Science.gov

Sample records for probing intermolecular couplings

  1. Probing intermolecular couplings in liquid water with two-dimensional infrared photon echo spectroscopy

    NASA Astrophysics Data System (ADS)

    Paarmann, A.; Hayashi, T.; Mukamel, S.; Miller, R. J. D.

    2008-05-01

    Two-dimensional infrared photon echo and pump probe studies of the OH stretch vibration provide a sensitive probe of the correlations and couplings in the hydrogen bond network of liquid water. The nonlinear response is simulated using numerical integration of the Schrödinger equation with a Hamiltonian constructed to explicitly treat intermolecular coupling and nonadiabatic effects in the highly disordered singly and doubly excited vibrational exciton manifolds. The simulated two-dimensional spectra are in close agreement with our recent experimental results. The high sensitivity of the OH stretch vibration to the bath dynamics is found to arise from intramolecular mixing between states in the two-dimensional anharmonic OH stretch potential. Surprisingly small intermolecular couplings reproduce the experimentally observed intermolecular energy transfer times.

  2. Intermolecular artifacts in probe microscope images of C60 assemblies

    NASA Astrophysics Data System (ADS)

    Jarvis, Samuel Paul; Rashid, Mohammad Abdur; Sweetman, Adam; Leaf, Jeremy; Taylor, Simon; Moriarty, Philip; Dunn, Janette

    2015-12-01

    Claims that dynamic force microscopy has the capability to resolve intermolecular bonds in real space continue to be vigorously debated. To date, studies have been restricted to planar molecular assemblies with small separations between neighboring molecules. Here we report the observation of intermolecular artifacts over much larger distances in 2D assemblies of C60 molecules, with compelling evidence that in our case the tip apex is terminated by a C60 molecule (rather than the CO termination typically exploited in ultrahigh resolution force microscopy). The complete absence of directional interactions such as hydrogen or halogen bonding, the nonplanar structure of C60, and the fullerene termination of the tip apex in our case highlight that intermolecular artifacts are ubiquitous in dynamic force microscopy.

  3. Probing Intermolecular Interactions in Polycyclic Aromatic Hydrocarbons with 2D IR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Krummel, Amber

    2014-03-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment and impact geochemical processes that are critical to sustainable energy resources. For example, asphaltenes exist naturally in geologic formations and their aggregates heavily impact the petroleum economy. Unfortunately, the chemical dynamics that drive asphaltene nanoaggregation processes are still poorly understood. Solvent dynamics and intermolecular interactions such as π-stacking interactions play integral roles in asphaltene nanoaggregation. Linear and nonlinear vibrational spectroscopy including two-dimensional infrared spectroscopy (2DIR), are well suited to explore these fundamental interactions. Teasing apart the vibrational characteristics in PAHs that model asphaltenic compounds represents an important step towards utilizing 2D IR spectroscopy to understand the intermolecular interactions that are prevalent in asphaltene nanoaggregation. A solar dye, N,N'-Dioctyl-3,4,9,10-perylenedicarboximide, is used in this work to model aphaltenes. Carbonyl and ring vibrations are used to probe the nanoaggregates of the model compounds. However, the characteristics of these normal modes change as a function of the size of the conjugated ring system. Thus, in order to fully understand the nature of these normal modes, we include a systematic study of a series of quinones. Our investigation employs a combination of 2DIR spectroscopy and electronic structure calculations to explore vibrational coupling in quinones and PAHs. We compare the calculated vibrational characteristics to those extracted from 2DIR spectra. ATK acknowledges the Donors of the American Chemical Society Petroleum Research Fund for support of this research.

  4. Visualizing coherent intermolecular dipole-dipole coupling in real space.

    PubMed

    Zhang, Yang; Luo, Yang; Zhang, Yao; Yu, Yun-Jie; Kuang, Yan-Min; Zhang, Li; Meng, Qiu-Shi; Luo, Yi; Yang, Jin-Long; Dong, Zhen-Chao; Hou, J G

    2016-03-31

    Many important energy-transfer and optical processes, in both biological and artificial systems, depend crucially on excitonic coupling that spans several chromophores. Such coupling can in principle be described in a straightforward manner by considering the coherent intermolecular dipole-dipole interactions involved. However, in practice, it is challenging to directly observe in real space the coherent dipole coupling and the related exciton delocalizations, owing to the diffraction limit in conventional optics. Here we demonstrate that the highly localized excitations that are produced by electrons tunnelling from the tip of a scanning tunnelling microscope, in conjunction with imaging of the resultant luminescence, can be used to map the spatial distribution of the excitonic coupling in well-defined arrangements of a few zinc-phthalocyanine molecules. The luminescence patterns obtained for excitons in a dimer, which are recorded for different energy states and found to resemble σ and π molecular orbitals, reveal the local optical response of the system and the dependence of the local optical response on the relative orientation and phase of the transition dipoles of the individual molecules in the dimer. We generate an in-line arrangement up to four zinc-phthalocyanine molecules, with a larger total transition dipole, and show that this results in enhanced 'single-molecule' superradiance from the oligomer upon site-selective excitation. These findings demonstrate that our experimental approach provides detailed spatial information about coherent dipole-dipole coupling in molecular systems, which should enable a greater understanding and rational engineering of light-harvesting structures and quantum light sources. PMID:27029277

  5. Visualizing coherent intermolecular dipole–dipole coupling in real space

    NASA Astrophysics Data System (ADS)

    Zhang, Yang; Luo, Yang; Zhang, Yao; Yu, Yun-Jie; Kuang, Yan-Min; Zhang, Li; Meng, Qiu-Shi; Luo, Yi; Yang, Jin-Long; Dong, Zhen-Chao; Hou, J. G.

    2016-03-01

    Many important energy-transfer and optical processes, in both biological and artificial systems, depend crucially on excitonic coupling that spans several chromophores. Such coupling can in principle be described in a straightforward manner by considering the coherent intermolecular dipole–dipole interactions involved. However, in practice, it is challenging to directly observe in real space the coherent dipole coupling and the related exciton delocalizations, owing to the diffraction limit in conventional optics. Here we demonstrate that the highly localized excitations that are produced by electrons tunnelling from the tip of a scanning tunnelling microscope, in conjunction with imaging of the resultant luminescence, can be used to map the spatial distribution of the excitonic coupling in well-defined arrangements of a few zinc-phthalocyanine molecules. The luminescence patterns obtained for excitons in a dimer, which are recorded for different energy states and found to resemble σ and π molecular orbitals, reveal the local optical response of the system and the dependence of the local optical response on the relative orientation and phase of the transition dipoles of the individual molecules in the dimer. We generate an in-line arrangement up to four zinc-phthalocyanine molecules, with a larger total transition dipole, and show that this results in enhanced ‘single-molecule’ superradiance from the oligomer upon site-selective excitation. These findings demonstrate that our experimental approach provides detailed spatial information about coherent dipole–dipole coupling in molecular systems, which should enable a greater understanding and rational engineering of light-harvesting structures and quantum light sources.

  6. Probing Intermolecular Interaction through Thermal-Lens Spectroscopy

    PubMed Central

    Bhattacharyya, Indrajit; Kumar, Pardeep; Goswami, Debabrata

    2013-01-01

    Binary liquid mixtures are studied using femtosecond pump–probe thermal-lens (TL) spectroscopy. Changes in the measured TL signals as a function of relative concentration of binary mixtures show that these result from a combined effect of physical and molecular properties of the constituent binary liquids. The experimental TL values deviate from the ones calculated from phenomenological equations. These, we argue, are due to an underestimation of the influence of molecular interactions when the TL signals are calculated by using physical parameters only. PMID:21166402

  7. Optical Activity Enhanced by Strong Inter-molecular Coupling in Planar Chiral Metamaterials

    PubMed Central

    Kim, Teun-Teun; Oh, Sang Soon; Park, Hyun-Sung; Zhao, Rongkuo; Kim, Seong-Han; Choi, Wonjune; Min, Bumki; Hess, Ortwin

    2014-01-01

    The polarization of light can be rotated in materials with an absence of molecular or structural mirror symmetry. While this rotating ability is normally rather weak in naturally occurring chiral materials, artificial chiral metamaterials have demonstrated extraordinary rotational ability by engineering intra-molecular couplings. However, while in general, chiral metamaterials can exhibit strong rotatory power at or around resonances, they convert linearly polarized waves into elliptically polarized ones. Here, we demonstrate that strong inter-molecular coupling through a small gap between adjacent chiral metamolecules can lead to a broadband enhanced rotating ability with pure rotation of linearly polarized electromagnetic waves. Strong inter-molecular coupling leads to nearly identical behaviour in magnitude, but engenders substantial difference in phase between transmitted left and right-handed waves. PMID:25209452

  8. Intermolecular electronic coupling in organic molecular thin films measured by temperature modulation spectroscopy

    SciTech Connect

    Yadav, Abhishek; Jin, Y; Chan, P. K. L.; Shtein, Max; Pipe, Kevin P.

    2010-01-01

    Temperature modulation spectroscopy is used to obtain the temperature dependences of oscillator strength, exciton transition energy, and line width for a copper phthalocyanine thin film. With increasing temperature, the oscillator strength exhibits a pronounced decrease for charge transfer (CT) excitons, making this technique suitable for differentiating exciton types. From the measured magnitude and temperature dependence of the CT oscillator strength, we obtain estimates for the intermolecular electronic coupling and its exponential decay coefficient.

  9. Density Analysis of Intra- and Intermolecular Vibronic Couplings toward Bath Engineering for Singlet Fission.

    PubMed

    Ito, Soichi; Nagami, Takanori; Nakano, Masayoshi

    2015-12-17

    Vibronic coupling plays a crucial role in singlet fission whereby a singlet exciton splits into two triplet excitons. In order to reveal the physicochemical origin of the vibronic coupling associated with singlet fission as well as to clarify its relationship with chemical structure, we evaluate relevant vibronic couplings from the viewpoint of their spatial contributions described by vibronic coupling density. From the analysis using a model tetracene dimer, a typical singlet fission system, the frequency dependence of vibronic couplings in each electronic state is found to be significantly different from that of another depending on the nature of the electronic structure (intra/intermolecular excitation) and the related vibrational motion. These findings contribute not only to the fundamental understanding of the singlet fission mechanism from the viewpoint of vibronic couplings but also to opening a new path to designing highly efficient singlet fission materials through phonon-bath engineering. PMID:26673196

  10. The origins of intra- and inter-molecular vibrational couplings: A case study of H2O-Ar on full and reduced-dimensional potential energy surface

    NASA Astrophysics Data System (ADS)

    Hou, Dan; Ma, Yong-Tao; Zhang, Xiao-Long; Li, Hui

    2016-01-01

    The origin and strength of intra- and inter-molecular vibrational coupling is difficult to probe by direct experimental observations. However, explicitly including or not including some specific intramolecular vibrational modes to study intermolecular interaction provides a precise theoretical way to examine the effects of anharmonic coupling between modes. In this work, a full-dimension intra- and inter-molecular ab initio potential energy surface (PES) for H2O-Ar, which explicitly incorporates interdependence on the intramolecular (Q1, Q2, Q3) normal-mode coordinates of the H2O monomer, has been calculated. In addition, four analytic vibrational-quantum-state-specific PESs are obtained by least-squares fitting vibrationally averaged interaction energies for the (v1, v2, v3) = (0, 0, 0), (0, 0, 1), (1, 0, 0), (0, 1, 0) states of H2O to the three-dimensional Morse/long-range potential function. Each vibrationally averaged PES fitted to 442 points has root-mean-square (rms) deviation smaller than 0.15 cm-1, and required only 58 parameters. With the 3D PESs of H2O-Ar dimer system, we employed the combined radial discrete variable representation/angular finite basis representation method and Lanczos algorithm to calculate rovibrational energy levels. This showed that the resulting vibrationally averaged PESs provide good representations of the experimental infrared data, with rms discrepancies smaller than 0.02 cm-1 for all three rotational branches of the asymmetric stretch fundamental transitions. The infrared band origin shifts associated with three fundamental bands of H2O in H2O-Ar complex are predicted for the first time and are found to be in good agreement with the (extrapolated) experimental values. Upon introduction of additional intramolecular degrees of freedom into the intermolecular potential energy surface, there is clear spectroscopic evidence of intra- and intermolecular vibrational couplings.

  11. Magnetic circuitry mutual coupling probe

    NASA Technical Reports Server (NTRS)

    Anthony, P. L.

    1972-01-01

    Development of magnetic probe for nondestructive testing of multilayer printed circuit boards to determine existence of opens or shorts is reported. Components of probe are described and procedures for operation are discussed. Two illustrations are provided to show magnetic circuits and principles of operation.

  12. Cross-dehydrogenative coupling for the intermolecular C–O bond formation

    PubMed Central

    Krylov, Igor B; Vil’, Vera A

    2015-01-01

    Summary The present review summarizes primary publications on the cross-dehydrogenative C–O coupling, with special emphasis on the studies published after 2000. The starting compound, which donates a carbon atom for the formation of a new C–O bond, is called the CH-reagent or the C-reagent, and the compound, an oxygen atom of which is involved in the new bond, is called the OH-reagent or the O-reagent. Alcohols and carboxylic acids are most commonly used as O-reagents; hydroxylamine derivatives, hydroperoxides, and sulfonic acids are employed less often. The cross-dehydrogenative C–O coupling reactions are carried out using different C-reagents, such as compounds containing directing functional groups (amide, heteroaromatic, oxime, and so on) and compounds with activated C–H bonds (aldehydes, alcohols, ketones, ethers, amines, amides, compounds containing the benzyl, allyl, or propargyl moiety). An analysis of the published data showed that the principles at the basis of a particular cross-dehydrogenative C–O coupling reaction are dictated mainly by the nature of the C-reagent. Hence, in the present review the data are classified according to the structures of C-reagents, and, in the second place, according to the type of oxidative systems. Besides the typical cross-dehydrogenative coupling reactions of CH- and OH-reagents, closely related C–H activation processes involving intermolecular C–O bond formation are discussed: acyloxylation reactions with ArI(O2CR)2 reagents and generation of O-reagents in situ from C-reagents (methylarenes, aldehydes, etc.). PMID:25670997

  13. Cross-dehydrogenative coupling for the intermolecular C-O bond formation.

    PubMed

    Krylov, Igor B; Vil', Vera A; Terent'ev, Alexander O

    2015-01-01

    The present review summarizes primary publications on the cross-dehydrogenative C-O coupling, with special emphasis on the studies published after 2000. The starting compound, which donates a carbon atom for the formation of a new C-O bond, is called the CH-reagent or the C-reagent, and the compound, an oxygen atom of which is involved in the new bond, is called the OH-reagent or the O-reagent. Alcohols and carboxylic acids are most commonly used as O-reagents; hydroxylamine derivatives, hydroperoxides, and sulfonic acids are employed less often. The cross-dehydrogenative C-O coupling reactions are carried out using different C-reagents, such as compounds containing directing functional groups (amide, heteroaromatic, oxime, and so on) and compounds with activated C-H bonds (aldehydes, alcohols, ketones, ethers, amines, amides, compounds containing the benzyl, allyl, or propargyl moiety). An analysis of the published data showed that the principles at the basis of a particular cross-dehydrogenative C-O coupling reaction are dictated mainly by the nature of the C-reagent. Hence, in the present review the data are classified according to the structures of C-reagents, and, in the second place, according to the type of oxidative systems. Besides the typical cross-dehydrogenative coupling reactions of CH- and OH-reagents, closely related C-H activation processes involving intermolecular C-O bond formation are discussed: acyloxylation reactions with ArI(O2CR)2 reagents and generation of O-reagents in situ from C-reagents (methylarenes, aldehydes, etc.). PMID:25670997

  14. Probing acid-amide intermolecular hydrogen bonding by NMR spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Chaudhari, Sachin Rama; Suryaprakash, N.

    2012-05-01

    Benzene carboxylic acids and benzamide act as their self-complement in molecular recognition to form inter-molecular hydrogen bonded dimers between amide and carboxylic acid groups, which have been investigated by 1H, 13C and 15N NMR spectroscopy. Extensive NMR studies using diffusion ordered spectroscopy (DOSY), variable temperature 1D, 2D NMR, established the formation of heterodimers of benzamide with benzoic acid, salicylic acid and phenyl acetic acid in deuterated chloroform solution. Association constants for the complex formation in the solution state have been determined. The results are ascertained by X-ray diffraction in the solid state. Intermolecular interactions in solution and in solid state were found to be similar. The structural parameters obtained by X-ray diffraction studies are compared with those obtained by DFT calculations.

  15. The origins of intra- and inter-molecular vibrational couplings: A case study of H2O-Ar on full and reduced-dimensional potential energy surface.

    PubMed

    Hou, Dan; Ma, Yong-Tao; Zhang, Xiao-Long; Li, Hui

    2016-01-01

    The origin and strength of intra- and inter-molecular vibrational coupling is difficult to probe by direct experimental observations. However, explicitly including or not including some specific intramolecular vibrational modes to study intermolecular interaction provides a precise theoretical way to examine the effects of anharmonic coupling between modes. In this work, a full-dimension intra- and inter-molecular ab initio potential energy surface (PES) for H2O-Ar, which explicitly incorporates interdependence on the intramolecular (Q1,  Q2,  Q3) normal-mode coordinates of the H2O monomer, has been calculated. In addition, four analytic vibrational-quantum-state-specific PESs are obtained by least-squares fitting vibrationally averaged interaction energies for the (v1,  v2,  v3) =  (0,  0,  0), (0,  0,  1), (1,  0,  0), (0,  1,  0) states of H2O to the three-dimensional Morse/long-range potential function. Each vibrationally averaged PES fitted to 442 points has root-mean-square (rms) deviation smaller than 0.15 cm(-1), and required only 58 parameters. With the 3D PESs of H2O-Ar dimer system, we employed the combined radial discrete variable representation/angular finite basis representation method and Lanczos algorithm to calculate rovibrational energy levels. This showed that the resulting vibrationally averaged PESs provide good representations of the experimental infrared data, with rms discrepancies smaller than 0.02 cm(-1) for all three rotational branches of the asymmetric stretch fundamental transitions. The infrared band origin shifts associated with three fundamental bands of H2O in H2O-Ar complex are predicted for the first time and are found to be in good agreement with the (extrapolated) experimental values. Upon introduction of additional intramolecular degrees of freedom into the intermolecular potential energy surface, there is clear spectroscopic evidence of intra- and intermolecular vibrational couplings. PMID:26747800

  16. Molecular and ionic diffusion in aqueous - deep eutectic solvent mixtures: probing inter-molecular interactions using PFG NMR.

    PubMed

    D'Agostino, Carmine; Gladden, Lynn F; Mantle, Mick D; Abbott, Andrew P; Ahmed, Essa I; Al-Murshedi, Azhar Y M; Harris, Robert C

    2015-06-21

    Pulsed field gradient (PFG) NMR has been used to probe self-diffusion of molecular and ionic species in aqueous mixtures of choline chloride (ChCl) based deep eutectic solvents (DESs), in order to elucidate the effect of water on motion and inter-molecular interactions between the different species in the mixtures, namely the Ch(+) cation and hydrogen bond donor (HBD). The results reveal an interesting and complex behaviour of such mixtures at a molecular level. In general, it is observed that the hydroxyl protons ((1)H) of Ch(+) and the hydrogen bond donor have diffusion coefficients significantly different from those measured for their parent molecules when water is added. This indicates a clear and significant change in inter-molecular interactions. In aqueous Ethaline, the hydroxyl species of Ch(+) and HBD show a stronger interaction with water as water is added to the system. In the case of Glyceline, water has little effect on both hydroxyl proton diffusion of Ch(+) and HBD. In Reline, it is likely that water allows the formation of small amounts of ammonium hydroxide. The most surprising observation is from the self-diffusion of water, which is considerably higher that expected from a homogeneous liquid. This leads to the conclusion that Reline and Glyceline form mixtures that are inhomogeneous at a microscopic level despite the hydrophilicity of the salt and HBD. This work shows that PFG NMR is a powerful tool to elucidate both molecular dynamics and inter-molecular interactions in complex liquid mixtures, such as the aqueous DES mixtures. PMID:25994171

  17. Similarity-transformed perturbation theory on top of truncated local coupled cluster solutions: Theory and applications to intermolecular interactions

    SciTech Connect

    Azar, Richard Julian Head-Gordon, Martin

    2015-05-28

    Your correspondents develop and apply fully nonorthogonal, local-reference perturbation theories describing non-covalent interactions. Our formulations are based on a Löwdin partitioning of the similarity-transformed Hamiltonian into a zeroth-order intramonomer piece (taking local CCSD solutions as its zeroth-order eigenfunction) plus a first-order piece coupling the fragments. If considerations are limited to a single molecule, the proposed intermolecular similarity-transformed perturbation theory represents a frozen-orbital variant of the “(2)”-type theories shown to be competitive with CCSD(T) and of similar cost if all terms are retained. Different restrictions on the zeroth- and first-order amplitudes are explored in the context of large-computation tractability and elucidation of non-local effects in the space of singles and doubles. To accurately approximate CCSD intermolecular interaction energies, a quadratically growing number of variables must be included at zeroth-order.

  18. Probing Intramolecular versus Intermolecular CO2 Adsorption on Amine-Grafted SBA-15.

    PubMed

    Yoo, Chun-Jae; Lee, Li-Chen; Jones, Christopher W

    2015-12-15

    A mesoporous silica SBA-15 is modified with an array of amine-containing organosilanes including (i) propylamine, SiCH2CH2CH2NH2 (MONO), (ii) propylethylenediamine, SiCH2CH2CH2NHCH2CH2NH2 (DI), (iii) propyldiethylenetriamine, SiCH2CH2CH2NHCH2CH2NHCH2CH2NH2 (TRI), and (iv) propyltriethylenetetramine, SiCH2CH2CH2NHCH2CH2N(CH2CH2NH2)2 (TREN) and the low loading silane adsorbents (∼0.45 mmol silane/g) are evaluated for their CO2 adsorption properties, with a focus on gaining insight into the propensity for intramolecular vs intermolecular CO2 adsorption. Adsorption isotherms at low CO2 coverages are measured while simultaneously recording the heat evolved via a Tian-Calvet calorimeter. The results are compared on a silane molecule efficiency basis (mol CO2 adsorbed/mol silane) to assess the potential for intramolecular CO2 adsorption, employing two amine groups in a single silane molecule. As the number of amines in the silane molecule increases (MONO < DI < TREN ∼ TRI), the silane molecule efficiency is enhanced owing to the ability to intramolecularly capture CO2. Analysis of the CO2 uptake for samples with the surface silanols removed by capping demonstrates that cooperative uptake due to amine-CO2-silanol interactions is also possible over these adsorbents and is the primary mode of sorption for the MONO material at the studied low silane loading. As the propensity for intramolecular CO2 capture increases due to the presence of multiple amines in a single silane molecule (MONO < DI < TREN ∼ TRI), the measured heat of adsorption also increases. This study of various amine-containing silanes at low coverage is the first to provide significant, direct evidence for intramolecular CO2 capture in a single silane molecule. Furthermore, it provides evidence for the relative heats of adsorption for physisorption on a silanol laden surface (ca. 37 kJ/mol), a silanol-capped surface (ca. 25 kJ/mol), via amine-CO2-silanol interactions (ca. 46 kJ/mol), and via amine-CO2

  19. NMR shielding as a probe of intermolecular interactions: ab initio and density functional theory studies.

    PubMed

    Platts, James A; Gkionis, Konstantinos

    2009-11-28

    Ab initio and density functional theory (DFT) calculations of nuclear magnetic resonance shielding tensors in benzene-methane and two isomers of the benzene dimer are reported, with the aim of probing the changes in shielding induced by the formation of supramolecular complexes from isolated molecules. It is shown that the changes in shielding (and hence of chemical shift) for hydrogen nuclei are broadly in line with expectations from "shielding cones" based on aromatic ring current, but that changes for carbon nuclei are rather more subtle. More detailed analysis indicates that the change in isotropic shielding results from much larger changes in individual components of the shielding tensor and in diamagnetic/paramagnetic shielding contributions. Benchmark data were obtained using Møller-Plesset 2nd order perturbation theory with a medium-sized basis set, but it is shown that Hartree-Fock and most density functional theory methods reproduce all essential changes in shielding, and do so in a reasonably basis set independent fashion. The chosen method is then applied to a DNA-intercalator complex. PMID:19890517

  20. Vibrational nano-spectroscopic imaging correlating structure with intermolecular coupling and dynamics

    PubMed Central

    Pollard, Benjamin; Muller, Eric A.; Hinrichs, Karsten; Raschke, Markus B.

    2014-01-01

    Molecular self-assembly, the function of biomembranes and the performance of organic solar cells rely on nanoscale molecular interactions. Understanding and control of such materials have been impeded by difficulties in imaging their properties with the desired nanometre spatial resolution, attomolar sensitivity and intermolecular spectroscopic specificity. Here we implement vibrational scattering-scanning near-field optical microscopy with high spectral precision to investigate the structure–function relationship in nano-phase separated block copolymers. A vibrational resonance is used as a sensitive reporter of the local chemical environment and we image, with few nanometre spatial resolution and 0.2 cm−1 spectral precision, solvatochromic Stark shifts and line broadening correlated with molecular-scale morphologies. We discriminate local variations in electric fields between nano-domains with quantitative agreement with dielectric continuum models. This ability to directly resolve nanoscale morphology and associated intermolecular interactions can form a basis for the systematic control of functionality in multicomponent soft matter systems. PMID:24721995

  1. Glycosaminoglycan and DNA Binding Induced Intra- and Intermolecular Exciton Coupling of the bis-4-Aminoquinoline Surfen.

    PubMed

    Zsila, Ferenc

    2015-09-01

    Despite the diverse biological activities of the glycosaminoglycan (GAG) antagonist surfen, the molecular details of its interaction with biomacromolecules remain poorly understood. Therefore, heparin and DNA binding properties of surfen were studied by circular dichroism (CD) and UV absorption spectroscopy methods. High-affinity (Ka  ~ 10(7)  M(-1)) association of surfen to the chiral heparin chain gives rise to a characteristic biphasic CD pattern due to the conformational twist of the aminoquinoline moieties around the central urea bridge. At higher drug loading, intermolecular stacking of surfen molecules alters the induced CD profile and also provokes strong UV hypochromism. In contrast to the right-handed heparin template, binding of surfen to the left-helicity chondroitin sulfate chains produces inverted CD pattern. Large UV hypochromism as well as polyphasic induced ellipticity bands indicate that surfen intercalates between the base pairs of calf-thymus DNA. Extensive CD spectroscopic changes observed at higher drug binding ratios refer to cooperative binding interactions between the intercalated drug molecules. The inherent conformational flexibility of surfen demonstrated here for the first time is important in its binding to distinct macromolecular targets and should be considered for rational drug design of novel GAG antagonists. PMID:26096963

  2. Cobalt-catalyzed intermolecular C(sp(2))-O cross-coupling.

    PubMed

    Kundu, Debasish; Tripathy, Manisha; Maity, Pintu; Ranu, Brindaban C

    2015-06-01

    Cobalt(II)-catalyzed C(sp(2) )O cross-coupling between aryl/heteroaryl alcohols and vinyl/aryl halides in the presence of Cu(I) has been achieved under ligand-free conditions. In this reaction, copper plays a significant role in transmetalation rather than being directly involved in the CO coupling. This unique Co/Cu-dual catalyst system provides an easy access to a library of aryl-vinyl, heteroaryl-styryl, aryl-aryl, and heteroaryl-heteroaryl ethers in the absence of any ligand or additive. PMID:25926040

  3. Computational IR spectroscopy of water: OH stretch frequencies, transition dipoles, and intermolecular vibrational coupling constants

    NASA Astrophysics Data System (ADS)

    Choi, Jun-Ho; Cho, Minhaeng

    2013-05-01

    The Hessian matrix reconstruction method initially developed to extract the basis mode frequencies, vibrational coupling constants, and transition dipoles of the delocalized amide I, II, and III vibrations of polypeptides and proteins from quantum chemistry calculation results is used to obtain those properties of delocalized O-H stretch modes in liquid water. Considering the water symmetric and asymmetric O-H stretch modes as basis modes, we here develop theoretical models relating vibrational frequencies, transition dipoles, and coupling constants of basis modes to local water configuration and solvent electric potential. Molecular dynamics simulation was performed to generate an ensemble of water configurations that was in turn used to construct vibrational Hamiltonian matrices. Obtaining the eigenvalues and eigenvectors of the matrices and using the time-averaging approximation method, which was developed by the Skinner group, to calculating the vibrational spectra of coupled oscillator systems, we could numerically simulate the O-H stretch IR spectrum of liquid water. The asymmetric line shape and weak shoulder bands were quantitatively reproduced by the present computational procedure based on vibrational exciton model, where the polarization effects on basis mode transition dipoles and inter-mode coupling constants were found to be crucial in quantitatively simulating the vibrational spectra of hydrogen-bond networking liquid water.

