.; Palmgren, P.; Brena, B.; Göthelid, E.; Hennies, F.; Huismans, Y.; Evangelista, F.; Rudolf, P.; Göthelid, M.; Mârtensson, N.; Puglia, C.

    2012-07-01

    X-ray spectroscopy studies of potassium intercalated metal-free phthalocyanine multilayers adsorbed on Al(110) have been undertaken. Photoelectron spectroscopy measurements show the presence of several charge states of the molecules upon K intercalation, due to a charge transfer from the alkali. In addition, the comparison of valence band photoemission spectra with the density functional theory calculations of the density of states of the H2Pc- anion indicates a filling of the formerly lowest unoccupied molecular orbital by charge transfer from the alkali. This is further confirmed by x-ray absorption spectroscopy (XAS) studies, which show a decreased density of unoccupied states. XAS measurements in different experimental geometries reveal that the molecules in the pristine film are standing upright on the surface or are only slightly tilted away from the surface normal but upon K intercalation, the molecular orientation is changed in that the tilt angle of the molecules increases.

  7. Mechanical design of the first proximal Ig domain of human cardiac titin revealed by single molecule force spectroscopy.

    PubMed

    Li, Hongbin; Fernandez, Julio M

    2003-11-14

    The elastic I-band part of muscle protein titin contains two tandem immunoglobulin (Ig) domain regions of distinct mechanical properties. Until recently, the only known structure was that of the I27 module of the distal region, whose mechanical properties have been reported in detail. Recently, the structure of the first proximal domain, I1, has been resolved at 2.1A. In addition to the characteristic beta-sandwich structure of all titin Ig domains, the crystal structure of I1 showed an internal disulfide bridge that was proposed to modulate its mechanical extensibility in vivo. Here, we use single molecule force spectroscopy and protein engineering to examine the mechanical architecture of this domain. In contrast to the predictions made from the X-ray crystal structure, we find that the formation of a disulfide bridge in I1 is a relatively rare event in solution, even under oxidative conditions. Furthermore, our studies of the mechanical stability of I1 modules engineered with point mutations reveal significant differences between the mechanical unfolding of the I1 and I27 modules. Our study illustrates the varying mechanical architectures of the titin Ig modules.

  8. Dynamic Modulation of Radiative Heat Transfer beyond the Blackbody Limit.

    PubMed

    Ito, Kota; Nishikawa, Kazutaka; Miura, Atsushi; Toshiyoshi, Hiroshi; Iizuka, Hideo

    2017-07-12

    Dynamic control of electromagnetic heat transfer without changing mechanical configuration opens possibilities in intelligent thermal management in nanoscale systems. We confirmed by experiment that the radiative heat transfer is dynamically modulated beyond the blackbody limit. The near-field electromagnetic heat exchange mediated by phonon-polariton is controlled by the metal-insulator transition of tungsten-doped vanadium dioxide. The functionalized heat flux is transferred over an area of 1.6 cm 2 across a 370 nm gap, which is maintained by the microfabricated spacers and applied pressure. The uniformity of the gap is validated by optical interferometry, and the measured heat transfer is well modeled as the sum of the radiative and the parasitic conductive components. The presented methodology to form a nanometric gap with functional heat flux paves the way to the smart thermal management in various scenes ranging from highly integrated systems to macroscopic apparatus.

  9. Modulation of spin transfer torque amplitude in double barrier magnetic tunnel junctions

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

    Clément, P.-Y.; Baraduc, C., E-mail: claire.baraduc@cea.fr; Chshiev, M.

    2015-09-07

    Magnetization switching induced by spin transfer torque is used to write magnetic memories (Magnetic Random Access Memory, MRAM) but can be detrimental to the reading process. It would be quite convenient therefore to modulate the efficiency of spin transfer torque. A solution is adding an extra degree of freedom by using double barrier magnetic tunnel junctions with two spin-polarizers, with controllable relative magnetic alignment. We demonstrate, for these structures, that the amplitude of in-plane spin transfer torque on the middle free layer can be efficiently tuned via the magnetic configuration of the electrodes. Using the proposed design could thus pavemore » the way towards more reliable read/write schemes for MRAM. Moreover, our results suggest an intriguing effect associated with the out-of-plane (field-like) spin transfer torque, which has to be further investigated.« less

  10. Robust sub-millihertz-level offset locking for transferring optical frequency accuracy and for atomic two-photon spectroscopy.

    PubMed

    Cheng, Wang-Yau; Chen, Ting-Ju; Lin, Chia-Wei; Chen, Bo-Wei; Yang, Ya-Po; Hsu, Hung Yi

    2017-02-06

    Robust sub-millihertz-level offset locking was achieved with a simple scheme, by which we were able to transfer the laser frequency stability and accuracy from either cesium-stabilized diode laser or comb laser to the other diode lasers who had serious frequency jitter previously. The offset lock developed in this paper played an important role in atomic two-photon spectroscopy with which record resolution and new determination on the hyperfine constants of cesium atom were achieved. A quantum-interference experiment was performed to show the improvement of light coherence as an extended design was implemented.

  11. Real-time investigation of cytochrome c release profiles in living neuronal cells undergoing amyloid beta oligomer-induced apoptosis

    NASA Astrophysics Data System (ADS)

    Lee, Jae Young; Park, Younggeun; Pun, San; Lee, Sung Sik; Lo, Joe F.; Lee, Luke P.

    2015-06-01

    Intracellular Cyt c release profiles in living human neuroblastoma undergoing amyloid β oligomer (AβO)-induced apoptosis, as a model Alzheimer's disease-associated pathogenic molecule, were analysed in a real-time manner using plasmon resonance energy transfer (PRET)-based spectroscopy.Intracellular Cyt c release profiles in living human neuroblastoma undergoing amyloid β oligomer (AβO)-induced apoptosis, as a model Alzheimer's disease-associated pathogenic molecule, were analysed in a real-time manner using plasmon resonance energy transfer (PRET)-based spectroscopy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02390d

  12. Effect of viscosity on photoinduced electron transfer reaction: An observation of the Marcus inverted region in homogeneous solvents

    NASA Astrophysics Data System (ADS)

    Saini, Rajesh Kumar; Kuchlyan, Jagannath; Sarkar, Nilmoni

    2016-09-01

    The viscosity effect of homogeneous solvents on the dynamics of photoinduced electron transfer (PET) reaction among the coumarins and N,N-dimethylaniline (DMA) is investigated using steady-state and time-resolved fluorescence spectroscopy. A bell shape Marcus inversion in the ET rates has been detected in the plot of ET rate constant (kq) with free energy change (ΔG0) in viscous solvents decanol and EG, but it is not observed in DMSO like low viscous solvent. We have also reported that there is no complex formation between the coumarin dye and DMA molecule by using fluorescence correlation spectroscopy.

  13. Charge Transfer Processes in OPV Materials as Revealed by EPR Spectroscopy

    DOE PAGES

    Niklas, Jens; Poluektov, Oleg

    2017-03-03

    Understanding charge separation and charge transport at a molecular level is crucial for improving the efficiency of organic photovoltaic (OPV) cells. Under illumination of Bulk Heterojunction (BHJ) blends of polymers and fullerenes, various paramagnetic species are formed including polymer and fullerene radicals, radical pairs, and photoexcited triplet states. Light-induced Electron Paramagnetic Resonance (EPR) spectroscopy is ideally suited to study these states in BHJ due to its selectivity in probing the paramagnetic intermediates. Some advanced EPR techniques like light-induced ENDOR spectroscopy and pulsed techniques allow the determination of hyperfine coupling tensors, while high-frequency EPR allows the EPR signals of the individualmore » species to be resolved and their g-tensors to be determined. In these magnetic resonance parameters reveal details about the delocalization of the positive polaron on the various polymer donors which is important for the efficient charge separation in BHJ systems. Time-resolved EPR can contribute to the study of the dynamics of charge separation, charge transfer and recombination in BHJ by probing the unique spectral signatures of charge transfer and triplet states. Furthermore, the potential of the EPR also allows characterization of the intermediates and products of BHJ degradation.« less

  14. UV-Vis spectroscopy and density functional study of solvent effect on the charge transfer band of the n → σ* complexes of 2-Methylpyridine and 2-Chloropyridine with molecular iodine

    NASA Astrophysics Data System (ADS)

    Gogoi, Pallavi; Mohan, Uttam; Borpuzari, Manash Protim; Boruah, Abhijit; Baruah, Surjya Kumar

    2017-03-01

    UV-Vis spectroscopy has established that Pyridine substitutes form n→σ* charge transfer (CT) complexes with molecular Iodine. This study is a combined approach of purely experimental UV-Vis spectroscopy, Multiple linear regression theory and Computational chemistry to analyze the effect of solvent upon the charge transfer band of 2-Methylpyridine-I2 and 2-Chloropyridine-I2 complexes. Regression analysis verifies the dependence of the CT band upon different solvent parameters. Dielectric constant and refractive index are considered among the bulk solvent parameters and Hansen, Kamlet and Catalan parameters are taken into consideration at the molecular level. Density Functional Theory results explain well the blue shift of the CT bands in polar medium as an outcome of stronger donor acceptor interaction. A logarithmic relation between the bond length of the bridging atoms of the donor and the acceptor with the dielectric constant of the medium is established. Tauc plot and TDDFT study indicates a non-vertical electronic transition in the complexes. Buckingham and Lippert Mataga equations are applied to check the Polarizability effect on the CT band.

  15. Spatial Data Transfer Standard (SDTS)

    USGS Publications Warehouse

    ,

    1995-01-01

    The Spatial Data Transfer Standard (SOTS) is a mechanism for the transfer of spatial data between dissimilar computer systems. The SOTS specifies exchange constructs, addressing formats, structure, and content for spatially referenced vector and raster (including gridded) data. SOTS components are a conceptual model, specifications for a quality report, transfer module specifications, data dictionary specifications, and definitions of spatial features and attributes.

  16. Transferable Training Modules: Building Environmental Education Opportunities With and for Mexican Community Health Workers (Promotores de Salud).

    PubMed

    Ramírez, Denise Moreno; Vea, Lourdes; Field, James A; Baker, Paul B; Gandolfi, A Jay; Maier, Raina M

    Community health workers (promotores de salud) have the ability to empower communities to mitigate negative health outcomes. Current training efforts in environmental topics are lacking. This project addressed this gap by developing 4 transferable training modules on environmental health. By applying a series of surveys, interviews, and trainings, we evaluated their relevance. Partners provided favorable feedback for 3 of the 4 modules. It was also learned that the development method could be improved by engaging technically trained promotores de salud in the role of co-creators. This project has implications for environmental justice communities as it can lessen information disparities.

  17. The selective digital integrator: A new device for modulated polarization spectroscopy

    NASA Astrophysics Data System (ADS)

    Vrancic, Aljosa

    1998-12-01

    A new device, a selective digital integrator (SDI), for the acquisition of modulated polarization spectroscopy (MPS) signals is described. Special attention is given to the accurate measurement of very small (AC component of interest <10-3 x DC component), rapidly modulated (~50 kHz) signals at or below noise levels. Various data acquisition methods and problems associated with the collection of modulated signals are discussed. The SDI solves most of these problems and has the following advantages: it provides the average-time resolved profile of a modulated signal; it eliminates errors if the modulation is not sinusoidal; it enables separate measurements of the various phases of the signal modulation cycle; it permits simultaneous measurement of absorption, circular dichroism (CD) and linear dichroism (LD) spectra; it facilitates 3-D absorbance measurements; it has a wide gain-switching-free dynamic range (10 orders of magnitude or more); it offers a constant S/N ratio mode of operation; it eliminates the need for photomultiplier voltage feedback, and it has faster scanning speeds. The time-resolution, selectivity, wide dynamic range, and low-overhead on-the-fly data processing are useful for other modulated spectroscopy (MS) and non-MS experiments such as pulse height distribution and time-resolved pulse counting measurements. The advantages of the MPS-SDI method are tested on the first Rydberg electronic transitions of (+)-3- methylcyclopentanone. The experimental results validate the predicted SDI capabilities. However, they also point to two difficulties that had not been noted previously: the presence of LD in a gaseous sample and a pressure- dependence of the relative peak heights of the CD spectrum. Models for these anomalies are proposed. The presence of the oscillatory LD (but not an LD background) is explained with a sample cell model based on the observed polarization-dependent time-resolved profiles of transmitted light intensity. To obtain expressions for these intensities, a theoretical background, which provides a new approach to the treatment of light/matter interaction, is included as an Appendix. To explain the second anomaly, present only at high optical densities, a model based on the presence of scattered light is introduced and verified. The mode of correction for the scattering problem is outlined.

  18. Enhanced photoresponse characteristics of transistors using CVD-grown MoS2/WS2 heterostructures

    NASA Astrophysics Data System (ADS)

    Shan, Junjie; Li, Jinhua; Chu, Xueying; Xu, Mingze; Jin, Fangjun; Fang, Xuan; Wei, Zhipeng; Wang, Xiaohua

    2018-06-01

    Semiconductor heterostructures based on transition metal dichalcogenides provide a broad platform to research two-dimensional nanomaterials and design atomically thin devices for fundamental and applied interests. The MoS2/WS2 heterostructure was prepared on SiO2/Si substrate by chemical vapor deposition (CVD) in our research. And the optical properties of the heterostructure was characterized by Raman and photoluminescence (PL) spectroscopy. The similar 2 orders of magnitude decrease of PL intensity in MoS2/WS2 heterostructures was tested, which is attribute to the electrical and optical modulation effects are connected with the interfacial charge transfer between MoS2 and WS2 films. Using MoS2/WS2 heterostructure as channel material of the phototransistor, we demonstrated over 50 folds enhanced photoresponsivity of multilayer MoS2 field-effect transistor. The results indicate that the MoS2/WS2 films can be a promising heterostructure material to enhance the photoresponse characteristics of MoS2-based phototransistors.

  19. RX GEMINORUM: PHOTOMETRIC SOLUTIONS, (NEARLY UNIFORM) GAINER ROTATION, DONOR RADIAL VELOCITY SOLUTION, NON-LTE ACCRETION DISK MODELS OF Hα EMISSION PROFILES, AND SECULAR LIGHT CURVE CHANGES IN THE 20TH CENTURY

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

    Olson, Edward C.; Etzel, Paul B., E-mail: olsoneco@aol.com, E-mail: pbetzel@mail.sdsu.edu

    We obtained full-orbit Iybvu intermediate-band photometry and CCD spectroscopy of the long-period Algol eclipsing binary RX Geminorum. Photometric solutions using the Wilson–Devinney code give a gainer rotation (hotter, mass-accreting component) about 15 times the synchronous rate. We describe a simple technique to detect departures from uniform rotation of the hotter component. These binaries radiate double-peaked Hα emission from a low-mass accretion disk around the gainer. We used an approximate non-LTE disk code to predict models in fair agreement with observations, except in the far wings of the emission profile, where the star–inner disk boundary layer emits extra radiation. Variations inmore » Hα emission derive from modulations in the transfer rate. A study of times of minima during the 20th century suggests that a perturbing third body is present near RX Gem.« less

  20. Digital modulation of the nickel valence state in a cuprate-nickelate heterostructure

    NASA Astrophysics Data System (ADS)

    Wrobel, F.; Geisler, B.; Wang, Y.; Christiani, G.; Logvenov, G.; Bluschke, M.; Schierle, E.; van Aken, P. A.; Keimer, B.; Pentcheva, R.; Benckiser, E.

    2018-03-01

    Layer-by-layer oxide molecular-beam epitaxy has been used to synthesize cuprate-nickelate multilayer structures of composition (La2CuO4)m/LaO /(LaNiO3)n . In a combined experimental and theoretical study, we show that these structures allow a clean separation of dopant and doped layers. Specifically, the LaO layer separating cuprate and nickelate blocks provides an additional charge that, according to density-functional theory calculations, is predominantly accommodated in the interfacial nickelate layers. This is reflected in an elongation of bond distances and changes in valence state, as observed by scanning transmission electron microscopy and x-ray absorption spectroscopy. Moreover, the predicted charge disproportionation in the nickelate interface layers leads to a metal-to-insulator transition when the thickness is reduced to n =2 , as observed in electrical transport measurements. The results exemplify the perspectives of charge transfer in metal-oxide multilayers to induce doping without introducing chemical and structural disorder.

  1. Emission switching of 4,6-diphenylpyrimidones: solvent and solid state effects.

    PubMed

    Adjaye-Mensah, Edward; Gonzalez, Walter G; Bussé, David R; Captain, Burjor; Miksovska, Jaroslava; Wilson, James N

    2012-08-30

    The photophysics of 1-ethyl-4,6-bis(4-methoxyphenyl)-2(1H)-pyrimidone (1) and 1-ethyl-4,6-bis(4-(dimethylamino)phenyl)-2(1H)-pyrimidone (2) were investigated to determine the mechanisms of emission switching in response to protonation. UV-vis and steady state emission spectroscopy of the protonated and unprotonated forms across a range of solvents reveal the polarity dependence of the vertical excitation energies. Emission lifetimes and quantum yields show the solvent dependency of the excited states. Emission enhancements were observed in polyethylene glycol solutions and in the solid state (both thin film and single crystal), demonstrating the role of intramolecular rotation in thermal relaxation of the excited states. TD-DFT calculations provide insights into the excited state geometries and the role of intramolecular charge transfer. The collected data show that emission of diphenylpyrimidones can be modulated by four factors, including the identity of the electron-donating auxochrome, protonation state, solvent polarity, and viscosity.

  2. Acousto-Optic Q-Switched Fiber Laser-Based Intra-Cavity Photoacoustic Spectroscopy for Trace Gas Detection

    PubMed Central

    Zhang, Qinduan; Chang, Jun; Wang, Zongliang; Wang, Fupeng; Qin, Zengguang

    2017-01-01

    We proposed a new method for gas detection in photoacoustic spectroscopy based on acousto-optic Q-switched fiber laser by merging a transmission PAS cell (resonant frequency f0 = 5.3 kHz) inside the fiber laser cavity. The Q-switching was achieved by an acousto-optic modulator, achieving a peak pulse power of ~679 mW in the case of the acousto-optic modulation signal with an optimized duty ratio of 10%. We used a custom-made fiber Bragg grating with a central wavelength of 1530.37 nm (the absorption peak of C2H2) to select the laser wavelength. The system achieved a linear response (R2 = 0.9941) in a concentration range from 400 to 7000 ppmv, and the minimum detection limit compared to that of a conventional intensity modulation system was enhanced by 94.2 times. PMID:29295599

  3. Interfacial Chemistry-Induced Modulation of Schottky Barrier Heights: In Situ Measurements of the Pt-Amorphous Indium Gallium Zinc Oxide Interface Using X-ray Photoelectron Spectroscopy

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

    Flynn, Brendan T.; Oleksak, Richard P.; Thevuthasan, Suntharampillai

    A method to modulate the Schottky barrier heights for platinum and amorphous indium gallium zinc oxide (a-IGZO) interfaces is demonstrated through thermal processing and background ambient pressure control. The interfacial chemistries that modulate barrier heights for the Pt/a-IGZO system were investigated using in-situ X-ray photoelectron spectroscopy. A significant reduction of indium, from In3+ to In0, occurs during deposition of Pt on to the a-IGZO surface in ultra-high vacuum. Post-annealing and controlling the background ambient O2 pressure allows tuning the degree of indium reduction and the corresponding Schottky barrier height between 0.17 to 0.77 eV. Understanding the detailed interfacial chemistries atmore » Pt/a-IGZO interfaces may allow for improved electronic device performance, including Schottky diodes, memristors, and metalsemiconductor field-effect transistors.« less

  4. Interfacial Chemistry-Induced Modulation of Schottky Barrier Heights: In Situ Measurements of the Pt–Amorphous Indium Gallium Zinc Oxide Interface Using X-ray Photoelectron Spectroscopy

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

    Flynn, Brendan T.; Oleksak, Richard P.; Thevuthasan, Suntharampillai

    A method to modulate the Schottky barrier heights for platinum and amorphous indium gallium zinc oxide (a-IGZO) interfaces is demonstrated through thermal processing and background ambient pressure control. The interfacial chemistries that modulate barrier heights for the Pt/a-IGZO system were investigated using in-situ X-ray photoelectron spectroscopy. A significant reduction of indium, from In 3+ to In 0, occurs during deposition of Pt on to the a-IGZO surface in ultra-high vacuum. Post-annealing and controlling the background ambient O 2 pressure allows tuning the degree of indium reduction and the corresponding Schottky barrier height between 0.17 to 0.77 eV. Understanding the detailedmore » interfacial chemistries at Pt/a-IGZO interfaces may allow for improved electronic device performance, including Schottky diodes, memristors, and metalsemiconductor field-effect transistors.« less

  5. Acousto-Optic Q-Switched Fiber Laser-Based Intra-Cavity Photoacoustic Spectroscopy for Trace Gas Detection.

    PubMed

    Zhang, Qinduan; Chang, Jun; Wang, Qiang; Wang, Zongliang; Wang, Fupeng; Qin, Zengguang

    2017-12-25

    We proposed a new method for gas detection in photoacoustic spectroscopy based on acousto-optic Q-switched fiber laser by merging a transmission PAS cell (resonant frequency f ₀ = 5.3 kHz) inside the fiber laser cavity. The Q-switching was achieved by an acousto-optic modulator, achieving a peak pulse power of ~679 mW in the case of the acousto-optic modulation signal with an optimized duty ratio of 10%. We used a custom-made fiber Bragg grating with a central wavelength of 1530.37 nm (the absorption peak of C₂H₂) to select the laser wavelength. The system achieved a linear response (R² = 0.9941) in a concentration range from 400 to 7000 ppmv, and the minimum detection limit compared to that of a conventional intensity modulation system was enhanced by 94.2 times.

  6. Photoinduced triplet-triplet energy transfer via the 2-ureido-4[1H]-pyrimidinone self-complementary quadruple hydrogen-bonded module.

    PubMed

    Wang, Su-Min; Yu, Mao-Lin; Ding, Jie; Tung, Chen-Ho; Wu, Li-Zhu

    2008-05-01

    Phosphorescence quenching and flash photolysis experiments demonstrate that photoinduced intra-assembly triplet-triplet energy transfer can take place via a 2-ureido-4[1H]-pyrimidinone-bridged benzophenone-naphthalene assembly I with a rate constant of 3.0 x 106 s-1 and an efficiency of 95% in CH2Cl2. This new finding suggests that with high binding strength and directionality, the 2-ureido-4[1H]-pyrimidinone hydrogen-bonded module may serve as a new model to illustrate the fundamental principles governing the triplet-triplet energy-transfer process through hydrogen bonds.

  7. Correlating electronic and vibrational motions in charge transfer systems

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

    Khalil, Munira

    2014-06-27

    The goal of this research program was to measure coupled electronic and nuclear motions during photoinduced charge transfer processes in transition metal complexes by developing and using novel femtosecond spectroscopies. The scientific highlights and the resulting scientific publications from the DOE supported work are outlined in the technical report.

  8. High-Resolution Dual-Comb Spectroscopy with Ultra-Low Noise Frequency Combs

    NASA Astrophysics Data System (ADS)

    Hänsel, Wolfgang; Giunta, Michele; Beha, Katja; Perry, Adam J.; Holzwarth, R.

    2017-06-01

    Dual-comb spectroscopy is a powerful tool for fast broad-band spectroscopy due to the parallel interrogation of thousands of spectral lines. Here we report on the spectroscopic analysis of acetylene vapor in a pressurized gas cell using two ultra-low noise frequency combs with a repetition rate around 250 MHz. Optical referencing to a high-finesse cavity yields a sub-Hertz stability of all individual comb lines (including the virtual comb lines between 0 Hz and the carrier) and permits one to pick a small difference of repetition rate for the two frequency combs on the order of 300 Hz, thus representing an optical spectrum of 100 THz (˜3300 \\wn) within half the free spectral range (125 MHz). The transmission signal is derived straight from a photodetector and recorded with a high-resolution spectrum analyzer or digitized with a computer-controlled AD converter. The figure to the right shows a schematic of the experimental setup which is all fiber-coupled with polarization-maintaining fiber except for the spectroscopic cell. The graph on the lower right reveals a portion of the recorded radio-frequency spectrum which has been scaled to the optical domain. The location of the measured absorption coincides well with data taken from the HITRAN data base. Due to the intrinsic linewidth of all contributing comb lines, each sampling point in the transmission graph corresponds to the probing at an optical frequency with sub-Hertz resolution. This resolution is maintained in coherent wavelength conversion processes such as difference-frequency generation (DFG), sum-frequency generation (SFG) or non-linear broadening (self-phase modulation), and is therefore easily transferred to a wide spectral range from the mid infrared up to the visible spectrum.