  4. Intermolecular (119)Sn,(31)P Through-Space Spin-Spin Coupling in a Solid Bivalent Tin Phosphido Complex.

    PubMed

    Arras, Janet; Eichele, Klaus; Maryasin, Boris; Schubert, Hartmut; Ochsenfeld, Christian; Wesemann, Lars

    2016-05-01

    A bivalent tin complex [Sn(NP)2] (NP = [(2-Me2NC6H4)P(C6H5)](-)) was prepared and characterized by X-ray diffraction and solution and solid-state nuclear magnetic resonance (NMR) spectroscopy. In agreement with the X-ray structures of two polymorphs of the molecule, (31)P and (119)Sn CP/MAS NMR spectra revealed one crystallographic phosphorus and tin site with through-bond (1)J((117/119)Sn,(31)P) and through-space (TS)J((117/119)Sn,(31)P) spin-spin couplings. Density functional theory (DFT) calculations of the NMR parameters confirm the experimental data. The observation of through-space (TS)J((117/119)Sn,(31)P) couplings was unexpected, as the distances of the phosphorus atoms of one molecule and the tin atom of the neighboring molecule (>4.6 Å) are outside the sum of the van der Waals radii of the atoms P and Sn (4.32 Å). The intermolecular Sn···P separations are clearly too large for bonding interactions, as supported by a natural bond orbital (NBO) analysis. PMID:27071033

  5. Intermolecular Transposition of Is10 Causes Coupled Homologous Recombination at the Transposition Site

    PubMed Central

    Eichenbaum, Z.; Livneh, Z.

    1995-01-01

    Interplasmid and chromosome to plasmid transposition of IS10 were studied by assaying inactivation of the phage 434 cI gene, carried on a low copy number plasmid. This was detected by the activity of the tet gene expressed from the phage 434 P(R) promoter. Each interplasmid transposition resulted in the fusion of the donor and acceptor plasmids into cointegrate structure, with a 9-bp duplication of the target DNA at the insertion site. Cointegrate formation was abolished in δrecA strains, although simple insertions of IS10 were observed. This suggests a two-stage mechanism involving IS10 conservative transposition, followed by homologous recombination between the donor and the acceptor. Two plasmids carrying inactive IS10 sequences were fused to cointegrates at a 100-fold lower frequency, suggesting that homologous recombination is coupled to and stimulated by the transposition event. Each IS10 transposition from the chromosome to the acceptor plasmid involved replicon fusion, providing a mechanism for IS10-mediated integration of extrachromosomal elements into the chromosome. This was accompanied by the formation of an additional copy of IS10 in the chromosome. Thus, like replicative transposition, conservative transposition of IS10 is accompanied by cointegrate formation and results in duplication of the IS10. PMID:7672587

  6. Probing anomalous gauge boson couplings at LEP

    SciTech Connect

    Dawson, S.; Valencia, G.

    1994-12-31

    We bound anomalous gauge boson couplings using LEP data for the Z {yields} {bar {integral}}{integral} partial widths. We use an effective field theory formalism to compute the one-loop corrections resulting from non-standard model three and four gauge boson vertices. We find that measurements at LEP constrain the three gauge boson couplings at a level comparable to that obtainable at LEPII.

  7. Energy of the quasi-free electron in hydrogen, deuterium and oxygen: Probing intermolecular potentials within the local Wigner-Seitz model

    NASA Astrophysics Data System (ADS)

    Krynski, Kamil; Streeter, Zachary; Evans, Cherice; Findley, Gary L.

    We present for the first time the quasi-free electron energy V0 (ρ) for H2, D2 and O2 from gas to liquid densities, on noncritical isotherms and on a near critical isotherm in each fluid. These data illustrate the ability of field enhanced photoemission (FEP) to determine V0 (ρ) accurately in strongly optically absorbing fluids (e.g., O2) and fluids with extremely low critical temperatures (e.g., H2 and D2). We also show that the isotropic local Wigner-Seitz model for V0 (ρ) - when coupled with thermodynamic data for the fluid - can yield optimized parameters for intermolecular potentials, as well as zero kinetic energy electron scattering lengths. All measurements were performed at the University of Wisconsin Synchrotron Radiation Center. This work was supported by a grant from the National Science Foundation (NSF CHE-0956719).

  8. Two-dimensional probe absorption in coupled quantum dots

    NASA Astrophysics Data System (ADS)

    Liu, Ningwu; Zhang, Yan; Kang, Chengxian; Wang, Zhiping; Yu, Benli

    2016-07-01

    We investigate the two-dimensional (2D) probe absorption in coupled quantum dots. It is found that, due to the position-dependent quantum interference effect, the 2D optical absorption spectrum can be easily controlled via adjusting the system parameters. Thus, our scheme may provide some technological applications in solid-state quantum communication.

  9. An energy decomposition analysis for intermolecular interactions from an absolutely localized molecular orbital reference at the coupled-cluster singles and doubles level

    SciTech Connect

    Azar, R. Julian; Head-Gordon, Martin

    2012-01-14

    We propose a wave function-based method for the decomposition of intermolecular interaction energies into chemically-intuitive components, isolating both mean-field- and explicit correlation-level contributions. We begin by solving the locally-projected self-consistent field for molecular interactions equations for a molecular complex, obtaining an intramolecularly polarized reference of self-consistently optimized, absolutely-localized molecular orbitals (ALMOs), determined with the constraint that each fragment MO be composed only of atomic basis functions belonging to its own fragment. As explicit inter-electronic correlation is integral to an accurate description of weak forces underlying intermolecular interaction potentials, namely, coordinated fluctuations in weakly interacting electronic densities, we add dynamical correlation to the ALMO polarized reference at the coupled-cluster singles and doubles level, accounting for explicit dispersion and charge-transfer effects, which map naturally onto the cluster operator. We demonstrate the stability of energy components with basis set extension, follow the hydrogen bond-breaking coordinate in the C{sub s}-symmetry water dimer, decompose the interaction energies of dispersion-bound rare gas dimers and other van der Waals complexes, and examine charge transfer-dominated donor-acceptor interactions in borane adducts. We compare our results with high-level calculations and experiment when possible.

  10. H2 and (H2)2 molecules with an ab initio optimization of wave functions in correlated state: electron-proton couplings and intermolecular microscopic parameters

    NASA Astrophysics Data System (ADS)

    Kądzielawa, Andrzej P.; Bielas, Agata; Acquarone, Marcello; Biborski, Andrzej; Maśka, Maciej M.; Spałek, Józef

    2014-12-01

    The hydrogen molecules H2 and {{≤ft( {{H}2} \\right)}2} are analyzed with electronic correlations taken into account between the 1s electrons in an exact manner. The optimal single-particle Slater orbitals are evaluated in the correlated state of H2 by combining their variational determination with the diagonalization of the full Hamiltonian in the second-quantization language. All electron-ion coupling constants are determined explicitly and their relative importance is discussed. Sizable zero-point motion amplitude and the corresponding energy are then evaluated by taking into account the anharmonic contributions up to the ninth order in the relative displacement of the ions from their static equilibrium value. The applicability of the model to solid molecular hydrogen is briefly analyzed by calculating intermolecular microscopic parameters for the 2× {{H}2} rectangular configuration, as well its ground state energy.

  11. Probing scalar coupling differences via long-lived singlet states

    NASA Astrophysics Data System (ADS)

    DeVience, Stephen J.; Walsworth, Ronald L.; Rosen, Matthew S.

    2016-01-01

    We probe small scalar coupling differences via the coherent interactions between two nuclear spin singlet states in organic molecules. We show that the spin-lock induced crossing (SLIC) technique enables the coherent transfer of singlet order between one spin pair and another. The transfer is mediated by the difference in syn and anti vicinal or long-range J couplings among the spins. By measuring the transfer rate, we calculate a J coupling difference of 8 ± 2 mHz in phenylalanine-glycine-glycine and 2.57 ± 0.04 Hz in glutamate. We also characterize a coherence between two singlet states in glutamate, which may enable the creation of a long-lived quantum memory.

  12. Intra- and Intermolecular Nickel-Catalyzed Reductive Cross-Electrophile Coupling Reactions of Benzylic Esters with Aryl Halides.

    PubMed

    Konev, Mikhail O; Hanna, Luke E; Jarvo, Elizabeth R

    2016-06-01

    Nickel-catalyzed cross-electrophile coupling reactions of benzylic esters and aryl halides have been developed. Both inter- and intramolecular variants proceed under mild reaction conditions. A range of heterocycles and functional groups are tolerated under the reaction conditions. Additionally, the first example of a stereospecific cross-electrophile coupling of a secondary benzylic ester is described. PMID:27099968

  13. Langmuir Probe Distortions and Probe Compensation in an Inductively Coupled Plasma

    NASA Technical Reports Server (NTRS)

    Ji, J. S.; Cappelli, M. A.; Kim, J. S.; Rao, M. V. V. S.; Sharma, S. P.

    1999-01-01

    In many RF discharges, Langmuir probe measurements are usually made against a background of sinusoidal (and not so sinusoidal) fluctuations in the plasma parameters such as the plasma potential (Vp), the electron number density (ne), and the electron temperature (Te). The compensation of sinusoidal fluctuations in Vp has been extensively studied and is relatively well understood. Less attention has been paid to the possible distortions introduced by small fluctuations in plasma density and/or plasma temperature, which may arise in the sheath and pre-sheath regions of RF discharges. Here, we present the results of a model simulation of probe characteristics subject to fluctuations in both Vp and ne. The modeling of probe distortion due to possible fluctuations in Te is less straightforward. A comparison is presented of calculations with experimental measurements using a compensated and uncompensated Langmuir probe in an inductively coupled GEC reference cell plasma, operating on Ar and Ar/CF4 mixtures. The plasma parameters determined from the compensated probe characteristics are compared to previous measurements of others made in similar discharges, and to our own measurements of the average electron density derived from electrical impedance measurements.

  14. Driving Forces for Covalent Assembly of Porphyrins by Selective C-H Bond Activation and Intermolecular Coupling on a Copper Surface.

    PubMed

    Floris, Andrea; Haq, Sam; In't Veld, Mendel; Amabilino, David B; Raval, Rasmita; Kantorovich, Lev

    2016-05-11

    Recent synthesis of covalent organic assemblies at surfaces has opened the promise of producing robust nanostructures for functional interfaces. To uncover how this new chemistry works at surfaces and understand the underlying mechanisms that control bond-breaking and bond-making processes at specific positions of the participating molecules, we study here the coupling reaction of tetra(mesityl)porphyrin molecules, which creates covalently connected networks on the Cu(110) surface by utilizing the 4-methyl groups as unique connection points. Using scanning tunneling microscopy (STM), state-of-the-art density functional theory (DFT), and Nudged Elastic Band (NEB) calculations, we show that the unique directionality of the covalent bonding is found to stem from a chain of highly selective C-H activation and dehydrogenation processes, followed by specific intermolecular C-C coupling reactions that are facilitated by the surface, by steric constraints, and by anisotropic molecular diffusion. These insights provide the first steps toward developing synthetic rules for complex two-dimensional covalent organic chemistry that can be enacted directly at a surface to deliver specific macromolecular structures designed for specific functions. PMID:27097295

  15. A fiber-optically coupled positron-sensitive surgical probe

    SciTech Connect

    Raylman, R.R.; Wahl, R.L.

    1994-05-01

    Positron-emitting radiopharmaceuticals such as {sup 18}F-labeled 2-deoxy-D-glucose (FDG) have considerable utility in the noninvasive imaging of cancers due to their rapid and excellent tumor-localizing properties. In addition, the relatively short range of positrons in tissue facilitates the precise delineation of FDG-avid tumors. Therefore, FDG used in conjunction with a positron-sensitive probe may be capable of guiding surgical procedures. Many of the current probe systems, however, are sensitive to the intense flux of background photons produced by positron annihilation. The authors describe the design, manufacture and initial in vitro and in vivo testing of a probe well-suited to the detection of positron-emitting isotopes in a high-photon background. The device consists of a small piece of plastic scintillator coupled by fiber-optic cable to a photomultiplier tube. Measurements of resolution and detector sensitivity were obtained. In addition, the reduction in resolution caused by the effects of various levels of background photon flux was determined. These measurements indicate that resolution is degraded minimally ({approximately}5% with a background-to-source ratio of 2:1) due to annihilation photon background. Sensitivity for positrons is good, detecting amounts of radioactivity as low as 10.2 nCi of FDG in vitro. In rats given FDG subcutaneously, lymph nodes containing as little as 11 nCi of FDG could be detected above the background activity levels present in normal surrounding tissues. A plastic scintillator probe system has been devised which may be highly suitable for intraoperative FDG-guided (or other positron or beta emitting-tracer) surgery. 29 refs., 7 figs.

  16. Intermolecular reductive coupling of esters with benzophenones by low-valent titanium: synthesis of diarylmethyl ketones revisited.

    PubMed

    Kise, Naoki; Sakurai, Toshihiko

    2015-04-01

    The reductive coupling of aliphatic esters with benzophenones by Zn-TiCl4 in THF gave two- and four-electron reduced products, diaryl(hydroxy)methyl ketones, and diarylmethyl ketones selectively by controlling the reaction conditions. In the reaction of aromatic esters with benzophenones, diarylmethyl ketones were obtained as the sole products. N-(Alkoxycarbonyl)-(S)-α-amino acid methyl esters gave optically active diphenylmethyl ketones by reduction with benzophenone. The obtained diphenylmethyl ketones were transformed to 4,5-cis-disubstituted oxazolidin-2-ones stereoselectively. PMID:25748528

  17. Control of the intermolecular coupling of dibromotetracene on Cu(110) by the sequential activation of C-Br and C-H bonds.

    PubMed

    Ferrighi, Lara; Píš, Igor; Nguyen, Thanh Hai; Cattelan, Mattia; Nappini, Silvia; Basagni, Andrea; Parravicini, Matteo; Papagni, Antonio; Sedona, Francesco; Magnano, Elena; Bondino, Federica; Di Valentin, Cristiana; Agnoli, Stefano

    2015-04-01

    Dibromotetracene molecules are deposited on the Cu(110) surface at room temperature. The complex evolution of this system has been monitored at different temperatures (i.e., 298, 523, 673, and 723 K) by means of a variety of complementary techniques that range from STM and temperature-programmed desorption (TPD) to high-resolution X-ray spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). State-of-the-art density-functional calculations were used to determine the chemical processes that take place on the surface. After deposition at room temperature, the organic molecules are transformed into organometallic monomers through debromination and carbon-radical binding to copper adatoms. Organometallic dimers, trimers, or small oligomers, which present copper-bridged molecules, are formed by increasing the temperature. Surprisingly, further heating to 673 K causes the formation of elongated chains along the Cu(110) close-packed rows as a consequence of radical-site migration to the thermodynamically more stable molecule heads. Finally, massive dehydrogenation occurs at the highest temperature followed by ring condensation to nanographenic patches. This study is a paradigmatic example of how intermolecular coupling can be modulated by the stepwise control of a simple parameter, such as temperature, through a sequence of domino reactions. PMID:25711882

  18. Determination of Multidimensional Intermolecular Potential Energy Surfaces

    NASA Astrophysics Data System (ADS)

    Cohen, Ronald Carl

    High resolution spectroscopy of the low frequency van der Waals vibrations (also referred to as Vibration -Rotation-Tunneling (VRT) spectroscopy) in weakly bound complexes provides the means to probe intermolecular forces with unprecedented detail and precision. We present an overview of the experimental information on intermolecular forces and intermolecular dynamics which has been obtained by far infrared VRT spectroscopy of 18 complexes. We then turn to a detailed examination of the Ar-H_2O complex, a simple prototype for the study of intermolecular forces. The measurement and analysis of 9 VRT bands is described. These data are first used to obtain a qualitative description of the intermolecular potential energy surface (IPS). A new simple and efficient method for calculating the eigenvalues of the multidimensional intermolecular dynamics on the IPS has been developed. This algorithm (an adaptation of the Collocation Method) was then used in a direct fit to obtain an accurate and detailed description of the intermolecular forces acting within the Ar-H_2O complex.

  19. Improving the Mass-Limited Performance of Routine NMR Probes using Coupled Coils.

    PubMed

    Marsden, Brian; Lim, Victor; Taber, Bob; Zens, Albert

    2016-07-01

    We report a method to convert, on demand, a general use dual-broadband probe to a high performance mass-limited probe for both high band and low band nuclei. This technology uses magnetic coupling of inductors to achieve this capability. The method offers a cost effective way of increasing the performance of routine NMR probes without having to change probes or increase the overall foot print of the spectrometer. PMID:27155588

  20. Improving the Mass-Limited Performance of Routine NMR Probes using Coupled Coils

    NASA Astrophysics Data System (ADS)

    Marsden, Brian; Lim, Victor; Taber, Bob; Zens, Albert

    2016-07-01

    We report a method to convert, on demand, a general use dual-broadband probe to a high performance mass-limited probe for both high band and low band nuclei. This technology uses magnetic coupling of inductors to achieve this capability. The method offers a cost effective way of increasing the performance of routine NMR probes without having to change probes or increase the overall foot print of the spectrometer.

  1. Remote coupling between a probe and a superconducting klystron cavity for use in gravitational wave detectors

    NASA Astrophysics Data System (ADS)

    de Paula, L. A. N.; Aguiar, O. D.; Oliveira, N. F., Jr.

    2013-08-01

    In this work the main task was to measure the remote coupling between a probe and some niobium superconducting reentrant cavities for use in parametric transducers of gravitational wave detectors. The cavities were manufactured from RRR300 niobium and cryogenically tested to determine the electromagnetic coupling among other parameters. These cavities were also closed using a RRR300 niobium cover forming a narrow axial gap with the post top. A hole was made at the base opposite the cover in order to the probe reach the cavity. Generally, the critical coupling (β ≈ 1) is achieved with the probe inside the cavity. The mechanical connection of the probe with the transducer and the external circuit introduces an unwanted seismic noise in the transducer. The microstrip antennas have been traditionally employed to make a wireless connection. However, this study has demonstrated coupling factor β ≈ 1 with the probe moved away 4.0 mm from the cavity with a 3.0 mm diameter hole. Couplings with the probe moved away 1.0 mm and 7.0 mm from cavities with 1.5 mm and 3.5 mm diameter holes, respectively, have also been obtained. These results have revealed the influence of the hole diameter with the remote coupling between an electric field probe and the klystron mode of a superconducting reentrant cavity. Due to the practicalities, this effect may replace the microstrip antennas making it possible to implement high sensitivity parametric transducers.

  2. Energy of the quasi-free electron in H{sub 2}, D{sub 2}, and O{sub 2}: Probing intermolecular potentials within the local Wigner-Seitz model

    SciTech Connect

    Evans, C. M. Krynski, Kamil; Streeter, Zachary; Findley, G. L.

    2015-12-14

    We present for the first time the quasi-free electron energy V{sub 0}(ρ) for H{sub 2}, D{sub 2}, and O{sub 2} from gas to liquid densities, on noncritical isotherms and on a near critical isotherm in each fluid. These data illustrate the ability of field enhanced photoemission (FEP) to determine V{sub 0}(ρ) accurately in strongly absorbing fluids (e.g., O{sub 2}) and fluids with extremely low critical temperatures (e.g., H{sub 2} and D{sub 2}). We also show that the isotropic local Wigner-Seitz model for V{sub 0}(ρ) — when coupled with thermodynamic data for the fluid — can yield optimized parameters for intermolecular potentials, as well as zero kinetic energy electron scattering lengths.

  3. Probe-Sample Coupling in the Magnetic Resonance Force Microscope

    NASA Astrophysics Data System (ADS)

    Suter, A.; Pelekhov, D. V.; Roukes, M. L.; Hammel, P. C.

    2002-02-01

    The magnetic resonance force microscope (MRFM) provides a route to achieving scanned probe magnetic resonance imaging with extremely high spatial resolution. Achieving this capability will require understanding the force exerted on a microscopic magnetic probe by a spatially extended sample over which the probe is scanned. Here we present a detailed analysis of this interaction between probe and sample. We focus on understanding the situation where the micromagnet mounted on the mechanical resonator generates a very inhomogeneous magnetic field and is scanned over a sample with at least one spatial dimension much larger than that of the micromagnet. This situation differs quite significantly from the conditions under which most MRFM experiments have been carried out where the sample is mounted on the mechanical resonator and placed in a rather weak magnetic field gradient. In addition to the concept of a sensitive slice (the spatial region where the magnetic resonance condition is met) it is valuable to map the forces exerted on the probe by spins at various locations; this leads to the concept of the force slice (the region in which spins exert force on the resonator). Results of this analysis, obtained both analytically and numerically, will be qualitatively compared with an initial experimental finding from an EPR-MRFM experiment carried out on DPPH at 4 K.

  4. Probe--sample coupling in the magnetic resonance force microscope.

    PubMed

    Suter, A; Pelekhov, D V; Roukes, M L; Hammel, P C

    2002-02-01

    The magnetic resonance force microscope (MRFM) provides a route to achieving scanned probe magnetic resonance imaging with extremely high spatial resolution. Achieving this capability will require understanding the force exerted on a microscopic magnetic probe by a spatially extended sample over which the probe is scanned. Here we present a detailed analysis of this interaction between probe and sample. We focus on understanding the situation where the micromagnet mounted on the mechanical resonator generates a very inhomogeneous magnetic field and is scanned over a sample with at least one spatial dimension much larger than that of the micromagnet. This situation differs quite significantly from the conditions under which most MRFM experiments have been carried out where the sample is mounted on the mechanical resonator and placed in a rather weak magnetic field gradient. In addition to the concept of a sensitive slice (the spatial region where the magnetic resonance condition is met) it is valuable to map the forces exerted on the probe by spins at various locations; this leads to the concept of the force slice (the region in which spins exert force on the resonator). Results of this analysis, obtained both analytically and numerically, will be qualitatively compared with an initial experimental finding from an EPR-MRFM experiment carried out on DPPH at 4 K. PMID:11846579

  5. Capacitively coupled RF voltage probe having optimized flux linkage

    DOEpatents

    Moore, James A.; Sparks, Dennis O.

    1999-02-02

    An RF sensor having a novel current sensing probe and a voltage sensing probe to measure voltage and current. The current sensor is disposed in a transmission line to link all of the flux generated by the flowing current in order to obtain an accurate measurement. The voltage sensor is a flat plate which operates as a capacitive plate to sense voltage on a center conductor of the transmission line, in which the measured voltage is obtained across a resistance leg of a R-C differentiator circuit formed by the characteristic impedance of a connecting transmission line and a capacitance of the plate, which is positioned proximal to the center conductor.

  6. The coupling of condensed matter excitations to electron probes

    SciTech Connect

    Ritchie, R.H.

    1988-01-01

    Aspects of coupling of a classical electron with bulk and surface excitations in condensed matter have been sketched. Some considerations of a self-energy approach to the complete quantal treatment of this coupling have been given. 19 refs., 3 figs.

  7. Control of the probe absorption in coupled quantum wells in two dimensions

    NASA Astrophysics Data System (ADS)

    Kang, Chengxian; Ma, Yangcheng; Wang, Zhiping; Yu, Benli

    2016-06-01

    We investigate the probe absorption of a weak probe field in two dimensions (the so-called two-dimensional probe absorption) in an asymmetric two coupled quantum wells. It is found that, due to the joint quantum interference induced by the standing-wave and coherent coupling fields, the probe absorption can be easily controlled via adjusting the system parameters in two dimensions. Most importantly, the pattern of probe absorption can be localized at a particular position and the maximal probability of finding the pattern in one period of the standing-wave fields reaches unity by properly adjusting the system parameters. Thus, our scheme may provide some technological applications in solid-state optoelectronics and quantum information science.

  8. Langmuir Probe Measurements in an Inductively Coupled GEC Reference Cell Plasma

    NASA Technical Reports Server (NTRS)

    Ji, J. S.; Kim, J. S.; Cappelli, M. A.; Sharma, S. P.; Arnold, J. O. (Technical Monitor)

    1998-01-01

    Measurements of electron number density, electron temperature, and electron energy distribution function (EEDF) using a compensated Langmuir probe have been performed on an inductively (transformer ) coupled Gaseous Electronics Conference (GEC) reference cell plasma. The plasma source is operated with CH4, CF4, or their mixtures with argon. The effect of independently driving the electrode supporting the wafer on the probe data is studied. In particular, we find that the plasma structure depends on the phase in addition to the magnitude of the power coupled to the electrode relative to that of the transformer coil. The Langmuir probe is translated in a plane parallel to the electrode to investigate the spatial structure of the plasma. The probe data is also compared with fluid model predictions.

  9. Probing strongly coupled anisotropic plasmas from higher curvature gravity

    NASA Astrophysics Data System (ADS)

    Jahnke, Viktor; Misobuchi, Anderson Seigo

    2016-06-01

    We consider five-dimensional AdS-axion-dilaton gravity with a Gauss-Bonnet term and use a black brane solution displaying spatial anisotropy as the gravity dual of a strongly coupled anisotropic plasma. We compute several observables relevant to the study of the plasma, namely, the drag force, the jet quenching parameter, the quarkonium potential, and the thermal photon production. The effects of higher derivative corrections and of the anisotropy are discussed and compared with previous results.

  10. Detection of glucose via enzyme-coupling reaction based on a DT-diaphorase fluorescence probe.

    PubMed

    Gao, Xinghui; Li, Xiaohua; Wan, Qiongqiong; Li, Zhao; Ma, Huimin

    2014-03-01

    Enzyme-coupling reactions play an important role in the assay of analytes. In this manuscript, we developed a new fluorescent probe for the detection of glucose through the enzyme-coupling reaction of DT-diaphorase (DTD). The probe was synthesized through a mild and simple synthetic procedure, and showed good fluorescence response to DTD. The reactions for the detection of glucose proceed as follows: glucose dehydrogenase oxidizes glucose to gluconolactone with NAD(+) as the electron acceptor to yield NADH, and NADH can be utilized by DTD to further react with the probe releasing resorufin. As a result of these tandem reactions, fluorescence off-on response will occur. The method showed high selectivity for glucose with a detection limit of 0.2 µM, which may provide a potential way for fluorescence detection of glucose through enzyme-coupling reactions. Furthermore, the applicability of the method has been demonstrated by detecting glucose in human urine samples. PMID:24468396

  11. Eddy current probe for nondestructive testing using cross-coupled figure-eight coils

    SciTech Connect

    Sasada, I.; Watanabe, N.

    1995-11-01

    It is shown that the pickup head consisting of cross-coupled figure-eight coils originally developed for the magnetostrictive torque sensor is well suited for the eddy current probe detecting small defects in a nonmagnetic conductive material. The probe is easily extended to a one dimensional array form, which substantially reduces number of times of scanning the targeted materials. The response of a single unit of the probe to a trough hole defect in an aluminum plate are presented. A half-way hole at the back of an aluminum plate of 1.2 mm in thickness was successfully detected from the front using this probe. A five-channel array was developed in which the excitation coil is shared by all the channel. A small through hole defect in an aluminum plate was detected clearly by a single scan with the array probe.

  12. Ultrasonic imaging of hidden defects using dry-coupled ultrasonic probes

    NASA Astrophysics Data System (ADS)

    Komsky, Igor N.

    2006-03-01

    Safety criteria of aircraft industry require careful inspection of aircraft components for structural integrity since airworthiness of aging aircraft can be significantly affected by combination of corrosion and fatigue damage. Surface defects can be efficiently detected by visual or other surface inspection techniques. Detection of hidden defects, on the other hand, is still a challenging task. Therefore, it is essential to develop non-destructive methods that can inspect different layers of the aircraft structures for internal defects before they become a safety concern. Ultrasonic probes with the dry-coupled substrates are highly efficient for all modalities of ultrasonic techniques including pulse-echo, pitch-catch, or through-transmission modes. The probes can be deployed in conjunction with portable ultrasonic instruments for B- and C-scanning. The dry-coupled probes have already been tested on a number of aircraft for rapid inspections of the aircraft structures from the outside without any disassembly. However, adequate inspection for small pitting corrosion and incipient fatigue cracks in metallic structures or delaminations in composite panels may require superior sensitivity and resolution of the applied ultrasonic technique. Several novel configurations of the dry-coupled probes with increased sensitivity and resolution will be presented. Ultrasonic imaging with single- or double-element dry-coupled probes will be demonstrated on the specimens with heavy pitting corrosion, machined planar and volumetric defects, and embedded internal flaws.

  13. Probing cell membrane dynamics using plasmon coupling microscopy

    NASA Astrophysics Data System (ADS)

    Rong, Guoxin

    The plasma membrane of mammalian cells is depicted as a two-dimensional hybrid material which is compartmentalized into submicron-sized domains. These membrane domains play a pivotal role in cellular signaling processes due to selective recruitment of specific cell surface receptors. The structural dynamics of the membrane domains and their exact biological functions are, however, still unclear, partially due to the wave nature of light, which limits the optical resolution in the visible light to approximately 400 nm in conventional optical microscopy. Here, we provide a non-fluorescence based approach for monitoring distance changes on subdiffraction limit length scales in a conventional far-field optical microscope. This approach, which is referred to as plasmon coupling microscopy (PCM), utilizes the distance dependent near-field coupling between noble metal nanoparticle (NP) labels to resolve close contacts on the length scale of approximately one NP diameter. We firstly utilize this PCM strategy to resolve interparticle separations during individual encounters of gold NP labeled fibronectin-integrin complexes in living HeLa cells. We then further refine this ratiometric detection methodology by augmenting it with a polarization-sensitive detection, which enables simultaneous monitoring of the distance and conformation changes in NP dimers and clusters. We apply this polarization resolved PCM approach to characterize the structural lateral heterogeneity of cell membranes on sub-micron length scales. Finally, we demonstrate that PCM can provide quantitative information about the structural dynamics of individual epidermal growth factor receptor (ErbB1)-enriched membrane domains in living cells.

  14. Probing transmembrane mechanical coupling and cytomechanics using magnetic twisting cytometry

    NASA Technical Reports Server (NTRS)

    Wang, N.; Ingber, D. E.

    1995-01-01

    We recently developed a magnetic twisting cytometry technique that allows us to apply controlled mechanical stresses to specific cell surface receptors using ligand-coated ferromagnetic microbeads and to simultaneously measure the mechanical response in living cells. Using this technique, we have previously shown the following: (i) beta 1 integrin receptors mediate mechanical force transfer across the cell surface and to the cytoskeleton, whereas other transmembrane receptors (e.g., scavenger receptors) do not; (ii) cytoskeletal stiffness increases in direct proportion to the level of stress applied to integrins; and (iii) the slope of this linear stiffening response differs depending on the shape of the cell. We now show that different integrins (beta 1, alpha V beta 3, alpha V, alpha 5, alpha 2) and other transmembrane receptors (scavenger receptor, platelet endothelial cell adhesion molecule) differ in their ability to mediate force transfer across the cell surface. In addition, the linear stiffening behavior previously observed in endothelial cells was found to be shared by other cell types. Finally, we demonstrate that dynamic changes in cell shape that occur during both cell spreading and retraction are accompanied by coordinate changes in cytoskeletal stiffness. Taken together, these results suggest that the magnetic twisting cytometry technique may be a powerful and versatile tool for studies analyzing the molecular basis of transmembrane mechanical coupling to the cytoskeleton as well as dynamic relations between changes in cytoskeletal structure and alterations in cell form and function.

  15. Pneumatic switched angle spinning NMR probe with capacitively coupled double saddle coil.

    PubMed

    Litvak, Ilya M; Espinosa, Catalina A; Shapiro, Rebecca A; Oldham, Andrew N; Duong, Vincent V; Martin, Rachel W

    2010-10-01

    Switched angle spinning (SAS) experiments can be used for generating isotropic-anisotropic correlations in oriented samples in a single experiment. In order for these methods to become widespread, specialized hardware is required. Here we describe the electronic and mechanical design and performance of a double-resonance SAS probe. Unlike many previous SAS probe implementations, the focus here is on systems where the dipolar couplings are partially averaged by molecular motion. This probe has a moving double saddle coil capacitively coupled to the stationary circuit. Angle switching is accomplished by a steam engine-type pneumatic mechanism. The speed and stability of the switching hardware for SAS experiments are demonstrated using spectra of model compounds. PMID:20673643

  16. Pneumatic switched angle spinning NMR probe with capacitively coupled double saddle coil

    NASA Astrophysics Data System (ADS)

    Litvak, Ilya M.; Espinosa, Catalina A.; Shapiro, Rebecca A.; Oldham, Andrew N.; Duong, Vincent V.; Martin, Rachel W.

    2010-10-01

    Switched angle spinning (SAS) experiments can be used for generating isotropic-anisotropic correlations in oriented samples in a single experiment. In order for these methods to become widespread, specialized hardware is required. Here we describe the electronic and mechanical design and performance of a double-resonance SAS probe. Unlike many previous SAS probe implementations, the focus here is on systems where the dipolar couplings are partially averaged by molecular motion. This probe has a moving double saddle coil capacitively coupled to the stationary circuit. Angle switching is accomplished by a steam engine-type pneumatic mechanism. The speed and stability of the switching hardware for SAS experiments are demonstrated using spectra of model compounds.

  17. Prediction of atomic force microscope probe dynamics through the receptance coupling method

    SciTech Connect

    Mehrpouya, M.; Park, S. S.

    2011-12-15

    The increased growth in the use of tip-based sensing, manipulations, and fabrication of devices in atomic force microscopy (AFM) necessitates the accurate prediction of the dynamic behavior of the AFM probe. The chip holder, to which the micro-sensing device is attached, and the rest of the AFM system can affect the overall dynamics of the probe. In order to consider these boundary effects, we propose a novel receptance coupling method to mathematically combine the dynamics of the AFM setup and probe, based on the equilibrium and compatibility conditions at the joint. Once the frequency response functions of displacement over force at the tool tip are obtained, the dynamic interaction forces between the tip and the sample in nanoscale can be determined by measuring the probe tip displacement.

  18. Probing electromechanical coupling in collagen at the nanoscale via scanning probe microscopy

    NASA Astrophysics Data System (ADS)

    Denning, Denise

    Electromechanical coupling is ubiquitous in nature and is a functional characteristic in a large range of inorganic and organic materials, including collagen type I -- a fibrous protein abundant in mammals. Understanding the biofunctionality of electromechanical coupling in its linear form -- piezoelectricity, has been a topic of research spanning over seven decades and yet many questions still remain unanswered. Piezoelectricity in bone and connective tissues such as tendon has been investigated at the macroscopic scale since the discovery of piezoelectricity in bone in 1957 and induced currents via the piezoelectric effect have been shown to activate the healing process in tissues under tension. Biological systems consist of complex hierarchical structures which results from a high degree of organization from the macroscale down to the nanoscale. These complex structures, however, make quantitative piezoelectric measurements difficult. Therefore, there exists a need to understand these processes at the individual protein level -- i.e. at the nanoscale. In this thesis, a voltage-modulated form of atomic force microscopy called piezoresponse force microscopy is utilized to investigate the counterpart which is responsible for piezoelectricity in bone and connective tissues -- collagen. The polar properties of collagen were revealed at the nanoscale and were shown to result in a highly complex polar architecture in natural tissue, which is important for understanding tissue development. Shear piezoelectricity was discovered to persist in engineered collagen hydrogels, a study intended to highlight the importance of replicating both structural and functional properties in replacement tissues. The electromechanical properties of collagen type II were investigated which were previously unknown. Collagen type II was shown to be a shear piezoelectric, exhibiting an angle dependence of the piezoelectric signal with cantilever-fibril angle. In addition, the piezoelectric

  19. Transient gain-absorption of the probe field in triple quantum dots coupled by double tunneling

    NASA Astrophysics Data System (ADS)

    Tian, Si-Cong; Zhang, Xiao-Jun; Wan, Ren-Gang; Zhao, Shuai; Wu, Hao; Shu, Shi-Li; Wang, Li-Jie; Tong, Cun-Zhu

    2016-06-01

    The transient gain-absorption property of the probe field in a linear triple quantum dots coupled by double tunneling is investigated. It is found that the additional tunneling can dramatically affect the transient behaviors under the transparency condition. The dependence of transient behaviors on other parameters, such as probe detuning, the pure dephasing decay rate of the quantum dots and the initial conditions of the population, are also discussed. The results can be explained by the properties of the dressed states generated by the additional tunneling. The scheme may have important application in quantum information network and communication.

  20. Tamm State-Coupled Emission: Effect of Probe Location and Emission Wavelength

    PubMed Central

    2015-01-01

    We report the effect of the probe location and wavelength on the emission spatial distribution and spectral properties of fluorophores located on structures which display Tamm states. Our structure consists of a one-dimensional photonic crystal (1DPC)—that is, a multilayer structure of alternate high and low refractive index dielectrics—and a thin top silver film. Simulations show the presence of Tamm and surface plasmon modes in the structure. The electric field intensities for the Tamm modes are located mostly in the dielectric layer below the metal film. The corresponding field intensities for the surface plamon modes are located above the metal film in the distal side. Tamm states can be in resonance with the incident light normal or near normal to the surface, within the light line, and can be accessed without the use of a coupling prism or gratings. We investigated the emission spectra and angular distribution of the emission for probes located above and below the metal film to explore the interaction of fluorophores with Tamm plasmons and surface plasmons modes. Three probes were chosen with different overlap of the emission spectra with the Tamm modes. The fluorophores below the metal film coupled predominantly with the Tamm state and displayed more intense and only Tamm state-coupled emission (TSCE). Probes above the metal film display both surface plasmon-coupled emission (SPCE) and Tamm state-coupled emission. In contrast to SPCE, which shows only KR, P-polarized emission, the Tamm states can display both S- and P-polarized emission and can be populated using both RK and KR illuminations. The TSCE angle is highly sensitive to wavelength, which suggests the use of Tamm structures to provide both directional emission and wavelength dispersion. The combination of plasmonic and photonic structures with directional emission close to surface normal offers the opportunities for new design formats for clinical testing, portable devices, and other

  1. Probing Spin-Orbit Coupling and Interlayer Coupling in Atomically Thin Molybdenum Disulfide Using Hydrostatic Pressure.

    PubMed

    Dou, Xiuming; Ding, Kun; Jiang, Desheng; Fan, Xiaofeng; Sun, Baoquan

    2016-01-26

    In two-dimensional transition-metal dichalcogenides, both spin-orbit coupling and interlayer coupling play critical roles in the electronic band structure and are desirable for the potential applications in spin electronics. Here, we demonstrate the pressure characteristics of the exciton absorption peaks (so-called excitons A, B and C) in monolayer, bilayer, and trilayer molybdenum disulfide (MoS2) by studying the reflectance spectra under hydrostatic pressure and performing the electronic band structure calculations based on density functional theory to account for the experimental observations. We find that the valence band maximum splitting at the K point in monolayer MoS2, induced by spin-orbit coupling, remains almost unchanged with increasing pressure applied up to 3.98 GPa, indicating that the spin-orbit coupling is insensitive to the pressure. For bilayer and trilayer MoS2, however, the splitting shows an increase with increasing pressure due to the pressure-induced strengthening of the interlayer coupling. The experimental results are in good agreement with the theoretical calculations. Moreover, the exciton C is identified to be the interband transition related to the van Hove singularity located at a special point which is approximately 1/4 of the total length of Γ-K away from the Γ point in the Brillouin zone. PMID:26745440

  2. Intermolecular perturbation theory

    NASA Astrophysics Data System (ADS)

    Hayes, I. C.; Hurst, G. J. B.; Stone, A. J.

    The new intermolecular perturbation theory described in the preceding papers is applied to some van der Waals molecules. HeBe is used as a test case, and the perturbation method converges well at interatomic distances down to about 4 a0, giving results in excellent agreement with supermolecule calculations. ArHF and ArHCl have been studied using large basis sets, and the results agree well with experimental data. The ArHX configuration is favoured over the ArXH configuration mainly because of larger polarization and charge-transfer contributions. In NeH2 the equilibrium geometry is determined by a delicate balance between opposing effects; with a double-zeta-polarization basis the correct configuration is predicted.

  3. Guidelines for the Synthesis of Small-Molecule Irreversible Probes Targeting G Protein-Coupled Receptors.

    PubMed

    Jörg, Manuela; Scammells, Peter J

    2016-07-19

    Irreversible probes have been proven to be useful pharmacological tools in the study of structural and functional features in drug receptor pharmacology. They have been demonstrated to be particularly valuable for the isolation and purification of receptors. Furthermore, irreversible probes are helpful tools for the identification and characterization of binding sites, thereby supporting the advancement of rational drug design. In this Minireview, we provide insight into universal strategies and guidelines to successfully synthesize irreversible probes that target G protein-coupled receptors (GPCRs). We provide an overview of commonly used chemoreactive and photoreactive groups, and make a comparison of their properties and potential applications. Furthermore, there is a particular focus on synthetic approaches to introduce these reactive groups based on commercially available reagents. PMID:27347648

  4. Near-Field Infrared Pump-Probe Imaging of Surface Phonon Coupling in Boron Nitride Nanotubes.

    PubMed

    Gilburd, Leonid; Xu, Xiaoji G; Bando, Yoshio; Golberg, Dmitri; Walker, Gilbert C

    2016-01-21

    Surface phonon modes are lattice vibrational modes of a solid surface. Two common surface modes, called longitudinal and transverse optical modes, exhibit lattice vibration along or perpendicular to the direction of the wave. We report a two-color, infrared pump-infrared probe technique based on scattering type near-field optical microscopy (s-SNOM) to spatially resolve coupling between surface phonon modes. Spatially varying couplings between the longitudinal optical and surface phonon polariton modes of boron nitride nanotubes are observed, and a simple model is proposed. PMID:26727539

  5. Probing hybridization of a single energy level coupled to superconducting leads

    NASA Astrophysics Data System (ADS)

    van Zanten, D. M. T.; Balestro, F.; Courtois, H.; Winkelmann, C. B.

    2015-11-01

    Electron transport through a quantum dot coupled to superconducting leads shows a sharp conductance onset when a quantum dot orbital level crosses the superconducting coherence peak of one lead. We study superconducting single electron transistors in the weak coupling limit by connecting individual gold nanoparticles with aluminum leads formed by electromigration. We show that the transport features close to the conductance onset threshold can be accurately described by the quantum dot levels' hybridization with the leads, which is strongly enhanced by the divergent density of states at the superconducting gap edge. This highlights the importance of electron cotunneling effects in spectroscopies with superconducting probes.

  6. Desensitization of metastable intermolecular composites

    DOEpatents

    Busse, James R.; Dye, Robert C.; Foley, Timothy J.; Higa, Kelvin T.; Jorgensen, Betty S.; Sanders, Victor E.; Son, Steven F.

    2011-04-26

    A method to substantially desensitize a metastable intermolecular composite material to electrostatic discharge and friction comprising mixing the composite material with an organic diluent and removing enough organic diluent from the mixture to form a mixture with a substantially putty-like consistency, as well as a concomitant method of recovering the metastable intermolecular composite material.

  7. Selective coupling of HE11 and TM01 modes into microfabricated fully metal-coated quartz probes.

    PubMed

    Tortora, P; Descrovi, E; Aeschimann, L; Vaccaro, L; Herzig, H-P; Dändliker, R

    2007-01-01

    We report computational and experimental investigations on injection and transmission of light in microfabricated fully Aluminum-coated quartz probes. In particular, we show that a selective coupling of either the HE(11) or the TM(01) mode can be carried out by injecting focused linearly or radially polarized beams into the probe. Optical fields, emitted by the probe after a controlled injection, are characterized in intensity and phase with the help of an interferometric technique. With the help of near-field measurement, we finally demonstrate that a longitudinally polarized spot localized at the tip apex is actually produced when the TM(01) mode is coupled into the probe. PMID:16942840

  8. Probing the Higgs Couplings to Photons in h→4l at the LHC

    SciTech Connect

    Chen, Yi; Harnik, Roni; Vega-Morales, Roberto

    2014-11-01

    We explore the sensitivity of the Higgs decay to four leptons, the so-called golden channel, to higher dimensional loop-induced couplings of the Higgs boson to $ZZ$, $Z\\gamma$, and $\\gamma\\gamma$, allowing for general CP mixtures. The larger standard model tree level coupling $hZ^\\mu Z_\\mu$ is the dominant "background" for the loop induced couplings. However this large background interferes with the smaller loop induced couplings, enhancing the sensitivity. We perform a maximum likelihood analysis based on analytic expressions of the fully differential decay width for $h\\to 4\\ell$ ($4\\ell \\equiv 2e2\\mu, 4e, 4\\mu$) including all interference effects. We find that the spectral shapes induced by Higgs couplings to photons are particularly different than the $hZ^\\mu Z_\\mu$ background leading to enhanced sensitivity to these couplings. We show that even if the $h\\to\\gamma\\gamma$ and $h\\to 4\\ell$ rates agree with that predicted by the Standard Model, the golden channel has the potential to probe both the CP nature as well as the overall sign of the Higgs coupling to photons well before the end of high-luminosity LHC running ($\\sim$3 ab$^{-1}$).

  9. Exclusive radiative Higgs decays as probes of light-quark Yukawa couplings

    NASA Astrophysics Data System (ADS)

    König, Matthias; Neubert, Matthias

    2015-08-01

    We present a detailed analysis of the rare exclusive Higgs boson decays into a single vector meson and a photon and investigate the possibility of using these processes to probe the light-quark Yukawa couplings. We work with an effective Lagrangian with modified Higgs couplings to account for possible new-physics effects in a model-independent way. The h → Vγ decay rate is governed by the destructive interference of two amplitudes, one of which involves the Higgs coupling to the quark anti-quark pair inside the vector meson. We derive this amplitude at next-to-leading order in α s using QCD factorization, including the resummation of large logarithmic corrections and accounting for the effects of flavor mixing. The high factorization scale μ ˜ m h ensures that our results are rather insensitive to the hadronic parameters characterizing the light-cone distribution amplitude of the vector meson. The second amplitude arises from the loop-induced effective hγγ * and hγZ * couplings, where the off-shell gauge boson converts into the vector meson. We devise a strategy to eliminate theoretical uncertainties related to this amplitude to almost arbitrary precision. This opens up the possibility to probe for modifications of the c- and b-quark Yukawa couplings and modifications of the s-quark Yukawa coupling in the high-luminosity LHC run. In particular, we show that measurements of the ratios Br( h → Υ( nS) γ)/Br( h → γγ) and can provide complementary information on the real and imaginary parts of the b-quark Yukawa coupling. More accurate measurements would be possible at a future 100 TeV proton-proton collider.

  10. Quantitative Probes of Electron-Phonon Coupling in an Organic Charge-Transfer Material

    NASA Astrophysics Data System (ADS)

    Rury, Aaron; Sorenson, Shayne; Driscoll, Eric; Dawlaty, Jahan

    While organic charge transfer (CT) materials may provide alternatives to inorganic materials in electronics and photonics applications, properties central to applications remain understudied in these organic materials. Specifically, electron-phonon coupling plays a pivotal role in electronic applications yet this coupling in CT materials remains difficult to directly characterize. To better understand the suitability of organic CT materials for electronic applications, we have devised an experimental technique that can directly assess electron-phonon coupling in a model organic CT material. Upon non-resonant interaction with an ultrafast laser pulse, we show that coherent excitation of Raman-active lattice vibrations of quinhydrone, a 1:1 co-crystal of the hydroquinone and p-benzoquinone, modulates the energies of electronic transitions probed by a white light pulse. Using a well-established theoretical framework of vibrational quantum beat spectra across the probe bandwidth, we quantitatively extract the parameters describing these electronic transitions to characterize electron-phonon coupling in this material. In conjunction with temperature-dependent resonance Raman measurements, we assess the hypothesis that several sharp transitions in the near-IR correspond to previously unknown excitonic states of this material. These results and their interpretation set the foundation for further elucidation of the one of the most important parameters in the application of organic charge-transfer materials to electronics and photonics.

  11. Probe And Enhancement Of SBS Based Phonons In Infrared Fibers Using Waveguide Coupled External Radiation

    NASA Astrophysics Data System (ADS)

    Yu, Chung; Chong, Yat C.; Fong, Chee K.

    1989-06-01

    Interaction of GHz and MHz radiation with CO2 laser propagation in a silver halide fiber using sBs based phonon coupling is furthet investigated. The external signal serves to both probe and enhance laser generated sBs phonons in the fiber. Efficient coupling of microwave radiation into the fiber is accomplished by placing the fiber in a hollow metallic waveguide, designed and constructed to transmit the dominant mode in the 0.9-2.0 GHz band. MHz radiation is conveniently coupled into the fiber using the guided microwave radiation as carrier. Phonon emissions from the fiber under CO2 laser pumping are first established on a spectrum analyzer; low frequency generators ale then tuned to match these frequencies and their maximum interaction recorded. Such interactions are systematically studied by monitoring the amplitude and waveform of the reflected and transmitted laser pulse at various power levels and frequencies of the externally coupled radiation. A plot of reflected laser power versus incident laser power reveals a distinct sBs generated phonon threshold. Variouslaunch directions of the GHz and MHz radiation with respect to the direction of laser propagation are realized to verify theory governing sBs interactions. The MHz radiation and its associated phonons in the fiber are convenient tools for probing sBs related phenomenon in infrared fibers.

  12. Prospective Real Time Head Motion Correction Using Inductively Coupled Wireless NMR Probes

    PubMed Central

    Sengupta, Saikat; Tadanki, Sasidhar; Gore, John C.; Welch, E. Brian

    2014-01-01

    Purpose Head motion continues to be a major source of artifacts and data quality degradation in MRI. The goal of this work was to develop and demonstrate a novel technique for prospective, 6 degrees of freedom (6DOF) rigid body motion estimation and real time motion correction using inductively coupled wireless nuclear magnetic resonance (NMR) probe markers. Methods Three wireless probes that are inductively coupled with the scanner’s RF setup serve as fiducials on the subject’s head. A 12 ms linear navigator module is interleaved with the imaging sequence for head position estimation, and scan geometry is updated in real time for motion compensation. Flip angle amplification in the markers allows the use of extremely small navigator flip angles (~1°). A novel algorithm is presented to identify marker positions in the absence of marker specific receive channels. The method is demonstrated for motion correction in 1 mm3 gradient recalled echo experiments in phantoms and humans. Results Significant improvement of image quality is demonstrated in phantoms and human volunteers under different motion conditions. Conclusion A novel real time 6 DOF head motion correction technique based on wireless NMR probes is demonstrated in high resolution imaging at 7 Tesla. PMID:24243810

  13. Coupled Ablation, Heat Conduction, Pyrolysis, Shape Change and Spallation of the Galileo Probe

    NASA Technical Reports Server (NTRS)

    Milos, Frank S.; Chen, Y.-K.; Rasky, Daniel J. (Technical Monitor)

    1995-01-01

    The Galileo probe enters the atmosphere of Jupiter in December 1995. This paper presents numerical methodology and detailed results of our final pre-impact calculations for the heat shield response. The calculations are performed using a highly modified version of a viscous shock layer code with massive radiation coupled with a surface thermochemical ablation and spallation model and with the transient in-depth thermal response of the charring and ablating heat shield. The flowfield is quasi-steady along the trajectory, but the heat shield thermal response is dynamic. Each surface node of the VSL grid is coupled with a one-dimensional thermal response calculation. The thermal solver includes heat conduction, pyrolysis, and grid movement owing to surface recession. Initial conditions for the heat shield temperature and density were obtained from the high altitude rarefied-flow calculations of Haas and Milos. Galileo probe surface temperature, shape, mass flux, and element flux are all determined as functions of time along the trajectory with spallation varied parametrically. The calculations also estimate the in-depth density and temperature profiles for the heat shield. All this information is required to determine the time-dependent vehicle mass and drag coefficient which are necessary inputs for the atmospheric reconstruction experiment on board the probe.

  14. Fiber optic probe having fibers with endfaces formed for improved coupling efficiency and method using same

    DOEpatents

    O'Rourke, Patrick E.; Livingston, Ronald R.

    1995-01-01

    A fiber optic probe for detecting scattered light, with transmitting and receiving fibers having slanted ends and bundled together to form a bevel within the tip of the probe. The probe comprises a housing with a transparent window across its tip for protecting the transmitting and receiving fibers held therein. The endfaces of the fibers are slanted, by cutting, polishing and the like, so that they lie in a plane that is not perpendicular to the longitudinal axis of the respective fiber. The fibers are held in the tip of the probe using an epoxy and oriented so that lines normal to the slanted endfaces are divergent with respect to one another. The epoxy, which is positioned substantially between the transmitting and receiving fibers, is tapered so that the transmitting fiber, the epoxy and the receiving fiber form a bevel of not more than 20 degrees. The angled fiber endfaces cause directing of the light cones toward each other, resulting in improved light coupling efficiency. A light absorber, such as carbon black, is contained in the epoxy to reduce crosstalk between the transmitting and receiving fibers.

  15. Fiber optic probe having fibers with endfaces formed for improved coupling efficiency and method using same

    DOEpatents

    O`Rourke, P.E.; Livingston, R.R.

    1995-03-28

    A fiber optic probe is disclosed for detecting scattered light, with transmitting and receiving fibers having slanted ends and bundled together to form a bevel within the tip of the probe. The probe comprises a housing with a transparent window across its tip for protecting the transmitting and receiving fibers held therein. The endfaces of the fibers are slanted, by cutting, polishing and the like, so that they lie in a plane that is not perpendicular to the longitudinal axis of the respective fiber. The fibers are held in the tip of the probe using an epoxy and oriented so that lines normal to the slanted endfaces are divergent with respect to one another. The epoxy, which is positioned substantially between the transmitting and receiving fibers, is tapered so that the transmitting fiber, the epoxy and the receiving fiber form a bevel of not more than 20 degrees. The angled fiber endfaces cause directing of the light cones toward each other, resulting in improved light coupling efficiency. A light absorber, such as carbon black, is contained in the epoxy to reduce crosstalk between the transmitting and receiving fibers. 3 figures.

  16. Probing anomalous quartic couplings in e{gamma} and {gamma}{gamma} colliders

    SciTech Connect

    Eboli, O. J. P.; Mizukoshi, J. K.

    2001-10-01

    We analyze the potential of the e{sup +}e{sup -} linear colliders, operating in the e{gamma} and {gamma}{gamma} modes, to probe anomalous quartic vector-boson interactions through the multiple production of W's and Z's. We examine all SU(2){sub L}(circle times)U(1){sub Y} chiral operators of order p{sup 4} that lead to new four-gauge-boson interactions but do not alter trilinear vertices. We show that the e{gamma} and {gamma}{gamma} modes are able not only to establish the existence of a strongly interacting symmetry breaking sector but also to probe for anomalous quartic couplings of the order of 10{sup -2} at 90% C.L. Moreover, the information gathered in the e{gamma} mode can be used to reduce the ambiguities of the e{sup +}e{sup -} mode.

  17. Single-molecule magnets ``without'' intermolecular interactions

    NASA Astrophysics Data System (ADS)

    Wernsdorfer, W.; Vergnani, L.; Rodriguez-Douton, M. J.; Cornia, A.; Neugebauer, P.; Barra, A. L.; Sorace, L.; Sessoli, R.

    2012-02-01

    Intermolecular magnetic interactions (dipole-dipole and exchange) affect strongly the magnetic relaxation of crystals of single-molecule magnets (SMMs), especially at low temperature, where quantum tunneling of the magnetization (QTM) dominates. This leads to complex many-body problems [l]. Measurements on magnetically diluted samples are desirable to clearly sort out the behaviour of magnetically-isolated SMMs and to reveal, by comparison, the effect of intermolecular interactions. Here, we diluted a Fe4 SMM into a diamagnetic crystal lattice, affording arrays of independent and iso-oriented magnetic units. We found that the resonant tunnel transitions are much sharper, the tunneling efficiency changes significantly, and two-body QTM transitions disappear. These changes have been rationalized on the basis of a dipolar shuffling mechanism and of transverse dipolar fields, whose effect has been analyzed using a multispin model. Our findings directly prove the impact of intermolecular magnetic couplings on the SMM behaviour and disclose the magnetic response of truly-isolated giant spins in a diamagnetic crystalline environment.[4pt] [1] W. Wernsdorfer, at al, PRL 82, 3903 (1999); PRL 89, 197201 (2002); Nature 416, 406 (2002); IS Tupitsyn, PCE Stamp, NV Prokof'ev, PRB 69, 132406 (2004).

  18. Remote estimation of phycocyanin (PC) for inland waters coupled with YSI PC fluorescence probe.

    PubMed

    Song, Kaishan; Li, Lin; Tedesco, Lenore; Clercin, Nicole; Hall, Bob; Li, Shuai; Shi, Kun; Liu, Dawei; Sun, Ying

    2013-08-01

    Nuisance cyanobacterial blooms degrade water resources through accelerated eutrophication, odor generation, and production of toxins that cause adverse effects on human health. Quick and effective methods for detecting cyanobacterial abundance in drinking water supplies are urgently needed to compliment conventional laboratory methods, which are costly and time consuming. Hyperspectral remote sensing can be an effective approach for rapid assessment of cyanobacterial blooms. Samples (n=250) were collected from five drinking water sources in central Indiana (CIN), USA, and South Australia (SA), which experience nuisance cyanobacterial blooms. In situ hyperspectral data were used to develop models by relating spectral signal with handheld fluorescence probe (YSI 6600 XLM-SV) measured phycocyanin (PC in cell/ml), a proxy pigment unique for indicating the presence of cyanobacteria. Three-band model (TBM), which is effective for chlorophyll-a estimates, was tuned to quantify cyanobacteria coupled with the PC probe measured cyanobacteria. As a comparison, two band model proposed by Simis et al. (Limnol Oceanogr, 50(11): 237-245, 2005; denoted as SM05) was paralleled to evaluate TBM model performance. Our observation revealed a high correlation between measured and estimated PC for SA dataset (R (2) =0.96; range: 534-20,200 cell/ml) and CIN dataset (R (2) =0.88; range: 1,300-44,500 cell/ml). The potential of this modeling approach for imagery data were assessed by simulated ESA/Centinel3/OLCI spectra, which also resulted in satisfactory performance with the TBM for both SA dataset (RMSE % =26.12) and CIN dataset (RMSE % =34.49). Close relationship between probe-measured PC and laboratory measured cyanobacteria biovolume was observed (R (2) =0.93, p<0.0001) for the CIN dataset, indicating a stable performance for PC probe. Based on our observation, field spectroscopic measurement coupled with PC probe measurements can provide quantitative cyanobacterial bloom

  19. Nanoscale resolved infrared probing of crystal structure and of plasmon-phonon coupling.

    PubMed

    Huber, A; Ocelic, N; Taubner, T; Hillenbrand, R

    2006-04-01

    We show that slight variations of a crystal lattice cause significant spectral modifications of phonon-polariton resonant near-field interaction between polar semiconductor crystals and a scanning metal tip. Exploiting the effect for near-field imaging a SiC polytype boundary, we establish infrared mapping of crystal structure and crystal defects at 20 nm spatial resolution (lambda/500). By spectroscopic probing of doped SiC polytypes, we find that phonon-polariton resonant near-field interaction is also sensitive to electronic properties due to plasmon-phonon coupling in the crystals. PMID:16608282

  20. Wave-vector-dependent spin pumping as a probe of exchange-coupled magnons

    NASA Astrophysics Data System (ADS)

    Fukami, Masaya; Tateno, Yuma; Sekiguchi, Koji; Ando, Kazuya

    2016-05-01

    We demonstrate that short-wavelength exchange-coupled magnons can be identified electrically through the combination of their spin-pumping and damping properties in a metal/magnetic insulator heterostructure. We present clear wave-vector dependence of the spin pumping from parametrically excited exchange-coupled magnons in the heterostructure. The efficiency of spin pumping by dipole-exchange magnons was measured to be sensitive to their wave numbers and propagation angles, while the efficiency was found to be almost constant in the exchange limit. This dependence enabled us to uncover nontrivial dual bistability in the system originating from drastic change in dominant nonequilibrium magnon modes. These findings pave a path for direct electric access to short-wavelength spin dynamics that cannot be probed by optical techniques.