  9. A detailed study on the working mechanism of a heteropoly acid modified TiO2 photoanode for efficient dye-sensitized solar cells.

    PubMed

    Jiang, Yanxia; Yang, Yulin; Qiang, Liangsheng; Fan, Ruiqing; Li, Liang; Ye, Tengling; Na, Yong; Shi, Yan; Luan, Tianzhu

    2015-03-14

    A novel heteropolyacid (HPA) K6SiW11O39Ni(H2O)·xH2O (SiW11Ni) modified TiO2 has been successfully synthesized and introduced into the photoanode of dye-sensitized solar cells (DSSCs). The performance of the cell with the HPA-modified photoanode (SiW11Ni/TiO2), mixed with P25 powder in the ratio of 2 : 8, is better than the cell with a pristine P25 photoanode. An increase of 31% in the photocurrent and 22% improvement in the conversion efficiency are obtained. The effect of the heteropolyacid was well studied by UV-vis spectroscopy, spectro-electrochemical spectroscopy, dark current, intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy, open-circuit voltage decay and electrochemical impedance spectroscopy. The results show that the interfacial layer modified by SiW11Ni can enhance the injection and transport of electrons, and then retard the recombination of electrons, which results in a longer electron lifetime. What's more, the introduction of SiW11Ni can simultaneously broaden the absorption in the visible region, eventually leading to an efficient increase in energy conversion efficiency.

  10. Scalable transfer of vertical graphene nanosheets for flexible supercapacitor applications

    NASA Astrophysics Data System (ADS)

    Sahoo, Gopinath; Ghosh, Subrata; Polaki, S. R.; Mathews, Tom; Kamruddin, M.

    2017-10-01

    Vertical graphene nanosheets (VGN) are the material of choice for application in next-generation electronic devices. The growing demand for VGN-based flexible devices for the electronics industry brings in restriction on VGN growth temperature. The difficulty associated with the direct growth of VGN on flexible substrates can be overcome by adopting an effective strategy of transferring the well-grown VGN onto arbitrary flexible substrates through a soft chemistry route. In the present study, we report an inexpensive and scalable technique for the polymer-free transfer of VGN onto arbitrary substrates without disrupting its morphology, structure, and properties. After transfer, the morphology, chemical structure, and electrical properties are analyzed by scanning electron microscopy, Raman spectroscopy, x-ray photoelectron spectroscopy, and four-probe resistive methods, respectively. The wetting properties are studied from the water contact angle measurements. The observed results indicate the retention of morphology, surface chemistry, structure, and electronic properties. Furthermore, the storage capacity of the transferred VGN-based binder-free and current collector-free flexible symmetric supercapacitor device is studied. A very low sheet resistance of 670 Ω/□ and excellent supercapacitance of 158 μF cm-2 with 86% retention after 10 000 cycles show the prospect of the damage-free VGN transfer approach for the fabrication of flexible nanoelectronic devices.

  11. Surface molecular imprinting onto fluorescein-coated magnetic nanoparticlesvia reversible addition fragmentation chain transfer polymerization: A facile three-in-one system for recognition and separation of endocrine disrupting chemicals

    NASA Astrophysics Data System (ADS)

    Li, Ying; Dong, Cunku; Chu, Jia; Qi, Jingyao; Li, Xin

    2011-01-01

    In this study, we present a general protocol for the making of surface-imprinted magnetic fluorescence beads viareversible addition-fragmentation chain transfer polymerization. The resulting composites were characterized by X-ray diffraction analysis, transmission electron microscopy, scanning electron microscopy, fluorescence spectroscopy, Fourier transform infrared spectroscopy, and energy dispersive spectroscopy. The as-synthesized beads exhibited homogeneous polymer films (thickness of about 5.7 nm), spherical shape, high fluorescence intensity and magnetic property (Magnetization (Ms) = 3.67 emu g-1). The hybrids bind the original template 17β-estradiol with an appreciable selectivity over structurally related compounds. In addition, the resulting hybrids performed without obvious deterioration after five repeated cycles. This study therefore demonstrates the potential of molecularly imprinted polymers for the recognition and separation of endocrine disrupting chemicals.In this study, we present a general protocol for the making of surface-imprinted magnetic fluorescence beads viareversible addition-fragmentation chain transfer polymerization. The resulting composites were characterized by X-ray diffraction analysis, transmission electron microscopy, scanning electron microscopy, fluorescence spectroscopy, Fourier transform infrared spectroscopy, and energy dispersive spectroscopy. The as-synthesized beads exhibited homogeneous polymer films (thickness of about 5.7 nm), spherical shape, high fluorescence intensity and magnetic property (Magnetization (Ms) = 3.67 emu g-1). The hybrids bind the original template 17β-estradiol with an appreciable selectivity over structurally related compounds. In addition, the resulting hybrids performed without obvious deterioration after five repeated cycles. This study therefore demonstrates the potential of molecularly imprinted polymers for the recognition and separation of endocrine disrupting chemicals. Electronic supplementary information (ESI) available: Supplementary figure S1. The hysteresis loop of Fe3O4 (a), Fe3O4@SiO2 (b), and Fe3O4@SiO2-Dye-SiO2 (c). See DOI: 10.1039/c0nr00614a

  12. Pump-Probe Noise Spectroscopy of Molecular Junctions.

    PubMed

    Ochoa, Maicol A; Selzer, Yoram; Peskin, Uri; Galperin, Michael

    2015-02-05

    The slow response of electronic components in junctions limits the direct applicability of pump-probe type spectroscopy in assessing the intramolecular dynamics. Recently the possibility of getting information on a sub-picosecond time scale from dc current measurements was proposed. We revisit the idea of picosecond resolution by pump-probe spectroscopy from dc measurements and show that any intramolecular dynamics not directly related to charge transfer in the current direction is missed by current measurements. We propose a pump-probe dc shot noise spectroscopy as a suitable alternative. Numerical examples of time-dependent and average responses of junctions are presented for generic models.

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

    PubMed

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

    2017-01-15

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

  14. Inhibition of melanosome transfer results in skin lightening.

    PubMed

    Seiberg, M; Paine, C; Sharlow, E; Andrade-Gordon, P; Costanzo, M; Eisinger, M; Shapiro, S S

    2000-08-01

    The chemical basis of melanogenesis is well documented, but the mechanism of melanosome transfer and the regulation of pigmentation by keratinocyte-melanocyte interactions are not well understood. Therefore we examined the effects of serine protease inhibitors on skin pigmentation and found that the protease-activated receptor 2, expressed on keratinocytes, may regulate pigmentation via keratinocyte-melanocyte interactions. Here we show that modulation of protease-activated receptor 2 activation affects melanosome transfer into keratinocytes, resulting in changes in pigment production and deposition. SLIGRL, the protease-activated receptor 2 activating peptide, enhanced melanosome ingestion by keratinocytes, thus increasing pigment deposition. RWJ-50353, a serine protease inhibitor, led to reduced pigment deposition in melanocytes and depigmentation. Electron microscopy studies illustrated an accumulation of immature melanosomes inside melanocytes and abnormal dendrite dynamics in RWJ-50353-treated epidermal equivalents. RWJ-50353 induced a visible and dose-dependent skin lightening effect in the dark-skinned Yucatan swine. Examinations by electron microscopy indicated that the in vivo transfer of melanosomes from melanocytes to keratinocytes was affected. Our data suggest that modulation of keratinocyte-melanocyte interactions via the protease-activated receptor 2 pathway affects melanosome transfer. The use of RWJ-50353 to modulate protease-activated receptor 2 activation could lead to a new class of depigmenting agents.

  15. Proton transfer mediated by the vibronic coupling in oxygen core ionized states of glyoxalmonoxime studied by infrared-X-ray pump-probe spectroscopy.

    PubMed

    Felicíssimo, V C; Guimarães, F F; Cesar, A; Gel'mukhanov, F; Agren, H

    2006-11-30

    The theory of IR-X-ray pump-probe spectroscopy beyond the Born-Oppenheimer approximation is developed and applied to the study of the dynamics of intramolecular proton transfer in glyoxalmonoxime leading to the formation of the tautomer 2-nitrosoethenol. Due to the IR pump pulses the molecule gains sufficient energy to promote a proton to a weakly bound well. A femtosecond X-ray pulse snapshots the wave packet route and, hence, the dynamics of the proton transfer. The glyoxalmonoxime molecule contains two chemically nonequivalent oxygen atoms that possess distinct roles in the hydrogen bond, a hydrogen donor and an acceptor. Core ionizations of these form two intersecting core-ionized states, the vibronic coupling between which along the OH stretching mode partially delocalizes the core hole, resulting in a hopping of the core hole from one site to another. This, in turn, affects the dynamics of the proton transfer in the core-ionized state. The quantum dynamical simulations of X-ray photoelectron spectra of glyoxalmonoxime driven by strong IR pulses demonstrate the general applicability of the technique for studies of intramolecular proton transfer in systems with vibronic coupling.

  16. Atomic and electronic structure of trilayer graphene/SiC(0001): Evidence of Strong Dependence on Stacking Sequence and charge transfer.

    PubMed

    Pierucci, Debora; Brumme, Thomas; Girard, Jean-Christophe; Calandra, Matteo; Silly, Mathieu G; Sirotti, Fausto; Barbier, Antoine; Mauri, Francesco; Ouerghi, Abdelkarim

    2016-09-15

    The transport properties of few-layer graphene are the directly result of a peculiar band structure near the Dirac point. Here, for epitaxial graphene grown on SiC, we determine the effect of charge transfer from the SiC substrate on the local density of states (LDOS) of trilayer graphene using scaning tunneling microscopy/spectroscopy and angle resolved photoemission spectroscopy (ARPES). Different spectra are observed and are attributed to the existence of two stable polytypes of trilayer: Bernal (ABA) and rhomboedreal (ABC) staking. Their electronic properties strongly depend on the charge transfer from the substrate. We show that the LDOS of ABC stacking shows an additional peak located above the Dirac point in comparison with the LDOS of ABA stacking. The observed LDOS features, reflecting the underlying symmetry of the two polytypes, were reproduced by explicit calculations within density functional theory (DFT) including the charge transfer from the substrate. These findings demonstrate the pronounced effect of stacking order and charge transfer on the electronic structure of trilayer or few layer graphene. Our approach represents a significant step toward understand the electronic properties of graphene layer under electrical field.

  17. Torsional Dynamics, Intramolecular Charge Transfer, and Solvent Friction in the S2 (11Bu+) Excited State of Peridinin: A Mechanism for Enhanced Mid-Visible Light Harvesting in the Peridinin-Chlorophyll a Protein

    NASA Astrophysics Data System (ADS)

    Beck, Warren; Roscioli, Jerome; Ghosh, Soumen; Bishop, Michael; Lafountain, Amy; Frank, Harry

    The structural mechanism that allows peridinin to provide one of the highest quantum efficiencies for excitation energy transfer to chlorophyll (Chl) a acceptors in the peridinin-chlorophyll a protein (PCP) from dinoflagellates involves an order-of-magnitude slowing of the S2 (11Bu+)--> S1 (21Ag-)nonradiative decay pathway compared to carotenoids lacking carbonyl substitution. Using femtosecond transient grating spectroscopy with heterodyne detection, we have determined for the first time that the decay of an intermediate state termed Sx, which we assign to a twisted form of the S2 state, is substantially slowed by solvent friction in peridinin due to its intramolecular charge transfer (ICT) character. The Sx intermediate exhibits a long enough lifetime to serve as an efficient excitation energy transfer donor to Chl a in PCP. The possibility that the Franck-Condon S2 state also transfers excitation via quantum coherent mechanisms is being considered currently using broadband two-dimensional electronic spectroscopy. Support from the DOE/BES Photosynthetic Systems Program, Grant DE-SC0010847.

  18. Energy transfer between surface-immobilized light-harvesting chlorophyll a/b complex (LHCII) studied by surface plasmon field-enhanced fluorescence spectroscopy (SPFS).

    PubMed

    Lauterbach, Rolf; Liu, Jing; Knoll, Wolfgang; Paulsen, Harald

    2010-11-16

    The major light-harvesting chlorophyll a/b complex (LHCII) of the photosynthetic apparatus in green plants can be viewed as a protein scaffold binding and positioning a large number of pigment molecules that combines rapid and efficient excitation energy transfer with effective protection of its pigments from photobleaching. These properties make LHCII potentially interesting as a light harvester (or a model thereof) in photoelectronic applications. Most of such applications would require the LHCII to be immobilized on a solid surface. In a previous study we showed the immobilization of recombinant LHCII on functionalized gold surfaces via a 6-histidine tag (His tag) in the protein moiety. In this work the occurrence and efficiency of Förster energy transfer between immobilized LHCII on a functionalized surface have been analyzed by surface plasmon field-enhanced fluorescence spectroscopy (SPFS). A near-infrared dye was attached to some but not all of the LHC complexes, serving as an energy acceptor to chlorophylls. Analysis of the energy transfer from chlorophylls to this acceptor dye yielded information about the extent of intercomplex energy transfer between immobilized LHCII.

  19. 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.

  20. Nuclear Engineering Computer Modules, Thermal-Hydraulics, TH-2: Liquid Metal Fast Breeder Reactors.

    ERIC Educational Resources Information Center

    Reihman, Thomas C.

    This learning module is concerned with the temperature field, the heat transfer rates, and the coolant pressure drop in typical liquid metal fast breeder reactor (LMFBR) fuel assemblies. As in all of the modules of this series, emphasis is placed on developing the theory and demonstrating the use with a simplified model. The heart of the module is…

  1. Nuclear Engineering Computer Modules, Thermal-Hydraulics, TH-1: Pressurized Water Reactors.

    ERIC Educational Resources Information Center

    Reihman, Thomas C.

    This learning module is concerned with the temperature field, the heat transfer rates, and the coolant pressure drop in typical pressurized water reactor (PWR) fuel assemblies. As in all of the modules of this series, emphasis is placed on developing the theory and demonstrating its use with a simplified model. The heart of the module is the PWR…

  2. Modulation transfer function of a triangular pixel array detector.

    PubMed

    Karimzadeh, Ayatollah

    2014-07-01

    The modulation transfer function (MTF) is the main parameter that is used to evaluate image quality in electro-optical systems. Detector sampling MTF in most electro-optical systems determines the cutoff frequency of the system. The MTF of the detector depends on its pixel shape. In this work, we calculated the MTF of a detector with an equilateral triangular pixel shape. Some new results were found in deriving the MTF for the equilateral triangular pixel shape.

  3. Modulated mass-transfer model for superhumps in SU Ursae Majoris stars

    NASA Technical Reports Server (NTRS)

    Mineshige, Shin

    1988-01-01

    The response of a circular accretion disk to rapid modulation of the mass-transfer rate into the disk is explored in order to model superhumps in SU UMa stars. It is proposed that periodically enhanced flow may disrupt or heat up the outer disk and produce the dips noted just before the superhump peaks. The elliptical accretion-disk model with extended vertical disk structure can account for the observed characteristics of superhumps in these stars.

  4. The partial coherence modulation transfer function in testing lithography lens

    NASA Astrophysics Data System (ADS)

    Huang, Jiun-Woei

    2018-03-01

    Due to the lithography demanding high performance in projection of semiconductor mask to wafer, the lens has to be almost free in spherical and coma aberration, thus, in situ optical testing for diagnosis of lens performance has to be established to verify the performance and to provide the suggesting for further improvement of the lens, before the lens has been build and integrated with light source. The measurement of modulation transfer function of critical dimension (CD) is main performance parameter to evaluate the line width of semiconductor platform fabricating ability for the smallest line width of producing tiny integrated circuits. Although the modulation transfer function (MTF) has been popularly used to evaluation the optical system, but in lithography, the contrast of each line-pair is in one dimension or two dimensions, analytically, while the lens stand along in the test bench integrated with the light source coherent or near coherent for the small dimension near the optical diffraction limit, the MTF is not only contributed by the lens, also by illumination of platform. In the study, the partial coherence modulation transfer function (PCMTF) for testing a lithography lens is suggested by measuring MTF in the high spatial frequency of in situ lithography lens, blended with the illumination of partial and in coherent light source. PCMTF can be one of measurement to evaluate the imperfect lens of lithography lens for further improvement in lens performance.

  5. Preparation of high performance NBR/HNTs nanocomposites using an electron transferring interaction method

    NASA Astrophysics Data System (ADS)

    Yang, Shuyan; Zhou, Yanxue; Zhang, Peng; Cai, Zhuodi; Li, Yangping; Fan, Hongbo

    2017-12-01

    Interfacial interaction is one of the key factors to improve comprehensive properties of polymer/inorganic filler nanocomposites. In this work, a new interfacial interaction called electron transferring interaction is reported in the nitrile-butadiene rubber/halloysite nanotubes (NBR/HNTs) nanocomposites. The X-ray photoelectron spectroscopy (XPS) and in-situ controlling temperature Fourier transform infrared spectroscopy (FTIR) have confirmed that electrons of electron-rich -CN groups in NBR can transfer to the electron-deficiency aluminum atoms of HNTs, which packs a part of NBR molecules onto the surface of HNTs to form bound rubber and stabilize the homogeneous dispersion of HNTs with few agglomeration as revealed by scanning electron microscope (SEM) and dynamic mechanical analysis (DMA) performances, even at high HNTs addition, resulting in high light transmittance. The tensile strength of NBR/30wt%HNTs nanocomposites is about 291% higher than pure NBR, without sacrificing the elongation at break.

  6. Charge Transfer Effect on Raman and Surface Enhanced Raman Spectroscopy of Furfural Molecules.

    PubMed

    Wan, Fu; Shi, Haiyang; Chen, Weigen; Gu, Zhaoliang; Du, Lingling; Wang, Pinyi; Wang, Jianxin; Huang, Yingzhou

    2017-08-02

    The detection of furfural in transformer oil through surface enhanced Raman spectroscopy (SERS) is one of the most promising online monitoring techniques in the process of transformer aging. In this work, the Raman of individual furfural molecules and SERS of furfural-M x (M = Ag, Au, Cu) complexes are investigated through density functional theory (DFT). In the Raman spectrum of individual furfural molecules, the vibration mode of each Raman peak is figured out, and the deviation from experimental data is analyzed by surface charge distribution. In the SERS of furfural-M x complexes, the influence of atom number and species on SERS chemical enhancement factors (EFs) are studied, and are further analyzed by charge transfer effect. Our studies strengthen the understanding of charge transfer effect in the SERS of furfural molecules, which is important in the online monitoring of the transformer aging process through SERS.

  7. Charge Transfer Effect on Raman and Surface Enhanced Raman Spectroscopy of Furfural Molecules

    PubMed Central

    Wan, Fu; Shi, Haiyang; Chen, Weigen; Gu, Zhaoliang; Du, Lingling; Wang, Pinyi; Wang, Jianxin

    2017-01-01

    The detection of furfural in transformer oil through surface enhanced Raman spectroscopy (SERS) is one of the most promising online monitoring techniques in the process of transformer aging. In this work, the Raman of individual furfural molecules and SERS of furfural-Mx (M = Ag, Au, Cu) complexes are investigated through density functional theory (DFT). In the Raman spectrum of individual furfural molecules, the vibration mode of each Raman peak is figured out, and the deviation from experimental data is analyzed by surface charge distribution. In the SERS of furfural-Mx complexes, the influence of atom number and species on SERS chemical enhancement factors (EFs) are studied, and are further analyzed by charge transfer effect. Our studies strengthen the understanding of charge transfer effect in the SERS of furfural molecules, which is important in the online monitoring of the transformer aging process through SERS. PMID:28767053

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

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

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

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

  9. Spectroscopy and energy transfer in lead borate glasses doubly doped with Dy(3)(+)-Tb(3+) and Tb(3)(+)-Eu(3+) ions.

    PubMed

    Pisarska, Joanna; Kos, Agnieszka; Pisarski, Wojciech A

    2014-08-14

    Lead borate glasses doubly doped with Dy(3)(+)-Tb(3+) and Tb(3+)-Eu(3+) were investigated using optical spectroscopy. Luminescence spectra of rare earths were detected under various excitation wavelengths. The main green emission band due to (5)D4→(7)F5 transition of Tb(3+) is observed under excitation of Dy(3+), whereas the main red emission band related to (5)D0→(7)F2 transition of Eu(3+) is successfully observed under direct excitation of Tb(3+). In both cases, the energy transfer processes from Dy(3+) to Tb(3+) and from Tb(3+) to Eu(3+) in lead borate glasses occur through a nonradiative processes with efficiencies up to 16% and 18%, respectively. The presence of energy transfer process was also confirmed by excitation spectra measurements. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Cascading electron and hole transfer dynamics in a CdS/CdTe core-shell sensitized with bromo-pyrogallol red (Br-PGR): slow charge recombination in type II regime.

    PubMed

    Maity, Partha; Debnath, Tushar; Chopra, Uday; Ghosh, Hirendra Nath

    2015-02-14

    Ultrafast cascading hole and electron transfer dynamics have been demonstrated in a CdS/CdTe type II core-shell sensitized with Br-PGR using transient absorption spectroscopy and the charge recombination dynamics have been compared with those of CdS/Br-PGR composite materials. Steady state optical absorption studies suggest that Br-PGR forms strong charge transfer (CT) complexes with both the CdS QD and CdS/CdTe core-shell. Hole transfer from the photo-excited QD and QD core-shell to Br-PGR was confirmed by both steady state and time-resolved emission spectroscopy. Charge separation was also confirmed by detecting electrons in the conduction band of the QD and the cation radical of Br-PGR as measured from femtosecond transient absorption spectroscopy. Charge separation in the CdS/Br-PGR composite materials was found to take place in three different pathways, by transferring the photo-excited hole of CdS to Br-PGR, electron injection from the photo-excited Br-PGR to the CdS QD, and direct electron transfer from the HOMO of Br-PGR to the conduction band of the CdS QD. However, in the CdS/CdTe/Br-PGR system hole transfer from the photo-excited CdS to Br-PGR and electron injection from the photo-excited Br-PGR to CdS take place after cascading through the CdTe shell QD. Charge separation also takes place via direct electron transfer from the Br-PGR HOMO to the conduction band of CdS/CdTe. Charge recombination (CR) dynamics between the electron in the conduction band of the CdS QD and the Br-PGR cation radical were determined by monitoring the bleach recovery kinetics. The CR dynamics were found to be much slower in the CdS/CdTe/Br-PGR system than in the CdS/Br-PGR system. The formation of the strong CT complex and the separation of charges cascading through the CdTe shell help to slow down charge recombination in the type II regime.

  11. Raman spectra of single cells with autofluorescence suppression by modulated wavelength excitation

    NASA Astrophysics Data System (ADS)

    Krafft, Christoph; Dochow, Sebastian; Bergner, Norbert; Clement, Joachim H.; Praveen, Bavishna B.; Mazilu, Michael; Marchington, Rob; Dholakia, Kishan; Popp, Jürgen

    2012-01-01

    Raman spectroscopy is a non-invasive technique offering great potential in the biomedical field for label-free discrimination between normal and tumor cells based on their biochemical composition. First, this contribution describes Raman spectra of lymphocytes after drying, in laser tweezers, and trapped in a microfluidic environment. Second, spectral differences between lymphocytes and acute myeloid leukemia cells (OCI-AML3) are compared for these three experimental conditions. Significant similarities of difference spectra are consistent with the biological relevance of the spectral features. Third, modulated wavelength Raman spectroscopy has been applied to this model system to demonstrate background suppression. Here, the laser excitation wavelength of 785 nm was modulated with a frequency of 40 mHz by 0.6 nm. 40 spectra were accumulated with an exposure time of 5 seconds each. These data were subjected to principal component analysis to calculate modulated Raman signatures. The loading of the principal component shows characteristics of first derivatives with derivative like band shapes. The derivative of this loading corresponds to a pseudo-second derivative spectrum and enables to determine band positions.

  12. The Modular Market. Studies in Further Education.

    ERIC Educational Resources Information Center

    Theodossin, Ernest

    Origins of modular courses and the module in British postcompulsory education are considered, along with characteristics of modules, credit transfer, five case studies, and marketing in further and higher education. A module is a measured part (or course) of an extended learning experience that leads to specified qualifications. A designated…

  13. Programming interfacial energetic offsets and charge transfer in β-Pb 0.33V 2O 5/quantum-dot heterostructures: Tuning valence-band edges to overlap with midgap states

    DOE PAGES

    Pelcher, Kate E.; Milleville, Christopher C.; Wangoh, Linda; ...

    2016-12-06

    Here, semiconductor heterostructures for solar energy conversion interface light-harvesting semiconductor nanoparticles with wide-band-gap semiconductors that serve as charge acceptors. In such heterostructures, the kinetics of charge separation depend on the thermodynamic driving force, which is dictated by energetic offsets across the interface. A recently developed promising platform interfaces semiconductor quantum dots (QDs) with ternary vanadium oxides that have characteristic midgap states situated between the valence and conduction bands. In this work, we have prepared CdS/β-Pb 0.33V 2O 5 heterostructures by both linker-assisted assembly and surface precipitation and contrasted these materials with CdSe/β-Pb 0.33V 2O 5 heterostructures prepared by the samemore » methods. Increased valence-band (VB) edge onsets in X-ray photoelectron spectra for CdS/β-Pb 0.33V 2O 5 heterostructures relative to CdSe/β-Pb 0.33V 2O 5 heterostructures suggest a positive shift in the VB edge potential and, therefore, an increased driving force for the photoinduced transfer of holes to the midgap state of β-Pb 0.33V 2O 5. This approach facilitates a ca. 0.40 eV decrease in the thermodynamic barrier for hole injection from the VB edge of QDs suggesting an important design parameter. Transient absorption spectroscopy experiments provide direct evidence of hole transfer from photoexcited CdS QDs to the midgap states of β-Pb 0.33V 2O 5 NWs, along with electron transfer into the conduction band of the β-Pb 0.33V 2O 5 NWs. Hole transfer is substantially faster and occurs at <1-ps time scales, whereas completion of electron transfer requires 5—30 ps depending on the nature of the interface. The differentiated time scales of electron and hole transfer, which are furthermore tunable as a function of the mode of attachment of QDs to NWs, provide a vital design tool for designing architectures for solar energy conversion. More generally, the approach developed here suggests that interfacing semiconductor QDs with transition-metal oxide NWs exhibiting intercalative midgap states yields a versatile platform wherein the thermodynamics and kinetics of charge transfer can be systematically modulated to improve the efficiency of charge separation across interfaces.« less

  14. Programming interfacial energetic offsets and charge transfer in β-Pb 0.33V 2O 5/quantum-dot heterostructures: Tuning valence-band edges to overlap with midgap states

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

    Pelcher, Kate E.; Milleville, Christopher C.; Wangoh, Linda

    Here, semiconductor heterostructures for solar energy conversion interface light-harvesting semiconductor nanoparticles with wide-band-gap semiconductors that serve as charge acceptors. In such heterostructures, the kinetics of charge separation depend on the thermodynamic driving force, which is dictated by energetic offsets across the interface. A recently developed promising platform interfaces semiconductor quantum dots (QDs) with ternary vanadium oxides that have characteristic midgap states situated between the valence and conduction bands. In this work, we have prepared CdS/β-Pb 0.33V 2O 5 heterostructures by both linker-assisted assembly and surface precipitation and contrasted these materials with CdSe/β-Pb 0.33V 2O 5 heterostructures prepared by the samemore » methods. Increased valence-band (VB) edge onsets in X-ray photoelectron spectra for CdS/β-Pb 0.33V 2O 5 heterostructures relative to CdSe/β-Pb 0.33V 2O 5 heterostructures suggest a positive shift in the VB edge potential and, therefore, an increased driving force for the photoinduced transfer of holes to the midgap state of β-Pb 0.33V 2O 5. This approach facilitates a ca. 0.40 eV decrease in the thermodynamic barrier for hole injection from the VB edge of QDs suggesting an important design parameter. Transient absorption spectroscopy experiments provide direct evidence of hole transfer from photoexcited CdS QDs to the midgap states of β-Pb 0.33V 2O 5 NWs, along with electron transfer into the conduction band of the β-Pb 0.33V 2O 5 NWs. Hole transfer is substantially faster and occurs at <1-ps time scales, whereas completion of electron transfer requires 5—30 ps depending on the nature of the interface. The differentiated time scales of electron and hole transfer, which are furthermore tunable as a function of the mode of attachment of QDs to NWs, provide a vital design tool for designing architectures for solar energy conversion. More generally, the approach developed here suggests that interfacing semiconductor QDs with transition-metal oxide NWs exhibiting intercalative midgap states yields a versatile platform wherein the thermodynamics and kinetics of charge transfer can be systematically modulated to improve the efficiency of charge separation across interfaces.« less

  15. Optoelectronic properties of type I indium gallium arsenide quantum cascade lasers with applications to optical modulation

    NASA Astrophysics Data System (ADS)

    Murawski, Robert K.

    Quantum Cascade Lasers (QCL) are unique unipolar conduction band devices designed to emit in the mid infrared region (MIR). They have been employed very successfully in spectroscopy and sensing applications. Motivated by predictions of modulation bandwidths above 100 GHz, communication links based on QCLs were recently demonstrated. However, the intrinsic device circuitry of the QCL limits its bandwidth. In this thesis a new All-Optical Modulation of the QCL is presented and investigated both theoretically and experimentally. This method of modulation allows for full access to the bandwidth as well as unique optical control of the MIR laser emission. For this purpose, conduction and valence band wave functions for the complex QCL structure are presented allowing for the first time calculations of their interband energy resonances. Based on this knowledge, a novel optical modulation scheme is developed utilizing interband transition for laser modulation. Using laser rate equations, more accurate predictions for the response function can be derived. Optical modulation is shown to be superior to direct modulation. In addition to this theoretical framework, first experiments are presented on the effects of illuminating a QCL with additional lasers at or above the interband gap. The first demonstration of All-Optical Modulation was achieved using time varying near infrared illumination and the complimentary signature in the MIR QCL emission was observed. In addition to extending the knowledge base of QCL research by a first calculation of its valence band structure, this work opens new possibilities in modulation and control of the QCL's MIR emission by interband transition. Application of this technique range from fundamental physics research (e.g. electron coherence) to ultrafast communication (e.g. free-space links) and high-resolution spectroscopy.

  16. Are training and transfer effects of working memory updating training modulated by achievement motivation?

    PubMed

    Zhao, Xin; Xu, Yiwenjie; Fu, Junjun; Maes, Joseph H R

    2018-04-01

    Previous studies examining effects of working memory (WM) updating training revealed mixed results. One factor that might modulate training gains, and possibly also transfer of those gains to non-trained cognitive tasks, is achievement motivation. In the present Studies 1 and 2, students with either a high (HAM) or low (LAM) achievement motivation completed a 14-day visuospatial WM updating training program. In Study 2, the students also performed a set of tasks measuring other executive functions and fluid intelligence prior to and after training. In both studies, the HAM students displayed a larger training gain than the LAM students. Study 2 revealed that after training, both groups showed better performance on the near-transfer but not far-transfer tasks. Importantly, the differential training gain was not associated with better post-training performance for the HAM compared to the LAM students on any of the transfer tasks. These results are taken to support a modulatory role of achievement motivation on WM training benefits, but not on transfer of those benefits to other tasks. Possible reasons for the general improvement on the near-transfer tasks and the absence of a modulatory role of achievement motivation on transfer-task performance are discussed.

  17. SPECS: Orbital debris removal

    NASA Technical Reports Server (NTRS)

    1991-01-01

    The debris problem has reached a stage at which the risk to satellites and spacecraft has become substantial in low Earth orbit (LEO). This research discovered that small particles posed little threat to spacecraft because shielding can effectively prevent these particles from damaging the spacecraft. The research also showed that, even though collision with a large piece of debris could destroy the spacecraft, the large pieces of debris pose little danger because they can be tracked and the spacecraft can be maneuvered away from these pieces. Additionally, there are many current designs to capture and remove large debris particles from the space environment. From this analysis, it was decided to concentrate on the removal of medium-sized orbital debris, that is, those pieces ranging from 1 cm to 50 cm in size. The current design incorporates a transfer vehicle and a netting vehicle to capture the medium-sized debris. The system is based near an operational space station located at 28.5 deg inclination and 400 km altitude. The system uses ground-based tracking to determine the location of a satellite breakup or debris cloud. These data are uploaded to the transfer vehicle, which proceeds to rendezvous with the debris at a lower altitude parking orbit. Next, the netting vehicle is deployed, tracks the targeted debris, and captures it. After expending the available nets, the netting vehicle returns to the transfer vehicle for a new netting module and continues to capture more debris in the target area. Once all the netting modules are expended, the transfer vehicle returns to the space station's orbit where it is resupplied with new netting modules from a space shuttle load. The new modules are launched by the shuttle from the ground and the expended modules are taken back to Earth for removal of the captured debris, refueling, and repacking of the nets. Once the netting modules are refurbished, they are taken back into orbit for reuse. In a typical mission, the system has the ability to capture 50 pieces of orbital debris. One mission will take approximately six months and the system is designed to allow for a 30 deg inclination change on the outgoing and incoming trips of the transfer vehicle.

  18. 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

  19. Temporally resolved diagnosis of an atmospheric-pressure pulse-modulated argon surface wave plasma by optical emission spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, Chuan-Jie; Li, Shou-Zhe; Zhang, Jialiang; Liu, Dongping

    2018-01-01

    A pulse-modulated argon surface wave plasma generated at atmospheric pressure is characterized by means of temporally resolved optical emission spectroscopy (OES). The temporal evolution of the gas temperature, the electron temperature and density, the radiative species of atomic Ar, and the molecular band of OH(A) and N2(C) are investigated experimentally by altering the instantaneous power, pulse repetitive frequency, and duty ratio. We focused on the physical phenomena occurring at the onset of the time-on period and after the power interruption at the start of the time-off period. Meanwhile, the results are discussed qualitatively for an in-depth insight of its dynamic evolution.

  20. Stand-alone polarization-modulation infrared reflection absorption spectroscopy instrument optimized for the study of catalytic processes at elevated pressures

    NASA Astrophysics Data System (ADS)

    Kestell, John D.; Mudiyanselage, Kumudu; Ye, Xinyi; Nam, Chang-Yong; Stacchiola, Dario; Sadowski, Jerzy; Boscoboinik, J. Anibal

    2017-10-01

    This paper describes the design and construction of a compact, "user-friendly" polarization-modulation infrared reflection absorption spectroscopy (PM-IRRAS) instrument at the Center for Functional Nanomaterials (CFN) of Brookhaven National Laboratory, which allows studying surfaces at pressures ranging from ultra-high vacuum to 100 Torr. Surface infrared spectroscopy is ideally suited for studying these processes as the vibrational frequencies of the IR chromophores are sensitive to the nature of the bonding environment on the surface. Relying on the surface selection rules, by modulating the polarization of incident light, it is possible to separate the contributions from the isotropic gas or solution phase, from the surface bound species. A spectral frequency range between 1000 cm-1 and 4000 cm-1 can be acquired. While typical spectra with a good signal to noise ratio can be obtained at elevated pressures of gases in ˜2 min at 4 cm-1 resolution, we have also acquired higher resolution spectra at 0.25 cm-1 with longer acquisition times. By way of verification, CO uptake on a heavily oxidized Ru(0001) sample was studied. As part of this test study, the presence of CO adsorbed on Ru bridge sites was confirmed, in agreement with previous ambient pressure X ray photoelectron spectroscopy studies. In terms of instrument performance, it was also determined that the gas phase contribution from CO could be completely removed even up to pressures close to 100 Torr. A second test study demonstrated the use of the technique for studying morphological properties of a spin coated polymer on a conductive surface. Note that this is a novel application of this technique. In this experiment, the polarization of incident light was modulated manually (vs. through a photoelastic modulator). It was demonstrated, in good agreement with the literature, that the polymer chains preferentially lie parallel with the surface. This PM-IRRAS system is small, modular, and easily reconfigurable. It also features a "vacuum suitcase" that allows for the integration of the PM-IRRAS system with the rest of the suite of instrumentation at our laboratory available to external users through the CFN user proposal system.

  1. General Conformity Training Modules: Appendix A Sample Emissions Calculations

    EPA Pesticide Factsheets

    Appendix A of the training modules gives example calculations for external and internal combustion sources, construction, fuel storage and transfer, on-road vehicles, aircraft operations, storage piles, and paved roads.

  2. Heat Transfer Analysis of an Optimized, Flexible Holder System for Freeze-Drying in Dual Chamber Cartridges Using Different State-of-the-Art PAT Tools.

    PubMed

    Korpus, Christoph; Pikal, Michael; Friess, Wolfgang

    2016-11-01

    The aim of this study was to determine the heat transfer characteristics of an optimized flexible holder device, using Tunable Diode Laser Absorption Spectroscopy, the Pressure Rise Test, and the gravimetric procedure. Two different controlled nucleation methods were tested, and an improved sublimation process, "preheated plate," was developed. Tunable Diode Laser Absorption Spectroscopy identified an initial sublimation burst phase. Accordingly, steady-state equations were adapted for the gravimetric procedure, to account for this initial non-steady-state period. The heat transfer coefficient, K DCC , describing the transfer from the holder to the DCC, was the only heat transfer coefficient showing a clear pressure dependence with values ranging from 3.81E-04 cal/(g·cm 2 ·K) at 40 mTorr to 7.38E-04 cal/(g·cm 2 ·K) at 200 mTorr. The heat transfer coefficient, K tot , reflecting the overall energy transfer via the holder, increased by around 24% from 40 to 200 mTorr. This resulted in a pressure-independent sublimation rate of around 42 ± 1.06 mg/h over the whole pressure range. Hence, this pressure-dependent increase in energy transfer completely compensated the decrease in driving force of sublimation. The "flexible holder" shows a substantially reduced impact of atypical radiation, improved drying homogeneity, and ultimately a better transferability of the freeze-drying cycle for process optimization. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  3. Kinetics of Hydrolysis of Acetic Anhydride by In-Situ FTIR Spectroscopy: An Experiment for the Undergraduate Laboratory

    ERIC Educational Resources Information Center

    Haji, Shaker; Erkey, Can

    2005-01-01

    A reaction kinetics experiment for the chemical engineering undergraduate laboratory course was developed in which in-situ Fourier Transfer Infrared spectroscopy was used to measure reactant and product concentrations. The kinetics of the hydrolysis of acetic anhydride was determined by experiments carried out in a batch reactor. The results…

  4. Saturation-resolved-fluorescence spectroscopy of Cr3+:mullite glass ceramic

    NASA Astrophysics Data System (ADS)

    Liu, Huimin; Knutson, Robert; Yen, W. M.

    1990-01-01

    We present a saturation-based technique designed to isolate and uncouple individual components of inhomogeneously broadened spectra that are simultaneously coupled to each other through spectral overlap and energy-transfer interactions. We have termed the technique saturation-resolved-fluorescence spectroscopy; we demonstrate its usefulness in deconvoluting the complex spectra of Cr3+:mullite glass ceramic.

  5. Sensitivity enhancement in whole-body natural abundance 13C spectroscopy using 13C/1H double-resonance techniques at 4 tesla.

    PubMed

    Bomsdorf, H; Röschmann, P; Wieland, J

    1991-11-01

    In vivo 13C spectroscopy experiments were performed using a whole-body MR system at a static field of 4 T. The main goal of the investigations was to evaluate the sensitivity increase achievable by means of 13C/1H double-resonance techniques at 4 T. Spectra from subcutaneous fat as well as muscle glycogen from the lower leg were acquired using frequency selective proton decoupling and the polarization transfer method SINEPT. With respect to measurements on subcutaneous fat, polarization transfer turned out to be more efficient than selective decoupling. About a fourfold enhancement in spectral peak intensity for the C = C line doublet of the unsaturated fatty acid chain was obtained. Combining polarization transfer with decoupling yielded a factor of 6 in signal amplitude. In contrast to that, the signal enhancement observed in measurements on the glycogen C-1 resonance was only around twofold. The lower efficiency is explained by fast T2 relaxation of the proton transition. A T2 value of about 3 ms was derived from the experimental data. Acquisition times as low as 3 min were realized for normal level glycogen in human calf muscle, enabling a time resolution adequate for dynamic studies on muscle glycogen depletion. Aspects of RF power absorption in tissue and the generally higher efficiency make polarization transfer methods preferable to selective decoupling in whole-body 13C spectroscopy at 4 T.

  6. Energy Transfer Processes in (Lu,Gd)AlO3:Ce

    DTIC Science & Technology

    2001-01-01

    studies on energy transfer processes in Ce-activated Lu, Y and Gd aluminum perovskite crystals that contribute to production of scintillation light in...LuAIO3, GdA10 3, cerium, scintillators, VUV spectroscopy, luminescence, time profiles, energy transfer 1. INTRODUCTION The yttrium aluminum perovskite...The Czochralski-grown monocrystals of LuAP:Ce were first evaluated in a garnet -free perovskite phase by Lempicki et al. in 1994 .4 More detailed

  7. Ultrafast Spectroscopy Reveals Electron-Transfer Cascade That Improves Hydrogen Evolution with Carbon Nitride Photocatalysts.

    PubMed

    Corp, Kathryn L; Schlenker, Cody W

    2017-06-14

    Solar hydrogen generation from water represents a compelling component of a future sustainable energy portfolio. Recently, chemically robust heptazine-based polymers known as graphitic carbon nitrides (g-C 3 N 4 ) have emerged as promising photocatalysts for hydrogen evolution using visible light while withstanding harsh chemical environments. However, since g-C 3 N 4 electron-transfer dynamics are poorly understood, rational design rules for improving activity remain unclear. Here, we use visible and near-infrared femtosecond transient absorption (TA) spectroscopy to reveal an electron-transfer cascade that correlates with a near-doubling in photocatalytic activity from 2050 to 3810 μmol h -1 g -1 when we infuse a suspension of bulk g-C 3 N 4 with 10% mass loading of chemically exfoliated carbon nitride. TA spectroscopy indicates that exfoliated carbon nitride quenches photogenerated electrons on g-C 3 N 4 at rates approaching the molecular diffusion limit. The TA signal for photogenerated electrons on g-C 3 N 4 decays with a time constant of 1/k e ' = 660 ps in the mixture versus 1/k e = 4.1 ns in g-C 3 N 4 alone. Our TA measurements suggest that the charge generation efficiency in g-C 3 N 4 is greater than 65%. Exfoliated carbon nitride, which liberates only trace hydrogen levels when photoexcited directly, does not appear to independently sustain appreciable long-lived charge generation. Thus, the activity enhancement in the two-component infusion evidently results from a cooperative effect in which charge is generated on g-C 3 N 4 , followed by electron transfer to exfoliated carbon nitride containing photocatalytic chain terminations. This correlation between electron transfer and photocatalytic activity provides new insight into structural modifications for controlling charge separation dynamics and activity of carbon-based photocatalysts.

  8. An Autoinhibitory Role for the Pleckstrin Homology Domain of Interleukin-2-Inducible Tyrosine Kinase and Its Interplay with Canonical Phospholipid Recognition.

    PubMed

    Devkota, Sujan; Joseph, Raji E; Boyken, Scott E; Fulton, D Bruce; Andreotti, Amy H

    2017-06-13

    Pleckstrin homology (PH) domains are well-known as phospholipid binding modules, yet evidence that PH domain function extends beyond lipid recognition is mounting. In this work, we characterize a protein binding function for the PH domain of interleukin-2-inducible tyrosine kinase (ITK), an immune cell specific signaling protein that belongs to the TEC family of nonreceptor tyrosine kinases. Its N-terminal PH domain is a well-characterized lipid binding module that localizes ITK to the membrane via phosphatidylinositol 3,4,5-trisphosphate (PIP 3 ) binding. Using a combination of nuclear magnetic resonance spectroscopy and mutagenesis, we have mapped an autoregulatory protein interaction site on the ITK PH domain that makes direct contact with the catalytic kinase domain of ITK, inhibiting the phospho-transfer reaction. Moreover, we have elucidated an important interplay between lipid binding by the ITK PH domain and the stability of the autoinhibitory complex formed by full length ITK. The ITK activation loop in the kinase domain becomes accessible to phosphorylation to the exogenous kinase LCK upon binding of the ITK PH domain to PIP 3 . By clarifying the allosteric role of the ITK PH domain in controlling ITK function, we have expanded the functional repertoire of the PH domain generally and opened the door to alternative strategies to target this specific kinase in the context of immune cell signaling.

  9. Dark States in the Light-Harvesting complex 2 Revealed by Two-dimensional Electronic Spectroscopy

    PubMed Central

    Ferretti, Marco; Hendrikx, Ruud; Romero, Elisabet; Southall, June; Cogdell, Richard J.; Novoderezhkin, Vladimir I.; Scholes, Gregory D.; van Grondelle, Rienk

    2016-01-01

    Energy transfer and trapping in the light harvesting antennae of purple photosynthetic bacteria is an ultrafast process, which occurs with a quantum efficiency close to unity. However the mechanisms behind this process have not yet been fully understood. Recently it was proposed that low-lying energy dark states, such as charge transfer states and polaron pairs, play an important role in the dynamics and directionality of energy transfer. However, it is difficult to directly detect those states because of their small transition dipole moment and overlap with the B850/B870 exciton bands. Here we present a new experimental approach, which combines the selectivity of two-dimensional electronic spectroscopy with the availability of genetically modified light harvesting complexes, to reveal the presence of those dark states in both the genetically modified and the wild-type light harvesting 2 complexes of Rhodopseudomonas palustris. We suggest that Nature has used the unavoidable charge transfer processes that occur when LH pigments are concentrated to enhance and direct the flow of energy. PMID:26857477

  10. In-situ sequential laser transfer and laser reduction of graphene oxide films

    NASA Astrophysics Data System (ADS)

    Papazoglou, S.; Petridis, C.; Kymakis, E.; Kennou, S.; Raptis, Y. S.; Chatzandroulis, S.; Zergioti, I.

    2018-04-01

    Achieving high quality transfer of graphene on selected substrates is a priority in device fabrication, especially where drop-on-demand applications are involved. In this work, we report an in-situ, fast, simple, and one step process that resulted in the reduction, transfer, and fabrication of reduced graphene oxide-based humidity sensors, using picosecond laser pulses. By tuning the laser illumination parameters, we managed to implement the sequential printing and reduction of graphene oxide flakes. The overall process lasted only a few seconds compared to a few hours that our group has previously published. DC current measurements, X-Ray Photoelectron Spectroscopy, X-Ray Diffraction, and Raman Spectroscopy were employed in order to assess the efficiency of our approach. To demonstrate the applicability and the potential of the technique, laser printed reduced graphene oxide humidity sensors with a limit of detection of 1700 ppm are presented. The results demonstrated in this work provide a selective, rapid, and low-cost approach for sequential transfer and photochemical reduction of graphene oxide micro-patterns onto various substrates for flexible electronics and sensor applications.

  11. Dark States in the Light-Harvesting complex 2 Revealed by Two-dimensional Electronic Spectroscopy

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

    Ferretti, Marco; Hendrikx, Ruud; Romero, Elisabet

    Energy transfer and trapping in the light harvesting antennae of purple photosynthetic bacteria is an ultrafast process, which occurs with a quantum efficiency close to unity. However the mechanisms behind this process have not yet been fully understood. Recently it was proposed that low-lying energy dark states, such as charge transfer states and polaron pairs, play an important role in the dynamics and directionality of energy transfer. However, it is difficult to directly detect those states because of their small transition dipole moment and overlap with the B850/B870 exciton bands. Here we present a new experimental approach, which combines themore » selectivity of two-dimensional electronic spectroscopy with the availability of genetically modified light harvesting complexes, to reveal the presence of those dark states in both the genetically modified and the wild-type light harvesting 2 complexes of Rhodopseudomonas palustris. In conclusion, we suggest that Nature has used the unavoidable charge transfer processes that occur when LH pigments are concentrated to enhance and direct the flow of energy.« less

  12. Dark States in the Light-Harvesting complex 2 Revealed by Two-dimensional Electronic Spectroscopy

    DOE PAGES

    Ferretti, Marco; Hendrikx, Ruud; Romero, Elisabet; ...