  1. Photopyroelectric thermal wave detection via contactless capacitive polyvinylidene fluoride (PVDF)-metal probe-tip coupling

    NASA Astrophysics Data System (ADS)

    Mieszkowski, Marek; Leung, Kwan F.; Mandelis, Andreas

    1989-03-01

    In the past, thin-film photopyroelectric detectors have provided a simple means of measuring thermal properties of solid samples. This article presents a theoretical model and experimental results demonstrating a new contactless capacitively coupled photopyroelectric detection technique. The photopyroelectric (P2E) effect with contactless capacitance PVDF-metal probe-tip coupling was demonstrated and used to obtain thermal information from a solid. Due to the small diameter of the probe, the local values of the thermal wave field in the solid were measured. The modulated photothermal source on the surface of the sample induces an oscillating temperature field in the pyroelectric material, which produces a displacement current proportional to the temperature change. The metalized surface of the pyroelectric thin film and a metal tip electrode facing the opposite unmetalized surface form a capacitor which is charged at the same frequency as the modulated light beam. The oscillating capacitive voltage provides a noncontact mechanism to extract photothermal information, since the electric field generated in the capacitor does not require plate contact with the PVDF element.

  2. Using magnetic coupling to implement 1H, 19F, 13C experiments in routine high resolution NMR probes

    NASA Astrophysics Data System (ADS)

    Bowyer, Paul; Finnigan, Jim; Marsden, Brian; Taber, Bob; Zens, Albert

    2015-12-01

    We report in this paper the design of 1H, 19F, 13C circuitry using magnetic coupling which can do on demand experiments where one of the three nuclei is observed and the other two are decoupled. The implementation of this circuitry in routine NMR probes is compared with capacitive coupling methods where it was found that by using magnetic coupling the performance of the routine NMR probe was not impacted by the addition of this circuitry. It is surmised that using this type of circuitry would be highly desirable for those chemists doing routine 19F NMR.

  3. Comparision of Emissive Probe assisted Measurements of Plasma Density to that of a Surface Wave Probe, in a Dual Frequency Confined Capacitively Coupled Discharge

    NASA Astrophysics Data System (ADS)

    Linnane, S.; Ellingboe, A. R.

    2003-10-01

    Dual frequency confined capacitively coupled plasmas are increasingly used in semiconductor manufacturing for dielectric etching, allowing greater (and independent) control of ion energies and ion flux on the etched substrate. One electrode is driven with the summation of 27MHz and 2MHz sinusoidal voltages, while the other electrode is grounded. The electrode areas are similar in size, giving an electrode aspect ratio less than 2. Because of this low aspect ratio, there are large oscillations in the plasma potential. The expectation is for sinusoidal oscillations at the higher driving frequency, due to capacitive sheaths, while a rectified oscillation is expected at the lower driving frequency [1]. The emissive probe and circuitry allows measurement of plasma potential oscillations at both driving frequencies and their harmonics, thus allowing measurement of the actual time-varying and time-independant plasma potential. Ion saturation current is measured with a single Langmuir probe. Tuned RF filters isolated the probe tip from the external voltage supply (which otherwise acts as a high frequency ground). To further enable the Langmuir probe to follow the plasma potential oscillations, the tip is capacitively coupled to the emissive probe. These results will then be compared with a simple surface wave probe technique [2], which uses the resonant absorption of surface waves by the plasma, to determine plasma density. [1] E. Kawamura, V. Vahedi, M. A. Lieberman and C. K. Birdsall, Plasma Sources Sci. Technology. 8 (1999) R45-R64 [2] Conference proceedings, Frontiers in Low Temperature Plasma Diagnostics V, 2003 pg 30. "Novel Plasma Monitoring by Surface Wave Probe" H.Sugai and K. Nakamura

  4. Direct observation of intermolecular interactions mediated by hydrogen bonding

    NASA Astrophysics Data System (ADS)

    De Marco, Luigi; Thämer, Martin; Reppert, Mike; Tokmakoff, Andrei

    2014-07-01

    Although intermolecular interactions are ubiquitous in physicochemical phenomena, their dynamics have proven difficult to observe directly, and most experiments rely on indirect measurements. Using broadband two-dimensional infrared spectroscopy (2DIR), we have measured the influence of hydrogen bonding on the intermolecular vibrational coupling between dimerized N-methylacetamide molecules. In addition to strong intramolecular coupling between N-H and C=O oscillators, cross-peaks in the broadband 2DIR spectrum appearing upon dimerization reveal strong intermolecular coupling that changes the character of the vibrations. In addition, dimerization changes the effects of intramolecular coupling, resulting in Fermi resonances between high and low-frequency modes. These results illustrate how hydrogen bonding influences the interplay of inter- and intramolecular vibrations, giving rise to correlated nuclear motions and significant changes in the vibrational structure of the amide group. These observations have direct impact on modeling and interpreting the IR spectra of proteins. In addition, they illustrate a general approach to direct molecular characterization of intermolecular interactions.

  5. Direct observation of intermolecular interactions mediated by hydrogen bonding

    SciTech Connect

    De Marco, Luigi; Reppert, Mike; Thämer, Martin; Tokmakoff, Andrei

    2014-07-21

    Although intermolecular interactions are ubiquitous in physicochemical phenomena, their dynamics have proven difficult to observe directly, and most experiments rely on indirect measurements. Using broadband two-dimensional infrared spectroscopy (2DIR), we have measured the influence of hydrogen bonding on the intermolecular vibrational coupling between dimerized N-methylacetamide molecules. In addition to strong intramolecular coupling between N–H and C=O oscillators, cross-peaks in the broadband 2DIR spectrum appearing upon dimerization reveal strong intermolecular coupling that changes the character of the vibrations. In addition, dimerization changes the effects of intramolecular coupling, resulting in Fermi resonances between high and low-frequency modes. These results illustrate how hydrogen bonding influences the interplay of inter- and intramolecular vibrations, giving rise to correlated nuclear motions and significant changes in the vibrational structure of the amide group. These observations have direct impact on modeling and interpreting the IR spectra of proteins. In addition, they illustrate a general approach to direct molecular characterization of intermolecular interactions.

  6. Interface-Induced Magnetic Coupling in Multiferroic/Ferromagnetic Bilayer: An Ultrafast Pump-Probe Study

    NASA Astrophysics Data System (ADS)

    Chia, Elbert; La-O-Vorakiat, Chan; Tian, Y. F.; Wu, Tom; Panagopoulos, Christos; Zhu, Jian-Xin; Su, Haibin

    2014-03-01

    By use of optical pump-probe measurement, we study the relaxation dynamics of a muliferroic-ferromagnetic TbMnO3/La0.7Sr0.3MnO3 bilayer. The relaxation dynamics of both layers are well separated in time allowing us to investigate the magnetic coupling across the bilayer. We observe that the relaxation dynamics of the individual layers in the bilayer sample are the result of the interplay between the intrinsic magnetic order and the induced interfacial effect. Our data suggest the existence of induced ferromagnetic order in the TbMnO3 layer, and antiferromagnetic order in the La0.7Sr0.3MnO3 layer. Singapore NRF CRP (NRF-CRP4-2008-04) and MOE AcRF Tier 1 (RG 13/12).

  7. Soft Particle Spectrometer, Langmuir Probe, and Data Analysis for Aerospace Magnetospheric/Thermospheric Coupling Rocket Program

    NASA Technical Reports Server (NTRS)

    Sharber, J. R.; Frahm, R. A.; Scherrer, J. R.

    1997-01-01

    Under this grant two instruments, a soft particle spectrometer and a Langmuir probe, were refurbished and calibrated, and flown on three instrumented rocket payloads as part of the Magnetosphere/Thermosphere Coupling program. The flights took place at the Poker Flat Research Range on February 12, 1994 (T(sub o) = 1316:00 UT), February 2, 1995 (T(sub o) = 1527:20 UT), and November 27, 1995 (T(sub o) = 0807:24 UT). In this report the observations of the particle instrumentation flown on all three of the flights are described, and brief descriptions of relevant geophysical activity for each flight are provided. Calibrations of the particle instrumentation for all ARIA flights are also provided.

  8. Beyond Higgs couplings: probing the Higgs with angular observables at future e + e - colliders

    NASA Astrophysics Data System (ADS)

    Craig, Nathaniel; Gu, Jiayin; Liu, Zhen; Wang, Kechen

    2016-03-01

    We study angular observables in the {e}+{e}-to ZHto {ell}+{ell}-boverline{b} channel at future circular e + e - colliders such as CEPC and FCC-ee. Taking into account the impact of realistic cut acceptance and detector effects, we forecast the precision of six angular asymmetries at CEPC (FCC-ee) with center-of-mass energy sqrt{s}=240 GeV and 5 (30) ab-1 integrated luminosity. We then determine the projected sensitivity to a range of operators relevant for he Higgs-strahlung process in the dimension-6 Higgs EFT. Our results show that angular observables provide complementary sensitivity to rate measurements when constraining various tensor structures arising from new physics. We further find that angular asymmetries provide a novel means of both probing BSM corrections to the HZγ coupling and constraining the "blind spot" in indirect limits on supersymmetric scalar top partners.

  9. Langmuir Probe Measurements in an Inductively Coupled Ar/CF4 Plasmas

    NASA Technical Reports Server (NTRS)

    Rao, M. V. V. S.; Meyyappan, M.; Sharma, S. P.; Arnold, James O. (Technical Monitor)

    2000-01-01

    Technological advancement in the microelectronics industry requires an understanding of the physical and chemical processes occurring in plasmas of fluorocarbon gases, such as carbon tetrafluoride (CF4) which is commonly used as an etchant, and their mixtures to optimize various operating parameters. In this paper we report data on electron number density (ne), electron temperature'(Te), electron energy distribution function (EEDF), mean electron energy, ion number density (ni), and plasma potential (Vp) measured by using Langmuir probe in an inductively coupled 13.56 MHz radio frequency plasmas generated in 50%Ar:50%CF4 mixture in the GEC cell. The probe data were recorded at various radial positions providing radial profiles of these plasma parameters at 10-50 mTorr pressures and 200 W and 300 W of RF power. Present measurements indicate that the electron and ion number densities increase with increase in pressure and power. Whereas the plasma potential and electron temperature decrease with increase in pressure, and they weakly depend on RF power. The radial profiles exhibit that the electron and ion number densities and the plasma potential peak at the center of the plasma with an exponential fall away from it, while the electron temperature has a minimum at the center and it increases steadily towards the electrode edge. The EEDFs have a characteristic drop near the low energy end at all pressures and pressures and their shapes represent non-Maxwellian plasma and exhibit more like Druyvesteyn energy distribution.v

  10. Langmuir Probe Measurements of Inductively Coupled Plasmas in CF4/Ar/O2 Mixtures

    NASA Technical Reports Server (NTRS)

    Rao, M. V. V. S.; Meyyappan, M.; Sharma, S. P.

    2000-01-01

    Fluorocarbon gases, such as CF4, and their mixtures are widely used in contemporary low-pressure and high-density plasma processing techniques. In such plasmas Langmuir probe is one of the most commonly employed diagnostic techniques to obtain electron number density (ne), electron temperature (Te), electron energy distribution function (EEDF), mean electron energy (Ee), ion number density (ni), and plasma potential (Vp). In this paper we report probe data for planar inductively coupled plasmas in CF4/O2/Ar mixtures. By varying the relative concentrations in the mixture, radial profiles of ne, ni, Te, Ee, Vp, EEDF were measured in the mid-plane of the plasma at 10 mTorr and 20 mTorr of gas pressures, and 200 W and 300 W of RF powers. Data show that ne and ni decrease with increase of CF4 content and decrease of gas-pressure but they increase with increase of RF-power, whereas Vp increases with decrease of gas-pressure and remains independent of RF-power. However, they all peak at the center of the plasma and decrease towards the edge while Te follows the other way and increases a little with increase of power. The measured EEDFs exhibit Druyvesteyn-like distribution at all pressures and powers. Data are analyzed and will be presented.

  11. Emissive Probe Measurements in a Dual-Frequency-Confined Capacitively-Coupled-Plasma System

    NASA Astrophysics Data System (ADS)

    Linnane, Shane; Ellingboe, Albert R.

    2002-10-01

    Dual frequency confined capacitively coupled plasmas (DFC-CCP) are increasingly used in semiconductor manufacturing for dielectric etching, allowing greater (and independent) control of ion energies and ion flux on the etched substrate. The powered electrode is driven with the summation of 27MHz and 2MHz sinusoidal voltages, while the other electrode is grounded. The electrode areas are similar in size, giving an electrode aspect ratio less than 2. Because of this low aspect ratio, there are large oscillations in the plasma potential. The expectation is for sinusoidal oscillations at the higher driving frequency, due to capacitive sheaths, while a rectified oscillation is expected at the lower driving frequency.(E. Kawamura, V. Vahedi, M. A. Lieberman and C. K. Birdsall, Plasma Sources Sci. Technology. 8 (1999) R45-R64 Work Supported by EURATOM.) Measurements of rf oscillation in the plasma potential taken with a floating emissive probe will be presented. The emissive probe and circuitry allows direct realtime measurement of plasma potential oscillation at both driving frequencies and the harmonics of each, thus allowing measurement of the actual potential on the driven electrode and ion energy incident on grounded electrode.

  12. Probing Single Molecules with a Tunable Femtosecond Laser Coupled RF-STM

    NASA Astrophysics Data System (ADS)

    Cao, Weicai

    Scanning Tunneling Microscope (STM) has become a powerful tool in nanoscience for imaging, manipulation and electronic spectroscopy. STM inelastic electron tunneling spectroscopy (IETS) first achieved chemical identification of molecular species by characterizing vibrational energies. Recently, with the STM itProbe and H2 rotational spectromicroscopy, molecular structure and chemical bonds are observed with the STM. Despite these successes in spatial resolution, various efforts have been made to combine fs laser with STM to overcome the temporal resolution limitation of STM, there is so far no clear evidence of simultaneous fs and A resolution. Electronic properties of organic molecules are of central importance to applications such as molecular electronics, organic LEDs, and solar cells. Properties of these molecules can be probed by the scanning tunneling microscope (STM) at the single molecule level and with sub-A spatial resolution. The molecular orbital of 4, 7-Di ([2, 20-bithiophen]-5-yl) benzo[c] [1, 2, 5] thiadiazole (4T-BTD) with intramolecular donor-acceptor-donor sites is probed with the electronic state dI/dV imaging and H2 rotational and vibrational spectromicroscopy. 1, 4-Phenylene Diisocyanide (PDI) is probed by imaging with a CO-terminated tip and H2. PDI can self-assemble on noble metal surfaces to form nanostructures, which could have potential applications in molecular electronics and catalysis. Further combination of a RF-STM with a tunable femtosecond laser enables the investigation of light-molecule interactions. In this dissertation, efforts are spent to setup a new tunable fs laser (220 nm˜1040 nm) to couple with the RF-STM. The effects of the femtosecond laser are followed by detecting photo induced electron emission and photochemistry. A new double lock-in technique is applied to detect the weak laser-induced signal in the tunneling regime. To sharpen the energy width and increase the lifetime of the excited states of molecules, thin

  13. Probing top quark neutral couplings in the Standard Model Effective Field Theory at NLO in QCD

    NASA Astrophysics Data System (ADS)

    Bylund, Olga Bessidskaia; Maltoni, Fabio; Tsinikos, Ioannis; Vryonidou, Eleni; Zhang, Cen

    2016-05-01

    Top quark pair production in association with a Z-boson or a photon at the LHC directly probes neutral top-quark couplings. We present predictions for these two processes in the Standard Model (SM) Effective Field Theory (EFT) at next-to-leading order (NLO) in QCD. We include the full set of CP-even dimension-six operators that enter the top-quark interactions with the SM gauge bosons. For comparison, we also present predictions in the SMEFT for top loop-induced HZ production at the LHC and for toverline{t} production at the ILC at NLO in QCD. Results for total cross sections and differential distributions are obtained and uncertainties coming from missing higher orders in the strong coupling and in the EFT expansions are discussed. NLO results matched to the parton shower are available, allowing for event generation to be directly employed in an experimental analyses. Our framework provides a solid basis for the interpretation of current and future measurements in the SMEFT, with improved accuracy and precision.

  14. Discovery of selective probes and antagonists for G-protein-coupled receptors FPR/FPRL1 and GPR30.

    PubMed

    Arterburn, Jeffrey B; Oprea, Tudor I; Prossnitz, Eric R; Edwards, Bruce S; Sklar, Larry A

    2009-01-01

    Recent technological advances in flow cytometry provide a versatile platform for high throughput screening of compound libraries coupled with high-content biological testing and drug discovery. The G protein-coupled receptors (GPCRs) constitute the largest class of signaling molecules in the human genome with frequent roles in disease pathogenesis, yet many examples of orphan receptors with unknown ligands remain. The complex biology and potential for drug discovery within this class provide strong incentives for chemical biology approaches seeking to develop small molecule probes to facilitate elucidation of mechanistic pathways and enable specific manipulation of the activity of individual receptors. We have initiated small molecule probe development projects targeting two distinct families of GPCRs: the formylpeptide receptors (FPR/FPRL1) and G protein-coupled estrogen receptor (GPR30). In each case the assay for compound screening involved the development of an appropriate small molecule fluorescent probe, and the flow cytometry platform provided inherently biological rich assays that enhanced the process of identification and optimization of novel antagonists. The contributions of cheminformatics analysis tools, virtual screening, and synthetic chemistry in synergy with the biomolecular screening program have yielded valuable new chemical probes with high binding affinity, selectivity for the targeted receptor, and potent antagonist activity. This review describes the discovery of novel small molecule antagonists of FPR and FPRL1, and GPR30, and the associated characterization process involving secondary assays, cell based and in vivo studies to define the selectivity and activity of the resulting chemical probes. PMID:19807662

  15. Comparison of various interpretation methods of the electric probe measurements in inductively coupled Ar and O{sub 2} plasmas

    SciTech Connect

    Woo Seo, Min; Keun Bae, Min; Chung, T. H.

    2014-02-15

    In low-pressure inductively coupled argon and oxygen discharges, the plasma density and electron temperature and the electron energy distribution function (EEDF) were obtained by using a cylindrical electric probe. The plasma densities were determined by various methods to interpret the probe current-voltage characteristic curve: the EEDF integration, the electron saturation current, the ion current at the floating potential, and the orbital-motion-limited (OML) ion current. Quite a good agreement exists between the plasma densities determined by various classical methods. Although the probe technique has some limitation in electronegative plasmas, the plasma densities determined from OML theory compare well with those measured by the ion saturation current at the floating potential in the oxygen discharges. In addition, the EEDFs of inductively coupled Ar and oxygen plasmas are observed to be nearly Maxwellian at the pressure range of 1-40 mTorr.

  16. Protein-Coupled Fluorescent Probe To Visualize Potassium Ion Transition on Cellular Membranes.

    PubMed

    Hirata, Tomoya; Terai, Takuya; Yamamura, Hisao; Shimonishi, Manabu; Komatsu, Toru; Hanaoka, Kenjiro; Ueno, Tasuku; Imaizumi, Yuji; Nagano, Tetsuo; Urano, Yasuteru

    2016-03-01

    K(+) is the most abundant metal ion in cells, and changes of [K(+)] around cell membranes play important roles in physiological events. However, there is no practical method to selectively visualize [K(+)] at the surface of cells. To address this issue, we have developed a protein-coupled fluorescent probe for K(+), TLSHalo. TLSHalo is responsive to [K(+)] in the physiological range, with good selectivity over Na(+) and retains its K(+)-sensing properties after covalent conjugation with HaloTag protein. By using cells expressing HaloTag on the plasma membrane, we successfully directed TLSHalo specifically to the outer surface of target cells. This enabled us to visualize localized extracellular [K(+)] change with TLSHalo under a fluorescence microscope in real time. To confirm the experimental value of this system, we used TLSHalo to monitor extracellular [K(+)] change induced by K(+) ionophores or by activation of a native Ca(2+)-dependent K(+) channel (BK channel). Further, we show that K(+) efflux via BK channel induced by electrical stimulation at the bottom surface of the cells can be visualized with TLSHalo by means of total internal reflection fluorescence microscope (TIRFM) imaging. Our methodology should be useful to analyze physiological K(+) dynamics with high spatiotemporal resolution. PMID:26894407

  17. Beyond Higgs couplings: Probing the Higgs with angular observables at future e$$^{+}$$e$$^{-}$$ colliders

    DOE PAGESBeta

    Craig, Nathaniel; Gu, Jiayin; Liu, Zhen; Wang, Kechen

    2016-03-09

    Here, we study angular observables in themore » $$ {e}^{+}{e}^{-}\\to ZH\\to {\\ell}^{+}{\\ell}^{-}b\\overline{b} $$ channel at future circular e$$^{+}$$ e$$^{-}$$ colliders such as CEPC and FCC-ee. Taking into account the impact of realistic cut acceptance and detector effects, we forecast the precision of six angular asymmetries at CEPC (FCC-ee) with center-of-mass energy $$ \\sqrt{s}=240 $$ GeV and 5 (30) ab$$^{-1}$$ integrated luminosity. We then determine the projected sensitivity to a range of operators relevant for he Higgs-strahlung process in the dimension-6 Higgs EFT. Our results show that angular observables provide complementary sensitivity to rate measurements when constraining various tensor structures arising from new physics. We further find that angular asymmetries provide a novel means of both probing BSM corrections to the HZγ coupling and constraining the “blind spot” in indirect limits on supersymmetric scalar top partners.« less

  18. Target-catalyzed hairpin assembly and intramolecular/intermolecular co-reaction for signal amplified electrochemiluminescent detection of microRNA.

    PubMed

    Yu, Yan-Qing; Wang, Ji-Peng; Zhao, Min; Hong, Lin-Ru; Chai, Ya-Qin; Yuan, Ruo; Zhuo, Ying

    2016-03-15

    Herein, a new electrochemiluminescence (ECL) strategy for enzyme-free microRNA-21 (miR-21) amplified detection was designed based on target-catalyzed hairpin assembly by combining the signal-amplification capability of both intramolecular and intermolecular ECL co-reaction. In this strategy, two hairpin DNA probes of H1 and H2 were designed as capture probes and detection probes, respectively. To be specific, the capture probes of H1 were immobilized on the multilayer interface of AuNPs and thiosemicarbazide (TSC) assembly on the single-walled carbon nanohorns decorated electrode, while the detection probes of H2 was anchored on the nanocarriers of gold nanoparticals functionalized reduced graphene oxide (Au-rGO) which were tagged with the self-enhanced ruthenium complex (PEI-Ru(ΙΙ)) in advance. Based on the target-catalyzed hairpin assembly, target miR-21 could trigger the hybridization of H1 and H2 to further be released for initiating the next hybridization process to capture a large number of H2 bioconjugates on the sensing surface. Herein, the TSC was used not only as a coupling reagent to attach the AuNPs via Au-S and Au-N bonds but also as a novel intermolecular coreactant to enhance the ECL intensity, and the PEI-Ru(ΙΙ) as emitters exhibited enhanced ECL efficiency. Therefore, a strong ECL signal was achieved by the dual amplification strategies of target recycle and the intramolecular/intermolecular co-reaction of PEI-Ru(ΙΙ) and TSC. The designed protocol provided an ultrasensitive ECL detection of miR-21 down to the sub-femtomolar level with a linear response about 6 orders of magnitude (from 1.0 × 10(-16)M to 1.0 × 10(-11)M) with a relatively low detection limit of 0.03 fM (S/N=3). PMID:26453905

  19. Lead geochronology of zircon by LaserProbe-inductively coupled plasma mass spectrometry (LP-ICPMS)

    NASA Astrophysics Data System (ADS)

    Feng, Rui; Machado, Nuno; Ludden, John

    1993-07-01

    LaserProbe-inductively coupled plasma mass spectrometry (LP-ICPMS) provides a sensitive, fast, and simple means to determine 207Pb /206Pb ages in single zircon grains. A Nd:YAG laser is used to irradiate the zircon surface and leaves a cylindrical pit of 30-60 μm, from which the vaporised materials are transported by argon gas to a Fisons-VG PQII+ ICPMS for analysis. No zircon abrasion, cleaning nor chemical separation procedures are required. The accuracy and the limitation of the method were evaluated by analyzing twenty-one zircon samples ranging in age from 2.7 Ga to 1.0 Ga, which have also been dated by the conventional U-Pb thermal ionization mass spectrometry technique (TIMS). The LP-ICPMS 207Pb /206Pb ages for zircons with grain size > 60 μm and 207Pb concentration > 3 ppm are within 1% of the TIMS ages. Smaller zircons (≤60 μm) and those with 207Pb concentration < 2 ppm yield inaccurate ages. Operating the LP-ICPMS at conditions that give a compromise between the ideal spatial resolution and instrument sensitivity, the limits of detection were found to be 0.2 ppm for 206Pb, 207Pb, and 208Pb. The precision of the 207Pb /206Pb ratio is generally 0.5-6% (1σ) from each sampling pit and is strongly dependent on the lead concentration. However, the precision for the average of the mean ratios from different pits in one grain or several grains of the same population are generally <1.5% (1σ). The results presented here demonstrate that the LP-ICPMS can be used to determine 207Pb /206Pb ages of zircons and that reliable ages can be obtained from high quality, limpid zircons with a simple Pb-loss history. Uses of the technique include screening of zircon populations from different rocks in areas of poorly known age relationships and provenance studies of detrital zircons from ancient and modern sedimentary sequences. Other applications include the study of growth zones and of inherited components in complex zircon populations. In comparison with the SHRIMP

  20. Langmuir Probe and Mass Spectroscopic Measurements in Inductively Coupled CF4 Plasmas

    NASA Technical Reports Server (NTRS)

    Rao, M. V. V. S.; Sharma, Surendra; Cruden, B. A.; Meyyappan, M.

    2001-01-01

    Abstract Electron and ion energy distribution functions and other plasma parameters such as plasma potential (V(sub p)) , electron temperature (T(sub e)), and electron and ion number densities (n (sub e) and n(sub i)) in low pressure CF4 plasmas have been measured. The experiments were conducted in a GEC cell using an inductively coupled plasma (ICP) device powered by a 13.56 MHz radio-frequency (rf) power source. The measurements were made at 300 W of input rf power at 10, 30 and 50 mTorr gas pressures. Langmuir probe measurements suggest that n(sub e), n(sub i) and V(sub p) remain constant over 60% of the central electrode area, beyond which they decrease. Within the limits of experimental error (+/- 0.25 eV), T(sub e) remains nearly constant over the electrode area. T(sub e) and V(sub p) increase with a decrease in pressure. n(sub e) and n(sub i) are not affected as significantly as T(sub e) or V(sub p) by variation in the gas pressure. The electron energy distribution function (EEDF) measurements indicate a highly non-Maxwellian plasma. CF3+ is the most dominant ion product of the plasma, followed by CF2+ and CF+. The concentrations of CF2+ and CF+ are much larger than that is possible from direct electron impact ionization of the parent gas. The cross-section data suggest that the direct electron impact ionization of fragment neutrals and negative ion production by electron attachment may be responsible for increase of the minor ions.

  1. DNA-based stable isotope probing coupled with cultivation methods implicates Methylophaga in hydrocarbon degradation

    PubMed Central

    Mishamandani, Sara; Gutierrez, Tony; Aitken, Michael D.

    2014-01-01

    Marine hydrocarbon-degrading bacteria perform a fundamental role in the oxidation and ultimate removal of crude oil and its petrochemical derivatives in coastal and open ocean environments. Those with an almost exclusive ability to utilize hydrocarbons as a sole carbon and energy source have been found confined to just a few genera. Here we used stable isotope probing (SIP), a valuable tool to link the phylogeny and function of targeted microbial groups, to investigate hydrocarbon-degrading bacteria in coastal North Carolina sea water (Beaufort Inlet, USA) with uniformly labeled [13C]n-hexadecane. The dominant sequences in clone libraries constructed from 13C-enriched bacterial DNA (from n-hexadecane enrichments) were identified to belong to the genus Alcanivorax, with ≤98% sequence identity to the closest type strain—thus representing a putative novel phylogenetic taxon within this genus. Unexpectedly, we also identified 13C-enriched sequences in heavy DNA fractions that were affiliated to the genus Methylophaga. This is a contentious group since, though some of its members have been proposed to degrade hydrocarbons, substantive evidence has not previously confirmed this. We used quantitative PCR primers targeting the 16S rRNA gene of the SIP-identified Alcanivorax and Methylophaga to determine their abundance in incubations amended with unlabeled n-hexadecane. Both showed substantial increases in gene copy number during the experiments. Subsequently, we isolated a strain representing the SIP-identified Methylophaga sequences (99.9% 16S rRNA gene sequence identity) and used it to show, for the first time, direct evidence of hydrocarbon degradation by a cultured Methylophaga sp. This study demonstrates the value of coupling SIP with cultivation methods to identify and expand on the known diversity of hydrocarbon-degrading bacteria in the marine environment. PMID:24578702

  2. User's guide for the computer code COLTS for calculating the coupled laminar and turbulent flow over a Jovian entry probe

    NASA Technical Reports Server (NTRS)

    Kumar, A.; Graeves, R. A.