    2016-02-09

    Energy transfer and trapping in the light harvesting antennae of purple photosynthetic bacteria is an ultrafast process, which occurs with a quantum efficiency close to unity. However the mechanisms behind this process have not yet been fully understood. Recently it was proposed that low-lying energy dark states, such as charge transfer states and polaron pairs, play an important role in the dynamics and directionality of energy transfer. However, it is difficult to directly detect those states because of their small transition dipole moment and overlap with the B850/B870 exciton bands. Here we present a new experimental approach, which combines themore » selectivity of two-dimensional electronic spectroscopy with the availability of genetically modified light harvesting complexes, to reveal the presence of those dark states in both the genetically modified and the wild-type light harvesting 2 complexes of Rhodopseudomonas palustris. In conclusion, we suggest that Nature has used the unavoidable charge transfer processes that occur when LH pigments are concentrated to enhance and direct the flow of energy.« less

  13. Controlled p-doping of black phosphorus by integration of MoS2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Jeon, Sumin; Kim, Minwoo; Jia, Jingyuan; Park, Jin-Hong; Lee, Sungjoo; Song, Young Jae

    2018-05-01

    Black phosphorus (BP), a new family of two dimensional (2D) layered materials, is an attractive material for future electronic, photonic and chemical sensing devices, thanks to its high carrier density and a direct bandgap of 0.3-2.0 eV, depending on the number of layers. Controllability over the properties of BP by electrical or chemical modulations is one of the critical requirements for future various device applications. Herein, we report a new doping method of BP by integration of density-controlled monolayer MoS2 nanoparticles (NPs). MoS2 NPs with different density were synthesized by chemical vapor deposition (CVD) and transferred onto a few-layer BP channel, which induced a p-doping effect. Scanning electron microscopy (SEM) confirmed the size and distribution of MoS2 NPs with different density. Raman and X-ray photoelectron spectroscopy (XPS) were measured to confirm the oxidation on the edge of MoS2 NPs and a doping effect of MoS2 NPs on a BP channel. The doping mechanism was explained by a charge transfer by work function differences between BP and MoS2 NPs, which was confirmed by Kelvin probe force microscopy (KPFM) and electrical measurements. The hole concentration of BP was controlled with different densities of MoS2 NPs in a range of 1012-1013 cm-2.

  14. Towards defining the role of glycans as hardware in information storage and transfer: basic principles, experimental approaches and recent progress.

    PubMed

    Solís, D; Jiménez-Barbero, J; Kaltner, H; Romero, A; Siebert, H C; von der Lieth, C W; Gabius, H J

    2001-01-01

    The term 'code' in biological information transfer appears to be tightly and hitherto exclusively connected with the genetic code based on nucleotides and translated into functional activities via proteins. However, the recent appreciation of the enormous coding capacity of oligosaccharide chains of natural glycoconjugates has spurred to give heed to a new concept: versatile glycan assembly by the genetically encoded glycosyltransferases endows cells with a probably not yet fully catalogued array of meaningful messages. Enciphered by sugar receptors such as endogenous lectins the information of code words established by a series of covalently linked monosaccharides as letters for example guides correct intra- and intercellular routing of glycoproteins, modulates cell proliferation or migration and mediates cell adhesion. Evidently, the elucidation of the structural frameworks and the recognition strategies within the operation of the sugar code poses a fascinating conundrum. The far-reaching impact of this recognition mode on the level of cells, tissues and organs has fueled vigorous investigations to probe the subtleties of protein-carbohydrate interactions. This review presents information on the necessarily concerted approach using X-ray crystallography, molecular modeling, nuclear magnetic resonance spectroscopy, thermodynamic analysis and engineered ligands and receptors. This part of the treatise is flanked by exemplarily chosen insights made possible by these techniques. Copyright 2001 S. Karger AG, Basel

  15. K2 photometry and HERMES spectroscopy of the blue supergiant ρ Leo: rotational wind modulation and low-frequency waves

    NASA Astrophysics Data System (ADS)

    Aerts, C.; Bowman, D. M.; Símon-Díaz, S.; Buysschaert, B.; Johnston, C.; Moravveji, E.; Beck, P. G.; De Cat, P.; Triana, S.; Aigrain, S.; Castro, N.; Huber, D.; White, T.

    2018-05-01

    We present an 80-d long uninterrupted high-cadence K2 light curve of the B1Iab supergiant ρ Leo (HD 91316), deduced with the method of halo photometry. This light curve reveals a dominant frequency of frot = 0.0373 d-1 and its harmonics. This dominant frequency corresponds with a rotation period of 26.8 d and is subject to amplitude and phase modulation. The K2 photometry additionally reveals multiperiodic low-frequency variability (<1.5 d-1) and is in full agreement with low-cadence high-resolution spectroscopy assembled during 1800 d. The spectroscopy reveals rotational modulation by a dynamic aspherical wind with an amplitude of about 20 km s-1 in the H α line, as well as photospheric velocity variations of a few km s-1 at frequencies in the range 0.2-0.6 d-1 in the Si III 4567 Å line. Given the large macroturbulence needed to explain the spectral line broadening of the star, we interpret the detected photospheric velocity as due to travelling superinertial low-degree large-scale gravity waves with dominant tangential amplitudes and discuss why ρ Leo is an excellent target to study how the observed photospheric variability propagates into the wind.

  16. Chapter 5: Modulation Excitation Spectroscopy with Phase-Sensitive Detection for Surface Analysis

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

    Shulda, Sarah; Richards, Ryan M.

    Advancements in in situ spectroscopic techniques have led to significant progress being made in elucidating heterogeneous reaction mechanisms. The potential of these progressive methods is often limited only by the complexity of the system and noise in the data. Short-lived intermediates can be challenging, if not impossible, to identify with conventional spectra analysis means. Often equally difficult is separating signals that arise from active and inactive species. Modulation excitation spectroscopy combined with phase-sensitive detection analysis is a powerful tool for removing noise from the data while simultaneously revealing the underlying kinetics of the reaction. A stimulus is applied at amore » constant frequency to the reaction system, for example, a reactant cycled with an inert phase. Through mathematical manipulation of the data, any signal contributing to the overall spectra but not oscillating with the same frequency as the stimulus will be dampened or removed. With phase-sensitive detection, signals oscillating with the stimulus frequency but with various lag times are amplified providing valuable kinetic information. In this chapter, some examples are provided from the literature that have successfully used modulation excitation spectroscopy with phase-sensitive detection to uncover previously unobserved reaction intermediates and kinetics. Examples from a broad range of spectroscopic methods are included to provide perspective to the reader.« less

  17. Stable radio frequency dissemination by simple hybrid frequency modulation scheme.

    PubMed

    Yu, Longqiang; Wang, Rong; Lu, Lin; Zhu, Yong; Wu, Chuanxin; Zhang, Baofu; Wang, Peizhang

    2014-09-15

    In this Letter, we propose a fiber-based stable radio frequency transfer system by a hybrid frequency modulation scheme. Creatively, two radio frequency signals are combined and simultaneously transferred by only one laser diode. One frequency component is used to detect the phase fluctuation, and the other one is the derivative compensated signal providing a stable frequency for the remote end. A proper ratio of the frequencies of the components is well maintained by parameter m to avoid interference between them. Experimentally, a stable 200 MHz signal is transferred over 100 km optical fiber with the help of a 1 GHz detecting signal, and fractional instability of 2×10(-17) at 10(5) s is achieved.

  18. Localized one-dimensional single voxel magnetic resonance spectroscopy without J coupling modulations.

    PubMed

    Lin, Yanqin; Lin, Liangjie; Wei, Zhiliang; Zhong, Jianhui; Chen, Zhong

    2016-12-01

    To acquire single voxel localized one-dimensional 1 H magnetic resonance spectroscopy (MRS) without J coupling modulations, free from amplitude and phase distortions. A pulse sequence, named PRESSIR, is developed for volume localized MRS without J modulations at arbitrary echo time (TE). The J coupling evolution is suppressed by the J-refocused module that uses a 90° pulse at the midpoint of a double spin echo. The localization performance of the PRESSIR sequence was tested with a two-compartment phantom. The proposed sequence shows similar voxel localization accuracy as PRESS. Both PRESSIR and PRESS sequences were performed on MRS brain phantom and pig brain tissue. PRESS spectra suffer from amplitude and phase distortions due to J modulations, especially under moderate and long TEs, while PRESSIR spectra are almost free from distortions. The PRESSIR sequence proposed herein enables the acquisition of single voxel in-phase MRS within a single scan. It allows an enhanced signal intensity of J coupling metabolites and reducing undesired broad resonances with short T2s while suppressing J modulations. Moreover, it provides an approach for direct measurement of nonoverlapping J coupling peaks and of transverse relaxation times T2s. Magn Reson Med 76:1661-1667, 2016. © 2015 International Society for Magnetic Resonance in Medicine. © 2015 International Society for Magnetic Resonance in Medicine.

  19. Dependence of triboelectric charging behavior on material microstructure

    NASA Astrophysics Data System (ADS)

    Wang, Andrew E.; Gil, Phwey S.; Holonga, Moses; Yavuz, Zelal; Baytekin, H. Tarik; Sankaran, R. Mohan; Lacks, Daniel J.

    2017-08-01

    We demonstrate that differences in the microstructure of chemically identical materials can lead to distinct triboelectric charging behavior. Contact charging experiments are carried out between strained and unstrained polytetrafluoroethylene samples. Whereas charge transfer is random between samples of identical strain, when one of the samples is strained, systematic charge transfer occurs. No significant changes in the molecular-level structure of the polymer are observed by XRD and micro-Raman spectroscopy after deformation. However, the strained surfaces are found to exhibit void and craze formation spanning the nano- to micrometer length scales by molecular dynamics simulations, SEM, UV-vis spectroscopy, and naked-eye observations. This suggests that material microstructure (voids and crazes) can govern the triboelectric charging behavior of materials.

  20. Evidence for a "metabolically inactive" inorganic phosphate pool in adenosine triphosphate synthase reaction using localized 31P saturation transfer magnetic resonance spectroscopy in the rat brain at 11.7 T.

    PubMed

    Tiret, Brice; Brouillet, Emmanuel; Valette, Julien

    2016-09-01

    With the increased spectral resolution made possible at high fields, a second, smaller inorganic phosphate resonance can be resolved on (31)P magnetic resonance spectra in the rat brain. Saturation transfer was used to estimate de novo adenosine triphosphate synthesis reaction rate. While the main inorganic phosphate pool is used by adenosine triphosphate synthase, the second pool is inactive for this reaction. Accounting for this new pool may not only help us understand (31)P magnetic resonance spectroscopy metabolic profiles better but also better quantify adenosine triphosphate synthesis. © The Author(s) 2016.

  1. Tracking coherent population transfer and thermal population relaxation in condensed system by broad-band transient grating spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Liu, Xiaosong; Wu, Honglin; Song, Yunfei; Liu, Weilong; Yang, Yanqiang

    2018-04-01

    Broad-band transient grating (BB-TG) spectroscopy was proposed to track both coherent population transfer (CPT) and thermal population relaxation processes in a condensed system of solvated molecules in solution (Rhodamine101 in methanol). A broad band around 1500 cm‑1 and a relative narrow band near 2900 cm‑1 emerge in TG and transient absorption contour plots when pump and probe pulses overlap in the sample. The experimental results matched well with the vibrational modes of Rhodamine101 that were obtained by theoretical calculation. In addition, it was found that the population of CPT particles can be evaluated quantitatively through the intensity of the TG signal.

  2. Thermoelectric generator for motor vehicle

    DOEpatents

    Bass, John C.

    1997-04-29

    A thermoelectric generator for producing electric power for a motor vehicle from the heat of the exhaust gasses produced by the engine of the motor vehicle. The exhaust gasses pass through a finned heat transfer support structure which has seat positions on its outside surface for the positioning of thermoelectric modules. A good contact cylinder provides a framework from which a spring force can be applied to the thermoelectric modules to hold them in good contact on their seats on the surface of the heat transfer support structure.

  3. Direct Absorption Spectroscopy with Electro-Optic Frequency Combs

    NASA Astrophysics Data System (ADS)

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

    2017-06-01

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

  4. Combined analysis of the radar cross-section modulation due to the long ocean waves around 14° and 34° incidence: Implication for the hydrodynamic modulation

    NASA Astrophysics Data System (ADS)

    Hauser, DanièLe; Caudal, GéRard

    1996-11-01

    The analysis of synthetic aperture radar observations over the ocean to derive the directional spectra of the waves is based upon a complex transfer function which is the sum of three terms: tilt modulation, hydrodynamic modulation, and velocity bunching effect. Both the hydrodynamic and the velocity bunching terms are still poorly known. Here we focus on the hydrodynamic part of the transfer function, from an experimental point of view. In this paper a new method is proposed to estimate the hydrodynamic modulation. The approach consists in analyzing observations obtained with an airborne real-aperture radar (called RESSAC). This radar (C band, HH polarized, broad beam of 14° × 3°) was used during the SEMAPHORE experiment, in two different modes. From the first mode (incidence angles from 7° to 21°) the directional spectra of the long waves are deduced under the assumption that the hydrodynamic modulation can be neglected (small incidence angles) and validated against in situ measurements. From the second mode (incidence angle from 27° to 41°) the amplitude and phase of the hydrodynamic modulation are deduced by combining the measured signal modulation spectrum at a mean incidence angle of 34° and the directional wave spectrum obtained from the first mode. The results, obtained in four different wind-wave cases of the SEMAPHORE experiment, show that the modulus of the hydrodynamic modulation is larger than that of the tilt modulation. Furthermore, we find that the modulus of the hydrodynamic transfer function is several times larger (by a factor 2-12) than the theoretical value proposed in previous works and 1.5-2.5 larger than experimental values reported in recent papers. The phase of the hydrodynamic modulation is found to be close to zero for waves propagating at an angle from the wind direction and between -20° and -40° for waves propagating along the wind direction. This indicates a significant influence of the wind-wave angle on the phase of the hydrodynamic modulation, in agreement with experimental results reported in recent papers.

  5. Collisional transfer of population and orientation in NaK

    NASA Astrophysics Data System (ADS)

    Wolfe, C. M.; Ashman, S.; Bai, J.; Beser, B.; Ahmed, E. H.; Lyyra, A. M.; Huennekens, J.

    2011-05-01

    Collisional satellite lines with |ΔJ| ≤ 58 have been identified in recent polarization spectroscopy V-type optical-optical double resonance (OODR) excitation spectra of the Rb2 molecule [H. Salami et al., Phys. Rev. A 80, 022515 (2009)]. Observation of these satellite lines clearly requires a transfer of population from the rotational level directly excited by the pump laser to a neighboring level in a collision of the molecule with an atomic perturber. However to be observed in polarization spectroscopy, the collision must also partially preserve the angular momentum orientation, which is at least somewhat surprising given the extremely large values of ΔJ that were observed. In the present work, we used the two-step OODR fluorescence and polarization spectroscopy techniques to obtain quantitative information on the transfer of population and orientation in rotationally inelastic collisions of the NaK molecules prepared in the 2(A)1Σ+(v' = 16, J' = 30) rovibrational level with argon and potassium perturbers. A rate equation model was used to study the intensities of these satellite lines as a function of argon pressure and heat pipe oven temperature, in order to separate the collisional effects of argon and potassium atoms. Using a fit of this rate equation model to the data, we found that collisions of NaK molecules with potassium atoms are more likely to transfer population and destroy orientation than collisions with argon atoms. Collisions with argon atoms show a strong propensity for population transfer with ΔJ = even. Conversely, collisions with potassium atoms do not show this ΔJ = even propensity, but do show a propensity for ΔJ = positive compared to ΔJ = negative, for this particular initial state. The density matrix equations of motion have also been solved numerically in order to test the approximations used in the rate equation model and to calculate fluorescence and polarization spectroscopy line shapes. In addition, we have measured rate coefficients for broadening of NaK 31Π ← 2(A)1Σ+spectral lines due to collisions with argon and potassium atoms. Additional broadening, due to velocity changes occurring in rotationally inelastic collisions, has also been observed.

  6. Collisional transfer of population and orientation in NaK.

    PubMed

    Wolfe, C M; Ashman, S; Bai, J; Beser, B; Ahmed, E H; Lyyra, A M; Huennekens, J

    2011-05-07

    Collisional satellite lines with |ΔJ| ≤ 58 have been identified in recent polarization spectroscopy V-type optical-optical double resonance (OODR) excitation spectra of the Rb(2) molecule [H. Salami et al., Phys. Rev. A 80, 022515 (2009)]. Observation of these satellite lines clearly requires a transfer of population from the rotational level directly excited by the pump laser to a neighboring level in a collision of the molecule with an atomic perturber. However to be observed in polarization spectroscopy, the collision must also partially preserve the angular momentum orientation, which is at least somewhat surprising given the extremely large values of ΔJ that were observed. In the present work, we used the two-step OODR fluorescence and polarization spectroscopy techniques to obtain quantitative information on the transfer of population and orientation in rotationally inelastic collisions of the NaK molecules prepared in the 2(A)(1)Σ(+)(v' = 16, J' = 30) rovibrational level with argon and potassium perturbers. A rate equation model was used to study the intensities of these satellite lines as a function of argon pressure and heat pipe oven temperature, in order to separate the collisional effects of argon and potassium atoms. Using a fit of this rate equation model to the data, we found that collisions of NaK molecules with potassium atoms are more likely to transfer population and destroy orientation than collisions with argon atoms. Collisions with argon atoms show a strong propensity for population transfer with ΔJ = even. Conversely, collisions with potassium atoms do not show this ΔJ = even propensity, but do show a propensity for ΔJ = positive compared to ΔJ = negative, for this particular initial state. The density matrix equations of motion have also been solved numerically in order to test the approximations used in the rate equation model and to calculate fluorescence and polarization spectroscopy line shapes. In addition, we have measured rate coefficients for broadening of NaK 3(1)Π ← 2(A)(1)Σ(+)spectral lines due to collisions with argon and potassium atoms. Additional broadening, due to velocity changes occurring in rotationally inelastic collisions, has also been observed.

  7. Resonance Raman investigation of the photoreduction of methylviologen with Ru(bpy) 2+3 and proflavine as sensitizers

    NASA Astrophysics Data System (ADS)

    Forster, Martin; Hester, Ronald E.

    1982-01-01

    Reduced methylviologen (MV +) is detected by conventional resonance Raman spectroscopy in photoreactions of Ru(bpy) 2+3 or proflavine (PFH +) with MV 2+ Using apparatus for modulated excitation resonance Raman (MERR) spectroscopy, the irreversible MV + production with PFH + as sensitizer is traced back to triplet-triplet annihilation with simultaneous destruction of PFH +.

  8. Optical gas monitor

    DOEpatents

    Wu, Sheng; Deev, Andrei; Palm, Steve L.; Tang, Yongchun; Goddard, William A.

    2010-11-30

    A frequency modulated spectroscopy system, including a photo-detector, a band-pass filter to filter the output of the photo-detector, and a rectifier to demodulate. The band-pass filter has a relatively high Q factor. With the high Q factor band-pass filter and rectifier, a reference sinusoid is not required for demodulation, resulting in phase-insensitive spectroscopy. Other embodiments are described and claimed.

  9. A prototype stationary Fourier transform spectrometer for near-infrared absorption spectroscopy.

    PubMed

    Li, Jinyang; Lu, Dan-feng; Qi, Zhi-mei

    2015-09-01

    A prototype stationary Fourier transform spectrometer (FTS) was constructed with a fiber-coupled lithium niobate (LiNbO3) waveguide Mach-Zehnder interferometer (MZI) for the purpose of rapid on-site spectroscopy of biological and chemical measurands. The MZI contains push-pull electrodes for electro-optic modulation, and its interferogram as a plot of intensity against voltage was obtained by scanning the modulating voltage from -60 to +60 V in 50 ms. The power spectrum of input signal was retrieved by Fourier transform processing of the interferogram combined with the wavelength dispersion of half-wave voltage determined for the MZI used. The prototype FTS operates in the single-mode wavelength range from 1200 to 1700 nm and allows for reproducible spectroscopy. A linear concentration dependence of the absorbance at λmax = 1451 nm for water in ethanolic solution was obtained using the prototype FTS. The near-infrared spectroscopy of solid samples was also implemented, and the different spectra obtained with different materials evidenced the chemical recognition capability of the prototype FTS. To make this prototype FTS practically applicable, work on improving its spectral resolution by increasing the maximum optical path length difference is in progress.

  10. Coherent cavity-enhanced dual-comb spectroscopy

    PubMed Central

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

    2016-01-01

    Dual-comb spectroscopy allows for the rapid, multiplexed acquisition of high-resolution spectra without the need for moving parts or low-resolution dispersive optics. This method of broadband spectroscopy is most often accomplished via tight phase locking of two mode-locked lasers or via sophisticated signal processing algorithms, and therefore, long integration times of phase coherent signals are difficult to achieve. Here we demonstrate an alternative approach to dual-comb spectroscopy using two phase modulator combs originating from a single continuous-wave laser capable of > 2 hours of coherent real-time averaging. The dual combs were generated by driving the phase modulators with step-recovery diodes where each comb consisted of > 250 teeth with 203 MHz spacing and spanned > 50 GHz region in the near-infrared. The step-recovery diodes are passive devices that provide low-phase-noise harmonics for efficient coupling into an enhancement cavity at picowatt optical powers. With this approach, we demonstrate the sensitivity to simultaneously monitor ambient levels of CO2, CO, HDO, and H2O in a single spectral region at a maximum acquisition rate of 150 kHz. Robust, compact, low-cost and widely tunable dual-comb systems could enable a network of distributed multiplexed optical sensors. PMID:27409866

  11. Tunable heat transfer with smart nanofluids.

    PubMed

    Bernardin, Michele; Comitani, Federico; Vailati, Alberto

    2012-06-01

    Strongly thermophilic nanofluids are able to transfer either small or large quantities of heat when subjected to a stable temperature difference. We investigate the bistability diagram of the heat transferred by this class of nanofluids. We show that bistability can be exploited to obtain a controlled switching between a conductive and a convective regime of heat transfer, so as to achieve a controlled modulation of the heat flux.

  12. Development and manufacture of reactive-transfer-printed CIGS photovoltaic modules

    NASA Astrophysics Data System (ADS)

    Eldada, Louay; Sang, Baosheng; Lu, Dingyuan; Stanbery, Billy J.

    2010-09-01

    In recent years, thin-film photovoltaic (PV) companies started realizing their low manufacturing cost potential, and grabbing an increasingly larger market share from multicrystalline silicon companies. Copper Indium Gallium Selenide (CIGS) is the most promising thin-film PV material, having demonstrated the highest energy conversion efficiency in both cells and modules. However, most CIGS manufacturers still face the challenge of delivering a reliable and rapid manufacturing process that can scale effectively and deliver on the promise of this material system. HelioVolt has developed a reactive transfer process for CIGS absorber formation that has the benefits of good compositional control, high-quality CIGS grains, and a fast reaction. The reactive transfer process is a two stage CIGS fabrication method. Precursor films are deposited onto substrates and reusable print plates in the first stage, while in the second stage, the CIGS layer is formed by rapid heating with Se confinement. High quality CIGS films with large grains were produced on a full-scale manufacturing line, and resulted in high-efficiency large-form-factor modules. With 14% cell efficiency and 12% module efficiency, HelioVolt started to commercialize the process on its first production line with 20 MW nameplate capacity.

  13. Geostationary platform systems concepts definition study. Volume 2: Technical, book 2

    NASA Technical Reports Server (NTRS)

    1980-01-01

    A selected concept for a geostationary platform is defined in sufficient detail to identify requirements for supporting research and technology, space demonstrations, GFE interfaces, costs, and schedules. This system consists of six platforms in geostationary orbit (GEO) over the Western Hemisphere and six over the Atlantic, to satisfy the total payload set associated with the nominal traffic model. Each platform is delivered to low Earth orbit (LEO) in a single shuttle flight, already mated to its LEO to GEO transfer vehicle and ready for deployment and transfer to GEO. An alternative concept is looked at briefly for comparison of configuration and technology requirements. This alternative consists of two large platforms, one over the Western Hemisphere consisting of three docked modules, and one over the Atlantic (two docked modules), to satisfy a high traffic model. The modules are full length orbiter cargo bay payloads, mated at LEO to orbital transfer vehicles (OTVs) delivered in other shuttle flights, for transfer to GEO, rendezvous, and docking. A preliminary feasibility study of an experimental platform is also performed to demonstrate communications and platform technologies required for the operational platforms of the 1990s.