    1980-01-01

    A user's guide for a computer code 'COLTS' (Coupled Laminar and Turbulent Solutions) is provided which calculates the laminar and turbulent hypersonic flows with radiation and coupled ablation injection past a Jovian entry probe. Time-dependent viscous-shock-layer equations are used to describe the flow field. These equations are solved by an explicit, two-step, time-asymptotic finite-difference method. Eddy viscosity in the turbulent flow is approximated by a two-layer model. In all, 19 chemical species are used to describe the injection of carbon-phenolic ablator in the hydrogen-helium gas mixture. The equilibrium composition of the mixture is determined by a free-energy minimization technique. A detailed frequency dependence of the absorption coefficient for various species is considered to obtain the radiative flux. The code is written for a CDC-CYBER-203 computer and is capable of providing solutions for ablated probe shapes also.

  3. Full counting statistics as a probe of quantum coherence in a side-coupled double quantum dot system

    SciTech Connect

    Xue, Hai-Bin

    2013-12-15

    We study theoretically the full counting statistics of electron transport through side-coupled double quantum dot (QD) based on an efficient particle-number-resolved master equation. It is demonstrated that the high-order cumulants of transport current are more sensitive to the quantum coherence than the average current, which can be used to probe the quantum coherence of the considered double QD system. Especially, quantum coherence plays a crucial role in determining whether the super-Poissonian noise occurs in the weak inter-dot hopping coupling regime depending on the corresponding QD-lead coupling, and the corresponding values of super-Poissonian noise can be relatively enhanced when considering the spins of conduction electrons. Moreover, this super-Poissonian noise bias range depends on the singly-occupied eigenstates of the system, which thus suggests a tunable super-Poissonian noise device. The occurrence-mechanism of super-Poissonian noise can be understood in terms of the interplay of quantum coherence and effective competition between fast-and-slow transport channels. -- Highlights: •The FCS can be used to probe the quantum coherence of side-coupled double QD system. •Probing quantum coherence using FCS may permit experimental tests in the near future. •The current noise characteristics depend on the quantum coherence of this QD system. •The super-Poissonian noise can be enhanced when considering conduction electron spin. •The side-coupled double QD system suggests a tunable super-Poissonian noise device.

  4. Fluorescence photoactivation by intermolecular proton transfer.

    PubMed

    Swaminathan, Subramani; Petriella, Marco; Deniz, Erhan; Cusido, Janet; Baker, James D; Bossi, Mariano L; Raymo, Françisco M

    2012-10-11

    We designed a strategy to activate fluorescence under the influence of optical stimulations based on the intermolecular transfer of protons. Specifically, the illumination of a 2-nitrobenzyl derivative at an activating wavelength is accompanied by the release of hydrogen bromide. In turn, the photogenerated acid encourages the opening of an oxazine ring embedded within a halochromic compound. This structural transformation extends the conjugation of an adjacent coumarin fluorophore and enables its absorption at an appropriate excitation wavelength. Indeed, this bimolecular system offers the opportunity to activate fluorescence in liquid solutions, within rigid matrixes and inside micellar assemblies, relying on the interplay of activating and exciting beams. Furthermore, this strategy permits the permanent imprinting of fluorescent patterns on polymer films, the monitoring of proton diffusion within such materials in real time on a millisecond time scale, and the acquisition of images with spatial resolution at the nanometer level. Thus, our operating principles for fluorescence activation can eventually lead to the development of valuable photoswitchable probes for imaging applications and versatile mechanisms for the investigation of proton transport. PMID:22994311

  5. Theoretical study on the effect of solvent and intermolecular fluctuations in proton transfer reactions: General theory

    SciTech Connect

    Kato, Nobuhiko; Ida, Tomonori; Endo, Kazunaka

    2004-04-30

    We present a theory of proton transfer reactions which incorporate the modulation of the proton's potential surface by intermolecular vibrations and the effect of coupling to solvent degree of freedom. The proton tunnels between states corresponding to it being localized in the wells of a double minimum potential. The resulting tunnel splitting depends on the intermolecular separation. The solvent response to the proton's charge is modeled as that of a continuous distribution of harmonic oscillators and the intermolecular stretching mode is also damped because of the interaction with solvent degree of freedom. The transition rate is given by the Fermi Gorlden Rule expression.

  6. Desensitization and recovery of metastable intermolecular composites

    DOEpatents

    Busse, James R.; Dye, Robert C.; Foley, Timothy J.; Higa, Kelvin T.; Jorgensen, Betty S.; Sanders, Victor E.; Son, Steven F.

    2010-09-07

    A method to substantially desensitize a metastable intermolecular composite material to electrostatic discharge and friction comprising mixing the composite material with an organic diluent and removing enough organic diluent from the mixture to form a mixture with a substantially putty-like consistency, as well as a concomitant method of recovering the metastable intermolecular composite material.

  7. Non-Covalent Fluorescent Labeling of Hairpin DNA Probe Coupled with Hybridization Chain Reaction for Sensitive DNA Detection.

    PubMed

    Song, Luna; Zhang, Yonghua; Li, Junling; Gao, Qiang; Qi, Honglan; Zhang, Chengxiao

    2016-04-01

    An enzyme-free signal amplification-based assay for DNA detection was developed using fluorescent hairpin DNA probes coupled with hybridization chain reaction (HCR). The hairpin DNAs were designed to contain abasic sites in the stem moiety. Non-covalent labeling of the hairpin DNAs was achieved when a fluorescent ligand was bound to the abasic sites through hydrogen bonding with the orphan cytosine present on the complementary strand, accompanied by quench of ligand fluorescence. As a result, the resultant probes, the complex formed between the hairpin DNA and ligand, showed almost no fluorescence. Upon hybridization with target DNA, the probe underwent a dehybridization of the stem moiety containing an abasic site. The release of ligand from the abasic site to the solution resulted in an effective fluorescent enhancement, which can be used as a signal. Compared with a sensing system without HCR, a 20-fold increase in the sensitivity was achieved using the sensing system with HCR. The fluorescent intensity of the sensing system increased with the increase in target DNA concentration from 0.5 nM to 100 nM. A single mismatched target ss-DNA could be effectively discriminated from complementary target DNA. Genotyping of a G/C single-nucleotide polymorphism of polymerase chain reaction (PCR) products was successfully demonstrated with the sensing system. Therefore, integrating HCR strategy with non-covalent labeling of fluorescent hairpin DNA probes provides a sensitive and cost-effective DNA assay. PMID:26879193

  8. Near-field examination of perovskite-based superlenses and superlens-enhanced probe-object coupling

    PubMed Central

    Kehr, S.C.; Liu, Y.M.; Martin, L.W.; Yu, P.; Gajek, M.; Yang, S.-Y.; Yang, C.-H.; Wenzel, M.T.; Jacob, R.; von Ribbeck, H.-G.; Helm, M.; Zhang, X.; Eng, L.M.; Ramesh, R.

    2011-01-01

    A planar slab of negative-index material works as a superlens with sub-diffraction-limited resolution, as propagating waves are focused and, moreover, evanescent waves are reconstructed in the image plane. Here we demonstrate a superlens for electric evanescent fields with low losses using perovskites in the mid-infrared regime. The combination of near-field microscopy with a tunable free-electron laser allows us to address precisely the polariton modes, which are critical for super-resolution imaging. We spectrally study the lateral and vertical distributions of evanescent waves around the image plane of such a lens, and achieve imaging resolution of λ/14 at the superlensing wavelength. Interestingly, at certain distances between the probe and sample surface, we observe a maximum of these evanescent fields. Comparisons with numerical simulations indicate that this maximum originates from an enhanced coupling between probe and object, which might be applicable for multifunctional circuits, infrared spectroscopy and thermal sensors. PMID:21427720

  9. Near-field examination of perovskite-based superlenses and superlens-enhanced probe-object coupling.

    PubMed

    Kehr, S C; Liu, Y M; Martin, L W; Yu, P; Gajek, M; Yang, S-Y; Yang, C-H; Wenzel, M T; Jacob, R; von Ribbeck, H-G; Helm, M; Zhang, X; Eng, L M; Ramesh, R

    2011-01-01

    A planar slab of negative-index material works as a superlens with sub-diffraction-limited resolution, as propagating waves are focused and, moreover, evanescent waves are reconstructed in the image plane. Here we demonstrate a superlens for electric evanescent fields with low losses using perovskites in the mid-infrared regime. The combination of near-field microscopy with a tunable free-electron laser allows us to address precisely the polariton modes, which are critical for super-resolution imaging. We spectrally study the lateral and vertical distributions of evanescent waves around the image plane of such a lens, and achieve imaging resolution of λ/14 at the superlensing wavelength. Interestingly, at certain distances between the probe and sample surface, we observe a maximum of these evanescent fields. Comparisons with numerical simulations indicate that this maximum originates from an enhanced coupling between probe and object, which might be applicable for multifunctional circuits, infrared spectroscopy and thermal sensors. PMID:21427720

  10. Enhanced cross-Kerr effect for probing tunnelling in coupled quantum dots

    NASA Astrophysics Data System (ADS)

    Peng, Yandong; Yang, Aihong; Chen, Bing; Zhang, Shaomei; Liu, Shande; Wang, Xueshui

    2016-02-01

    An efficient scheme for probing electron tunnelling is proposed based on the enhanced cross-Kerr nonlinearity in a double-dot system. Due to resonant tunnelling, the cross-Kerr nonlinearity arises in a transparency window. Its intensity is nearly two orders of magnitude greater than that of the self-Kerr effect under any given conditions, where residual absorption is suppressed due to the competition of nonlinear gain and absorption. The enhanced cross-Kerr effect is sensitive to the tunnelling, so the probe spectrum can detect subtle tunnelling changes. The simulation results show that the probe sensitivity of the nonlinear phase shift is about 0.28 rad/μeV.

  11. Probing the Dipolar Coupling in a Heterospin Endohedral Fullerene-Phthalocyanine Dyad.

    PubMed

    Zhou, Shen; Yamamoto, Masanori; Briggs, G Andrew D; Imahori, Hiroshi; Porfyrakis, Kyriakos

    2016-02-01

    Paramagnetic endohedral fullerenes and phthalocyanine (Pc) complexes are promising building blocks for molecular quantum information processing, for which tunable dipolar coupling is required. We have linked these two spin qubit candidates together and characterized the resulting electron paramagnetic resonance properties, including the spin dipolar coupling between the fullerene spin and the copper spin. Having interpreted the distance-dependent coupling strength quantitatively and further discussed the antiferromagnetic aggregation effect of the CuPc moieties, we demonstrate two ways of tuning the dipolar coupling in such dyad systems: changing the spacer group and adjusting the solution concentration. PMID:26745202

  12. Probing Subdiffraction Limit Separations with Plasmon Coupling Microscopy: Concepts and Applications

    PubMed Central

    Wu, Linxi

    2014-01-01

    Due to their advantageous materials properties, noble metal nanoparticles are versatile tools in biosensing and imaging. A characteristic feature of gold and silver nanoparticles is their ability to sustain localized surface plasmons that provide both large optical cross-sections and extraordinary photophysical stability. Plasmon Coupling Microscopy takes advantage of the beneficial optical properties and utilizes electromagnetic near-field coupling between individual noble metal nanoparticle labels to resolve subdiffraction limit separations in an all-optical fashion. This Tutorial provides an introduction into the physical concepts underlying distance dependent plasmon coupling, discusses potential experimental implementations of Plasmon Coupling Microscopy, and reviews applications in the area of biosensing and imaging. PMID:24390574

  13. Tightly wrapped semiconductor-axon microtubes for probing hybrid networks: Modeling the capacitive coupling strength

    NASA Astrophysics Data System (ADS)

    Diedrich, Daniel; Blick, Robert H.

    2015-02-01

    We present finite-element simulations modeling the electromagnetic interaction between axons and semiconductor microtubes. These tubes are tightly wrapped around the axons, enabling highly efficient capacitive coupling. The calculations reveal that the capacitive coupling strength is in the pA regime.

  14. Resolving Intra- and Inter-Molecular Structure with Non-Contact Atomic Force Microscopy

    PubMed Central

    Jarvis, Samuel Paul

    2015-01-01

    A major challenge in molecular investigations at surfaces has been to image individual molecules, and the assemblies they form, with single-bond resolution. Scanning probe microscopy, with its exceptionally high resolution, is ideally suited to this goal. With the introduction of methods exploiting molecularly-terminated tips, where the apex of the probe is, for example, terminated with a single CO, Xe or H2 molecule, scanning probe methods can now achieve higher resolution than ever before. In this review, some of the landmark results related to attaining intramolecular resolution with non-contact atomic force microscopy (NC-AFM) are summarised before focussing on recent reports probing molecular assemblies where apparent intermolecular features have been observed. Several groups have now highlighted the critical role that flexure in the tip-sample junction plays in producing the exceptionally sharp images of both intra- and apparent inter-molecular structure. In the latter case, the features have been identified as imaging artefacts, rather than real intermolecular bonds. This review discusses the potential for NC-AFM to provide exceptional resolution of supramolecular assemblies stabilised via a variety of intermolecular forces and highlights the potential challenges and pitfalls involved in interpreting bonding interactions. PMID:26307976

  15. Resolving Intra- and Inter-Molecular Structure with Non-Contact Atomic Force Microscopy.

    PubMed

    Jarvis, Samuel Paul

    2015-01-01

    A major challenge in molecular investigations at surfaces has been to image individual molecules, and the assemblies they form, with single-bond resolution. Scanning probe microscopy, with its exceptionally high resolution, is ideally suited to this goal. With the introduction of methods exploiting molecularly-terminated tips, where the apex of the probe is, for example, terminated with a single CO, Xe or H2 molecule, scanning probe methods can now achieve higher resolution than ever before. In this review, some of the landmark results related to attaining intramolecular resolution with non-contact atomic force microscopy (NC-AFM) are summarised before focussing on recent reports probing molecular assemblies where apparent intermolecular features have been observed. Several groups have now highlighted the critical role that flexure in the tip-sample junction plays in producing the exceptionally sharp images of both intra- and apparent inter-molecular structure. In the latter case, the features have been identified as imaging artefacts, rather than real intermolecular bonds. This review discusses the potential for NC-AFM to provide exceptional resolution of supramolecular assemblies stabilised via a variety of intermolecular forces and highlights the potential challenges and pitfalls involved in interpreting bonding interactions. PMID:26307976

  16. Thin-layer chromatography and mass spectrometry coupled using proximal probe thermal desorption with electrospray or atmospheric pressure chemica lionization

    SciTech Connect

    Ovchinnikova, Olga S; Van Berkel, Gary J

    2010-01-01

    An atmospheric pressure proximal probe thermal desorption sampling method coupled with secondary ionization by electrospray or atmospheric pressure chemical ionization was demonstrated for the mass spectrometric analysis of a diverse set of compounds (dyestuffs, pharmaceuticals, explosives and pesticides) separated on various high-performance thin-layer chromatography plates. Line scans along or through development lanes on the plates were carried out by moving the plate relative to a stationary heated probe positioned close to or just touching the stationary phase surface. Vapors of the compounds thermally desorbed from the surface were drawn into the ionization region of a combined electrospray ionization/atmospheric pressure chemical ionization source where they merged with reagent ions and/or charged droplets from a corona discharge or an electrospray emitter and were ionized. The ionized components were then drawn through the atmospheric pressure sampling orifice into the vacuum region of a triple quadrupole mass spectrometer and detected using full scan, single ion monitoring, or selected reaction monitoring mode. Studies of variable parameters and performance metrics including the proximal probe temperature, gas flow rate into the ionization region, surface scan speed, read-out resolution, detection limits, and surface type are discussed.

  17. Characterization of an inductively coupled nitrogen-argon plasma by Langmuir probe combined with optical emission spectroscopy

    SciTech Connect

    Song, M. A.; Lee, Y. W.; Chung, T. H.

    2011-02-15

    The properties of low-pressure inductively coupled nitrogen-argon plasmas were investigated by using a Langmuir probe combined with optical emission spectroscopy (OES) under the conditions of pressures in the range of 1-30 mTorr and applied rf powers of 200-600 W. In the experiments, the argon was introduced as an actinometer and as an adding gas. The effect of the argon content in the gas mixture was examined in the range of 5%-80%. The electron energy probability function (EEPF), the electron density, and the electron temperature were obtained by using an rf-compensated Langmuir probe. The dissociation fractions were obtained from the OES actinometry. The electron temperature was also obtained by OES corona model and compared with that measured by the probe. The second positive and first negative systems of spectral bands from nitrogen molecules were analyzed to estimate the vibrational and rotational temperatures. The effects of the control parameters on the plasma parameters and dissociation fraction were investigated. While the calculated nitrogen atom density increased with power, it exhibited a maximum value near the Ar content of 30%.

  18. Magnetic probe (B-dot) measurements in an inductively coupled plasma (ICP): Techniques and results

    SciTech Connect

    Piejak, R.B.

    1998-12-31

    There has been a considerable amount of study of ICP sources in recent years because these discharges have been found to be useful in plasma processing and light source applications. In view of their practical relevance, the authors have made a fairly extensive experimental study of ICP sources using B-dot (dB/dt) probes to measure the magnitude and phase of the magnetic field (as well as Langmuir probes to measure the electron energy distribution function). The measurements span gas pressures ranging between 0.3 and 300 mTorr, discharge powers ranging between 25 and 200W and include three driving frequencies: 3.39, 6.78 and 13.56 MHz. This talk is based mainly upon these measurements.

  19. Thermoelectric transport of mesoscopic conductors coupled to voltage and thermal probes

    NASA Astrophysics Data System (ADS)

    Sánchez, David; Serra, Llorenç

    2011-11-01

    We investigate the basic properties of the thermopower (Seebeck coefficient) of phase-coherent conductors under the influence of dephasing and inelastic processes. Transport across the system is caused by a voltage bias or a thermal gradient applied between two terminals. Inelastic scattering is modeled with the aid of an additional probe acting as an ideal potentiometer and thermometer. We find that inelastic scattering reduces the conductor's thermopower and, more unexpectedly, generates a magnetic field asymmetry in the Seebeck coefficient. The latter effect is shown to be a higher-order effect in the Sommerfeld expansion. We discuss our result by using two illustrative examples. First, we consider a generic mesoscopic system described within random matrix theory and demonstrate that thermopower fluctuations disappear quickly as the number of probe modes increases. Second, the asymmetry is explicitly calculated in the quantum limit of a ballistic microjunction. We find that asymmetric scattering strongly enhances the effect and discuss its dependence on temperature and Fermi energy.

  20. Visualizing the orientational dependence of an intermolecular potential

    PubMed Central

    Sweetman, Adam; Rashid, Mohammad A.; Jarvis, Samuel P.; Dunn, Janette L.; Rahe, Philipp; Moriarty, Philip

    2016-01-01

    Scanning probe microscopy can now be used to map the properties of single molecules with intramolecular precision by functionalization of the apex of the scanning probe tip with a single atom or molecule. Here we report on the mapping of the three-dimensional potential between fullerene (C60) molecules in different relative orientations, with sub-Angstrom resolution, using dynamic force microscopy (DFM). We introduce a visualization method which is capable of directly imaging the variation in equilibrium binding energy of different molecular orientations. We model the interaction using both a simple approach based around analytical Lennard–Jones potentials, and with dispersion-force-corrected density functional theory (DFT), and show that the positional variation in the binding energy between the molecules is dominated by the onset of repulsive interactions. Our modelling suggests that variations in the dispersion interaction are masked by repulsive interactions even at displacements significantly larger than the equilibrium intermolecular separation. PMID:26879386

  1. Visualizing the orientational dependence of an intermolecular potential

    NASA Astrophysics Data System (ADS)

    Sweetman, Adam; Rashid, Mohammad A.; Jarvis, Samuel P.; Dunn, Janette L.; Rahe, Philipp; Moriarty, Philip

    2016-02-01

    Scanning probe microscopy can now be used to map the properties of single molecules with intramolecular precision by functionalization of the apex of the scanning probe tip with a single atom or molecule. Here we report on the mapping of the three-dimensional potential between fullerene (C60) molecules in different relative orientations, with sub-Angstrom resolution, using dynamic force microscopy (DFM). We introduce a visualization method which is capable of directly imaging the variation in equilibrium binding energy of different molecular orientations. We model the interaction using both a simple approach based around analytical Lennard-Jones potentials, and with dispersion-force-corrected density functional theory (DFT), and show that the positional variation in the binding energy between the molecules is dominated by the onset of repulsive interactions. Our modelling suggests that variations in the dispersion interaction are masked by repulsive interactions even at displacements significantly larger than the equilibrium intermolecular separation.

  2. Reprint of : Correlated voltage probe model of relaxation in two Coulomb-coupled edge channels

    NASA Astrophysics Data System (ADS)

    Nigg, Simon E.

    2016-08-01

    A phenomenological correlated voltage probe model is introduced to mimic the effects of inelastic scattering between particles in different conduction channels of a phase coherent conductor. As an illustration, the non-equilibrium distribution functions of two noisy co-propagating chiral edge channels of the integer quantum Hall effect are calculated and compared with recent experiments. The method is further applied to calculate the linear response current noise through an interacting Mach-Zehnder interferometer.

  3. Correlated voltage probe model of relaxation in two Coulomb-coupled edge channels

    NASA Astrophysics Data System (ADS)

    Nigg, Simon E.

    2016-01-01

    A phenomenological correlated voltage probe model is introduced to mimic the effects of inelastic scattering between particles in different conduction channels of a phase coherent conductor. As an illustration, the non-equilibrium distribution functions of two noisy co-propagating chiral edge channels of the integer quantum Hall effect are calculated and compared with recent experiments. The method is further applied to calculate the linear response current noise through an interacting Mach-Zehnder interferometer.

  4. Probing the Charm Quark Yukawa Coupling in Higgs+Charm Production.

    PubMed

    Brivio, Ilaria; Goertz, Florian; Isidori, Gino

    2015-11-20

    We propose a new method for determining the coupling of the Higgs boson to charm quarks, via Higgs production in association with a charm-tagged jet: pp→hc. As a first estimate, we find that at the LHC with 3000 fb^{-1}, it should be possible to derive a constraint of order one, relative to the standard model (SM) value of the charm Yukawa coupling. As a by-product of this analysis, we present an estimate of the exclusive pp→hD^{(*)} electroweak cross section. Within the SM, the latter turns out to be not accessible at the LHC even in the high-luminosity phase. PMID:26636844

  5. Long-lived coherence in pentafluorobenzene as a probe of ππ* - πσ* vibronic coupling

    NASA Astrophysics Data System (ADS)

    Hüter, O.; Sala, M.; Neumann, H.; Zhang, S.; Studzinski, H.; Egorova, D.; Temps, F.

    2016-07-01

    The dynamics of pentafluorobenzene after femtosecond laser excitation to the optically bright ππ* first excited electronic state have been investigated by femtosecond time-resolved time-of-flight mass spectrometry and femtosecond time-resolved photoelectron imaging spectroscopy. The observed temporal profiles exhibit a bi-exponential decay behavior with a superimposed, long-lived, large-amplitude oscillation with a frequency of νosc = 78-74 cm-1 and a damping time of τD = 5-2 ps. On the basis of electronic structure and quantum dynamics calculations, the oscillations have been shown to arise due to vibronic coupling between the optically bright ππ* state and the energetically close-lying optically dark πσ* state. The coupling leads to a pronounced double-well character of the lowest excited adiabatic potential energy surface along several out-of-plane modes of b1 symmetry. The optical electronic excitation initiates periodic wavepacket motion along these modes. In the out-of-plane distorted molecular configuration, the excited state acquires substantial πσ* character, thus modulating the ionization probability. The photoelectron spectra and the anisotropy of their angular distribution confirm the periodically changing electronic character. The ionizing probe laser pulse directly maps the coupled electron-nuclear motion into the observed signal oscillations.

  6. Long-lived coherence in pentafluorobenzene as a probe of ππ(*) - πσ(*) vibronic coupling.

    PubMed

    Hüter, O; Sala, M; Neumann, H; Zhang, S; Studzinski, H; Egorova, D; Temps, F

    2016-07-01

    The dynamics of pentafluorobenzene after femtosecond laser excitation to the optically bright ππ(*) first excited electronic state have been investigated by femtosecond time-resolved time-of-flight mass spectrometry and femtosecond time-resolved photoelectron imaging spectroscopy. The observed temporal profiles exhibit a bi-exponential decay behavior with a superimposed, long-lived, large-amplitude oscillation with a frequency of νosc = 78-74 cm(-1) and a damping time of τD = 5-2 ps. On the basis of electronic structure and quantum dynamics calculations, the oscillations have been shown to arise due to vibronic coupling between the optically bright ππ(*) state and the energetically close-lying optically dark πσ(*) state. The coupling leads to a pronounced double-well character of the lowest excited adiabatic potential energy surface along several out-of-plane modes of b1 symmetry. The optical electronic excitation initiates periodic wavepacket motion along these modes. In the out-of-plane distorted molecular configuration, the excited state acquires substantial πσ(*) character, thus modulating the ionization probability. The photoelectron spectra and the anisotropy of their angular distribution confirm the periodically changing electronic character. The ionizing probe laser pulse directly maps the coupled electron-nuclear motion into the observed signal oscillations. PMID:27394103

  7. Mode coupling in a hanging-fiber AFM used as a rheological probe

    NASA Astrophysics Data System (ADS)

    Devailly, C.; Laurent, J.; Steinberger, A.; Bellon, L.; Ciliberto, S.

    2014-06-01

    We analyze the advantages and drawbacks of a method which measures the viscosity of liquids at microscales, using a thin glass fiber fixed on the tip of a cantilever of an ultra-low-noise Atomic Force Microscope (AFM). When the fiber is dipped into a liquid, the dissipation of the cantilever-fiber system, which is linked to the liquid viscosity, can be computed from the power spectral density of the thermal fluctuations of the cantilever deflection. The high sensitivity of the AFM allows us to show the existence and to develop a model of the coupling between the dynamics of the fiber and that of the cantilever. This model, which accurately fits the experimental data, gives also more insights into the dynamics of coupled microdevices in a viscous environment.

  8. Probing the interlayer coupling of twisted bilayer MoS2 using photoluminescence spectroscopy.

    PubMed

    Huang, Shengxi; Ling, Xi; Liang, Liangbo; Kong, Jing; Terrones, Humberto; Meunier, Vincent; Dresselhaus, Mildred S

    2014-10-01

    Two-dimensional molybdenum disulfide (MoS2) is a promising material for optoelectronic devices due to its strong photoluminescence emission. In this work, the photoluminescence of twisted bilayer MoS2 is investigated, revealing a tunability of the interlayer coupling of bilayer MoS2. It is found that the photoluminescence intensity ratio of the trion and exciton reaches its maximum value for the twisted angle 0° or 60°, while for the twisted angle 30° or 90° the situation is the opposite. This is mainly attributed to the change of the trion binding energy. The first-principles density functional theory analysis further confirms the change of the interlayer coupling with the twisted angle, which interprets our experimental results. PMID:25171263

  9. Nonplanar 4-Jets in Quarkonium Decays as a Probe for 3-Gluon Coupling

    NASA Astrophysics Data System (ADS)

    Muta, T.; Niuya, T.

    1982-11-01

    We calculate the acoplanarity (à la Fox-Wolfram) distribution of 4 jets generated by orthoquarkonium decays: 3S1(Qbar{Q})→ GGGG, GGqbar{q}. The result shows that the deviation from planar event due to 4 jets is significantly large showing the importance of the effect of 3-gluon couplings in quantum chromodynamics. The average acoplanarity is calculated to be =(0.45+0.153Nf)αs/π with Nf the number of flavors of produced quarks and αs the QCD coupling strength. As a by-product we calculated the decay rate of the parapositronium into 4 photons which results in Γ4γ=(0.0139±0.0001)α7 me with me the electron mass.

  10. Probing phonon-rotation coupling in helium nanodroplets: Infrared spectroscopy of CO and its isotopomers

    SciTech Connect

    Haeften, Klaus von; Rudolph, Stephan; Simanovski, Iaroslav; Havenith, Martina; Zillich, Robert E.; Whaley, K. Birgitta

    2006-02-01

    We have recorded the R(0){nu}{sub CO}=1(leftarrow)0 IR spectrum of CO and its isotopomers in superfluid helium nanodroplets. For droplets with average size N > or approx. 2000 helium atoms, the transition exhibits a Lorentzian shaped linewidth of 0.034 cm{sup -1}, indicating a homogeneous broadening mechanism. The rotational constants could be deduced and were found to be reduced to about 60% of the corresponding gas-phase values (63% for the reference {sup 12}C {sup 16}O species). Accompanying calculations of the pure rotational spectra were carried out using the method of correlated basis functions in combination with diffusion Monte Carlo (CBF/DMC). These calculations show that both the reduction of the rotational B constant and the line broadening can be attributed to phonon-rotation coupling. The reduction in B is confirmed by path integral correlation function calculations for a cluster of 64 {sup 4}He atoms, which also reveal a non-negligible effect of finite size on the collective modes. The phonon-rotation coupling strength is seen to depend strongly on the strength and anisotropy of the molecule-helium interaction potential. Comparison with other light rotors shows that this coupling is particularly high for CO. The CBF/DMC analysis shows that the J=1 rotational state couples effectively to phonon states, which are only present in large helium droplets or bulk. In particular, they are not present in small clusters with n{<=}20, thereby accounting for the much narrower linewidths and larger B constant measured for these sizes.

  11. Antiferromagnetic Spin Coupling between Rare Earth Adatoms and Iron Islands Probed by Spin-Polarized Tunneling.

    PubMed

    Coffey, David; Diez-Ferrer, José Luis; Serrate, David; Ciria, Miguel; de la Fuente, César; Arnaudas, José Ignacio

    2015-01-01

    High-density magnetic storage or quantum computing could be achieved using small magnets with large magnetic anisotropy, a requirement that rare-earth iron alloys fulfill in bulk. This compelling property demands a thorough investigation of the magnetism in low dimensional rare-earth iron structures. Here, we report on the magnetic coupling between 4f single atoms and a 3d magnetic nanoisland. Thulium and lutetium adatoms deposited on iron monolayer islands pseudomorphically grown on W(110) have been investigated at low temperature with scanning tunneling microscopy and spectroscopy. The spin-polarized current indicates that both kind of adatoms have in-plane magnetic moments, which couple antiferromagnetically with their underlying iron islands. Our first-principles calculations explain the observed behavior, predicting an antiparallel coupling of the induced 5d electrons magnetic moment of the lanthanides with the 3d magnetic moment of iron, as well as their in-plane orientation, and pointing to a non-contribution of 4f electrons to the spin-polarized tunneling processes in rare earths. PMID:26333417

  12. Antiferromagnetic Spin Coupling between Rare Earth Adatoms and Iron Islands Probed by Spin-Polarized Tunneling

    NASA Astrophysics Data System (ADS)

    Coffey, David; Diez-Ferrer, José Luis; Serrate, David; Ciria, Miguel; Fuente, César De La; Arnaudas, José Ignacio

    2015-09-01

    High-density magnetic storage or quantum computing could be achieved using small magnets with large magnetic anisotropy, a requirement that rare-earth iron alloys fulfill in bulk. This compelling property demands a thorough investigation of the magnetism in low dimensional rare-earth iron structures. Here, we report on the magnetic coupling between 4f single atoms and a 3d magnetic nanoisland. Thulium and lutetium adatoms deposited on iron monolayer islands pseudomorphically grown on W(110) have been investigated at low temperature with scanning tunneling microscopy and spectroscopy. The spin-polarized current indicates that both kind of adatoms have in-plane magnetic moments, which couple antiferromagnetically with their underlying iron islands. Our first-principles calculations explain the observed behavior, predicting an antiparallel coupling of the induced 5d electrons magnetic moment of the lanthanides with the 3d magnetic moment of iron, as well as their in-plane orientation, and pointing to a non-contribution of 4f electrons to the spin-polarized tunneling processes in rare earths.

  13. Antiferromagnetic Spin Coupling between Rare Earth Adatoms and Iron Islands Probed by Spin-Polarized Tunneling

    PubMed Central

    Coffey, David; Diez-Ferrer, José Luis; Serrate, David; Ciria, Miguel; Fuente, César de la; Arnaudas, José Ignacio

    2015-01-01

    High-density magnetic storage or quantum computing could be achieved using small magnets with large magnetic anisotropy, a requirement that rare-earth iron alloys fulfill in bulk. This compelling property demands a thorough investigation of the magnetism in low dimensional rare-earth iron structures. Here, we report on the magnetic coupling between 4f single atoms and a 3d magnetic nanoisland. Thulium and lutetium adatoms deposited on iron monolayer islands pseudomorphically grown on W(110) have been investigated at low temperature with scanning tunneling microscopy and spectroscopy. The spin-polarized current indicates that both kind of adatoms have in-plane magnetic moments, which couple antiferromagnetically with their underlying iron islands. Our first-principles calculations explain the observed behavior, predicting an antiparallel coupling of the induced 5d electrons magnetic moment of the lanthanides with the 3d magnetic moment of iron, as well as their in-plane orientation, and pointing to a non-contribution of 4f electrons to the spin-polarized tunneling processes in rare earths. PMID:26333417

  14. Direct coupling of a flow-flow electromembrane extraction probe to LC-MS.

    PubMed

    Fuchs, David; Gabel-Jensen, Charlotte; Jensen, Henrik; Rand, Kasper D; Pedersen-Bjergaard, Stig; Hansen, Steen Honoré; Petersen, Nickolaj Jacob

    2016-01-28

    A fully integrated and automated electromembrane extraction LC-MS (EME-LC-MS) system has been developed and characterized. Hyphenation of a flow-flow EME probe to LC-MS was accomplished by using an in-built 10-port switching valve of the LC-MS system. The 10-port switching valve decoupled the high pressure of the UHPLC-system from the low pressure required for operation of the EME-probe by automated switching between a sample extraction/analysis and a sample load position. In the sample load position the extracted analytes were loaded into a HPLC sample loop. By switching the valve to the sample extraction/analysis position the setup allowed simultaneous analysis of previously loaded analytes while extracting a new sample. Performance of the system was characterized with respect to precision and linearity (RSD < 2.5%, R(2): 0.998) and the setup was applied for studying the in-vitro metabolism of methadone by rat liver microsomes. As the metabolic reaction proceeded, methadone and its metabolites were extracted and analyzed in parallel by LC-MS using either isocratic or gradient elution. Compared to a conventional in-vitro metabolism analysis based on protein precipitation followed by LC-MS analysis the fully automated EME-LC-MS system offers a significant time saving and in addition demonstrates increased sensitivity as the analytes were automatically enriched during the extraction process. The experiment revealed 6 to 16 times higher S/N ratios of the EME-LC-MS method compared to protein precipitation followed by LC-MS and thus concomitantly lower LOD and LOQ. The setup integrates a complete analytical workflow of rapid extraction, enrichment, separation and detection of analytes in a fully automated manner. These attributes make the developed system a powerful alternative approach for a wide range of analytical applications. PMID:26755142

  15. Characterization of O2/Ar inductively coupled plasma studied by using a Langmuir probe and global model

    NASA Astrophysics Data System (ADS)

    Liu, Wei; Wen, De-Qi; Zhao, Shu-Xia; Gao, Fei; Wang, You-Nian

    2015-04-01

    An O2/Ar inductively coupled plasma is investigated by a Langmuir probe and a global model (volume averaged model). The electron density, electron temperature and electron energy distribution function (EEDF) are measured at different O2 contents, gas pressures and applied powers. At fixed pressure and power, the electron density first drops quickly with the O2 ratio and then tends to saturate in the high O2 ratio range. The effective electron temperature exhibits completely opposite behaviors at low and high pressures. This is caused by the different evolving behaviors of low and high energy electrons of the EEDFs with the O2 ratio. Both the Langmuir probe and the global model predict that the electron density of O2/Ar mixed plasma first increases, peaks and then drops constantly, upon increasing the pressure. An analysis based on the simulation reveals that the non-monotonic variation of electron density with the pressure is due to the non-monotonic variation of the ionizations from both ground state O and metastable O*. Due to the strong ionizations, the electron density increases linearly with the power. The effective electron temperature is unchanged because the EEDF shape that determines the electron temperature is not varied upon increasing the power. The calculated electron density and temperature when varying the power agree better with the experiments at high pressure, i.e. 45 mTorr. The quantitative deviation between the model and the experiment when varying the pressure and the O2 ratio can be explained by two aspects. (1) The electron energy probability function is assumed to have a Maxwellian distribution in the global model while the realistic EEDFs vary significantly with the pressure and/or the O2 ratio, as revealed by the experiment. (2) The power transfer efficiency (i.e. the fraction of the power coupled into plasma) increases with the pressure.

  16. Combination Bands of the Nonpolar OCS Dimer Involving Intermolecular Modes

    NASA Astrophysics Data System (ADS)

    Rezaei, M.; Oliaee, J. Norooz; Moazzen-Ahmadi, N.; McKellar, A. R. W.

    2012-06-01

    Spectra of the nonpolar carbonyl sulfide in the region of the OCS ν_1 fundamental band were observed in a supersonic slit-jet apparatus. The expansion gas was probed using radiation from a tunable diode laser employed in a rapid-scan signal averaging mode. Three bands centered at 2085.906, 2103.504, and 2114.979 cm-1 were observed and anlysed. The rotational assignment and fitting of the bands were made by fixing the lower state parameters to those for the ground state of nonpolar (OCS)_2, thus confirming that they were indeed combination bands of the of the most stable isomer of OCS dimer. The band centered at 2085.906 cm-1 is a combination of the forbidden A_g intramolecular mode plus the geared bend intermolecular mode and that centered at 2114.979 cm-1 is a combination of the allowed B_u intramolecular mode plus the intermolecular van der Waals stretch. The combination at 2103.504 cm-1 can be assigned as a band whose upper state involves four quanta of the intramolecular bend or the B_u intramolecular mode plus two quanta of the intermolecular torsional mode. Isotopic work is needed to conclusively identify the vibrational assignment of this band. Our experimental frequencies for the geared bend and van der Waals modes are in good agreement with a recent high level ab initio calculation by Brown et al. J. Brown, Xiao-Gang Wang, T. Carrington Jr. and Richard Dawes, Journal of Chemical Physics, submitted.

  17. Development of Feedhorn-Coupled Multichroic Polarimeters for the Inflation Probe Mission

    NASA Astrophysics Data System (ADS)

    McMahon, Jeff

    This proposal seeks support for the development of millimeter-wavelength multichroic polarimeters optimized for detecting Cosmic Microwave Background (CMB) polarization signals with a future NASA Inflation Probe Mission. The technologies developed under this proposal would also have applications in future submillimeter astrophysics satellite missions. The proposed technology would increase the overall experimental sensitivity of an Inflation Probe Mission over that achievable by single-frequency pixels, making efficient use of available diffraction-limited focal plane area while maintaining unmatched control over systematics through the use of corrugated feedhorns. The sensitivity, multi-frequency coverage, and control of detector systematics offered by this technology on the Inflation Probe Mission would provide the definitive measurement of CMB polarization and foreground sources. These data would unambiguously detect or rule out all models of Grand Unified Theory (GUT) scale inflation, provide a precise measurement of the sum of the neutrino masses, and enable a wide variety of astrophysical and additional cosmological measurements. Control of systematics and foregrounds are paramount for a successful detection of the faint inflationary signal. Corrugated feedhorns are the gold standard for producing symmetric beams with low cross-polarization. Using ring-loaded slots, they can be designed to exceed one octave in bandwidth, allowing for multiple bands using a single feed. For the optimal characterization and control of foregrounds, approximately 10 bands are needed over a frequency range roughly spanning 40-300 GHz. Our plan is to develop a scalable multichroic architecture with four frequency bands within an octave of bandwidth, which we will then scale to three different frequency ranges, for a total of 12 bands with band centers on a logarithmic scale ranging from 40-288 GHz. At the key frequencies for CMB polarization (100-150 GHz) our proposed detectors

  18. Single-molecular surface-enhanced resonance Raman scattering as a quantitative probe of local electromagnetic field: The case of strong coupling between plasmonic and excitonic resonance

    NASA Astrophysics Data System (ADS)

    Itoh, Tamitake; Yamamoto, Yuko S.; Tamaru, Hiroharu; Biju, Vasudevanpillai; Wakida, Shin-ichi; Ozaki, Yukihiro

    2014-05-01

    We investigate electromagnetic coupling between plasmonic and molecular electronic resonances using single-molecular surface-enhanced resonance Raman scattering (SERRS) from single silver nanoparticle dimers. When dimers exhibit SERRS activity, their elastic light scattering spectra show two lines, which are temporally closing toward each other. The higher energy line eventually disappears at the time of SERRS quenching. A coupled-oscillator model composed of plasmonic and molecular electronic resonances consistently reproduces the above interesting results by decreasing coupling energy, indicating that SERRS can be a quantitative probe for strong coupling between the two resonances.

  19. Coherent coupling of magneto-excitons probed by two-dimensional Fourier transform spectroscopy

    NASA Astrophysics Data System (ADS)

    Paul, Jagannath; Liu, Cunming; McGill, Stephen; Hilton, David; Karaiskaj, Denis

    We present the coherent two dimensional Fourier Transform (2DFT) spectra of magneto-excitons in undoped GaAs quantum wells at high magnetic field up to 10 Tesla. The 2DFT data reveal strong coherent coupling between resonances and line shapes which are strikingly different from the zero field spectra. 2DFT spectra measured using co-linear and co-circular polarizations at low temperatures will be discussed. The work at USF and UAB was supported by the National Science Foundation under Grant Number DMR-1409473. The work at NHMFL, Florida State University was supported by the National Science Foundation under Grant Numbers DMR-1157490 and DMR-1229217.

  20. Probing Nonadiabaticity in the Proton-Coupled Electron Transfer Reaction Catalyzed by Soybean Lipoxygenase

    PubMed Central

    2014-01-01

    Proton-coupled electron transfer (PCET) plays a vital role in many biological and chemical processes. PCET rate constant expressions are available for various well-defined regimes, and determining which expression is appropriate for a given system is essential for reliable modeling. Quantitative diagnostics have been devised to characterize the vibronic nonadiabaticity between the electron–proton quantum subsystem and the classical nuclei, as well as the electron–proton nonadiabaticity between the electrons and proton(s) within the quantum subsystem. Herein these diagnostics are applied to a model of the active site of the enzyme soybean lipoxygenase, which catalyzes a PCET reaction that exhibits unusually high deuterium kinetic isotope effects at room temperature. Both semiclassical and electronic charge density diagnostics illustrate vibronic and electron–proton nonadiabaticity for this PCET reaction, supporting the use of the Golden rule nonadiabatic rate constant expression with a specific form of the vibronic coupling. This type of characterization will be useful for theoretical modeling of a broad range of PCET processes. PMID:25258676

  1. Trajectory-probed instability and statistics of desynchronization events in coupled chaotic systems

    NASA Astrophysics Data System (ADS)

    de Oliveira, Gilson F.; Chevrollier, Martine; Passerat de Silans, Thierry; Oriá, Marcos; de Souza Cavalcante, Hugo L. D.

    2015-11-01

    Complex systems, such as financial markets, earthquakes, and neurological networks, exhibit extreme events whose mechanisms of formation are not still completely understood. These mechanisms may be identified and better studied in simpler systems with dynamical features similar to the ones encountered in the complex system of interest. For instance, sudden and brief departures from the synchronized state observed in coupled chaotic systems were shown to display non-normal statistical distributions similar to events observed in the complex systems cited above. The current hypothesis accepted is that these desynchronization events are influenced by the presence of unstable object(s) in the phase space of the system. Here, we present further evidence that the occurrence of large events is triggered by the visitation of the system's phase-space trajectory to the vicinity of these unstable objects. In the system studied here, this visitation is controlled by a single parameter, and we exploit this feature to observe the effect of the visitation rate in the overall instability of the synchronized state. We find that the probability of escapes from the synchronized state and the size of those desynchronization events are enhanced in attractors whose shapes permit the chaotic trajectories to approach the region of strong instability. This result shows that the occurrence of large events requires not only a large local instability to amplify noise, or to amplify the effect of parameter mismatch between the coupled subsystems, but also that the trajectories of the system wander close to this local instability.

  2. Probing triple Higgs couplings of the two Higgs doublet model at a linear collider

    SciTech Connect

    Arhrib, Abdesslam; Benbrik, Rachid; Chiang, C.-W.

    2008-06-01

    We study double Higgs production at the future linear collider in the framework of the two Higgs doublet models through the following channels: e{sup +}e{sup -}{yields}{phi}{sub i}{phi}{sub j}Z, {phi}{sub i}=h{sup 0}, H{sup 0}, A{sup 0}, H{sup {+-}}. All these processes are sensitive to triple Higgs couplings. Hence observations of them provide information on the triple Higgs couplings that help reconstructing the scalar potential. We also discuss the double Higgs-Strahlung e{sup +}e{sup -}{yields}h{sup 0}h{sup 0}Z in the decoupling limit where h{sup 0} mimics the standard model Higgs boson. The processes e{sup +}e{sup -}{yields}h{sup 0}h{sup 0}Z and e{sup +}e{sup -}{yields}h{sup 0}H{sup 0}Z are also discussed in the fermiophobic limit where distinctive signatures such as 4{gamma}+X, 2{gamma}+X, and 6{gamma}+X are expected in the Type-I two Higgs doublet model.

  3. Trajectory-probed instability and statistics of desynchronization events in coupled chaotic systems

    SciTech Connect

    Oliveira, Gilson F. de Chevrollier, Martine; Oriá, Marcos; Passerat de Silans, Thierry; Souza Cavalcante, Hugo L. D. de

    2015-11-15

    Complex systems, such as financial markets, earthquakes, and neurological networks, exhibit extreme events whose mechanisms of formation are not still completely understood. These mechanisms may be identified and better studied in simpler systems with dynamical features similar to the ones encountered in the complex system of interest. For instance, sudden and brief departures from the synchronized state observed in coupled chaotic systems were shown to display non-normal statistical distributions similar to events observed in the complex systems cited above. The current hypothesis accepted is that these desynchronization events are influenced by the presence of unstable object(s) in the phase space of the system. Here, we present further evidence that the occurrence of large events is triggered by the visitation of the system's phase-space trajectory to the vicinity of these unstable objects. In the system studied here, this visitation is controlled by a single parameter, and we exploit this feature to observe the effect of the visitation rate in the overall instability of the synchronized state. We find that the probability of escapes from the synchronized state and the size of those desynchronization events are enhanced in attractors whose shapes permit the chaotic trajectories to approach the region of strong instability. This result shows that the occurrence of large events requires not only a large local instability to amplify noise, or to amplify the effect of parameter mismatch between the coupled subsystems, but also that the trajectories of the system wander close to this local instability.

  4. Probing the holographic principle using dynamical gauge effects from open spin-orbit coupling

    NASA Astrophysics Data System (ADS)

    Zhao, Jianshi; Price, Craig; Liu, Qi; Gemelke, Nathan

    2016-05-01

    Dynamical gauge fields result from locally defined symmetries and an effective over-labeling of quantum states. Coupling atoms weakly to a reservoir of laser modes can create an effective dynamical gauge field purely due to the disregard of information in the optical states. Here we report measurements revealing effects of open spin-orbit coupling in a system where an effective model can be formed from a non-abelian SU(2) × U(1) field theory following the Yang-Mills construct. Forming a close analogy to dynamical gauge effects in quantum chromodynamics, we extract a measure of atomic motion which reveals the analog of a closing mass gap for the relevant gauge boson, shedding insight on long standing open problems in gauge-fixing scale anomalies. Using arguments following the holographic principle, we measure scaling relations which can be understood by quantifying information present in the local potential. New prospects using these techniques for developing fractionalization of multi-particle and macroscopic systems using dissipative and non-abelian gauge fields will also be discussed. We acknowledge support from NSF Award No. 1068570, and the Charles E. Kaufman Foundation.

  5. Hydrated fractions of cellulosics probed by infrared spectroscopy coupled with dynamics of deuterium exchange.

    PubMed

    Driemeier, Carlos; Mendes, Fernanda M; Ling, Liu Yi

    2015-08-20

    This article presents a novel method to selectively probe the non-crystalline, hydrated fractions of cellulosic biomass. The method is based on time-resolved infrared spectra analyzed to provide information on spectral and dynamical features of deuterium exchange (OH → OD) in D2O atmosphere. We assign deuterium exchange spectral regions (700-3800 cm(-1)) and explore changes due to relative humidity, different cellulosic samples, and infrared polarization. Here, two results are highlighted. First, a wide range of celluloses isolated from plants show remarkable spectral similarities whatever the relative amounts of cellulose and xylan. This result supports an inherent type of hydrated disorder which is mostly insensitive to the molecular identities of the associated polysaccharides. Second, polarized infrared analysis of cotton reveals hydrated cellulose having chains preferentially aligned with those of crystals, while the hydroxyls of hydrated cellulose present much more randomized orientation. Our results provide new insights on molecular and group orientation and on hydrogen bonding in hydrated fractions of cellulosic biomass. PMID:25965468

  6. Interrogation of the intersubunit interface of the open Hv1 proton channel with a probe of allosteric coupling

    PubMed Central

    Hong, Liang; Singh, Vikrant; Wulff, Heike; Tombola, Francesco

    2015-01-01

    The Hv1 voltage-gated proton channel is a dimeric complex consisting of two voltage-sensing domains (VSDs), each containing a gated proton permeation pathway. Dimerization is controlled by a cytoplasmic coiled-coil domain. The transitions from the closed to the open state in the two VSDs are known to occur cooperatively; however, the underlying mechanism is poorly understood. Intersubunit interfaces play a critical role in allosteric processes; but, such interfaces have not been determined in the open Hv1 channel. Here we show that 2-guanidinothiazole derivatives block the two Hv1 VSDs in a cooperative way, and use one of the compounds as a probe of allosteric coupling between open subunits. We find that the extracellular ends of the first transmembrane segments of the VSDs form the intersubunit interface that mediates coupling between binding sites, while the coiled-coil domain does not directly participate in the process. We also find strong evidence that the channel’s proton selectivity filter controls blocker binding cooperativity. PMID:26365828

  7. Coupled effect of salt and pH on proteins probed with NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Kukic, Predrag; O'Meara, Fergal; Hewage, Chandralal; Erik Nielsen, Jens

    2013-07-01

    The coupled effect of ionic strength (50-400 mM) and pH (2-8) on ionization and conformation equilibria of lysozyme was studied using NMR spectroscopy. Observed changes in pKa values of the ionizable groups were found to originate from perturbations in the geometry of hydrogen bonds rather than screening of electric fields. Moreover, at the ionic strengths used here, salt-induced local conformational changes had a dominant effect on chemical shifts measured on 1HN and 15N amide nuclei. Accurate modeling of these localized perturbations in structure-based energy calculations is a necessary prerequisite on the way to complete understanding of any salt-induced processes in proteins.

  8. DNA-Linked Enzyme-Coupled Assay for Probing Glucosyltransferase Specificity.

    PubMed

    Sukovich, David J; Modavi, Cyrus; de Raad, Markus; Prince, Robin N; Anderson, J Christopher

    2015-07-17

    Traditional enzyme characterization methods are low-throughput and therefore limit engineering efforts in synthetic biology and biotechnology. Here, we propose a DNA-linked enzyme-coupled assay (DLEnCA) to monitor enzyme reactions in a high-throughput manner. Throughput is improved by removing the need for protein purification and by limiting the need for liquid chromatography mass spectrometry (LCMS) product detection by linking enzymatic function to DNA modification. We demonstrate the DLEnCA methodology using glucosyltransferases as an illustration. The assay utilizes cell free transcription/translation systems to produce enzymes of interest, while UDP-glucose and T4-β-glucosyltransferase are used to modify DNA, which is detected postreaction using qPCR or a similar means of DNA analysis. OleD and two glucosyltransferases from Arabidopsis were used to verify the assay's generality toward glucosyltransferases. We further show DLEnCA's utility by mapping out the substrate specificity for these enzymes. PMID:25621860

  9. Magnetoelectric coupling of multiferroic chromium doped barium titanate thin film probed by magneto-impedance spectroscopy

    SciTech Connect

    Shah, Jyoti Kotnala, Ravinder K. E-mail: rkkotnala@gmail.com

    2014-04-07

    Thin film of BaTiO{sub 3} doped with 0.1 at. % Cr (Cr:BTO) has been prepared by pulsed laser deposition technique. Film was deposited on Pt/SrTiO{sub 3} substrate at 500 °C in 50 mTorr Oxygen gas pressure using KrF (298 nm) laser. Polycrystalline growth of single phase Cr:BTO thin film has been confirmed by grazing angle X-ray diffraction. Cr:BTO film exhibited remnant polarization 6.4 μC/cm{sup 2} and 0.79 MV/cm coercivity. Magnetization measurement of Cr:BTO film showed magnetic moment 12 emu/cc. Formation of weakly magnetic domains has been captured by magnetic force microscopy. Theoretical impedance equation fitted to experimental data in Cole-Cole plot for thin film in presence of transverse magnetic field resolved the increase in grain capacitance from 4.58 × 10{sup −12} to 5.4 × 10{sup −11} F. Film exhibited high value 137 mV/cm-Oe magneto-electric (ME) coupling coefficient at room temperature. The high value of ME coupling obtained can reduce the typical processing steps involved in multilayer deposition to obtain multiferrocity in thin film. Barium titanate being best ferroelectric material has been tailored to be multiferroic by non ferromagnetic element, Cr, doping in thin film form opens an avenue for more stable and reliable spintronic material for low power magnetoelectric random excess memory applications.

  10. Direct Observation of Coupling between Structural Fluctuation and Ultrafast Hydration Dynamics of Fluorescent Probes in Anionic Micelles.

    PubMed

    Choudhury, Susobhan; Mondal, Prasanna Kumar; Sharma, V K; Mitra, S; Sakai, V Garcia; Mukhopadhyay, R; Pal, Samir Kumar

    2015-08-27

    The coupling of structural fluctuation and the dynamics of associated water molecules of biological macromolecules is vital for various biological activities. Although a number of molecular dynamics (MD) studies on proteins/DNA predicted the importance of such coupling, experimental evidence of variation of hydration dynamics with controlled structural fluctuation even in model macromolecule is sparse and raised controversies in the contemporary literature. Here, we have investigated dynamics of hydration at the surfaces of two similar anionic micelles sodium dodecyl sulfate (SDS) and sodium dodecylbenzenesulfonate (SDBS) as model macromolecules using coumarin 500 (C500) as spectroscopic probe with femtosecond to picosecond time resolution up to 20 ns time window. The constituting surfactants SDS and SDBS are structurally similar except one benzene moiety in the SDBS may offer additional rigidity to the SDBS micelles through π-stacking and added bulkiness. The structural integrity of the micelles in the aqueous medium is confirmed in dynamic light scattering (DLS) studies. A variety of studies including polarization gated fluorescence spectroscopy and quasielastic neutron scattering (QENS) have been used to confirm differential structural fluctuation of SDS and SDBS micelles. We have also employed femtosecond-resolved Förster resonance energy transfer (FRET) in order to study binding of a cationic organic ligand ethidium bromide (EtBr) salt at the micellar surfaces. The distance distribution of the donor (C500)-acceptor (EtBr) in the micellar media reveals the manifestation of the structural flexibility of the micelles. Our studies on dynamical coupling of the structural flexibility with surface hydration in the nanoscopic micellar media may find the relevance in the "master-slave" type water dynamics in biologically relevant macromolecules. PMID:25874585

  11. Observed Coupling Between the International Space Station PCU Plasma and a FPMU Langmuir Probe Facilitated by the Geomagnetic Field

    NASA Technical Reports Server (NTRS)

    Hartman, William; Koontz, Steven L.

    2010-01-01

    Electrical charging of the International Space Station (ISS) is a matter of serious concern resulting from the possibility of vehicle arcing and electrical shock hazard to crew during extravehicular activity (EVA). A Plasma Contactor Unit (PCU) was developed and integrated into ISS in order to control the ISS floating potential, thereby, minimize vehicle charging and associated hazards. One of the principle factors affecting ISS electrical charging is the ionosphere plasma state (i.e., electron temperature and density). To support ISS electrical charging studies a Floating Potential Monitoring Unit (FPMU) is also integrated into ISS in order to measure the ionosphere properties using Langmuir probes (LP). The FPMU was located on the Starboard side of ISS. The PCU is located near the center of ISS with its plasma exhaust pointed to port. From its integration on ISS in 2006 through November of 2009, the FPMU data exhibited nominal characteristics during PCU operation. On November 21, 2009 the FPMU was relocated from the Starboard location to a new Port location. After relocation significant enhanced noise was observed in both the LP current-voltage sweeps and the derived electron temperature data. The enhanced noise only occurred when the PCU was in discharge and at unique and repeatable locations of the ISS orbit. The cause of this enhanced noise was investigated. It was found that there is coupling occurring between the PCU plasma and the FPMU LP. In this paper we shall 1) present the on-orbit data and the presence of enhanced noise, 2) demonstrate that the coupling of the PCU plasma and the FPMU measurements is geomagnetically organized, 3) show that coupling of the PCU plasma and the FPMU is primarily due to and driven by particle-wave interaction and 4) show that the ionosphere conditions are adequate for Alfven waves to be generated by the PCU plasma.