  14. Health Instruction Packages: Dental Personnel.

    ERIC Educational Resources Information Center

    Hayes, Gary E.; And Others

    Text, illustrations, and exercises are utilized in this set of four learning modules designed to instruct non-professional dental personnel in selected job-related skills. The first module, by Gary E. Hayes, describes how to locate the hinge axis point of the jaw, place and secure a bitefork, and perform a facebow transfer. The second module,…

  15. Students' Design of Experiments: An Inquiry Module on the Conduction of Heat

    ERIC Educational Resources Information Center

    Hatzikraniotis, E.; Kallery, M.; Molohidis, A.; Psillos, D.

    2010-01-01

    This article examines secondary students' design of experiments after engagement in an innovative and inquiry-oriented module on heat transfer. The module consists of an integration of hands-on experiments, simulated experiments and microscopic model simulations, includes a structured series of guided investigative tasks and was implemented for a…

  16. Magnet measurement interfacing to the G-64 Euro standard bus and testing G-64 modules

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

    Hogrefe, R.L.

    1995-07-01

    The Magnet Measurement system utilizes various modules with a G-64 Euro (Gespac) Standard Interface. All modules are designed to be software controlled, normally under the constraints of the OS-9 operating system with all data transfers to a host computer accomplished by a serial link.

  17. Development of a three-dimensional core dynamics analysis program for commercial boiling water reactors

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

    Bessho, Yasunori; Yokomizo, Osamu; Yoshimoto, Yuichiro

    1997-03-01

    Development and qualification results are described for a three-dimensional, time-domain core dynamics analysis program for commercial boiling water reactors (BWRs). The program allows analysis of the reactor core with a detailed mesh division, which eliminates calculational ambiguity in the nuclear-thermal-hydraulic stability analysis caused by reactor core regional division. During development, emphasis was placed on high calculational speed and large memory size as attained by the latest supercomputer technology. The program consists of six major modules, namely a core neutronics module, a fuel heat conduction/transfer module, a fuel channel thermal-hydraulic module, an upper plenum/separator module, a feedwater/recirculation flow module, and amore » control system module. Its core neutronics module is based on the modified one-group neutron kinetics equation with the prompt jump approximation and with six delayed neutron precursor groups. The module is used to analyze one fuel bundle of the reactor core with one mesh (region). The fuel heat conduction/transfer module solves the one-dimensional heat conduction equation in the radial direction with ten nodes in the fuel pin. The fuel channel thermal-hydraulic module is based on separated three-equation, two-phase flow equations with the drift flux correlation, and it analyzes one fuel bundle of the reactor core with one channel to evaluate flow redistribution between channels precisely. Thermal margin is evaluated by using the GEXL correlation, for example, in the module.« less

  18. Chirped-pulse coherent-OTDR with predistortion

    NASA Astrophysics Data System (ADS)

    Xiong, Ji; Jiang, Jialin; Wu, Yue; Chen, Yongxiang; Xie, Lianlian; Fu, Yun; Wang, Zinan

    2018-03-01

    In this paper, a novel method for generating high-quality chirped pulses with IQ modulator is studied theoretically and experimentally, which is a crucial building block for high-performance coherent optical time-domain reflectometry (COTDR). In order to compensate the nonlinearity of the modulator transfer function, we present a predistortion technique for chirped-pulse coherent optical time-domain reflectometry (CP-COTDR), the arcsin predistortion method and the single sideband with a suppressed carrier analog modulation used to generate the high quality chirped optical pulse. The high order sidebands, due to the large amplitude of the modulation signal and the nonlinear transfer function of the IQ modulator, can be relieved by the predistortion process, which means the power and the quality of the generated chirped pulse has been improved. In the experiment, this method increases the peak power of the chirped pulse by 4.2 dB compared to the case without predistortion process, as for the CP-COTDR system, this method increases the signal-to-noise ratio of the demodulated phase variation by 6.3 dB.

  19. Fiber-ring laser-based intracavity photoacoustic spectroscopy for trace gas sensing.

    PubMed

    Wang, Qiang; Wang, Zhen; Chang, Jun; Ren, Wei

    2017-06-01

    We demonstrated a novel trace gas sensing method based on fiber-ring laser intracavity photoacoustic spectroscopy. This spectroscopic technique is a merging of photoacoustic spectroscopy (PAS) with a fiber-ring cavity for sensitive and all-fiber gas detection. A transmission-type PAS gas cell (resonant frequency f0=2.68  kHz) was placed inside the fiber-ring laser to fully utilize the intracavity laser power. The PAS signal was excited by modulating the laser wavelength at f0/2 using a custom-made fiber Bragg grating-based modulator. We used this spectroscopic technique to detect acetylene (C2H2) at 1531.6 nm as a proof of principle. With a low Q-factor (4.9) of the PAS cell, our sensor achieved a good linear response (R2=0.996) to C2H2 concentration and a minimum detection limit of 390 ppbv at 2-s response time.

  20. Fluorescence suppression using wavelength modulated Raman spectroscopy in fiber-probe-based tissue analysis.

    PubMed

    Praveen, Bavishna B; Ashok, Praveen C; Mazilu, Michael; Riches, Andrew; Herrington, Simon; Dholakia, Kishan

    2012-07-01

    In the field of biomedical optics, Raman spectroscopy is a powerful tool for probing the chemical composition of biological samples. In particular, fiber Raman probes play a crucial role for in vivo and ex vivo tissue analysis. However, the high-fluorescence background typically contributed by the auto fluorescence from both a tissue sample and the fiber-probe interferes strongly with the relatively weak Raman signal. Here we demonstrate the implementation of wavelength-modulated Raman spectroscopy (WMRS) to suppress the fluorescence background while analyzing tissues using fiber Raman probes. We have observed a significant signal-to-noise ratio enhancement in the Raman bands of bone tissue, which have a relatively high fluorescence background. Implementation of WMRS in fiber-probe-based bone tissue study yielded usable Raman spectra in a relatively short acquisition time (∼30  s), notably without any special sample preparation stage. Finally, we have validated its capability to suppress fluorescence on other tissue samples such as adipose tissue derived from four different species.

  1. Gas sensing using wavelength modulation spectroscopy

    NASA Astrophysics Data System (ADS)

    Viveiros, D.; Ribeiro, J.; Flores, D.; Ferreira, J.; Frazao, O.; Santos, J. L.; Baptista, J. M.

    2014-08-01

    An experimental setup has been developed for different gas species sensing based on the Wavelength Modulation Spectroscopy (WMS) principle. The target is the measurement of ammonia, carbon dioxide and methane concentrations. The WMS is a rather sensitive technique for detecting atomic/molecular species presenting the advantage that it can be used in the near-infrared region using optical telecommunications technology. In this technique, the laser wavelength and intensity are modulated applying a sine wave signal through the injection current, which allows the shift of the detection bandwidth to higher frequencies where laser intensity noise is reduced. The wavelength modulated laser light is tuned to the absorption line of the target gas and the absorption information can be retrieved by means of synchronous detection using a lock-in amplifier, where the amplitude of the second harmonic of the laser modulation frequency is proportional to the gas concentration. The amplitude of the second harmonic is normalised by the average laser intensity and detector gain through a LabVIEW® application, where the main advantage of normalising is that the effects of laser output power fluctuations and any variations in laser transmission, or optical-electrical detector gain are eliminated. Two types of sensing heads based on free space light propagation with different optical path length were used, permitting redundancy operation and technology validation.

  2. Electron transfer and conformational change in complexes of trimethylamine dehydrogenase and electron transferring flavoprotein.

    PubMed

    Jones, Matthew; Talfournier, Francois; Bobrov, Anton; Grossmann, J Günter; Vekshin, Nikolai; Sutcliffe, Michael J; Scrutton, Nigel S

    2002-03-08

    The trimethylamine dehydrogenase-electron transferring flavoprotein (TMADH.ETF) electron transfer complex has been studied by fluorescence and absorption spectroscopies. These studies indicate that a series of conformational changes occur during the assembly of the TMADH.ETF electron transfer complex and that the kinetics of assembly observed with mutant TMADH (Y442F/L/G) or ETF (alpha R237A) complexes are much slower than are the corresponding rates of electron transfer in these complexes. This suggests that electron transfer does not occur in the thermodynamically most favorable state (which takes too long to form), but that one or more metastable states (which are formed more rapidly) are competent in transferring electrons from TMADH to ETF. Additionally, fluorescence spectroscopy studies of the TMADH.ETF complex indicate that ETF undergoes a stable conformational change (termed structural imprinting) when it interacts transiently with TMADH to form a second, distinct, structural form. The mutant complexes compromise imprinting of ETF, indicating a dependence on the native interactions present in the wild-type complex. The imprinted form of semiquinone ETF exhibits an enhanced rate of electron transfer to the artificial electron acceptor, ferricenium. Overall molecular conformations as probed by small-angle x-ray scattering studies are indistinguishable for imprinted and non-imprinted ETF, suggesting that changes in structure likely involve confined reorganizations within the vicinity of the FAD. Our results indicate a series of conformational events occur during the assembly of the TMADH.ETF electron transfer complex, and that the properties of electron transfer proteins can be affected lastingly by transient interaction with their physiological redox partners. This may have significant implications for our understanding of biological electron transfer reactions in vivo, because ETF encounters TMADH at all times in the cell. Our studies suggest that caution needs to be exercised in extrapolating the properties of in vitro interprotein electron transfer reactions to those occurring in vivo.

  3. Ocean wave-radar modulation transfer functions from the West Coast experiment

    NASA Technical Reports Server (NTRS)

    Wright, J. W.; Plant, W. J.; Keller, W. C.; Jones, W. L.

    1980-01-01

    Short gravity-capillary waves, the equilibrium, or the steady state excitations of the ocean surface are modulated by longer ocean waves. These short waves are the predominant microwave scatterers on the ocean surface under many viewing conditions so that the modulation is readily measured with CW Doppler radar used as a two-scale wave probe. Modulation transfer functions (the ratio of the cross spectrum of the line-of-sight orbital speed and backscattered microwave power to the autospectrum of the line-of-sight orbital speed) were measured at 9.375 and 1.5 GHz (Bragg wavelengths of 2.3 and 13 cm) for winds up to 10 m/s and ocean wave periods from 2-18 s. The measurements were compared with the relaxation-time model; the principal result is that a source of modulation other than straining by the horizontal component of orbital speed, possibly the wave-induced airflow, is responsible for most of the modulation by waves of typical ocean wave period (10 s). The modulations are large; for unit coherence, spectra of radar images of deep-water waves should be proportional to the quotient of the slope spectra of the ocean waves by the ocean wave frequency.

  4. SMRT: A new, modular snow microwave radiative transfer model

    NASA Astrophysics Data System (ADS)

    Picard, Ghislain; Sandells, Melody; Löwe, Henning; Dumont, Marie; Essery, Richard; Floury, Nicolas; Kontu, Anna; Lemmetyinen, Juha; Maslanka, William; Mätzler, Christian; Morin, Samuel; Wiesmann, Andreas

    2017-04-01

    Forward models of radiative transfer processes are needed to interpret remote sensing data and derive measurements of snow properties such as snow mass. A key requirement and challenge for microwave emission and scattering models is an accurate description of the snow microstructure. The snow microwave radiative transfer model (SMRT) was designed to cater for potential future active and/or passive satellite missions and developed to improve understanding of how to parameterize snow microstructure. SMRT is implemented in Python and is modular to allow easy intercomparison of different theoretical approaches. Separate modules are included for the snow microstructure model, electromagnetic module, radiative transfer solver, substrate, interface reflectivities, atmosphere and permittivities. An object-oriented approach is used with carefully specified exchanges between modules to allow future extensibility i.e. without constraining the parameter list requirements. This presentation illustrates the capabilities of SMRT. At present, five different snow microstructure models have been implemented, and direct insertion of the autocorrelation function from microtomography data is also foreseen with SMRT. Three electromagnetic modules are currently available. While DMRT-QCA and Rayleigh models need specific microstructure models, the Improved Born Approximation may be used with any microstructure representation. A discrete ordinates approach with stream connection is used to solve the radiative transfer equations, although future inclusion of 6-flux and 2-flux solvers are envisioned. Wrappers have been included to allow existing microwave emission models (MEMLS, HUT, DMRT-QMS) to be run with the same inputs and minimal extra code (2 lines). Comparisons between theoretical approaches will be shown, and evaluation against field experiments in the frequency range 5-150 GHz. SMRT is simple and elegant to use whilst providing a framework for future development within the community.

  5. Oral Gene Application Using Chitosan-DNA Nanoparticles Induces Transferable Tolerance

    PubMed Central

    Ensminger, Stephan M.; Spriewald, Bernd M.

    2012-01-01

    Oral tolerance is a promising approach to induce unresponsiveness to various antigens. The development of tolerogenic vaccines could be exploited in modulating the immune response in autoimmune disease and allograft rejection. In this study, we investigated a nonviral gene transfer strategy for inducing oral tolerance via antigen-encoding chitosan-DNA nanoparticles (NP). Oral application of ovalbumin (OVA)-encoding chitosan-DNA NP (OVA-NP) suppressed the OVA-specific delayed-type hypersensitivity (DTH) response and anti-OVA antibody formation, as well as spleen cell proliferation following OVA stimulation. Cytokine expression patterns following OVA stimulation in vitro showed a shift from a Th1 toward a Th2/Th3 response. The OVA-NP-induced tolerance was transferable from donor to naïve recipient mice via adoptive spleen cell transfer and was mediated by CD4+CD25+ T cells. These findings indicate that nonviral oral gene transfer can induce regulatory T cells for antigen-specific immune modulation. PMID:22933401

  6. Heat Transfer and Geometrical Analysis of Thermoelectric Converters Driven by Concentrated Solar Radiation

    PubMed Central

    Suter, Clemens; Tomeš, Petr; Weidenkaff, Anke; Steinfeld, Aldo

    2010-01-01

    A heat transfer model that couples radiation/conduction/convection heat transfer with electrical potential distribution is developed for a thermoelectric converter (TEC) subjected to concentrated solar radiation. The 4-leg TEC module consists of two pairs of p-type La1.98Sr0.02CuO4 and n-type CaMn0.98Nb0.02O3 legs that are sandwiched between two ceramic Al2O3 hot/cold plates and connected electrically in series and thermally in parallel. The governing equations for heat transfer and electrical potential are formulated, discretized and solved numerically by applying the finite volume (FV) method. The model is validated in terms of experimentally measured temperatures and voltages/power using a set of TEC demonstrator modules, subjected to a peak radiative flux intensity of 300 suns. The heat transfer model is then applied to examine the effect of the geometrical parameters (e.g. length/width of legs) on the solar-to-electricity energy conversion efficiency.

  7. Adhesion and transfer of polytetrafluorethylene to metals studied by Auger emission spectroscopy

    NASA Technical Reports Server (NTRS)

    Pepper, S. V.; Buckley, D. H.

    1972-01-01

    The adhesion and transfer of polytetrafluoroethylene (PTFE) to metals in ultrahigh vacuum were studied. The transfer was effected both by compressive static contact and by sliding contact. The transfer observed after static contact was independent of the chemical constitution of the substrate. Electron-induced desorption of the fluorine in the transferred PTFE showed that the fluorine had no chemical interaction with the metal substrate. The coefficient of friction on metals was independent of the chemical constitution of the substrate. However, sliding PTFE on soft metals, such as aluminum, generated wear fragments that lodged in the PTFE and machined the substrate.

  8. Measurement of Lactate Content and Amide Proton Transfer Values in the Basal Ganglia of a Neonatal Piglet Hypoxic-Ischemic Brain Injury Model Using MRI.

    PubMed

    Zheng, Y; Wang, X-M

    2017-04-01

    As amide proton transfer imaging is sensitive to protein content and intracellular pH, it has been widely used in the nervous system, including brain tumors and stroke. This work aimed to measure the lactate content and amide proton transfer values in the basal ganglia of a neonatal piglet hypoxic-ischemic brain injury model by using MR spectroscopy and amide proton transfer imaging. From 58 healthy neonatal piglets (3-5 days after birth; weight, 1-1.5 kg) selected initially, 9 piglets remained in the control group and 43 piglets, in the hypoxic-ischemic brain injury group. Single-section amide proton transfer imaging was performed at the coronal level of the basal ganglia. Amide proton transfer values of the bilateral basal ganglia were measured in all piglets. The ROI of MR spectroscopy imaging was the right basal ganglia, and the postprocessing was completed with LCModel software. After hypoxic-ischemic insult, the amide proton transfer values immediately decreased, and at 0-2 hours, they remained at their lowest level. Thereafter, they gradually increased and finally exceeded those of the control group at 48-72 hours. After hypoxic-ischemic insult, the lactate content increased immediately, was maximal at 2-6 hours, and then gradually decreased to the level of the control group. The amide proton transfer values were negatively correlated with lactate content ( r = -0.79, P < .05). This observation suggests that after hypoxic-ischemic insult, the recovery of pH was faster than that of lactate homeostasis. © 2017 by American Journal of Neuroradiology.

  9. Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy

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

    Enriquez, Miriam M.; Zhang, Cheng; Tan, Howe-Siang, E-mail: howesiang@ntu.edu.sg

    2015-06-07

    The pathways and dynamics of excitation energy transfer between the chlorophyll (Chl) domains in solubilized trimeric and aggregated light-harvesting complex II (LHCII) are examined using two-dimensional electronic spectroscopy (2DES). The LHCII trimers and aggregates exhibit the unquenched and quenched excitonic states of Chl a, respectively. 2DES allows direct correlation of excitation and emission energies of coupled states over population time delays, hence enabling mapping of the energy flow between Chls. By the excitation of the entire Chl b Q{sub y} band, energy transfer from Chl b to Chl a states is monitored in the LHCII trimers and aggregates. Global analysismore » of the two-dimensional (2D) spectra reveals that energy transfer from Chl b to Chl a occurs on fast and slow time scales of 240–270 fs and 2.8 ps for both forms of LHCII. 2D decay-associated spectra resulting from the global analysis identify the correlation between Chl states involved in the energy transfer and decay at a given lifetime. The contribution of singlet–singlet annihilation on the kinetics of Chl energy transfer and decay is also modelled and discussed. The results show a marked change in the energy transfer kinetics in the time range of a few picoseconds. Owing to slow energy equilibration processes, long-lived intermediate Chl a states are present in solubilized trimers, while in aggregates, the population decay of these excited states is significantly accelerated, suggesting that, overall, the energy transfer within the LHCII complexes is faster in the aggregated state.« less

  10. Multilayer graphene as an effective corrosion protection coating for copper

    NASA Astrophysics Data System (ADS)

    Ravishankar, Vasumathy; Ramaprabhu, S.; Jaiswal, Manu

    2018-04-01

    Graphene grown by chemical vapor deposition (CVD) has been studied as a protective layer against corrosion of copper. The layer number dependence on the protective nature of graphene has been investigated using techniques such as Tafel analysis and Electroimpedance Spectroscopy. Multiple layers of graphene were achieved by wet transfer above CVD grown graphene. Though this might cause grain boundaries, the sites where corrosion is initiated, to be staggered, wet transfer inherently carries the disadvantage of tearing of graphene, as confirmed by Raman spectroscopy measurements. However, Electroimpedance Spectroscopy (EIS) reflects that graphene protected copper has a layer dependent resistance to corrosion. Decrease in corrosion current (Icorr) for graphene protected copper is presented. There is only small dependence of corrosion current on the layer number, Tafel plots clearly indicate passivation in the presence of graphene, whether it be single layer or multiple layers. Notwithstanding the crystallite size, defect free layers of graphene with staggered grain boundaries combined with passivation could offer good corrosion protection for metals.

  11. Minimally buffered data transfers between nodes in a data communications network

    DOEpatents

    Miller, Douglas R.

    2015-06-23

    Methods, apparatus, and products for minimally buffered data transfers between nodes in a data communications network are disclosed that include: receiving, by a messaging module on an origin node, a storage identifier, a origin data type, and a target data type, the storage identifier specifying application storage containing data, the origin data type describing a data subset contained in the origin application storage, the target data type describing an arrangement of the data subset in application storage on a target node; creating, by the messaging module, origin metadata describing the origin data type; selecting, by the messaging module from the origin application storage in dependence upon the origin metadata and the storage identifier, the data subset; and transmitting, by the messaging module to the target node, the selected data subset for storing in the target application storage in dependence upon the target data type without temporarily buffering the data subset.

  12. Solid state rapid thermocycling

    DOEpatents

    Beer, Neil Reginald; Spadaccini, Christopher

    2014-05-13

    The rapid thermal cycling of a material is targeted. A solid state heat exchanger with a first well and second well is coupled to a power module. A thermoelectric element is coupled to the first well, the second well, and the power module, is configured to transfer thermal energy from the first well to the second well when current from the power module flows through the thermoelectric element in a first direction, and is configured to transfer thermal energy from the second well to the first well when current from the power module flows through the thermoelectric element in a second direction. A controller may be coupled to the thermoelectric elements, and may switch the direction of current flowing through the thermoelectric element in response to a determination by sensors coupled to the wells that the amount of thermal energy in the wells falls below or exceeds a pre-determined threshold.

  13. Diode laser detection of greenhouse gases in the near-infrared region by wavelength modulation spectroscopy: pressure dependence of the detection sensitivity.

    PubMed

    Asakawa, Takashi; Kanno, Nozomu; Tonokura, Kenichi

    2010-01-01

    We have investigated the pressure dependence of the detection sensitivity of CO(2), N(2)O and CH(4) using wavelength modulation spectroscopy (WMS) with distributed feed-back diode lasers in the near infrared region. The spectral line shapes and the background noise of the second harmonics (2f) detection of the WMS were analyzed theoretically. We determined the optimum pressure conditions in the detection of CO(2), N(2)O and CH(4), by taking into consideration the background noise in the WMS. At the optimum total pressure for the detection of CO(2), N(2)O and CH(4), the limits of detection in the present system were determined.

  14. Spatial Data Transfer Standard (SDTS)

    USGS Publications Warehouse

    ,

    1999-01-01

    The American National Standards Institute?s (ANSI) Spatial Data Transfer Standard (SDTS) is a mechanism for archiving and transferring of spatial data (including metadata) between dissimilar computer systems. The SDTS specifies exchange constructs, such as format, structure, and content, for spatially referenced vector and raster (including gridded) data. The SDTS includes a flexible conceptual model, specifications for a quality report, transfer module specifications, data dictionary specifications, and definitions of spatial features and attributes.

  15. Correcting reaction rates measured by saturation-transfer magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Gabr, Refaat E.; Weiss, Robert G.; Bottomley, Paul A.

    2008-04-01

    Off-resonance or spillover irradiation and incomplete saturation can introduce significant errors in the estimates of chemical rate constants measured by saturation-transfer magnetic resonance spectroscopy (MRS). Existing methods of correction are effective only over a limited parameter range. Here, a general approach of numerically solving the Bloch-McConnell equations to calculate exchange rates, relaxation times and concentrations for the saturation-transfer experiment is investigated, but found to require more measurements and higher signal-to-noise ratios than in vivo studies can practically afford. As an alternative, correction formulae for the reaction rate are provided which account for the expected parameter ranges and limited measurements available in vivo. The correction term is a quadratic function of experimental measurements. In computer simulations, the new formulae showed negligible bias and reduced the maximum error in the rate constants by about 3-fold compared to traditional formulae, and the error scatter by about 4-fold, over a wide range of parameters for conventional saturation transfer employing progressive saturation, and for the four-angle saturation-transfer method applied to the creatine kinase (CK) reaction in the human heart at 1.5 T. In normal in vivo spectra affected by spillover, the correction increases the mean calculated forward CK reaction rate by 6-16% over traditional and prior correction formulae.

  16. Parametric dependence of ocean wave-radar modulation transfer functions

    NASA Technical Reports Server (NTRS)

    Plant, W. J.; Keller, W. C.; Cross, A.