  12. Rhodium(i)-catalysed intermolecular alkyne insertion into (2-pyridylmethylene)cyclobutenes.

    PubMed

    Matsuda, Takanori; Matsumoto, Takeshi

    2016-06-14

    Cyclobutenes with 2-pyridylmethylene groups at the 3 position underwent an intermolecular alkyne insertion reaction in the presence of a rhodium(i) catalyst at 170 °C to afford substituted benzenes. Among the different 2-pyridylmethylene groups examined, 3-methyl-2-pyridyl derivatives showed superior activity and readily coupled with various alkynes, including sterically demanding, heteroaromatic and terminal alkynes. PMID:27193826

  13. Tyrosine analogues for probing proton-coupled electron transfer processes in peptides and proteins.

    PubMed

    Nara, Susheel J; Valgimigli, Luca; Pedulli, Gian Franco; Pratt, Derek A

    2010-01-20

    A series of amino acids analogous to tyrosine, but differing in the physicochemical properties of the aryl alcohol side chain, have been prepared and characterized. These compounds are expected to be useful in understanding the relationships between structure, thermodynamics, and kinetics in long-range proton-coupled electron transfer processes in peptides and proteins. Systematic changes in the acidity, redox potential, and O-H bond strength of the tyrosine side chain could be induced upon substituting the phenol for pyridinol and pyrimidinol moieties. Further modulation was possible by introducing methyl and t-butyl substitution in the position ortho to the phenolic hydroxyl. The unnatural amino acids were prepared by Pd-catalyzed cross-coupling of the corresponding halogenated aryl alcohol protected as their benzyl ethers with an organozinc reagent derived from N-Boc L-serine carboxymethyl ester. Subsequent debenzylation by catalytic hydrogenation yielded the tyrosine analogues in good yield. Spectrophotometric titrations revealed a decrease in tyrosine pK(a) of ca. 1.5 log units per included nitrogen atom, along with a corresponding increase in the oxidation (peak) potentials of ca. 200 mV, respectively. All told, the six novel amino acids described here have phenol-like side chains with pK(a)'s that span a range of 7.0 to greater than 10, and an oxidation (peak) potential range of greater than 600 mV at and around physiological pH. Radical equilibration EPR experiments were carried out to reveal that the O-H bond strengths increase systematically upon nitrogen incorporation (by ca. 0.5-1.0 kcal/mol), and radical stability and persistence increase systematically upon introduction of alkyl substitution in the ortho positions. The EPR spectra of the aryloxyl radicals derived from tyrosine and each of the analogues could be determined at room temperature, and each featured distinct spectral properties. The uniqueness of their spectra will be helpful in discerning

  14. Probing the Electronic Environment of Methylindoles using Internal Rotation and (14)N Nuclear Quadrupole Coupling.

    PubMed

    Gurusinghe, Ranil M; Tubergen, Michael J

    2016-05-26

    High-resolution rotational spectra were recorded in the 10.5-21.0 GHz frequency range for seven singly methylated indoles. (14)N nuclear quadrupole hyperfine structure and spectral splittings arising from tunneling along the internal rotation of the methyl group were resolved for all indole species. The nuclear quadrupole coupling constants were used to characterize the electronic environment of the nitrogen atom, and the program XIAM was used to fit the barrier to internal rotation to the measured transition frequencies. The best fit barriers were found to be 277.1(2), 374.32(4), 414.(5), 331.6(2), 126.8675(15), 121.413(4), and 426(3) cm(-1) for 1-methylindole through 7-methylindole, respectively. The fitted barriers were found to be in good agreement with barriers calculated at the ωB97XD/6-311++G(d,p) level. The complete set of experimental barriers is compared to theoretical investigations of the origins of methyl torsional barriers and confirms that the magnitude of these barriers is an overall effect of individual hyperconjugative and structural interactions of many bonding/antibonding orbitals. PMID:27128828

  15. Langmuir Probe Measurements of Inductively Coupled Plasma in CF4/AR/O2 Mixtures

    NASA Technical Reports Server (NTRS)

    Rao, M. V. V. S.; Cruden, Brett; Sharma, Surendra; Meyyappan, Meyya

    2001-01-01

    Inductively coupled plasmas of CF4:Ar:O2, which have been of importance to material processing, were studied in the GEC cell at 80:10:10, 60:20:20, and 40:30:30 mixture ratios. Radial distributions of plasma potential (V(sub p)), electron and ion number densities (n(sub e) and n(sub i)), electron temperature (T(sub e)), and electron energy distribution functions (EEDFs) were measured in the mid-plane of plasma across the electrodes in the pressure range of 10-50 mTorr, and RF power of 200 and 300 W. V(sub p), n(sub e) and n(sub i), which peak in the center of the plasma, increase with decrease of pressure. T(sub e) also increases with pressure but peaks toward the electrode edge. Both V(sub p) and T(sub e) remain nearly independent of RF power, whereas n(sub e) and n(sub i) increase with power. In all conditions the EEDFs exhibit non-Maxwellian shape and are more like Druyvesteyn form at higher energies. They exhibit a broad lip in the energy range 0-10 eV suggesting an electron loss mechanism, which could be due to via resonance electron attachment processes producing negative ions in this rich electronegative gas mixture. This behavior is more prominent towards the electrode edge.

  16. Langmuir Probe Measurements of Inductively Coupled Plasmas in CF4/Ar/O2 Mixtures

    NASA Technical Reports Server (NTRS)

    Rao, M. V. V. S.; Cruden, Brett; Sharma, Surendra; Meyyappan, Meyya

    2001-01-01

    Inductively coupled plasmas of CF4:Ar:O2, which have been of importance to material processing, were studied in the GEC cell at 80:10:10, 60:20:20, and 40:30:30 mixture ratios. Radial distributions of plasma potential (V(sub p)), electron and ion number densities (n(sub e) and n(sub i), electron temperature (T(sub e)), and electron energy distribution functions (EEDFs) were measured in the mid-plane of plasma across the electrodes in the pressure range of 10-50 mTorr, and RF (radio frequency) power of 200 and 300 W. V(sub p), n(sub e) and n(sub i), which peak in the center of the plasma, increase with decrease of pressure. T(sub e) also increases with pressure but peaks toward the electrode edge. Both V(sub p) and T(sub e) remain nearly independent of RF power, whereas n(sub e) and n(sub i) increase with power. In all conditions the EEDFs exhibit non-Maxwellian shape and are more like Druyvesteyn form at higher energies. They exhibit a broad dip in the energy range 0-10 eV suggesting an electron loss mechanism, which could be due to via resonance electron attachment processes producing negative ions in this rich electronegative gas mixture. This behavior is more prominent towards the electrode edge.

  17. Mapping intermolecular bonding in C60

    PubMed Central

    Sundqvist, Bertil

    2014-01-01

    The formation of intermolecular bonds in C60 has been investigated in detail at pressures below 2.2 GPa and up to 750 K. Fullerene samples were heated in a temperature gradient to obtain data on the formation of dimers and low-dimensional polymers along isobars. Intermolecular bonding was analyzed ex situ by Raman scattering, using both intramolecular modes and intermolecular stretching modes. Semi-quantitative reaction maps are given for the formation of dimers and chains. The activation energy for dimer formation decreases by 0.2 meV pm−1 when intermolecular distances decrease and dimer formation is noticeably affected by the rotational state of molecules. Above 400–450 K larger oligomers are formed; below 1.4 GPa most of these are disordered, with small domains of linear chains, but above this the appearance of stretching modes indicates the existence of ordered one-dimensional polymers. At the highest pressures and temperatures two-dimensional polymers are also observed. PMID:25145952

  18. Estimation of intermolecular interactions in polymer networks

    SciTech Connect

    Subrananian, P.R.; Galiatsatos, V.

    1993-12-31

    Strain-birefringence measurements have been used to estimate intermolecular interactions in polymer networks. The intensity of the interaction has been quantified through a theoretical scheme recently proposed by Erman. The results show that these interactions diminish with decreasing molecular weight between cross-links and decreasing cross-link functionality.

  19. An improved intermolecular potential for sulfur hexafluoride

    SciTech Connect

    Aziz, R.A.; Slaman, M.J. ); Taylor, W.L.; Hurly, J.J. Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221 )

    1991-01-15

    Second virial coefficient data and viscosity were used to evaluate effective isotropic intermolecular potential functions proposed in the literature for sulfur hexafluoride. It was found that none of the potentials could predict the properties simultaneously. We have constructed a Morse--Morse--Spline--van der Waals (MMSV) potential which satisfactorily correlates second virial coefficient and viscosity data at the same time.

  20. Probing the transition between seismically coupled and decoupled segments along an ancient subduction interface

    NASA Astrophysics Data System (ADS)

    Angiboust, Samuel; Kirsch, Josephine; Oncken, Onno; Glodny, Johannes; Monié, Patrick; Rybacki, Erik

    2015-06-01

    The transition zone at the downdip end of seismic coupling along subduction interfaces is often the site of megathrust earthquake nucleation and concentrated postseismic afterslip, as well as the focus site of episodic tremor and slip features. Exhumed remnants of the former Alpine subduction zone found in the Swiss Alps allow analyzing fluid and deformation processes near the transition zone region (30-40 km paleodepth). The Dent Blanche Thrust (DBT) is a lower blueschist-facies shear zone interpreted as a fossilized subduction interface where granitic mylonites overlie a metamorphosed accretionary wedge. We report field observations from the DBT region where multiple, several tens of meters thick foliated cataclastic networks are interlayered within the basal DBT mylonites. Petrological results and microstructural observations indicate that the various cataclasis events took place at near-peak metamorphic conditions (400-500°C, 1.1-1.3 GPa) during subduction of the Tethyan seafloor in Eocene times (42-48 Ma). Some of these networks exhibit mutual crosscutting relationships between mylonites, foliated cataclasites, and vein systems indicating mutual overprinting between brittle deformation and ductile creep. Whole-rock chemical compositions, in situ 40Ar-39Ar age data of recrystallized phengite, and Sr isotopic signatures reveal that DBT rocks also underwent multiple hydrofracturing and metasomatic events via the infiltration of fluids mainly derived from the oceanic metasediments underneath the DBT. From the rock fabrics, we infer strain rate fluctuations of several orders of magnitude beyond subduction strain rates (˜10-12 s-1) accompanied by fluctuation of supralithostatic and quasi-lithostatic fluid pressures (1 ≥ λ > 0.95). DBT brittle-plastic deformation switches highlight the diversity of deformation processes and fluid-rock interactions in the transition zone region of the subduction interface.

  1. Probing the transition between seismically coupled and decoupled segments along an ancient subduction interface

    NASA Astrophysics Data System (ADS)

    Angiboust, Samuel; Kirsch, Josephine; Oncken, Onno; Glodny, Johannes; Monié, Patrick; Rybacki, Erik

    2015-04-01

    Although of paramount importance for understanding the nature of mechanical coupling in subduction zones, the portions downdip of the locked segments of subduction interfaces remain poorly understood. These deep transition zones often are sites of megathrust earthquake nucleation and concentrated postseismic afterslip, as well as the focus sites of episodic tremor and slip features, recently discovered at several plate boundaries. The extensive, exhumed remnants of the former Alpine subduction zone found in the Swiss Alps allow analyzing fluid and deformation processes at the original depths of 30-40 km, typical for the depth range of such transition zones. We identify the shear zone at the base of the Dent Blanche complex (Dent Blanche Thrust, DBT) as a lower blueschist-facies, fossilized subduction interface where granitic mylonites overlie a metamorphosed ophiolite. We report field observations from the DBT region where a complex, discontinuous network of meter- to tens of meters-thick foliated cataclasites is interlayered with the basal DBT mylonites. Petrological results indicate that cataclasis took place at near peak metamorphic conditions (450-500°C, c. 1.2 GPa) during subduction of the Tethyan seafloor in Eocene times (42-48 Ma). Despite some tectonic reactivation during exhumation, these networks exhibit mutual cross-cutting relationships between mylonites, foliated cataclasites and vein systems indicating multiple switching between brittle deformation and ductile creep. Whole-rock chemical compositions, in situ 40Ar-39Ar age data of newly formed phengite, and strontium isotopic signatures reveal that these rocks also underwent multiple hydrofracturing events via infiltration of fluids mainly derived from the ophiolitic metasediments underneath the DBT. From the rock fabrics we infer strain rate fluctuations of several orders of magnitude beyond subduction strain rates (c. 10-12s-1) accompanied by fluctuation of near-lithostatic fluid pressures (1>λ>0

  2. Water protein dynamic coupling and new opportunities for probing it at low to physiological temperatures in aqueous solutions

    SciTech Connect

    Mamontov, Eugene; Chu, Xiang-Qiang

    2012-01-01

    Both the structure and dynamics of biomolecules are known to be essential for their biological function. In the dehydrated state, the function of biomolecules, such as proteins, is severely impeded, so hydration is required for bioactivity. The dynamics of the hydrated biomolecules and their hydration water are related - but how closely? The problem involves several layers of complexity. Even for water in the bulk state, the contribution from various dynamic components to the overall dynamics is not fully understood. In biological systems, the effects of confinement on the hydration water further complicate the picture. Even if the various components of the hydration water dynamics are properly understood, which of them are coupled to the protein dynamics, and how? The studies of protein dynamics over the wide temperature range, from physiological to low temperatures, provide some answers to these question. At low temperatures, both the protein and its hydration water behave as solids, with only vibrational degrees of freedom. As the temperature is increased, non-vibrational dynamic components start contributing to the measurable dynamics and eventually become dominant at physiological temperatures. Thus, the temperature dependence of the dynamics of protein and its hydration water may allow probing various dynamic components separately. In order to suppress the water freezing, the low-temperature studies of protein rely on either low-hydrated samples (essentially, hydrated protein powders), or cryo-protective solutions. Both approaches introduce the hydration environments not characteristic of the protein environments in living systems, which are typically aqueous protein solutions of various concentrations. In this paper, we discuss the coupling between the dynamic components of the protein and its hydration water by critical examining of the existing literature, and then propose that proteins can be studied in an aqueous solution that is remarkably similar in

  3. Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid.

    PubMed

    Rury, Aaron S; Sorenson, Shayne; Dawlaty, Jahan M

    2016-03-14

    Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm(-1) oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology. PMID:26979698

  4. Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid

    NASA Astrophysics Data System (ADS)

    Rury, Aaron S.; Sorenson, Shayne; Dawlaty, Jahan M.

    2016-03-01

    Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm-1 oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.

  5. STM probe on the surface electronic states of spin-orbit coupled materials

    NASA Astrophysics Data System (ADS)

    Zhou, Wenwen

    Spin-orbit coupling (SOC) is the interaction of an electron's intrinsic angular momentum (spin) with its orbital momentum. The strength of this interaction is proportional to Z4 where Z is the atomic number, so generally it is stronger in atoms with higher atomic number, such as bismuth (Z=83) and iridium (Z=77). In materials composed of such heavy elements, the prominent SOC can be sufficient to modify the band structure of the system and lead to distinct phase of matter. In recent years, SOC has been demonstrated to play a critical role in determining the unusual properties of a variety of compounds. SOC associated materials with exotic electronic states have also provided a fertile platform for studying emergent phenomena as well as new physics. As a consequence, the research on these interesting materials with any insight into understanding the microscopic origin of their unique properties and complex phases is of great importance. In this context, we implement scanning tunneling microscopy (STM) and spectroscopy (STS) to explore the surface states (SS) of the two major categories of SOC involved materials, Bi-based topological insulators (TI) and Ir-based transition metal oxides (TMO). As a powerful tool in surface science which has achieved great success in wide variety of material fields, STM/STS is ideal to study the local density of states of the subject material with nanometer length scales and is able to offer detailed information about the surface electronic structure. In the first part of this thesis, we report on the electronic band structures of three-dimensional TIs Bi2Te3 and Bi2Se 3. Topological insulators are distinct quantum states of matter that have been intensely studied nowadays. Although they behave like ordinary insulators in showing fully gapped bulk bands, they host a topologically protected surface state consisting of two-dimensional massless Dirac fermions which exhibits metallic behavior. Indeed, this unique gapless surface state is a

  6. Langmuir Probe Measurements of Inductively Coupled CHF3/Ar and Ar/CHF3/O2 Plasmas

    NASA Technical Reports Server (NTRS)

    Sharma, S. P.; Rao, M. V. V. S.; Meyyappan, M.

    2000-01-01

    Plasma parameters, such as, electron number density (ne), electron temperature (Te), y electron energy distribution function (EEDF), mean electron energy (Ee), ion number density (ni), and plasma potential (Vp), have been measured by using Langmuir probe in low-pressure (10-50 mTorr) inductively coupled CHF3/Ar and CHF3/Ar/O2 plasmas generated in the GEC cell. The measurements were made at the center of the plasma, keeping the lower electrode grounded, for various CHF3/Ar and Ar/CHF3/O2 mixtures operating at 10-50 mTorr pressures and two input RF power levels, 200 and 300 W. EEDF data show a strong Druyvesteyn distribution with relatively lower number of low energy electrons as compared to a Maxwell distribution and a large electron population with energies higher than the plasma potential. The results further show that at low CHF3 concentrations (less than 50%) the electron number density remains nearly constant with increase in pressure. At higher CHF3 concentrations, however, it decreases with increase in pressure. Plasma potential and electron temperature increase with decrease in pressure and with increase in CHF3 concentration. An analysis of the above observations and mechanisms will be presented.

  7. An improved thin-layer chromatography/mass spectrometry coupling using a surface sampling probe electrospray ion trap system

    SciTech Connect

    Ford, Michael J; Van Berkel, Gary J

    2004-01-01

    A combined surface sampling probe/electrospray emitter coupled with an ion trap mass spectrometer was used for the direct read out of unmodified reversed-phase C18 thin-layer chromatography (TLC) plates. The operation of the surface sampling electrospray ionization interface in positive and negative ionization modes was demonstrated through the direct analysis of TLC plates on which a commercial test mix comprised of four dye compounds viz., rhodamine B, fluorescein, naphthol blue black, and fast green FCF, and an extract of the caffeine-containing plant Ilex vomitoria, were spotted and developed. Acquisition of full-scan mass spectra and automated collection of MS/MS product ion spectra while scanning a development lane along the surface of a TLC plate demonstrated the advantages of using an ion trap in this combination. Details of the sampling system, benefits of analyzing a developed lane in both positive ion and negative ion modes, levels of detection while surface scanning, surface scan speed effects, and the utility of three-dimensional data display, are also discussed.

  8. Developing a fluorescence-coupled capillary electrophoresis based method to probe interactions between QDs and colorectal cancer targeting peptides.

    PubMed

    Liu, Feifei; Wang, Jianhao; Yang, Li; Liu, Li; Ding, Shumin; Fu, Minli; Deng, Linhong; Gao, Li-Qian

    2016-08-01

    As is well known, quantum dots (QDs) have become valuable probes for cancer imaging. In particular, QD-labeled targeting peptides are capable of identifying cancer or tumors cells. A new colorectal cancer targeting peptide, cyclo(1, 9)-CTPSPFSHC, has strong targeting ability and also shows great potential in the identification and treatment of colon cancer. Herein, we synthesized a dual functional polypeptide, cyclo(1, 9)-CTPSPFSHCD2 G2 DP9 G3 H6 (H6 -TCP), to investigate its interaction with QDs inside the capillary. Fluorescence-coupled CE was adopted and applied to characterize the self-assembly of H6 -TCP onto QDs. It was indicated that the formation of the assembly was affected by H6 -TCP/QD molar ratio and sampling time. This novel in-capillary assay greatly reduced the sample consumption and the detection time, which was beneficial for the environment. It is expected that this kind of detection method could find more applications to provide more useful information for cancer diagnosis and detection of harm and hazardous substances/organisms in the environment in the future. PMID:27159348

  9. A jet emission model to probe the dynamics of accretion and ejection coupling in black hole X-ray binaries

    NASA Astrophysics Data System (ADS)

    Malzac, Julien

    2016-07-01

    Compact jets are probably the most common form of jets in X-ray binaries and Active Galactic Nuclei. They seem to be present in all sources in the so-called hard X-ray spectral state. They are characterised by a nearly flat Spectral Energy Distribution (SED) extending from the radio to the infrared bands. This emission is usually interpreted as partially self absorbed synchrotron emission from relativistic leptons accelerated in the jet. The observed flat spectral shape requires energy dissipation and acceleration of particules over a wide range of distances along the jet. This distributed energy dissipation is likely to be powered by internal shocks caused by fluctuations of the outflow velocity. I will discuss such an internal shock model in the context of black hole binaries. I will show that internal shocks can produce the observed SEDs and also predict a strong, wavelength dependent, variability that resembles the observed one. The assumed velocity fluctuations of the jet must originate in the accretion flow. The model thus predicts a strong connection between the observable properties of the jet in the radio to IR bands, and the variability of the accretion flow as observed in X-rays. If the model is correct, this offers a unique possibility to probe the dynamics of the coupled accretion and ejection processes leading to the formation of compact jets.

  10. COUPLING

    DOEpatents

    Hawke, B.C.

    1963-02-26

    This patent relates to a releasable coupling connecting a control rod to a control rod drive. This remotely operable coupling mechanism can connect two elements which are laterally and angviarly misaligned, and provides a means for sensing the locked condition of the elements. The coupling utilizes a spherical bayonet joint which is locked against rotation by a ball detent lock. (AEC)

  11. Intermolecular electrostatic energies using density fitting

    PubMed Central

    Cisneros, G. Andrés; Piquemal, Jean-Philip; Darden, Thomas A.

    2009-01-01

    A method is presented to calculate the electron-electron and nuclear-electron intermolecular Coulomb interaction energy between two molecules by separately fitting the unperturbed molecular electron density of each monomer. This method is based on the variational Coulomb fitting method which relies on the expansion of the ab initio molecular electron density in site-centered auxiliary basis sets. By expanding the electron density of each monomer in this way the integral expressions for the intermolecular electrostatic calculations are simplified, lowering the operation count as well as the memory usage. Furthermore, this method allows the calculation of intermolecular Coulomb interactions with any level of theory from which a one-electron density matrix can be obtained. Our implementation is initially tested by calculating molecular properties with the density fitting method using three different auxiliary basis sets and comparing them to results obtained from ab initio calculations. These properties include dipoles for a series of molecules, as well as the molecular electrostatic potential and electric field for water. Subsequently, the intermolecular electrostatic energy is tested by calculating ten stationary points on the water dimer potential-energy surface. Results are presented for electron densities obtained at four different levels of theory using two different basis sets, fitted with three auxiliary basis sets. Additionally, a one-dimensional electrostatic energy surface scan is performed for four different systems (H2O dimer, Mg2+–H2O, Cu+–H2O, and n-methyl-formamide dimer). Our results show a very good agreement with ab initio calculations for all properties as well as interaction energies. PMID:16095348

  12. An isotopic mass effect on the intermolecular potential

    NASA Astrophysics Data System (ADS)

    Herman, Michael F.; Currier, Robert P.; Clegg, Samuel M.

    2015-10-01

    The impact of isotopic variation on the electronic energy and intermolecular potentials is often suppressed when calculating isotopologue thermodynamics. Intramolecular potential energy surfaces for distinct isotopologues are in fact equivalent under the Born-Oppenheimer approximation, which is sometimes used to imply that the intermolecular interactions are independent of isotopic mass. In this communication, the intermolecular dipole-dipole interaction between hetero-nuclear diatomic molecules is considered. It is shown that the intermolecular potential contains mass-dependent terms even though each nucleus moves on a Born-Oppenheimer surface. The analysis suggests that mass dependent variations in intermolecular potentials should be included in comprehensive descriptions of isotopologue thermodynamics.

  13. An assay for intermolecular exchange of alpha crystallin

    NASA Technical Reports Server (NTRS)

    Gopalakrishnan, S.; Takemoto, L.; Spooner, B. S. (Principal Investigator)

    1992-01-01

    An affinity column of alpha crystallin linked to cyanogen bromide-activated Sepharose was developed to study the exchange of alpha subunits. Alpha crystallin bound to the Sepharose-alpha complex was dissociated with 8 mol/l urea, followed by quantitation using high-performance reverse-phase liquid chromatography. The time course of binding at 37 degrees C showed a hyperbolic binding pattern reaching equilibrium between 6-18 hr. Under these conditions, binding of beta and gamma crystallins to the same matrix was less than 10% of the alpha values, as was binding of alpha to glycine-coupled Sepharose. This assay was used to demonstrate changes in the subunit exchange of alpha crystallins present in high molecular weight versus lower molecular weight aggregates of the human lens. These results show that this binding procedure was a specific reproducible assay that might be used to study intermolecular interactions of the alpha crystallins.

  14. Intermolecular shielding from molecular magnetic susceptibility. A new view of intermolecular ring current effects.

    PubMed

    Facelli, Julio C

    2006-03-01

    This paper presents calculations of the NICS (nuclear independent chemical shieldings) in a rectangular grid surrounding the molecules of benzene, naphthalene and coronene. Using the relationship between calculated NICS and the induced magnetic field, the calculated NICS are used to predict intermolecular effects due to molecular magnetic susceptibility or ring current effects. As expected from approximate ring current models, these intermolecular shielding effects are concentrated along the direction perpendicular to the molecular plane and they approach asymptotically to a dipolar functional dependence, i.e. (1-3 cos(2)theta)/r(3)). The deviations from the dipolar functional form require that the calculations of these intermolecular effects be done using a suitable interpolation scheme of the NICS calculated on the grid. The analysis of the NICS tensor components shows that these intermolecular shielding effects should be primarily expected on shielding components of the neighboring molecules nuclei, which are perpendicular to the molecular plane of the aromatic compound generating the induced field. The analysis of the calculated NICS along the series benzene, naphthalene and coronene shows that these intermolecular effects increase monotonically with the number of aromatic rings. PMID:16477673

  15. Probing C P -violating h t ¯t coupling in e+e-→h γ

    NASA Astrophysics Data System (ADS)

    Li, Gang; Wang, Hao-Ran; Zhu, Shou-hua

    2016-03-01

    We investigate the possibility of probing the C P -violating h t ¯t coupling in the process e+e-→h γ at the future high luminosity e+e- colliders. Our numerical results show that the cross section for this process can be significantly increased for the allowed C P phase ξ and center of mass energy. For example, the cross section is about 10 times that in the standard model (SM) for √{s }=350 GeV and ξ =3 π /5 (see text for ξ definition). The simulation for the signal process e+e-→h γ →b b ¯ γ and its backgrounds shows that the signal significance can reach about 5 σ and more than 2.1 σ for √{s }=350 GeV and 500 GeV, respectively, with the integrated luminosity L =3 ab-1 and ξ ∈[π /2 ,3 π /5 ]. For L =10 ab-1 , the signal significance can be greater than 5 σ for √{s }=350 GeV and about 4 σ for √{s }=500 GeV with the C P phase ξ ∈[π /2 ,3 π /5 ]. Besides the cross section enhancement, the C P -violating h t ¯t coupling will induce a forward-backward asymmetry AF B which is absent in the SM and is a clear signal of new C P violation. Compared with the AF B in the Higgs decay h →l+l-γ , the AF B can be greatly enhanced in the production process. For example, AF B can reach -0.55 for ξ =π /4 and √{s }=500 GeV . Because of the large backgrounds, the significance of the expected AF B can be observed only at 1.68 σ with L =10 ab-1 and √{s }=500 GeV . It is essential to trigger the single photon in the final state to separate the bottom jets arising from scalar or vector bosons, in order to isolate the signal from the backgrounds more efficiently.

  16. Optical emission diagnostics with electric probe measurements of inductively coupled Ar/O{sub 2}/Ar-O{sub 2} plasmas

    SciTech Connect

    Chung, T. H.; Kang, Hae Ra; Bae, Min Keun

    2012-11-15

    Physical properties of low-pressure inductively coupled argon, oxygen, and Ar-O{sub 2} mixture plasmas are investigated using optical emission spectroscopy (OES) combined with an rf-compensated Langmuir probe measurement. In each gas discharge, the electron density and the electron temperature were obtained by using the probe. The electron temperature was also obtained by OES models and compared with that measured by the probe. The electron temperature was observed to decrease with increasing power and pressure and also observed to decrease with increasing Ar content. Argon metastable densities were calculated based on an optical transition model. In Ar-O{sub 2} discharges, the dissociation fraction of O{sub 2} molecules was estimated using optical emission actinometry. The dissociation fraction was observed to increase with increasing power and Ar content.

  17. Simulating two-dimensional infrared-Raman and Raman spectroscopies for intermolecular and intramolecular modes of liquid water.

    PubMed

    Ito, Hironobu; Tanimura, Yoshitaka

    2016-02-21

    Full classical molecular dynamics (MD) simulations of two-dimensional (2D) infrared-Raman and 2D Raman spectroscopies of liquid water were carried out to elucidate a mode-mode coupling mechanism using a polarizable water model for intermolecular and intramolecular vibrational spectroscopy (POLI2VS). This model is capable of describing both infrared and Raman spectra. Second-order response functions, which consist of one molecular polarizability and two molecular dipole moments for 2D IR-Raman and three molecular polarizabilities for 2D Raman spectroscopies, were calculated using an equilibrium-non-equilibrium hybrid MD approach. The obtained signals were analyzed using a multi-mode Brownian oscillator (BO) model with nonlinear system-bath interactions representing the intramolecular OH stretching, intramolecular HOH bending, hydrogen bonded (HB)-intermolecular librational motion and HB-intermolecular vibrational (translational) motion of liquid water. This model was applied through use of hierarchal Fokker-Planck equations. The qualitative features of the peak profiles in the 2D spectra obtained from the MD simulations are accurately reproduced with the BO model. This indicates that this model captures the essential features of the intermolecular and intramolecular motion. We elucidate the mechanisms governing the 2D signal profiles involving anharmonic mode-mode coupling, the nonlinearities of the polarizability and dipole moment, and the vibrational dephasing processes of liquid water even in the case that the 2D spectral peaks obtained from the MD simulation overlap or are unclear. The mode coupling peaks caused by electrical anharmonic coupling (EAHC) and mechanical anharmonic coupling (MAHC) are observed in all of the 2D spectra. We find that the strength of the MAHC between the OH-stretching and HB-intermolecular vibrational modes is comparable to that between the OH-stretching and HOH bending modes. Moreover, we find that this OH-stretching and HB-intermolecular

  18. COUPLING

    DOEpatents

    Frisch, E.; Johnson, C.G.

    1962-05-15

    A detachable coupling arrangement is described which provides for varying the length of the handle of a tool used in relatively narrow channels. The arrangement consists of mating the key and keyhole formations in the cooperating handle sections. (AEC)

  19. Cathodoluminescence, laser ablasion inductively coupled plasma mass spectrometry, electron probe microanalysis and electron paramagnetic resonance analyses of natural sphalerite

    USGS Publications Warehouse

    Karakus, M.; Hagni, R.D.; Koenig, A.; Ciftc, E.