    1983-01-01

    Microwave techniques at X and L band were used to determine the dependence of ocean-wave radar modulation transfer functions (MTFs) on various environmental and radar parameters during the Marine Remote Sensing experiment of 1979 (MARSEN 79). These MIF are presented, as are coherence functions between the AM and FM parts of the backscattered microwave signal. It is shown that they both depend on several of these parameters. Besides confirming many of the properties of transfer functions reported by previous authors, indications are found that MTFs decrease with increasing angle between wave propagation and antenna-look directions but are essentially independent of small changes in air-sea temperature difference. However, coherence functions are much smaller when the antennas are pointed perpendicular to long waves. It is found that X band transfer functions measured with horizontally polarized microwave radiation have larger magnitudes than those obtained by using vertical polarization.

  17. Modulation and Functional Role of the Orientations of the N- and P-Domains of Cu+ -Transporting ATPase along the Ion Transport Cycle.

    PubMed

    Meng, Dan; Bruschweiler-Li, Lei; Zhang, Fengli; Brüschweiler, Rafael

    2015-08-18

    Ion transport of different P-type ATPases is regulated similarly through the interplay of multiple protein domains. In the presence of ATP, binding of a cation to the ion binding site in the transmembrane helices leads to the phosphorylation of the P-domain, allowing ion transfer across the membrane. The details of the mechanism, however, are not clear. Here, we report the modulation of the orientation between the N- and P-domains of Cu(+)-transporting ATPase along the ion transport cycle using high-resolution nuclear magnetic resonance spectroscopy in solution. On the basis of residual dipolar coupling measurements, it is found that the interdomain orientation (relative openness) of the N- and P-domains is distinctly modulated depending on the specific state of the N- and P-domains along the ion translocation cycle. The two domains' relative position in the apo state is semiopen, whereas it becomes closed upon binding of ATP to the N-domain. After phosphorylation of the P-domain and the release of ADP, the opening, however, becomes the widest among all the states. We reason such wide opening resulting from the departure of ADP prepares the N- and P-domains to accommodate the A-domain for interaction and, hence, promote ion transport and allow dephosphorylation of the P-domain. Such wide interdomain opening is abolished when an Asn to Asp mutation is introduced into the conserved DXXK motif located in the hinge region of the N- and P-domains of Cu(+)-ATPase, suggesting the indispensible role of the N- and P-interdomain orientation during ion transportation. Our results shed new light on the structural and mechanistic details of P-type ATPase function at large.

  18. Interfacial Chemistry-Induced Modulation of Schottky Barrier Heights: In Situ Measurements of the Pt-Amorphous Indium Gallium Zinc Oxide Interface Using X-ray Photoelectron Spectroscopy.

    PubMed

    Flynn, Brendan T; Oleksak, Richard P; Thevuthasan, Suntharampillai; Herman, Gregory S

    2018-01-31

    A method to understand the role of interfacial chemistry on the modulation of Schottky barrier heights for platinum and amorphous indium gallium zinc oxide (a-IGZO) interfaces is demonstrated through thermal processing and background ambient pressure control. In situ X-ray photoelectron spectroscopy was used to characterize the interfacial chemistries that modulate barrier heights in this system. The primary changes were a significant chemical reduction of indium, from In 3+ to In 0 , that occurs during deposition of Pt on to the a-IGZO surface in ultrahigh vacuum. Postannealing and controlling the background ambient O 2 pressure allows further tuning of the reduction of indium and the corresponding Schottky barrier heights from 0.17 to 0.77 eV. Understanding the detailed interfacial chemistries at Pt/a-IGZO interfaces may allow for improved electronic device performance, including Schottky diodes, memristors, and metal-semiconductor field-effect transistors.

  19. 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

  20. Extending the applicability of the Arndt formula in wavelength modulation spectroscopy for absorbance in the lower percent range

    NASA Astrophysics Data System (ADS)

    Hartmann, A.; Strzoda, R.; Schrobenhauser, R.; Weigel, R.

    2014-01-01

    The Arndt formula for Lorentzian signals broadened by modulation is enhanced for the usage on 2f WMS (wavelength modulation spectroscopy) signals produced by spectroscopic lines with high absorption (percent range). Next to the first order approach of the Beer-Lambert law, which is covered by the Arndt formula, a second order term is included for a better approximation of the damped Lorentzian line shape. This second order approximation of the 2f signal can be described by a combination of several components created by the Arndt formula. The error of a pure Arndt evaluation and the improvement of the Arndt extended technique are illustrated in the example of a humidity measurement performed at 100 °C and up to 100 vol%. The energy transition at ν=10,526.274910 cm-1 is used in this setup. With the presented technique, the error is reduced by a factor of 90.

  1. APOLLO-SATURN (A/S)-204 - SPACECRAFT (S/C)- 012 COMMAND SERVICE MODULE (CSM) - A/S MATING - CAPE

    NASA Image and Video Library

    1967-01-03

    S67-15704 (3 Jan. 1967) --- Transfer of Apollo Spacecraft 012 Command/Service Module (CSM) for mating with the Saturn Lunar Module (LM) Adapter No.05 in the Manned Spacecraft Operations Building. Spacecraft 012 will be flown on the Apollo/Saturn 1 (204) mission. Photo credit: NASA

  2. Helium Evolution from the Transfer of Helium Saturated Propellant in Space

    NASA Technical Reports Server (NTRS)

    Nguyen, Bich N.

    2000-01-01

    Helium evolution from the transfer of helium saturated propellant in space is quantified to determine its impact from creating a two-phase mixture in the transfer line. The transfer line is approximately 1/2 inch in diameter and 2400 inches in length comprised of the Fluid Interconnect System (FICS), the Orbiter Propellant Transfer System (OPTS) and the International Space Station (ISS) Propulsion Module (ISSPM). The propellant transfer rate is approximately two to three gallons per minute, and the supply tank pressure is maintained at approximately 250 psig.

  3. Temperature modulation with an esophageal heat transfer device - a pediatric swine model study.

    PubMed

    Kulstad, Erik B; Naiman, Melissa; Shanley, Patrick; Garrett, Frank; Haryu, Todd; Waller, Donald; Azarafrooz, Farshid; Courtney, Daniel Mark

    2015-01-01

    An increasing number of conditions appear to benefit from control and modulation of temperature, but available techniques to control temperature often have limitations, particularly in smaller patients with high surface to mass ratios. We aimed to evaluate a new method of temperature modulation with an esophageal heat transfer device in a pediatric swine model, hypothesizing that clinically significant modulation in temperature (both increases and decreases of more than 1°C) would be possible. Three female Yorkshire swine averaging 23 kg were anesthetized with inhalational isoflurane prior to placement of the esophageal device, which was powered by a commercially available heat exchanger. Swine temperature was measured rectally and cooling and warming were performed by selecting the appropriate external heat exchanger mode. Temperature was recorded over time in order to calculate rates of temperature change. Histopathology of esophageal tissue was performed after study completion. Average swine baseline temperature was 38.3°C. Swine #1 exhibited a cooling rate of 3.5°C/hr; however, passive cooling may have contributed to this rate. External warming blankets maintained thermal equilibrium in swine #2 and #3, demonstrating maximum temperature decrease of 1.7°C/hr. Warming rates averaged 0.29°C/hr. Histopathologic analysis of esophageal tissue showed no adverse effects. An esophageal heat transfer device successfully modulated the temperature in a pediatric swine model. This approach to temperature modulation may offer a useful new modality to control temperature in conditions warranting temperature management (such as maintenance of normothermia, induction of hypothermia, fever control, or malignant hyperthermia).

  4. A pyrophosphate-responsive gadolinium(III) MRI contrast agent.

    PubMed

    Surman, Andrew J; Bonnet, Célia S; Lowe, Mark P; Kenny, Gavin D; Bell, Jimmy D; Tóth, Eva; Vilar, Ramon

    2011-01-03

    This study shows that the relaxivity and optical properties of functionalised lanthanide-DTPA-bis-amide complexes (lanthanide=Gd(3+) and Eu(3+) , DTPA=diethylene triamine pentaacetic acid) can be successfully modulated by addition of specific anions, without direct Ln(3+) /anion coordination. Zinc(II)-dipicolylamine moieties, which are known to bind strongly to phosphates, were introduced in the amide "arms" of these ligands, and the interaction of the resulting Gd-Zn(2) complexes with a range of anions was screened by using indicator displacement assays (IDAs). Considerable selectivity for polyphosphorylated species (such as pyrophosphate and adenosine-5'-triphosphate (ATP)) over a range of other anions (including monophosphorylated anions) was apparent. In addition, we show that pyrophosphate modulates the relaxivity of the gadolinium(III) complex, this modulation being sufficiently large to be observed in imaging experiments. To establish the binding mode of the pyrophosphate and gain insight into the origin of the relaxometric modulation, a series of studies including UV/Vis and emission spectroscopy, luminescence lifetime measurements in H(2) O and D(2) O, (17) O and (31) P NMR spectroscopy and nuclear magnetic resonance dispersion (NMRD) studies were carried out. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Precision saturated absorption spectroscopy of H3+

    NASA Astrophysics Data System (ADS)

    Guan, Yu-Chan; Chang, Yung-Hsiang; Liao, Yi-Chieh; Peng, Jin-Long; Wang, Li-Bang; Shy, Jow-Tsong

    2018-03-01

    In our previous work on the Lamb-dips of the ν2 fundamental band transitions of H3+, the saturated absorption spectrum was obtained by third-derivative spectroscopy using frequency modulation with an optical parametric oscillator (OPO). However, frequency modulation also caused errors in the absolute frequency determination. To solve this problem, we built a tunable offset locking system to lock the pump frequency of the OPO to an iodine-stabilized Nd:YAG laser. With this improvement, we were able to scan the OPO idler frequency precisely and obtain the saturated absorption profile using intensity modulation. Furthermore, ion concentration modulation was employed to subtract the background noise and increase the signal-to-noise ratio. To determine the absolute frequency of the idler wave, the OPO signal frequency was locked to an optical frequency comb. The absolute frequency accuracy of our spectrometer was better than 7 kHz, demonstrated by measuring the wavelength standard transition of methane at 3.39 μm. Finally, we measured 16 transitions of H3+ and our results agree very well with other precision measurements. This work successfully resolved the discrepancies between our previous measurements and other precision measurements.

  6. Coherent sources for mid-infrared laser spectroscopy

    NASA Astrophysics Data System (ADS)

    Honzátko, Pavel; Baravets, Yauhen; Mondal, Shyamal; Peterka, Pavel; Todorov, Filip

    2016-12-01

    Mid-infrared laser absorption spectroscopy (LAS) is useful for molecular trace gas concentration measurements in gas mixtures. While the gas chromatography-mass spectrometry is still the gold standard in gas analysis, LAS offers several advantages. It takes tens of minutes for a gas mixture to be separated in the capillary column precluding gas chromatography from real-time control of industrial processes, while LAS can measure the concentration of gas species in seconds. LAS can be used in a wide range of applications such as gas quality screening for regulation, metering and custody transfer,1 purging gas pipes to avoid explosions,1 monitoring combustion processes,2 detection and quantification of gas leaks,3 by-products monitoring to provide feedback for the real-time control of processes in petrochemical industry,4 real-time control of inductively coupled plasma etch reactors,5, 6 and medical diagnostics by means of time-resolved volatile organic compound (VOC) analysis in exhaled breath.7 Apart from the concentration, it also permits us to determine the temperature, pressure, velocity and mass flux of the gas under observation. The selectivity and sensitivity of LAS is linked to a very high spectral resolution given by the linewidth of single-frequency lasers. Measurements are performed at reduced pressure where the collisional and Doppler broadenings are balanced. The sensitivity can be increased to ppb and sometimes to ppt ranges by increasing the interaction length in multi-pass gas cells or resonators and also by adopting modulation techniques.8

  7. Cross mode modulation in multimode fibers.

    PubMed

    Kroushkov, Dimitar I; Rademacher, Georg; Petermann, Klaus

    2013-05-15

    We show that Kerr nonlinearity induced intermodal power transfer in a particular mode group of a multimode fiber can be formulated by the same type of equation used to describe the effect of cross polarization modulation in single-mode fibers.

  8. Application of surface analysis to solve problems of wear

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1981-01-01

    Results are presented for the use of surface analytical tools including field ion microscopy, Auger emission spectroscopy analysis (AES), cylindrical mirror Auger analysis and X-ray photoelectron spectroscopy (XPS). Data from the field ion microscope reveal adhesive transfer (wear) at the atomic level with the formation of surface compounds not found in the bulk, and AES reveals that this transfer will occur even in the presence of surface oxides. Both AES and XPS reveal that in abrasive wear with silicon carbide and diamond contacting the transition metals, the surface and the abrasive undergo a chemical or structural change which effects wear. With silicon carbide, silicon volatilizes leaving behind a pseudo-graphitic surface and the surface of diamond is observed to graphitize.

  9. Monitoring long-range electron transfer pathways in proteins by stimulated attosecond broadband X-ray Raman spectroscopy

    DOE PAGES

    Zhang, Yu; Biggs, Jason D.; Govind, Niranjan; ...

    2014-10-09

    In this study, long-range electron transfer (ET) plays a key role in many biological energy conversion and synthesis processes. We show that nonlinear spectroscopy with attosecond X-ray pulses provides a real time movie of the evolving oxidation states and electron densities around atoms, and can probe these processes with high spatial and temporal resolution. This is demonstrated in a simulation study of the stimulated X-ray Raman (SXRS) signals in Re-modified azurin, which had long served as a benchmark for long-range ET in proteins. Nonlinear SXRS signals are sensitive to the local electronic structure and should offer a novel window formore » long-range ET.« less

  10. Spatially Mapping Energy Transfer from Single Plasmonic Particles to Semiconductor Substrates via STEM/EELS.

    PubMed

    Li, Guoliang; Cherqui, Charles; Bigelow, Nicholas W; Duscher, Gerd; Straney, Patrick J; Millstone, Jill E; Masiello, David J; Camden, Jon P

    2015-05-13

    Energy transfer from plasmonic nanoparticles to semiconductors can expand the available spectrum of solar energy-harvesting devices. Here, we spatially and spectrally resolve the interaction between single Ag nanocubes with insulating and semiconducting substrates using electron energy-loss spectroscopy, electrodynamics simulations, and extended plasmon hybridization theory. Our results illustrate a new way to characterize plasmon-semiconductor energy transfer at the nanoscale and bear impact upon the design of next-generation solar energy-harvesting devices.

  11. Energy transfer dynamics in strongly inhomogeneous hot-dense-matter systems

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

    Stillman, C. R.; Nilson, P. M.; Sefkow, A. B.

    Direct measurements of energy transfer across steep density and temperature gradients in a hot-dense-matter system are presented. Hot dense plasma conditions were generated by high-intensity laser irradiation of a thin-foil target containing a buried metal layer. Energy transfer to the layer was measured using picosecond time-resolved x-ray emission spectroscopy. Here, the data show two x-ray flashes in time. Fully explicit, coupled particle-in-cell and collisional-radiative atomic kinetics model predictions reproduce these observations, connecting the two x-ray flashes with staged radial energy transfer within the target.

  12. Energy transfer dynamics in strongly inhomogeneous hot-dense-matter systems

    DOE PAGES

    Stillman, C. R.; Nilson, P. M.; Sefkow, A. B.; ...

    2018-06-25

    Direct measurements of energy transfer across steep density and temperature gradients in a hot-dense-matter system are presented. Hot dense plasma conditions were generated by high-intensity laser irradiation of a thin-foil target containing a buried metal layer. Energy transfer to the layer was measured using picosecond time-resolved x-ray emission spectroscopy. Here, the data show two x-ray flashes in time. Fully explicit, coupled particle-in-cell and collisional-radiative atomic kinetics model predictions reproduce these observations, connecting the two x-ray flashes with staged radial energy transfer within the target.

  13. Enhanced electron transfer kinetics through hybrid graphene-carbon nanotube films.

    PubMed

    Henry, Philémon A; Raut, Akshay S; Ubnoske, Stephen M; Parker, Charles B; Glass, Jeffrey T

    2014-11-01

    We report the first study of the electrochemical reactivity of a graphenated carbon nanotube (g-CNT) film. The electron transfer kinetics of the ferri-ferrocyanide couple were examined for a g-CNT film and compared to the kinetics to standard carbon nanotubes (CNTs). The g-CNT film exhibited much higher catalytic activity, with a heterogeneous electron-transfer rate constant, k 0 , approximately two orders of magnitude higher than for standard CNTs. Scanning electron microscopy and Raman spectroscopy were used to correlate the higher electron transfer kinetics with the higher edge-density of the g-CNT film.

  14. The Eighth International Symposium On Radiative Transfer

    NASA Astrophysics Data System (ADS)

    Lemonnier, Denis; Webb, Brent W.; Mengüç, M. Pınar

    2017-08-01

    This Special Issue of The Journal of Quantitative Spectroscopy and Radiative Transfer is based on the papers selected from RAD-16, the Eighth International Symposium on Radiative Transfer, which was held June 2016, in Cappadocia, Turkey. This Symposium is a follow-up of the seven previous meetings held in Kuşadası in 1995, 1997, and 2013; Antalya in 2001 and 2010; Istanbul in 2004; and Bodrum in 2007, all in Turkey. The Symposium was another enjoyable opportunity for the international radiation transfer community to assemble in a comfortable setting to present and discuss the state-of-the-art in research and application.

  15. Urban area change detection procedures with remote sensing data

    NASA Technical Reports Server (NTRS)

    Maxwell, E. L. (Principal Investigator); Riordan, C. J.

    1980-01-01

    The underlying factors affecting the detection and identification of nonurban to urban land cover change using satellite data were studied. Computer programs were developed to create a digital scene and to simulate the effect of the sensor point spread function (PSF) on the transfer of modulation from the scene to an image of the scene. The theory behind the development of a digital filter representing the PSF is given as well as an example of its application. Atmospheric effects on modulation transfer are also discussed. A user's guide and program listings are given.

  16. Forbidden atomic transitions driven by an intensity-modulated laser trap.

    PubMed

    Moore, Kaitlin R; Anderson, Sarah E; Raithel, Georg

    2015-01-20

    Spectroscopy is an essential tool in understanding and manipulating quantum systems, such as atoms and molecules. The model describing spectroscopy includes the multipole-field interaction, which leads to established spectroscopic selection rules, and an interaction that is quadratic in the field, which is not often employed. However, spectroscopy using the quadratic (ponderomotive) interaction promises two significant advantages over spectroscopy using the multipole-field interaction: flexible transition rules and vastly improved spatial addressability of the quantum system. Here we demonstrate ponderomotive spectroscopy by using optical-lattice-trapped Rydberg atoms, pulsating the lattice light and driving a microwave atomic transition that would otherwise be forbidden by established spectroscopic selection rules. This ability to measure frequencies of previously inaccessible transitions makes possible improved determinations of atomic characteristics and constants underlying physics. The spatial resolution of ponderomotive spectroscopy is orders of magnitude better than the transition frequency would suggest, promising single-site addressability in dense particle arrays for quantum computing applications.

  17. Activation Thermodynamics and H/D Kinetic Isotope Effect of the Hox to HredH+ Transition in [FeFe] Hydrogenase.

    PubMed

    Ratzloff, Michael W; Wilker, Molly B; Mulder, David W; Lubner, Carolyn E; Hamby, Hayden; Brown, Katherine A; Dukovic, Gordana; King, Paul W

    2017-09-20

    Molecular complexes between CdSe nanocrystals and Clostridium acetobutylicum [FeFe] hydrogenase I (CaI) enabled light-driven control of electron transfer for spectroscopic detection of redox intermediates during catalytic proton reduction. Here we address the route of electron transfer from CdSe→CaI and activation thermodynamics of the initial step of proton reduction in CaI. The electron paramagnetic spectroscopy of illuminated CdSe:CaI showed how the CaI accessory FeS cluster chain (F-clusters) functions in electron transfer with CdSe. The H ox →H red H + reduction step measured by Fourier-transform infrared spectroscopy showed an enthalpy of activation of 19 kJ mol -1 and a ∼2.5-fold kinetic isotope effect. Overall, these results support electron injection from CdSe into CaI involving F-clusters, and that the H ox →H red H + step of catalytic proton reduction in CaI proceeds by a proton-dependent process.

  18. Charge Transfer Dynamics at Dye-Sensitized ZnO and TiO2 Interfaces Studied by Ultrafast XUV Photoelectron Spectroscopy

    PubMed Central

    Borgwardt, Mario; Wilke, Martin; Kampen, Thorsten; Mähl, Sven; Xiao, Manda; Spiccia, Leone; Lange, Kathrin M.; Kiyan, Igor Yu.; Aziz, Emad F.

    2016-01-01

    Interfacial charge transfer from photoexcited ruthenium-based N3 dye molecules into ZnO thin films received controversial interpretations. To identify the physical origin for the delayed electron transfer in ZnO compared to TiO2, we probe directly the electronic structure at both dye-semiconductor interfaces by applying ultrafast XUV photoemission spectroscopy. In the range of pump-probe time delays between 0.5 to 1.0 ps, the transient signal of the intermediate states was compared, revealing a distinct difference in their electron binding energies of 0.4 eV. This finding strongly indicates the nature of the charge injection at the ZnO interface associated with the formation of an interfacial electron-cation complex. It further highlights that the energetic alignment between the dye donor and semiconductor acceptor states appears to be of minor importance for the injection kinetics and that the injection efficiency is dominated by the electronic coupling. PMID:27073060

  19. Preparation and Structural Studies on Hybrid Core-Shell Nanoparticles Consisting of Silica Core and Conjugated Block Copolymer Shell Prepared by Surface-Initiated Polymerization

    NASA Astrophysics Data System (ADS)

    Chatterjee, Sourav; Karam, Tony; Rosu, Cornelia; Li, Xin; Do, Changwoo; Youm, Sang Gil; Haber, Louis; Russo, Paul; Nesterov, Evgueni

    Controlled Kumada catalyst-transfer polymerization occurring by chain-growth mechanism was developed for the synthesis of conjugated polymers and block copolymers from the surface of inorganic substrates such as silica nanoparticles. Although synthesis of conjugated polymers via Kumada polymerization became an established method for solution polymerization, carrying out the same reaction in heterogeneous conditions to form monodisperse polymer chains still remains a challenge. We developed and described a simple and efficient approach to the preparation of surface-immobilized layer of catalytic Ni(II) initiator, and demonstrated using it to prepare polymers and block copolymers on silica nanoparticle. The structure of the resulting hybrid nanostructures was thoroughly studied using small-angle neutron and X-ray scattering, thermal analysis, and optical spectroscopy. The photoexcitation energy transfer processes in the conjugated polymer shell were studied via steady-state and time resolved transient absorption spectroscopy. This study uncovered important details of the energy transfer, which will be discussed in this presentation.

  20. Coherence and population dynamics of chlorophyll excitations in FCP complex: Two-dimensional spectroscopy study

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

    Butkus, Vytautas; Gelzinis, Andrius; Valkunas, Leonas

    2015-06-07

    Energy transfer processes and coherent phenomena in the fucoxanthin–chlorophyll protein complex, which is responsible for the light harvesting function in marine algae diatoms, were investigated at 77 K by using two-dimensional electronic spectroscopy. Experiments performed on femtosecond and picosecond timescales led to separation of spectral dynamics, witnessing evolutions of coherence and population states of the system in the spectral region of Q{sub y} transitions of chlorophylls a and c. Analysis of the coherence dynamics allowed us to identify chlorophyll (Chl) a and fucoxanthin intramolecular vibrations dominating over the first few picoseconds. Closer inspection of the spectral region of the Q{submore » y} transition of Chl c revealed previously not identified, mutually non-interacting chlorophyll c states participating in femtosecond or picosecond energy transfer to the Chl a molecules. Consideration of separated coherent and incoherent dynamics allowed us to hypothesize the vibrations-assisted coherent energy transfer between Chl c and Chl a and the overall spatial arrangement of chlorophyll molecules.« less

  1. Analysis of calibration-free wavelength-scanned wavelength modulation spectroscopy for practical gas sensing using tunable diode lasers

    NASA Astrophysics Data System (ADS)

    Sun, K.; Chao, X.; Sur, R.; Goldenstein, C. S.; Jeffries, J. B.; Hanson, R. K.

    2013-12-01

    A novel strategy has been developed for analysis of wavelength-scanned, wavelength modulation spectroscopy (WMS) with tunable diode lasers (TDLs). The method simulates WMS signals to compare with measurements to determine gas properties (e.g., temperature, pressure and concentration of the absorbing species). Injection-current-tuned TDLs have simultaneous wavelength and intensity variation, which severely complicates the Fourier expansion of the simulated WMS signal into harmonics of the modulation frequency (fm). The new method differs from previous WMS analysis strategies in two significant ways: (1) the measured laser intensity is used to simulate the transmitted laser intensity and (2) digital lock-in and low-pass filter software is used to expand both simulated and measured transmitted laser intensities into harmonics of the modulation frequency, WMS-nfm (n = 1, 2, 3,…), avoiding the need for an analytic model of intensity modulation or Fourier expansion of the simulated WMS harmonics. This analysis scheme is valid at any optical depth, modulation index, and at all values of scanned-laser wavelength. The method is demonstrated and validated with WMS of H2O dilute in air (1 atm, 296 K, near 1392 nm). WMS-nfm harmonics for n = 1 to 6 are extracted and the simulation and measurements are found in good agreement for the entire WMS lineshape. The use of 1f-normalization strategies to realize calibration-free wavelength-scanned WMS is also discussed.

  2. Microresonator soliton dual-comb spectroscopy

    NASA Astrophysics Data System (ADS)

    Suh, Myoung-Gyun; Yang, Qi-Fan; Yang, Ki Youl; Yi, Xu; Vahala, Kerry J.

    2016-11-01

    Measurement of optical and vibrational spectra with high resolution provides a way to identify chemical species in cluttered environments and is of general importance in many fields. Dual-comb spectroscopy has emerged as a powerful approach for acquiring nearly instantaneous Raman and optical spectra with unprecedented resolution. Spectra are generated directly in the electrical domain, without the need for bulky mechanical spectrometers. We demonstrate a miniature soliton-based dual-comb system that can potentially transfer the approach to a chip platform. These devices achieve high-coherence pulsed mode locking. They also feature broad, reproducible spectral envelopes, an essential feature for dual-comb spectroscopy. Our work shows the potential for integrated spectroscopy with high signal-to-noise ratios and fast acquisition rates.

  3. Atmospheric pressure reaction cell for operando sum frequency generation spectroscopy of ultrahigh vacuum grown model catalysts

    NASA Astrophysics Data System (ADS)

    Roiaz, Matteo; Pramhaas, Verena; Li, Xia; Rameshan, Christoph; Rupprechter, Günther

    2018-04-01

    A new custom-designed ultrahigh vacuum (UHV) chamber coupled to a UHV and atmospheric-pressure-compatible spectroscopic and catalytic reaction cell is described, which allows us to perform IR-vis sum frequency generation (SFG) vibrational spectroscopy during catalytic (kinetic) measurements. SFG spectroscopy is an exceptional tool to study vibrational properties of surface adsorbates under operando conditions, close to those of technical catalysis. This versatile setup allows performing surface science, SFG spectroscopy, catalysis, and electrochemical investigations on model systems, including single crystals, thin films, and deposited metal nanoparticles, under well-controlled conditions of gas composition, pressure, temperature, and potential. The UHV chamber enables us to prepare the model catalysts and to analyze their surface structure and composition by low energy electron diffraction and Auger electron spectroscopy, respectively. Thereafter, a sample transfer mechanism moves samples under UHV to the spectroscopic cell, avoiding air exposure. In the catalytic cell, SFG spectroscopy and catalytic tests (reactant/product analysis by mass spectrometry or gas chromatography) are performed simultaneously. A dedicated sample manipulation stage allows the model catalysts to be examined from LN2 temperature to 1273 K, with gaseous reactants in a pressure range from UHV to atmospheric. For post-reaction analysis, the SFG cell is rapidly evacuated and samples are transferred back to the UHV chamber. The capabilities of this new setup are demonstrated by benchmark results of CO adsorption on Pt and Pd(111) single crystal surfaces and of CO adsorption and oxidation on a ZrO2 supported Pt nanoparticle model catalyst grown by atomic layer deposition.

  4. Low-Temperature Ozone Exposure Technique to Modulate the Stoichiometry of WO(x) Nanorods and Optimize the Electrochromic Performance

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

    Lin, F.; Li, C. P.; Chen, G.

    A low-temperature ozone exposure technique was employed for the post-treatment of WO{sub x} nanorod thin films fabricated from hot-wire chemical vapor deposition (HWCVD) and ultrasonic spray deposition (USD) techniques. The resulting films were characterized with x-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, UV-vis-NIR spectroscopy and x-ray photoelectron spectroscopy (XPS). The stoichiometry and surface crystallinity of the WO{sub x} thin films were subsequently modulated upon ozone exposure and thermal annealing without particle growth. The electrochromic performance was studied in a LiClO{sub 4}-propylene carbonate electrolyte, and the results suggest that the low-temperature ozone exposure technique is superior to the traditionalmore » high-temperature thermal annealing (employed to more fully oxidize the WO{sub x}). The optical modulation at 670 nm was improved from 35% for the as-deposited film to 57% for the film after ozone exposure at 150 C. The coloration efficiency was improved and the switching speed to the darkened state was significantly accelerated from 18.0 s for the as-deposited film to 11.8 s for the film after the ozone exposure. The process opens an avenue for low-temperature and cost-effective manufacturing of electrochromic films, especially on flexible polymer substrates.« less

  5. Monitoring of catalyst performance in CO2 lasers using frequency modulation spectroscopy with diode lasers

    NASA Technical Reports Server (NTRS)

    Wang, Liang-Guo; Sachse, Glen

    1990-01-01

    Closed-cycle CO2 laser operation with removal of O2 and regeneration of CO2 can be achieved by catalytic CO-O2 recombination. Both parametric studies of the optimum catalyst formulation and long-term performance tests require on line monitoring of CO, O2 and CO2 concentrations. There are several existing methods for molecular oxygen detection. These methods are either intrusive (such as electrochemical method or mass spectrometry) or very expensive (such as CARS, UV laser absorption). Researchers demonstrated a high-sensitivity spectroscopic measurement of O2 using the two-tone frequency modulation spectroscopy (FMS) technique with a near infrared GaAlAs diode laser. Besides its inexpensive cost, fast response time, nonintrusive measurements and high sensitivity, this technique may also be used to differentiate between isotopes due to its high spectroscopic resolution. This frequency modulation spectroscopy technique could also be applied for the on-line monitoring of CO and CO2 using InGaAsP diode lasers operation in the 1.55 microns region and H2O in the 1.3 microns region. The existence of single mode optical fibers at the near infrared region makes it possible to combine FMS with optical fiber technology. Optical fiber FMS is particularly suitable for making point-measurements at one or more locations in the CO2 laser/catalyst system.

  6. Proton transfer events in GFP.

    PubMed

    Di Donato, Mariangela; van Wilderen, Luuk J G W; Van Stokkum, Ivo H M; Stuart, Thomas Cohen; Kennis, John T M; Hellingwerf, Klaas J; van Grondelle, Rienk; Groot, Marie Louise

    2011-09-28

    Proton transfer is one of the most important elementary processes in biology. Green fluorescent protein (GFP) serves as an important model system to elucidate the mechanistic details of this reaction, because in GFP proton transfer can be induced by light absorption. Illumination initiates proton transfer through a 'proton-wire', formed by the chromophore (the proton donor), water molecule W22, Ser205 and Glu222 (the acceptor), on a picosecond time scale. To obtain a more refined view of this process, we have used a combined approach of time resolved mid-infrared spectroscopy and visible pump-dump-probe spectroscopy to resolve with atomic resolution how and how fast protons move through this wire. Our results indicate that absorption of light by GFP induces in 3 ps (10 ps in D(2)O) a shift of the equilibrium positions of all protons in the H-bonded network, leading to a partial protonation of Glu222 and to a so-called low barrier hydrogen bond (LBHB) for the chromophore's proton, giving rise to dual emission at 475 and 508 nm. This state is followed by a repositioning of the protons on the wire in 10 ps (80 ps in D(2)O), ultimately forming the fully deprotonated chromophore and protonated Glu222.

  7. Electronic structures of 1-ML C84/Ag(111): Energy level alignment and work function variation

    NASA Astrophysics Data System (ADS)

    Wang, Peng; Zhao, Li-Li; Zhang, Jin-Juan; Li, Wen-Jie; Liu, Wei-Hui; Chen, Da; Sheng, Chun-Qi; Wang, Jia-Ou; Qian, Hai-Jie; Ibrahim, Kurash; Li, Hong-Nian

    2017-12-01

    The electronic structures of fullerene/metal interface are critical to the performance of devices based on fullerene in molecular electronics and organic electronics. Herein, we investigate the electronic structures at the interface between C84 and Ag(111) by photoelectron spectroscopy and soft X-ray absorption spectroscopy techniques. It is observed that C84 monolayer on Ag(111) surface (1-ML C84/Ag(111)) has metallic nature. A charge transfer from substrate to the unoccupied states of C84 is determined to be 1.3 electrons per molecule. However, the work function of 1-ML C84 (4.72 eV) is observed slightly larger than that of the clean Ag(111) substrate (4.50 eV). A bidirectional charge transfer model is introduced to understand the work function variation of the fullerene/metal system. In addition to the charge transfer from substrate to the adsorbate's unoccupied states, there exists non-negligible back charge transfer from fullerene occupied molecular orbital to the metal substrate through interfacial hybridization. The Fermi level will be pinned at ∼4.72 eV for C84 monolayer on coinage metal substrate.

  8. Shifts of Gamma Phase across Primary Visual Cortical Sites Reflect Dynamic Stimulus-Modulated Information Transfer.

    PubMed

    Besserve, Michel; Lowe, Scott C; Logothetis, Nikos K; Schölkopf, Bernhard; Panzeri, Stefano

    2015-01-01

    Distributed neural processing likely entails the capability of networks to reconfigure dynamically the directionality and strength of their functional connections. Yet, the neural mechanisms that may allow such dynamic routing of the information flow are not yet fully understood. We investigated the role of gamma band (50-80 Hz) oscillations in transient modulations of communication among neural populations by using measures of direction-specific causal information transfer. We found that the local phase of gamma-band rhythmic activity exerted a stimulus-modulated and spatially-asymmetric directed effect on the firing rate of spatially separated populations within the primary visual cortex. The relationships between gamma phases at different sites (phase shifts) could be described as a stimulus-modulated gamma-band wave propagating along the spatial directions with the largest information transfer. We observed transient stimulus-related changes in the spatial configuration of phases (compatible with changes in direction of gamma wave propagation) accompanied by a relative increase of the amount of information flowing along the instantaneous direction of the gamma wave. These effects were specific to the gamma-band and suggest that the time-varying relationships between gamma phases at different locations mark, and possibly causally mediate, the dynamic reconfiguration of functional connections.

  9. Shifts of Gamma Phase across Primary Visual Cortical Sites Reflect Dynamic Stimulus-Modulated Information Transfer

    PubMed Central

    Besserve, Michel; Lowe, Scott C.; Logothetis, Nikos K.; Schölkopf, Bernhard; Panzeri, Stefano

    2015-01-01

    Distributed neural processing likely entails the capability of networks to reconfigure dynamically the directionality and strength of their functional connections. Yet, the neural mechanisms that may allow such dynamic routing of the information flow are not yet fully understood. We investigated the role of gamma band (50–80 Hz) oscillations in transient modulations of communication among neural populations by using measures of direction-specific causal information transfer. We found that the local phase of gamma-band rhythmic activity exerted a stimulus-modulated and spatially-asymmetric directed effect on the firing rate of spatially separated populations within the primary visual cortex. The relationships between gamma phases at different sites (phase shifts) could be described as a stimulus-modulated gamma-band wave propagating along the spatial directions with the largest information transfer. We observed transient stimulus-related changes in the spatial configuration of phases (compatible with changes in direction of gamma wave propagation) accompanied by a relative increase of the amount of information flowing along the instantaneous direction of the gamma wave. These effects were specific to the gamma-band and suggest that the time-varying relationships between gamma phases at different locations mark, and possibly causally mediate, the dynamic reconfiguration of functional connections. PMID:26394205

  10. Development and Assessment of Modules to Integrate Quantitative Skills in Introductory Biology Courses

    PubMed Central

    Hoffman, Kathleen; Leupen, Sarah; Dowell, Kathy; Kephart, Kerrie; Leips, Jeff

    2016-01-01

    Redesigning undergraduate biology courses to integrate quantitative reasoning and skill development is critical to prepare students for careers in modern medicine and scientific research. In this paper, we report on the development, implementation, and assessment of stand-alone modules that integrate quantitative reasoning into introductory biology courses. Modules are designed to improve skills in quantitative numeracy, interpreting data sets using visual tools, and making inferences about biological phenomena using mathematical/statistical models. We also examine demographic/background data that predict student improvement in these skills through exposure to these modules. We carried out pre/postassessment tests across four semesters and used student interviews in one semester to examine how students at different levels approached quantitative problems. We found that students improved in all skills in most semesters, although there was variation in the degree of improvement among skills from semester to semester. One demographic variable, transfer status, stood out as a major predictor of the degree to which students improved (transfer students achieved much lower gains every semester, despite the fact that pretest scores in each focus area were similar between transfer and nontransfer students). We propose that increased exposure to quantitative skill development in biology courses is effective at building competency in quantitative reasoning. PMID:27146161

  11. Cavity-Enhanced Spectroscopy of Molecular Ions in the Mid-Infrared with Up-Conversion Detection and Brewster-Plate Spoilers

    NASA Astrophysics Data System (ADS)

    Markus, Charles R.; McCollum, Jefferson E.; Hodges, James Neil; Perry, Adam J.; McCall, Benjamin J.

    2017-06-01

    Molecular ions are challenging to study with conventional spectroscopic methods. Laboratory discharges produce ions in trace quantities which can be obscured by the abundant neutral molecules present. The technique Noise Immune Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy (NICE-OHVMS) overcomes these challenges by combining the ion-neutral discrimination of velocity modulation spectroscopy with the sensitivity of Noise-Immune Cavity-Enhanced Optical Heterodyne Molecular Spectroscopy (NICE-OHMS), and has been able to determine transition frequencies of molecular ions in the mid-infrared (mid-IR) with sub-MHz uncertainties when calibrated with an optical frequency comb. However, the extent of these studies was limited by the presence of fringes due to parasitic etalons and the speed and noise characteristics of mid-IR detectors. Recently, we have overcome these limitations by implementing up-conversion detection and dithered optics. We performed up-conversion using periodically poled lithium niobate to convert light from the mid-IR to the visible to be within the coverage of sensitive and fast silicon detectors while maintaining our heterodyne and velocity modulation signals. The parasitic etalons were removed by rapidly rotating CaF_2 windows with galvanometers, which is known as a Brewster-plate spoiler, which averaged out the fringes in detection. Together, these improved the sensitivity by more than an order of magnitude and have enabled extended spectroscopic surveys of molecular ions in the mid-IR. J. N. Hodges, A. J. Perry, P. A. Jenkins II, B. M. Siller, and B. J. McCall, J. Chem. Phys. (2013), 139, 164201. C. R. Webster, J. Opt. Soc. Am. B (1985), 2, 1464. C. R. Markus, A. J. Perry, J. N. Hodges, and B. J. McCall, Opt. Express (2017), 25, 3709-3721.

  12. X-ray spectroscopy studies of nonradiative energy transfer processes in luminescent lanthanide materials

    NASA Astrophysics Data System (ADS)

    Pacold, Joseph I.

    Luminescent materials play important roles in energy sciences, through solid state lighting and possible applications in solar energy utilization, and in biomedical research and applications, such as in immunoassays and fluorescence microscopy. The initial excitation of a luminescent material leads to a sequence of transitions between excited states, ideally ending with the emission of one or more optical-wavelength photons. It is essential to understand the microscopic physics of this excited state cascade in order to rationally design materials with high quantum efficiencies or with other fine-tuning of materials response. While optical-wavelength spectroscopies have unraveled many details of the energy transfer pathways in luminescent materials, significant questions remain open for many lanthanide-based luminescent materials. For organometallic dyes in particular, quantum yields remain limited in comparison with inorganic phosphors. This dissertation reports on a research program of synchrotron x-ray studies of the excited state electronic structure and energy-relaxation cascade in trivalent lanthanide phosphors and dyes. To this end, one of the primary results presented here is the first time-resolved x-ray absorption near edge spectroscopy studies of the transient 4f excited states in lanthanide-activated luminescent dyes and phosphors. This is a new application of time-resolved x-ray absorption spectroscopy that makes it possible to directly observe and, to some extent, quantify intramolecular nonradiative energy transfer processes. We find a transient increase in 4f spectral weight associated with an excited state confined to the 4f shell of trivalent Eu. This result implies that it is necessary to revise the current theoretical understanding of 4f excitation in trivalent lanthanide activators: either transient 4f-5d mixing effects are much stronger than previously considered, or else the lanthanide 4f excited state has an unexpectedly large contribution having a strong charge-transfer character. A second primary result comes from an an x-ray excited optical luminescence (XEOL) study that demonstrates, for the first time, that the high flux of modern synchrotron light sources can induce high fractional populations of excited states in trivalent lanthanide phosphors. In this work we have identified the leading-order nonlinear-response mechanism by drawing on strong similarities between XEOL and cathodoluminescence. These results establish the groundwork for studies that would allow deeper inquiry into energy-transfer mechanisms through time-resolved x-ray pump/optical-probe spectroscopies, through time-resolved x-ray emission spectroscopy, or through quantifying of higher-order nonlinear effects at further-enhanced fractional excitation levels. The above scientific results are augmented by a supporting effort in instrumental methodology. This includes the development of high-efficiency x-ray emission spectrometers and their use in collaborations to study pressure-induced changes in f-electron physics and to characterize the intermediate states that occur after photoexcitation of the photosystem-II protein.

  13. In-line thermoelectric module

    DOEpatents

    Pento, Robert; Marks, James E.; Staffanson, Clifford D.

    2000-01-01

    A thermoelectric module with a plurality of electricity generating units each having a first end and a second end, the units being arranged first end to second end along an in-line axis. Each unit includes first and second elements each made of a thermoelectric material, an electrically conductive hot member arranged to heat one side of the first element, and an electrically conductive cold member arranged to cool another side of the first element and to cool one side of the second element. The hot member, the first element, the cold member and the second element are supported in a fixture, are electrically connected respectively to provide an electricity generating unit, and are arranged respectively in positions along the in-line axis. The individual components of each generating unit and the respective generating units are clamped in their in-line positions by a loading bolt at one end of the fixture and a stop wall at the other end of the fixture. The hot members may have a T-shape and the cold members an hourglass shape to facilitate heat transfer. The direction of heat transfer through the hot members may be perpendicular to the direction of heat transfer through the cold members, and both of these heat transfer directions may be perpendicular to the direction of current flow through the module.

  14. Design of a fast crew transfer vehicle to Mars

    NASA Technical Reports Server (NTRS)

    1988-01-01

    A final report is made on the trajectory and vehicle requirements for a fast crew transfer vehicle to Mars which will complete an Earth to Mars (and Mars to Earth) transfer in 150 days and will have a stay time at Mars of 40 days. This vehicle will maximize the crew's effectiveness on Mars by minimizing detrimental physiological effects such as bone demineralization and loss of muscle tone caused by long period exposure to zero gravity and radiation from cosmic rays and solar flares. The crew transfer vehicle discussed will complete the second half of a Split Mission to Mars. In the Split Mission, a slow, unmanned cargo vehicle, nicknamed the Barge, is sent to Mars ahead of the crew vehicle. Once the Barge is in orbit around Mars, the fast crew vehicle will be launched to rendezvous with the Barge in Mars orbit. The vehicle presented is designed to carry six astronauts for a mission duration of one year. The vehicle uses a chemical propulsion system and a nuclear power system. Four crew modules, similar to the proposed Space Station Common Modules, are used to house the crew and support equipment during the mission. The final design also includes a command module that is shielded to protect the crew during radiation events.

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

    Utschig, L. M.; Poluektov, O.; Schlesselman, S. L.

    The interaction of metal ions with isolated photosynthetic reaction centers (RCs) from the purple bacteria Rhodobacter sphaeroides, Rhodobacter capsulatus, and Rhodopseudomonas viridis has been investigated with transient optical and magnetic resonance techniques. In RCs from all species, the electrochromic response of the bacteriopheophytin cofactors associated with Q{sub A}{sup -}Q{sub B} {yields} Q{sub A}Q{sub B}{sup -} electron transfer is slowed in the presence of Cu{sup 2+}. This slowing is similar to the metal ion effect observed for RCs from Rb. sphaeroides where Zn{sup 2+} was bound to a specific site on the surface of the RC [Utschig et al. (1998) Biochemistrymore » 37, 8278]. The coordination environments of the Cu{sup 2+} sites were probed with electron paramagnetic resonance (EPR) spectroscopy, providing the first direct spectroscopic evidence for the existence of a second metal site in RCs from Rb. capsulatus and Rps. viridis. In the dark, RCs with Cu{sup 2+} bound to the surface exhibit axially symmetric EPR spectra. Electron spin echo envelope modulation (ESEEM) spectral results indicate multiple weakly hyperfine coupled {sup 14}N nuclei in close proximity to Cu{sup 2+}. These ESEEM spectra resemble those observed for Cu{sup 2+} RCs from Rb. sphaeroides [Utschig et al. (2000) Biochemistry 39, 2961] and indicate that two or more histidines ligate the Cu{sup 2+} at the surface site in each RC. Thus, RCs from Rb. sphaeroides, Rb. capsulatus, and Rps. viridis each have a structurally analogous Cu{sup 2+} binding site that is involved in modulating the Q{sub A}{sup -}Q{sub B} {yields} Q{sub A}Q{sub B}{sup -} electron-transfer process. Inspection of the Rps. viridis crystal structure reveals four potential histidine ligands from three different subunits (M16, H178, H72, and L211) located beneath the Q{sub B} binding pocket. The location of these histidines is surprisingly similar to the grouping of four histidine residues (H68, H126, H128, and L211) observed in the Rb. sphaeroides RC crystal structure. Further elucidation of these Cu{sup 2+} sites will provide a means to investigate localized proton entry into the RCs of Rb. capsulatus and Rps. viridis as well as locate a site of protein motions coupled with electron transfer.« less

  16. Stand-alone polarization-modulation infrared reflection absorption spectroscopy instrument optimized for the study of catalytic processes at elevated pressures

    DOE PAGES

    Kestell, John D.; Mudiyanselage, Kumudu; Ye, Xinyi; ...

    2017-10-01

    This article describes the design and construction of a compact, “user-friendly” polarization-modulation infrared reflection absorption spectroscopy (PM-IRRAS) instrument at the Center for Functional Nanomaterials (CFN) of Brookhaven National Laboratory, which allows studying surfaces at pressures ranging from ultra-high vacuum to 100 Torr. Surface infrared spectroscopy is ideally suited for studying these processes as the vibrational frequencies of the IR chromophores are sensitive to the nature of the bonding environment on the surface. Relying on the surface selection rules, by modulating the polarization of incident light, it is possible to separate the contributions from the isotropic gas or solution phase, frommore » the surface bound species. A spectral frequency range between 1000 cm -1 and 4000 cm -1 can be acquired. While typical spectra with a good signal to noise ratio can be obtained at elevated pressures of gases in ~2 min at 4 cm -1 resolution, we have also acquired higher resolution spectra at 0.25 cm -1 with longer acquisition times. By way of verification, CO uptake on a heavily oxidized Ru(0001) sample was studied. As part of this test study, the presence of CO adsorbed on Ru bridge sites was confirmed, in agreement with previous ambient pressure X ray photoelectron spectroscopy studies. In terms of instrument performance, it was also determined that the gas phase contribution from CO could be completely removed even up to pressures close to 100 Torr. A second test study demonstrated the use of the technique for studying morphological properties of a spin coated polymer on a conductive surface. Note that this is a novel application of this technique. In this experiment, the polarization of incident light was modulated manually (vs. through a photoelastic modulator). It was demonstrated, in good agreement with the literature, that the polymer chains preferentially lie parallel with the surface. This PM-IRRAS system is small, modular, and easily reconfigurable. It also features a “vacuum suitcase” that allows for the integration of the PM-IRRAS system with the rest of the suite of instrumentation at our laboratory available to external users through the CFN user proposal system.« less

  17. Stand-alone polarization-modulation infrared reflection absorption spectroscopy instrument optimized for the study of catalytic processes at elevated pressures

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

    Kestell, John D.; Mudiyanselage, Kumudu; Ye, Xinyi

    This article describes the design and construction of a compact, “user-friendly” polarization-modulation infrared reflection absorption spectroscopy (PM-IRRAS) instrument at the Center for Functional Nanomaterials (CFN) of Brookhaven National Laboratory, which allows studying surfaces at pressures ranging from ultra-high vacuum to 100 Torr. Surface infrared spectroscopy is ideally suited for studying these processes as the vibrational frequencies of the IR chromophores are sensitive to the nature of the bonding environment on the surface. Relying on the surface selection rules, by modulating the polarization of incident light, it is possible to separate the contributions from the isotropic gas or solution phase, frommore » the surface bound species. A spectral frequency range between 1000 cm -1 and 4000 cm -1 can be acquired. While typical spectra with a good signal to noise ratio can be obtained at elevated pressures of gases in ~2 min at 4 cm -1 resolution, we have also acquired higher resolution spectra at 0.25 cm -1 with longer acquisition times. By way of verification, CO uptake on a heavily oxidized Ru(0001) sample was studied. As part of this test study, the presence of CO adsorbed on Ru bridge sites was confirmed, in agreement with previous ambient pressure X ray photoelectron spectroscopy studies. In terms of instrument performance, it was also determined that the gas phase contribution from CO could be completely removed even up to pressures close to 100 Torr. A second test study demonstrated the use of the technique for studying morphological properties of a spin coated polymer on a conductive surface. Note that this is a novel application of this technique. In this experiment, the polarization of incident light was modulated manually (vs. through a photoelastic modulator). It was demonstrated, in good agreement with the literature, that the polymer chains preferentially lie parallel with the surface. This PM-IRRAS system is small, modular, and easily reconfigurable. It also features a “vacuum suitcase” that allows for the integration of the PM-IRRAS system with the rest of the suite of instrumentation at our laboratory available to external users through the CFN user proposal system.« less

  18. ATV ops

    NASA Image and Video Library

    2013-06-18

    ISS036-E-009184 (18 June 2013) --- Russian cosmonaut Pavel Vinogradov, Expedition 36 commander, opens the hatch in the Zvezda Service Module transfer tunnel/ATV vestibule of the International Space Station after European Space Agency's Automated Transfer Vehicle-4 (ATV-4) "Albert Einstein" docked with the station.

  19. MEMBRANE BIOTREATMENT OF VOC-LADEN AIR

    EPA Science Inventory

    The paper discusses membrane biotreatment of air laden with volatile organic compounds (VOCs). Microporous flat-sheet and hollow-fiber membrane contactors were used to support air-liquid mass transfer interfaces. These modules were used in a two-step process to transfer VOCs fr...

  20. Polyamines: naturally occurring small molecule modulators of electrostatic protein-protein interactions.

    PubMed

    Berwanger, Anja; Eyrisch, Susanne; Schuster, Inge; Helms, Volkhard; Bernhardt, Rita

    2010-02-01

    Modulations of protein-protein interactions are a key step in regulating protein function, especially in networks. Modulators of these interactions are supposed to be candidates for the development of novel drugs. Here, we describe the role of the small, polycationic and highly abundant natural polyamines that could efficiently bind to charged spots at protein interfaces as modulators of such protein-protein interactions. Using the mitochondrial cytochrome P45011A1 (CYP11A1) electron transfer system as a model, we have analyzed the capability of putrescine, spermidine, and spermine at physiologically relevant concentrations to affect the protein-protein interactions between adrenodoxin reductase (AdR), adrenodoxin (Adx), and CYP11A1. The actions of polyamines on the individual components, on their association/dissociation, on electron transfer, and on substrate conversion were examined. These studies revealed modulating effects of polyamines on distinct interactions and on the entire system in a complex way. Modulation via changed protein-protein interactions appeared plausible from docking experiments that suggested favourable high-affinity binding sites of polyamines (spermine>spermidine>putrescine) at the AdR-Adx interface. Our findings imply for the first time that small endogenous compounds are capable of interfering with distinct components of transient protein complexes and might control protein functions by modulating electrostatic protein-protein interactions.

  1. Electro-optic modulator with ultra-low residual amplitude modulation for frequency modulation and laser stabilization.

    PubMed

    Tai, Zhaoyang; Yan, Lulu; Zhang, Yanyan; Zhang, Xiaofei; Guo, Wenge; Zhang, Shougang; Jiang, Haifeng

    2016-12-01

    The reduction of the residual amplitude modulation (RAM) induced by electro-optic modulation is essential for many applications of frequency modulation spectroscopy requiring a lower system noise floor. Here, we demonstrate a simple passive approach employing an electro-optic modulator (EOM) cut at Brewster's angle. The proposed EOM exhibits a RAM of a few parts per million, which is comparable with that achieved by a common EOM under critical active temperature and bias voltage controls. The frequency instability of a 10 cm cavity-stabilized laser induced by the RAM effect of the proposed EOM is below 3×10-17 for integration times from 1 to 1000 s, and below 4×10-16 for comprehensive noise contributions for integration times from 1 to 100 s.

  2. Optical Detection and Spectroscopy of Single Molecules in a Solid.

    DTIC Science & Technology

    1989-03-23

    the optical absorption spectrum of single dopant molecules of pentacene in a p-terphenyl host crystal at liquid-helium temperatures. To achieve this...dopant molecules of pentacene in a p-terphenyl host crystal at liquid-helium temperatures. To achieve this, frequency-modulation spectroscopy was combined...solid would provide an important new tool for the study of local absorber-host interactions that would be uncomplicated by the normal averaging over

  3. Coherent cavity-enhanced dual-comb spectroscopy.

    PubMed

    Fleisher, Adam J; Long, David A; Reed, Zachary D; Hodges, Joseph T; Plusquellic, David F

    2016-05-16

    Dual-comb spectroscopy allows for the rapid, multiplexed acquisition of high-resolution spectra without the need for moving parts or low-resolution dispersive optics. This method of broadband spectroscopy is most often accomplished via tight phase locking of two mode-locked lasers or via sophisticated signal processing algorithms, and therefore, long integration times of phase coherent signals are difficult to achieve. Here we demonstrate an alternative approach to dual-comb spectroscopy using two phase modulator combs originating from a single continuous-wave laser capable of > 2 hours of coherent real-time averaging. The dual combs were generated by driving the phase modulators with step-recovery diodes where each comb consisted of > 250 teeth with 203 MHz spacing and spanned > 50 GHz region in the near-infrared. The step-recovery diodes are passive devices that provide low-phase-noise harmonics for efficient coupling into an enhancement cavity at picowatt optical powers. With this approach, we demonstrate the sensitivity to simultaneously monitor ambient levels of CO2, CO, HDO, and H2O in a single spectral region at a maximum acquisition rate of 150 kHz. Robust, compact, low-cost and widely tunable dual-comb systems could enable a network of distributed multiplexed optical sensors.

  4. All-fiber mid-infrared difference frequency generation source and its application to molecular dispersion spectroscopy

    NASA Astrophysics Data System (ADS)

    Krzempek, K.; Abramski, K. M.; Nikodem, M.

    2017-09-01

    A widely tunable, fully monolithic, mid-infrared difference frequency generation source and its application in the dispersion-spectroscopy-based laser trace gas detection of methane and ethane, near 2938 and 2998 cm-1, is presented. Utilizing a fiber pigtailed nonlinear crystal module radically simplified the optical setup, while maintaining a superb conversion efficiency of 20% W-1. Seeded directly from two laser diodes, the source delivered ~0.5 mW of tunable radiation, which was used in a chirped laser dispersion spectroscopy setup, enabling the highly sensitive detection of hydrocarbons.

  5. What Controls the Rate of Ultrafast Charge Transfer and Charge Separation Efficiency in Organic Photovoltaic Blends.

    PubMed

    Jakowetz, Andreas C; Böhm, Marcus L; Zhang, Jiangbin; Sadhanala, Aditya; Huettner, Sven; Bakulin, Artem A; Rao, Akshay; Friend, Richard H

    2016-09-14

    In solar energy harvesting devices based on molecular semiconductors, such as organic photovoltaics (OPVs) and artificial photosynthetic systems, Frenkel excitons must be dissociated via charge transfer at heterojunctions to yield free charges. What controls the rate and efficiency of charge transfer and charge separation is an important question, as it determines the overall power conversion efficiency (PCE) of these systems. In bulk heterojunctions between polymer donor and fullerene acceptors, which provide a model system to understand the fundamental dynamics of electron transfer in molecular systems, it has been established that the first step of photoinduced electron transfer can be fast, of order 100 fs. But here we report the first study which correlates differences in the electron transfer rate with electronic structure and morphology, achieved with sub-20 fs time resolution pump-probe spectroscopy. We vary both the fullerene substitution and donor/fullerene ratio which allow us to control both aggregate size and the energetic driving force for charge transfer. We observe a range of electron transfer times from polymer to fullerene, from 240 fs to as short as 37 fs. Using ultrafast electro-optical pump-push-photocurrent spectroscopy, we find the yield of free versus bound charges to be weakly dependent on the energetic driving force, but to be very strongly dependent on fullerene aggregate size and packing. Our results point toward the importance of state accessibility and charge delocalization and suggest that energetic offsets between donor and acceptor levels are not an important criterion for efficient charge generation. This provides design rules for next-generation materials to minimize losses related to driving energy and boost PCE.

  6. Generalizing attentional control across dimensions and tasks: evidence from transfer of proportion-congruent effects.

    PubMed

    Wühr, Peter; Duthoo, Wout; Notebaert, Wim

    2015-01-01

    Three experiments investigated transfer of list-wide proportion congruent (LWPC) effects from a set of congruent and incongruent items with different frequency (inducer task) to a set of congruent and incongruent items with equal frequency (diagnostic task). Experiments 1 and 2 mixed items from horizontal and vertical Simon tasks. Tasks always involved different stimuli that varied on the same dimension (colour) in Experiment 1 and on different dimensions (colour, shape) in Experiment 2. Experiment 3 mixed trials from a manual Simon task with trials from a vocal Stroop task, with colour being the relevant stimulus in both tasks. There were two major results. First, we observed transfer of LWPC effects in Experiments 1 and 3, when tasks shared the relevant dimension, but not in Experiment 2. Second, sequential modulations of congruency effects transferred in Experiment 1 only. Hence, the different transfer patterns suggest that LWPC effects and sequential modulations arise from different mechanisms. Moreover, the observation of transfer supports an account of LWPC effects in terms of list-wide cognitive control, while being at odds with accounts in terms of stimulus-response (contingency) learning and item-specific control.

  7. Apollo Soyuz, mission evaluation report

    NASA Technical Reports Server (NTRS)

    1975-01-01

    The Apollo Soyuz mission was the first manned space flight to be conducted jointly by two nations - the United States and the Union of Soviet Socialist Republics. The primary purpose of the mission was to test systems for rendezvous and docking of manned spacecraft that would be suitable for use as a standard international system, and to demonstrate crew transfer between spacecraft. The secondary purpose was to conduct a program of scientific and applications experimentation. With minor modifications, the Apollo and Soyuz spacecraft were like those flown on previous missions. However, a new module was built specifically for this mission - the docking module. It served as an airlock for crew transfer and as a structural base for the docking mechanism that interfaced with a similar mechanism on the Soyuz orbital module. The postflight evaluation of the performance of the docking system and docking module, as well as the overall performance of the Apollo spacecraft and experiments is presented. In addition, the mission is evaluated from the viewpoints of the flight crew, ground support operations, and biomedical operations. Descriptions of the docking mechanism, docking module, crew equipment and experiment hardware are given.

  8. Temporal modulation transfer functions for listeners with real and simulated hearing loss

    PubMed Central

    Desloge, Joseph G.; Reed, Charlotte M.; Braida, Louis D.; Perez, Zachary D.; Delhorne, Lorraine A.

    2011-01-01

    A functional simulation of hearing loss was evaluated in its ability to reproduce the temporal modulation transfer functions (TMTFs) for nine listeners with mild to profound sensorineural hearing loss. Each hearing loss was simulated in a group of three age-matched normal-hearing listeners through spectrally shaped masking noise or a combination of masking noise and multiband expansion. TMTFs were measured for both groups of listeners using a broadband noise carrier as a function of modulation rate in the range 2 to 1024 Hz. The TMTFs were fit with a lowpass filter function that provided estimates of overall modulation-depth sensitivity and modulation cutoff frequency. Although the simulations were capable of accurately reproducing the threshold elevations of the hearing-impaired listeners, they were not successful in reproducing the TMTFs. On average, the simulations resulted in lower sensitivity and higher cutoff frequency than were observed in the TMTFs of the hearing-impaired listeners. Discrepancies in performance between listeners with real and simulated hearing loss are possibly related to inaccuracies in the simulation of recruitment. PMID:21682411

  9. Power Generator with Thermo-Differential Modules

    NASA Technical Reports Server (NTRS)

    Saiz, John R.; Nguyen, James

    2010-01-01

    A thermoelectric power generator consists of an oven box and a solar cooker/solar reflector unit. The solar reflector concentrates sunlight into heat and transfers the heat into the oven box via a heat pipe. The oven box unit is surrounded by five thermoelectric modules and is located at the bottom end of the solar reflector. When the heat is pumped into one side of the thermoelectric module and ejected from the opposite side at ambient temperatures, an electrical current is produced. Typical temperature accumulation in the solar reflector is approximately 200 C (392 F). The heat pipe then transfers heat into the oven box with a loss of about 40 percent. At the ambient temperature of about 20 C (68 F), the temperature differential is about 100 C (180 F) apart. Each thermoelectric module, generates about 6 watts of power. One oven box with five thermoelectric modules produces about 30 watts. The system provides power for unattended instruments in remote areas, such as space colonies and space vehicles, and in polar and other remote regions on Earth.

  10. Research on the trace detection of carbon dioxide gas and modulation parameter optimization based on the TDLAS technology

    NASA Astrophysics Data System (ADS)

    Zhao, Peng; Tao, Jun; Yu, Chang-rui; Li, Ye

    2014-02-01

    Based on the technology of tunable diode laser absorption spectroscopy, modulation of the center wavelength of 2004 nm distributed feedback laser diode at a room-temperature, the second harmonic amplitude of CO2 at 2004nm can be obtained. The CO2 concentration can be calculated via the Beer-Lambert law. Sinusoidal modulation parameter is an important factor that affects the sensitivity and accuracy of the system, through the research on the relationship between sinusoidal modulation signal frequency, amplitude and Second harmonic linetype, we finally achieve the detection limit of 10ppm under 12 m optical path.

  11. Ru–protein–Co biohybrids designed for solar hydrogen production: understanding electron transfer pathways related to photocatalytic function† †Electronic supplementary information (ESI) available: Time traces of photocatalysis, additional EPR spectra and parameters, UV-visible spectroscopy data, and kinetic fits of TA traces. See DOI: 10.1039/c6sc03121h Click here for additional data file.

    PubMed Central

    Soltau, Sarah R.; Dahlberg, Peter D.; Niklas, Jens; Poluektov, Oleg G.; Mulfort, Karen L.

    2016-01-01

    A series of Ru–protein–Co biohybrids have been prepared using the electron transfer proteins ferredoxin (Fd) and flavodoxin (Fld) as scaffolds for photocatalytic hydrogen production. The light-generated charge separation within these hybrids has been monitored by transient optical and electron paramagnetic resonance spectroscopies. Two distinct electron transfer pathways are observed. The Ru–Fd–Co biohybrid produces up to 650 turnovers of H2 utilizing an oxidative quenching mechanism for Ru(ii)* and a sequential electron transfer pathway via the native [2Fe–2S] cluster to generate a Ru(iii)–Fd–Co(i) charge separated state that lasts for ∼6 ms. In contrast, a direct electron transfer pathway occurs for the Ru–ApoFld–Co biohybrid, which lacks an internal electron relay, generating Ru(i)–ApoFld–Co(i) charge separated state that persists for ∼800 μs and produces 85 turnovers of H2 by a reductive quenching mechanism for Ru(ii)*. This work demonstrates the utility of protein architectures for linking donor and catalytic function via direct or sequential electron transfer pathways to enable stabilized charge separation which facilitates photocatalysis for solar fuel production. PMID:28451142

  12. Quartz tuning fork-based frequency modulation atomic force spectroscopy and microscopy with all digital phase-locked loop

    NASA Astrophysics Data System (ADS)

    An, Sangmin; Hong, Mun-heon; Kim, Jongwoo; Kwon, Soyoung; Lee, Kunyoung; Lee, Manhee; Jhe, Wonho

    2012-11-01

    We present a platform for the quartz tuning fork (QTF)-based, frequency modulation atomic force microscopy (FM-AFM) system for quantitative study of the mechanical or topographical properties of nanoscale materials, such as the nano-sized water bridge formed between the quartz tip (˜100 nm curvature) and the mica substrate. A thermally stable, all digital phase-locked loop is used to detect the small frequency shift of the QTF signal resulting from the nanomaterial-mediated interactions. The proposed and demonstrated novel FM-AFM technique provides high experimental sensitivity in the measurement of the viscoelastic forces associated with the confined nano-water meniscus, short response time, and insensitivity to amplitude noise, which are essential for precision dynamic force spectroscopy and microscopy.

  13. Quartz tuning fork-based frequency modulation atomic force spectroscopy and microscopy with all digital phase-locked loop.

    PubMed

    An, Sangmin; Hong, Mun-heon; Kim, Jongwoo; Kwon, Soyoung; Lee, Kunyoung; Lee, Manhee; Jhe, Wonho

    2012-11-01

    We present a platform for the quartz tuning fork (QTF)-based, frequency modulation atomic force microscopy (FM-AFM) system for quantitative study of the mechanical or topographical properties of nanoscale materials, such as the nano-sized water bridge formed between the quartz tip (~100 nm curvature) and the mica substrate. A thermally stable, all digital phase-locked loop is used to detect the small frequency shift of the QTF signal resulting from the nanomaterial-mediated interactions. The proposed and demonstrated novel FM-AFM technique provides high experimental sensitivity in the measurement of the viscoelastic forces associated with the confined nano-water meniscus, short response time, and insensitivity to amplitude noise, which are essential for precision dynamic force spectroscopy and microscopy.

  14. Probing the Bond Order Wave Phase Transitions of the Ionic Hubbard Model by Superlattice Modulation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Loida, Karla; Bernier, Jean-Sébastien; Citro, Roberta; Orignac, Edmond; Kollath, Corinna

    2017-12-01

    An exotic phase, the bond order wave, characterized by the spontaneous dimerization of the hopping, has been predicted to exist sandwiched between the band and Mott insulators in systems described by the ionic Hubbard model. Despite growing theoretical evidence, this phase still evades experimental detection. Given the recent realization of the ionic Hubbard model in ultracold atomic gases, we propose here to detect the bond order wave using superlattice modulation spectroscopy. We demonstrate, with the help of time-dependent density-matrix renormalization group and bosonization, that this spectroscopic approach reveals characteristics of both the Ising and Kosterlitz-Thouless transitions signaling the presence of the bond order wave phase. This scheme also provides insights into the excitation spectra of both the band and Mott insulators.

  15. Deflecting light into resonant cavities for spectroscopy

    DOEpatents

    Zare, R.N.; Martin, J.; Paldus, B.A.

    1998-09-29

    Light is coupled into a cavity ring down spectroscopy (CRDS) resonant cavity using an acousto-optic modulator. The AOM allows in-coupling efficiencies in excess of 40%, which is two to three orders of magnitude higher than in conventional systems using a cavity mirror for in-coupling. The AOM shutoff time is shorter than the roundtrip time of the cavity. The higher light intensities lead to a reduction in shot noise, and allow the use of relatively insensitive but fast-responding detectors such as photovoltaic detectors. Other deflection devices such as electro-optic modulators or elements used in conventional Q-switching may be used instead of the AOM. The method is particularly useful in the mid-infrared, far-infrared, and ultraviolet wavelength ranges, for which moderately reflecting input mirrors are not widely available. 5 figs.

  16. Deflecting light into resonant cavities for spectroscopy

    DOEpatents

    Zare, Richard N.; Martin, Juergen; Paldus, Barbara A.

    1998-01-01

    Light is coupled into a cavity ring down spectroscopy (CRDS) resonant cavity using an acousto-optic modulator. The AOM allows in-coupling efficiencies in excess of 40%, which is two to three orders of magnitude higher than in conventional systems using a cavity mirror for in-coupling. The AOM shutoff time is shorter than the roundtrip time of the cavity. The higher light intensities lead to a reduction in shot noise, and allow the use of relatively insensitive but fast-responding detectors such as photovoltaic detectors. Other deflection devices such as electro-optic modulators or elements used in conventional Q-switching may be used instead of the AOM. The method is particularly useful in the mid-infrared, far-infrared, and ultraviolet wavelength ranges, for which moderately reflecting input mirrors are not widely available.

  17. Exploring two-dimensional electron gases with two-dimensional Fourier transform spectroscopy

    DOE PAGES

    Paul, J.; Dey, P.; Tokumoto, T.; ...

    2014-10-07

    The dephasing of excitons in a modulation doped single quantum well was carefully measured using time integrated four-wave mixing (FWM) and two-dimensional Fourier transform (2DFT) spectroscopy. These are the first 2DFT measurements performed on a modulation doped single quantum well. The inhomogeneous and homogeneous excitonic line widths were obtained from the diagonal and cross-diagonal profiles of the 2DFT spectra. The laser excitation density and temperature were varied and 2DFT spectra were collected. A very rapid increase of the dephasing decay, and as a result, an increase in the cross-diagonal 2DFT linewidths with temperature was observed. Furthermore, the lineshapes of themore » 2DFT spectra suggest the presence of excitation induced dephasing and excitation induced shift.« less

  18. Mid infrared quantum cascade laser operating in pure amplitude modulation for background-free trace gas spectroscopy.

    PubMed

    Bidaux, Yves; Bismuto, Alfredo; Patimisco, Pietro; Sampaolo, Angelo; Gresch, Tobias; Strubi, Gregory; Blaser, Stéphane; Tittel, Frank K; Spagnolo, Vincenzo; Muller, Antoine; Faist, Jérôme

    2016-11-14

    We present a single mode multi-section quantum cascade laser source composed of three different sections: master oscillator, gain and phase section. Non-uniform pumping of the QCL's gain reveals that the various laser sections are strongly coupled. Simulations of the electronic and optical properties of the laser (based on the density matrix and scattering matrix formalisms, respectively) were performed and a good agreement with measurements is obtained. In particular, a pure modulation of the laser output power can be achieved. This capability of the device is applied in tunable-laser spectroscopy of N2O where background-free quartz enhanced photo acoustic spectral scans with nearly perfect Voigt line shapes for the selected absorption line are obtained.

  19. Modulation transfer function of partial gating detector by liquid crystal auto-controlling light intensity

    NASA Astrophysics Data System (ADS)

    Yang, Xusan; Tang, Yuanhe; Liu, Kai; Liu, Hanchen; Gao, Haiyang; Li, Qing; Zhang, Ruixia; Ye, Na; Liang, Yuan; Zhao, Gaoxiang

    2008-12-01

    Based on the electro-optical properties of liquid crystal, we have designed a novel partial gating detector. Liquid crystal can be taken to change its own transmission according to the light intensity outside. Every single pixel of the image is real-time modulated by liquid crystal, thus the strong light is weakened and low light goes through the detector normally .The purpose of partial-gating strong light (>105lx) can be achieved by this detector. The modulation transfer function (MTF) equations of the main optical sub-systems are calculated in this paper, they are liquid crystal panels, linear fiber panel and CCD array detector. According to the relevant size, the MTF value of this system is fitted out. The result is MTF= 0.518 at Nyquist frequency.

  20. SIERRA Low Mach Module: Fuego User Manual Version 4.46.

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

    Sierra Thermal/Fluid Team

    2017-09-01

    The SIERRA Low Mach Module: Fuego along with the SIERRA Participating Media Radiation Module: Syrinx, henceforth referred to as Fuego and Syrinx, respectively, are the key elements of the ASCI fire environment simulation project. The fire environment simulation project is directed at characterizing both open large-scale pool fires and building enclosure fires. Fuego represents the turbulent, buoyantly-driven incompressible flow, heat transfer, mass transfer, combustion, soot, and absorption coefficient model portion of the simulation software. Syrinx represents the participating-media thermal radiation mechanics. This project is an integral part of the SIERRA multi-mechanics software development project. Fuego depends heavily upon the coremore » architecture developments provided by SIERRA for massively parallel computing, solution adaptivity, and mechanics coupling on unstructured grids.« less

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