    2008-01-01

    Natural sphalerite associated with copper, silver, lead-zinc, tin and tungsten deposits from various world-famous mineral deposits have been studied by cathodoluminescence (CL), laser ablasion inductively coupled plasma mass spectrometry (LA-ICP-MS), electron probe microanalysis (EPMA) and electron paramagnetic resonance (EPR) to determine the relationship between trace element type and content and the CL properties of sphalerite. In general, sphalerite produces a spectrum of CL colour under electron bombardment that includes deep blue, turquoise, lime green, yellow-orange, orange-red and dull dark red depending on the type and concentration of trace quantities of activator ions. Sphalerite from most deposits shows a bright yellow-orange CL colour with ??max centred at 585 nm due to Mn2+ ion, and the intensity of CL is strongly dependent primarily on Fe2+ concentration. The blue emission band with ??max centred at 470-490 nm correlates with Ga and Ag at the Tsumeb, Horn Silver, Balmat and Kankoy mines. Colloform sphalerite from older well-known European lead-zinc deposits and late Cretaceous Kuroko-type VMS deposits of Turkey shows intense yellowish CL colour and their CL spectra are characterised by extremely broad emission bands ranging from 450 to 750 nm. These samples are characterised by low Mn (<10 ppm) and Ag (<1 ppm), and they are enriched in Tl (1-30 ppm) and Pb (80-1500 ppm). Strong green CL is produced by sphalerite from the Balmat-Edwards district. Amber, lime-green and red-orange sphalerite produced weak orange-red CL at room temperatures, with several emission bands centred at 490, 580, 630, 680, 745, with ??max at 630 nm being the strongest. These emission bands are well correlated with trace quantities of Sn, In, Cu and Mn activators. Sphalerite from the famous Ogdensburg and Franklin mines exhibited brilliant deep blue and orange CL colours and the blue CL may be related to Se. Cathodoluminescence behaviour of sphalerite serves to characterise ore

  20. Tip relaxation in atomic force microscopy imaging simulations to resolve intermolecular bonds

    NASA Astrophysics Data System (ADS)

    Lee, Alex; Sakai, Yuki; Chelikowsky, Jim

    Experimental noncontact atomic force microscopy (AFM) studies have reported distinct lines in regions with no electron density for a variety of systems. The appearance of these lines is unexpected because Pauli repulsion is thought to be the dominant factor in the AFM imaging mechanism. These lines have been proposed to represent intermolecular bonding. Recent theoretical studies have shown that accounting for tip probe relaxation can sharpen images and highlight features that make simulations more comparable to experiment. We will apply a similar tip relaxation scheme to our computational method-which uses an ab initio real-space pseudopotential formalism with frozen density embedding theory added-to the study of dibenzo[a,h]thianthrene and an 8-hydroxyquinoline dimer to develop our interpretation of imaged intermolecular bonds. Work is supported by the DOE under DOE/DE-FG02-06ER46286 and by the Welch Foundation under Grant F-1837. Computational resources were provided by NERSC and XSEDE.

  1. Maximizing Singlet Fission by Intermolecular Packing.

    PubMed

    Wang, Linjun; Olivier, Yoann; Prezhdo, Oleg V; Beljonne, David

    2014-10-01

    A novel nonadiabatic molecular dynamics scheme is applied to study the singlet fission (SF) process in pentacene dimers as a function of longitudinal and lateral displacements of the molecular backbones. Detailed two-dimensional mappings of both instantaneous and long-term triplet yields are obtained, characterizing the advantageous and unfavorable stacking arrangements, which can be achieved by chemical substitutions to the bare pentacene molecule. We show that the SF rate can be increased by more than an order of magnitude through tuning the intermolecular packing, most notably when going from cofacial to the slipped stacked arrangements encountered in some pentacene derivatives. The simulations indicate that the SF process is driven by thermal electron-phonon fluctuations at ambient and high temperatures, expected in solar cell applications. Although charge-transfer states are key to construct continuous channels for SF, a large charge-transfer character of the photoexcited state is found to be not essential for efficient SF. The reported time domain study mimics directly numerous laser experiments and provides novel guidelines for designing efficient photovoltaic systems exploiting the SF process with optimum intermolecular packing. PMID:26278443

  2. Indole-3-acetic acid biosensor based on G-rich DNA labeled AuNPs as chemiluminescence probe coupling the DNA signal amplification

    NASA Astrophysics Data System (ADS)

    Hun, Xu; Mei, Zhenghua; Wang, Zhouping; He, Yunhua

    2012-09-01

    A highly sensitive chemiluminescence (CL) method for detection of phytohormone indole-3-acetic acid (IAA) was developed by using G-rich DNA labeled gold nanoparticles (AuNPs) as CL probe coupling the DNA signal amplification technology. The IAA antibody was immobilized on carboxyl terminated magnetic beads (MBs). In the presence of IAA, antibody labeled AuNPs were captured by antibody functionalized MBs. The DNA on AuNPs is released by a ligand exchange process induced by the addition of DTT. The released DNA is then acted as the linker and hybridized with the capture DNA on MBs and probe DNA on AuNPs CL probe. The CL signal is obtained via the instantaneous derivatization reaction between a specific CL reagent, 3,4,5-trimethoxyl-phenylglyoxal (TMPG), and the G-rich DNA on AuNPs CL probe. IAA can be detected in the concentration range from 0.02 ng/mL to 30 ng/mL, and the limit of detection is 0.01 ng/mL.

  3. Interpreting the widespread nonlinear force spectra of intermolecular bonds

    PubMed Central

    Friddle, Raymond W.; Noy, Aleksandr; De Yoreo, James J.

    2012-01-01

    Single molecule force spectroscopy probes the strength, lifetime, and energetic details of intermolecular interactions in a simple experiment. A growing number of these studies have reported distinctly nonlinear trends in rupture force with loading rate that are typically explained in conventional models by invoking complex escape pathways. Recent analyses suggested that these trends should be expected even for simple barriers based on the basic assumptions of bond rupture dynamics and thus may represent the norm rather than the exception. Here we explore how these nonlinear trends reflect the two fundamental regimes of bond rupture: (i) a near-equilibrium regime, produced either by bond reforming in the case of a single bond or by asynchronized rupture of multiple individual bonds, and (ii) a kinetic regime produced by fast, non-equilibrium bond rupture. We analyze both single- and multi-bonded cases, describe the full evolution of the system as it transitions between near- and far-from-equilibrium loading regimes, and show that both interpretations produce essentially identical force spectra. Data from 10 different molecular systems show that this model provides a comprehensive description of force spectra for a diverse suite of bonds over experimentally relevant loading rates, removes the inconsistencies of previous interpretations of transition state distances, and gives ready access to both kinetic and thermodynamic information about the interaction. These results imply that single-molecule binding free energies for a vast number of bonds have already been measured. PMID:22869712

  4. The origins of the directionality of noncovalent intermolecular interactions.

    PubMed

    Wang, Changwei; Guan, Liangyu; Danovich, David; Shaik, Sason; Mo, Yirong

    2016-01-01

    The recent σ-hole concept emphasizes the contribution of electrostatic attraction to noncovalent bonds, and implies that the electrostatic force has an angular dependency. Here a set of clusters, which includes hydrogen bonding, halogen bonding, chalcogen bonding, and pnicogen bonding systems, is investigated to probe the magnitude of covalency and its contribution to the directionality in noncovalent bonding. The study is based on the block-localized wavefunction (BLW) method that decomposes the binding energy into the steric and the charge transfer (CT) (hyperconjugation) contributions. One unique feature of the BLW method is its capability to derive optimal geometries with only steric effect taken into account, while excluding the CT interaction. The results reveal that the overall steric energy exhibits angular dependency notably in halogen bonding, chalcogen bonding, and pnicogen bonding systems. Turning on the CT interactions further shortens the intermolecular distances. This bond shortening enhances the Pauli repulsion, which in turn offsets the electrostatic attraction, such that in the final sum, the contribution of the steric effect to bonding is diminished, leaving the CT to dominate the binding energy. In several other systems particularly hydrogen bonding systems, the steric effect nevertheless still plays the major role whereas the CT interaction is minor. However, in all cases, the CT exhibits strong directionality, suggesting that the linearity or near linearity of noncovalent bonds is largely governed by the charge-transfer interaction whose magnitude determines the covalency in noncovalent bonds. PMID:26010349

  5. Sensitive Glycoprotein Sandwich Assays by the Synergistic Effect of In Situ Generation of Raman Probes and Plasmonic Coupling of Ag Core-Au Satellite Nanostructures.

    PubMed

    Bi, Xiaoshuang; Li, Xueyuan; Chen, Dong; Du, Xuezhong

    2016-05-01

    Sensitive surface-enhanced Raman scattering (SERS) assays of glycoproteins have been proposed using p-aminothiophenol (PATP)-embedded Ag core-Au satellite nanostructures modified with p-mercaptophenylboronic acid (PMBA) and the self-assembled monolayer of PMBA on a smooth gold-coated wafer. The apparent Raman probe PATP on the surfaces of the Ag cores underwent a photodimerization to generate 4,4'-dimercaptoazobenzene (DMAB) in situ upon excitation of laser, and the in situ generated DMAB acted as the actual Raman probe with considerably strong SERS signals, which was further enhanced by the plasmonic coupling of the Ag core-Au satellite nanostructures due to the synergistic effect. The sandwich assays of glycoproteins showed high sensitivity and excellent selectivity against nonglycoproteins. The Ag core-Au satellite SERS nanostructures can be used for highly sensitive SERS assays of other analytes. PMID:27064515

  6. Highly specific quantification of microRNA by coupling probe-rolling circle amplification and Förster resonance energy transfer.

    PubMed

    Wu, Xuri; Zhu, Shenrong; Huang, Peiyu; Chen, Yijun

    2016-06-01

    MicroRNA (miRNA) plays vital roles in various biological processes. In general, sensitivity and specificity are the major parameters for the quantification of miRNA. In this study, padlock probe-rolling circle amplification and Förster resonance energy transfer (pRCA-FRET) were coupled for specific and quantitative detection of miRNA. pRCA-FRET showed superior specificity to differentiate single-base mismatch and excellent sensitivity with a detection limit of 103 aM. The current method has the potential to quantify low amounts of miRNA in the same family for studies on their biological functions. PMID:26973220

  7. Spin-lattice coupling in uranium dioxide probed by magnetostriction measurements at high magnetic fields (P08358-E001-PF)

    SciTech Connect

    Gofryk, K.; Jaime, M.

    2014-12-01

    Our preliminary magnetostriction measurements have already shown a strong interplay of lattice dynamic and magnetism in both antiferromagnetic and paramagnetic states, and give unambiguous evidence of strong spin- phonon coupling in uranium dioxide. Further studies are planned to address the puzzling behavior of UO2 in magnetic and paramagnetic states and details of the spin-phonon coupling.

  8. X-ray Intermolecular Structure Factor (XISF): separation of intra- and intermolecular interactions from total X-ray scattering data

    SciTech Connect

    Mou, Q.; Benmore, C. J.; Yarger, J. L.

    2015-06-01

    XISF is a MATLAB program developed to separate intermolecular structure factors from total X-ray scattering structure factors for molecular liquids and amorphous solids. The program is built on a trust-region-reflective optimization routine with the r.m.s. deviations of atoms physically constrained. XISF has been optimized for performance and can separate intermolecular structure factors of complex molecules.

  9. Coupling solid-phase microextraction with ambient mass spectrometry using surface coated wooden-tip probe for rapid analysis of ultra trace perfluorinated compounds in complex samples.

    PubMed

    Deng, Jiewei; Yang, Yunyun; Fang, Ling; Lin, Li; Zhou, Haiyun; Luan, Tiangang

    2014-11-18

    Coupling solid-phase microextraction (SPME) with ambient mass spectrometry using surface coated wooden-tip probe was achieved for the first time and applied in the analysis of ultra trace perfluorinated compounds (PFCs) in complex environmental and biological samples. We modified n-octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride on the surface of sharp wooden tip via silanization to form a novel SPME probe, which was then used for highly selective enrichment of PFCs from complex matrices and applied as a solid substrate to induce electrospray ionization for mass spectrometric analysis. The porous structural surface together with the dual extraction mechanisms (reversed phase adsorption and ion exchange adsorption) demonstrated that the SPME probe has an outstanding enrichment capacity, enhancing sensitivity by approximately 4000-8000 folds for the detection in aqueous samples, and 100-500-fold in whole blood and milk samples. The method showed good linearity, with correlation coefficient values (r(2)) of no less than 0.9931 for eight target PFCs. The limits of detection and qualification of the eight PFCs were 0.06-0.59 and 0.21-1.98 ng/L, respectively. Quantification of real samples was achieved by isotope internal standard calibration curve method or isotope dilution method, and ultratrace levels of PFCs present in lake water, river water, whole blood, and milk samples had been successfully detected and qualified. PMID:25354323

  10. Theoretical and numerical evaluation of polarimeter using counter-circularly-polarized-probing-laser under the coupling between Faraday and Cotton-Mouton effect

    NASA Astrophysics Data System (ADS)

    Imazawa, Ryota; Kawano, Yasunori; Itami, Kiyoshi

    2016-04-01

    This study evaluated an effect of an coupling between the Faraday and Cotton-Mouton effect to a measurement signal of the Dodel-Kunz method which uses counter-circular-polarized probing-laser for measuring the Faraday effect. When the coupling is small (the Faraday effect is dominant and the characteristic eigenmodes are approximately circularly polarized), the measurement signal can be algebraically expressed and it is shown that the finite effect of the coupling is still significant. When the Faraday effect is not dominant, a numerical calculation is necessary. The numerical calculation under an ITER-like condition (Bt = 5.3 T, Ip = 15 MA, a = 2 m, ne = 1020 m-3 and λ = 119 μm) showed that difference between the pure Faraday rotation and the measurement signal of the Dodel-Kunz method was an order of one degree, which exceeds allowable error of ITER poloidal polarimeter. In conclusion, similar to other polarimeter techniques, the Dodel-Kunz method is not free from the coupling between the Faraday and Cotton-Mouton effect.

  11. Coupling an electrospray source and a solids probe/chemical ionization source to a selected ion flow tube apparatus

    SciTech Connect

    Melko, Joshua J.; Ard, Shaun G.; Shuman, Nicholas S.; Viggiano, Albert A.; Pedder, Randall E.; Taormina, Christopher R.

    2015-08-15

    A new ion source region has been constructed and attached to a variable temperature selected ion flow tube. The source features the capabilities of electron impact, chemical ionization, a solids probe, and electrospray ionization. The performance of the instrument is demonstrated through a series of reactions from ions created in each of the new source regions. The chemical ionization source is able to create H{sub 3}O{sup +}, but not as efficiently as similar sources with larger apertures. The ability of this source to support a solids probe, however, greatly expands our capabilities. A variety of rhenium cations and dications are created from the solids probe in sufficient abundance to study in the flow tube. The reaction of Re{sup +} with O{sub 2} proceeds with a rate constant that agrees with the literature measurements, while the reaction of Re{sub 2}{sup 2+} is found to charge transfer with O{sub 2} at about 60% of the collision rate; we have also performed calculations that support the charge transfer pathway. The electrospray source is used to create Ba{sup +}, which is reacted with N{sub 2}O to create BaO{sup +}, and we find a rate constant that agrees with the literature.

  12. Study of ablation and implosion stages in wire arrays using coupled ultraviolet and X-ray probing diagnostics

    NASA Astrophysics Data System (ADS)

    Anderson, A. A.; Ivanov, V. V.; Astanovitskiy, A. L.; Papp, D.; Wiewior, P. P.; Chalyy, O.

    2015-11-01

    Star and cylindrical wire arrays were studied using laser probing and X-ray radiography at the 1-MA Zebra pulse power generator at the University of Nevada, Reno. The Leopard laser provided backlighting, producing a laser plasma from a Si target which emitted an X-ray probing pulse at the wavelength of 6.65 Å. A spherically bent quartz crystal imaged the backlit wires onto X-ray film. Laser probing diagnostics at the wavelength of 266 nm included a 3-channel polarimeter for Faraday rotation diagnostic and two-frame laser interferometry with two shearing interferometers to study the evolution of the plasma electron density at the ablation and implosion stages. Dynamics of the plasma density profile in Al wire arrays at the ablation stage were directly studied with interferometry, and expansion of wire cores was measured with X-ray radiography. The magnetic field in the imploding plasma was measured with the Faraday rotation diagnostic, and current was reconstructed.

  13. Study of ablation and implosion stages in wire arrays using coupled ultraviolet and X-ray probing diagnostics

    SciTech Connect

    Anderson, A. A.; Ivanov, V. V.; Astanovitskiy, A. L.; Wiewior, P. P.; Chalyy, O.; Papp, D.

    2015-11-15

    Star and cylindrical wire arrays were studied using laser probing and X-ray radiography at the 1-MA Zebra pulse power generator at the University of Nevada, Reno. The Leopard laser provided backlighting, producing a laser plasma from a Si target which emitted an X-ray probing pulse at the wavelength of 6.65 Å. A spherically bent quartz crystal imaged the backlit wires onto X-ray film. Laser probing diagnostics at the wavelength of 266 nm included a 3-channel polarimeter for Faraday rotation diagnostic and two-frame laser interferometry with two shearing interferometers to study the evolution of the plasma electron density at the ablation and implosion stages. Dynamics of the plasma density profile in Al wire arrays at the ablation stage were directly studied with interferometry, and expansion of wire cores was measured with X-ray radiography. The magnetic field in the imploding plasma was measured with the Faraday rotation diagnostic, and current was reconstructed.

  14. Coupling an electrospray source and a solids probe/chemical ionization source to a selected ion flow tube apparatus.

    PubMed

    Melko, Joshua J; Ard, Shaun G; Shuman, Nicholas S; Pedder, Randall E; Taormina, Christopher R; Viggiano, Albert A

    2015-08-01

    A new ion source region has been constructed and attached to a variable temperature selected ion flow tube. The source features the capabilities of electron impact, chemical ionization, a solids probe, and electrospray ionization. The performance of the instrument is demonstrated through a series of reactions from ions created in each of the new source regions. The chemical ionization source is able to create H3O(+), but not as efficiently as similar sources with larger apertures. The ability of this source to support a solids probe, however, greatly expands our capabilities. A variety of rhenium cations and dications are created from the solids probe in sufficient abundance to study in the flow tube. The reaction of Re(+) with O2 proceeds with a rate constant that agrees with the literature measurements, while the reaction of Re2(2+) is found to charge transfer with O2 at about 60% of the collision rate; we have also performed calculations that support the charge transfer pathway. The electrospray source is used to create Ba(+), which is reacted with N2O to create BaO(+), and we find a rate constant that agrees with the literature. PMID:26329209

  15. Coupling an electrospray source and a solids probe/chemical ionization source to a selected ion flow tube apparatus

    NASA Astrophysics Data System (ADS)

    Melko, Joshua J.; Ard, Shaun G.; Shuman, Nicholas S.; Pedder, Randall E.; Taormina, Christopher R.; Viggiano, Albert A.

    2015-08-01

    A new ion source region has been constructed and attached to a variable temperature selected ion flow tube. The source features the capabilities of electron impact, chemical ionization, a solids probe, and electrospray ionization. The performance of the instrument is demonstrated through a series of reactions from ions created in each of the new source regions. The chemical ionization source is able to create H3O+, but not as efficiently as similar sources with larger apertures. The ability of this source to support a solids probe, however, greatly expands our capabilities. A variety of rhenium cations and dications are created from the solids probe in sufficient abundance to study in the flow tube. The reaction of Re+ with O2 proceeds with a rate constant that agrees with the literature measurements, while the reaction of Re22+ is found to charge transfer with O2 at about 60% of the collision rate; we have also performed calculations that support the charge transfer pathway. The electrospray source is used to create Ba+, which is reacted with N2O to create BaO+, and we find a rate constant that agrees with the literature.

  16. Propagation studies of metastable intermolecular composites (MIC).

    SciTech Connect

    Son, S. F.; Busse, J. R.; Asay, B. W.; Peterson, P. D.; Mang, J. T.; Bockmon, B.; Pantoya, M.

    2002-01-01

    Thermite materials are attractive energetic materials because the reactions are highly exothermic, have high energy densities, and high temperatures of combustion. However, the application of thermite materials has been limited because of the relative slow release of energy compared to other energetic materials. Engineered nano-scale composite energetic materials, such as Al/MoO{sub 3}, show promise for additional energetic material applications because they can react very rapidly. The composite material studied in this work consists of tailored, ultra-fine grain (30-200 nm diameter) aluminum particles that dramatically increase energy release rates of these thermite materials. These reactant clusters of fuel and oxidizer particles are in nearly atomic scale proximity to each other but are constrained from reaction until triggered. Despite the growing importance of nano-scale energetic materials, even the most basic combustion characteristics of these materials have not been thoroughly studied. This paper reports initial studies of the ignition and combustion of metastable intermolecular composites (MIC) materials. The goals were lo obtain an improved understanding of flame propagation mechanisms and combustion behaviors associated with nano-structured energetic materials. Information on issues such as reaction rate and behavior as a function of composition (mixture ratio), initial static charge, and particle size are essential and will allow scientists to design applications incorporating the benefits of these compounds. The materials have been characterized, specifically focusing on particle size, shape, distribution and morphology.

  17. Mechanism of Intermolecular Electron Transfer in Bionanostructures

    NASA Astrophysics Data System (ADS)

    Gruodis, A.; Galikova, N.; Šarka, K.; Saulė, R.; Batiuškaitė, D.; Saulis, G.

    Hepatocellular carcinoma (HCC) is one of the most common malignant tumors worldwide. Most patients are inoperable and hepatoma cells are resistant to conventional chemotherapies. Thus, the development of novel therapies for HCC treatment is of paramount importance. Amongst different alimentary factors, vitamin C and vitamin K3 In the present work, it has been shown that the treatment of mouse hepatoma MH-22A cells by vitamin C and vitamin K3 at the ratio of 100:1 greatly enhanced their cytotoxicity. When cells were subjected to vitamin C at 200 μM or to vitamin K3 at 2 μM separately, their viability reduced by only about 10%. However, when vitamins C and K3 were combined at the same concentrations, they killed more than 90% of cells. To elucidate the mechanism of the synergistic cytotoxicity of the C&K3 mixture, theoretical quantum-chemical analysis of the dynamics of intermolecular electron transfer (IET) processes within the complexes containing C (five forms) and K3 (one form) has been carried out. Optimization of the ground state complex geometry has been provided by means of GAUSSIAN03 package. Simulation of the IET has been carried out using NUVOLA package, in the framework of molecular orbitals (MO). The rate of IET has been calculated using Fermi Golden rule. The results of simulations allow us to create the preliminary model of the reaction pathway.

  18. Intermolecular domain docking in the hairpin ribozyme

    PubMed Central

    Sumita, Minako; White, Neil A.; Julien, Kristine R.; Hoogstraten, Charles G.

    2013-01-01

    The hairpin ribozyme is a prototype small, self-cleaving RNA motif. It exists naturally as a four-way RNA junction containing two internal loops on adjoining arms. These two loops interact in a cation-driven docking step prior to chemical catalysis to form a tightly integrated structure, with dramatic changes occurring in the conformation of each loop upon docking. We investigate the thermodynamics and kinetics of the docking process using constructs in which loop A and loop B reside on separate molecules. Using a novel CD difference assay to isolate the effects of metal ions linked to domain docking, we find the intermolecular docking process to be driven by sub-millimolar concentrations of the exchange-inert Co(NH3)63+. RNA self-cleavage requires binding of lower-affinity ions with greater apparent cooperativity than the docking process itself, implying that, even in the absence of direct coordination to RNA, metal ions play a catalytic role in hairpin ribozyme function beyond simply driving loop-loop docking. Surface plasmon resonance assays reveal remarkably slow molecular association, given the relatively tight loop-loop interaction. This observation is consistent with a “double conformational capture” model in which only collisions between loop A and loop B molecules that are simultaneously in minor, docking-competent conformations are productive for binding. PMID:23324606

  19. Infrared probe of spin-phonon coupling in antiferromagnetic honeycomb lattice compound Li2MnO3

    NASA Astrophysics Data System (ADS)

    Song, Seungjae; Lee, Sanghyun; Jeon, Seyoung; Park, Je-Geun; Moon, S. J.

    2015-12-01

    We investigated temperature-dependent infrared-active phonon modes of honeycomb Li2MnO3 which shows an antiferromagnetic transition at T N  =  36 K. In the far-infrared frequency region, we observed fourteen phonon modes. We obtained the temperature dependence of each phonon mode from the analysis of optical conductivity spectra by using the Lorentz and the Fano-type oscillator models. We found that the resonance frequencies of nine phonon modes showed an anomalous behavior near T N that should be attributed to the spin-phonon coupling. We calculated the magnitude of the spin-phonon coupling constant from the shift in the resonance frequencies of the phonon modes below T N. Our results suggest that Li2MnO3 is weakly frustrated and that spin-phonon coupling plays a role in antiferromagnetic ordering.

  20. Generalization of Ryan's theorem: Probing tidal coupling with gravitational waves from nearly circular, nearly equatorial, extreme-mass-ratio inspirals

    SciTech Connect

    Li Chao; Lovelace, Geoffrey

    2008-03-15

    Extreme-mass-ratio inspirals (EMRIs) and intermediate-mass-ratio inspirals (IMRIs) - binaries in which a stellar-mass object spirals into a massive black hole or other massive, compact body - are important sources of gravitational waves for LISA and LIGO, respectively. Thorne has speculated that the waves from EMRIs and IMRIs encode, in principle, all the details of (i) the central body's spacetime geometry (metric), (ii) the tidal coupling (energy and angular momentum exchange) between the central body and orbiting object, and (iii) the evolving orbital elements. Fintan Ryan has given a first partial proof that this speculation is correct: Restricting himself to nearly circular, nearly equatorial orbits and ignoring tidal coupling, Ryan proved that the central body's metric is encoded in the waves. In this paper we generalize Ryan's theorem. Retaining Ryan's restriction to nearly circular and nearly equatorial orbits, and dropping the assumption of no tidal coupling, we prove that Thorne's conjecture is nearly fully correct: the waves encode not only the central body's metric but also the evolving orbital elements and (in a sense slightly different from Thorne's conjecture) the evolving tidal coupling.

  1. Quantitative analysis of cell surface membrane proteins using membrane-impermeable chemical probe coupled with 18O labeling

    SciTech Connect

    Zhang, Haizhen; Brown, Roslyn N.; Qian, Weijun; Monroe, Matthew E.; Purvine, Samuel O.; Moore, Ronald J.; Gritsenko, Marina A.; Shi, Liang; Romine, Margaret F.; Fredrickson, Jim K.; Pasa-Tolic, Ljiljana; Smith, Richard D.; Lipton, Mary S.

    2010-05-03

    We report a mass spectrometry-based strategy for quantitative analysis of cell surface membrane proteome changes. The strategy includes enrichment of surface membrane proteins using a membrane-impermeable chemical probe followed by stable isotope 18O labeling and LC-MS analysis. We applied this strategy for enriching membrane proteins expressed by Shewanella oneidensis MR-1, a gram-negative bacterium with known metal-reduction capability via extracellular electron transfer between outer membrane proteins and environmental electron receptors. LC/MS/MS analysis resulted in the identification of about 79% membrane proteins among all proteins identified from the enriched sample. To illustrate the quantification of membrane proteome changes, enriched membrane protein samples from wild-type and mutant cells (generated from deletion of a type II secretion protein, GspD) were further labeled with 16O and 18O at the peptide level prior to LC-MS analysis. A chemical-probe-labeled pure protein has also been used as an internal standard for normalization purpose. The quantitative data revealed reduced abundances of many outer membrane proteins such as OmcA and MtrC in ΔgspD mutant cells, which agreed well with previously published studies.

  2. Quantitative analysis of cell surface membrane proteins using membrane-impermeable chemical probe coupled with 18O labeling

    PubMed Central

    Zhang, Haizhen; Brown, Roslyn N.; Qian, Wei-Jun; Monroe, Matthew E.; Purvine, Samuel O.; Moore, Ronald J.; Gritsenko, Marina A.; Shi, Liang; Romine, Margaret F; Fredrickson, James K.; Paša-Tolić, Ljiljana; Smith, Richard D.; Lipton, Mary S.

    2010-01-01

    We report a mass spectrometry-based strategy for quantitative analysis of cell surface membrane proteome changes. The strategy includes enrichment of surface membrane proteins using a membrane-impermeable chemical probe followed by stable isotope 18O labeling and LC-MS analysis. We applied this strategy for enriching membrane proteins expressed by Shewanella oneidensis MR-1, a gram-negative bacterium with known metal-reduction capability via extracellular electron transfer between outer membrane proteins and extracellular electron receptors. LC/MS/MS analysis resulted in the identification of about 400 proteins with 79% of them being predicted to be membrane localized. Quantitative aspects of the membrane enrichment were shown by peptide level 16O and 18O labeling of proteins from wild-type and mutant cells (generated from deletion of a type II secretion protein, GspD) prior to LC-MS analysis. Using a chemical probe labeled pure protein as an internal standard for normalization, the quantitative data revealed reduced abundances in ΔgspD mutant cells of many outer membrane proteins including the outer membrane c-cype cytochromes OmcA and MtrC, in agreement with previously investigation demonstrating that these proteins are substrates of the type II secretion system. PMID:20380418

  3. Radio frequency-compensated Langmuir probe with auxiliary double probes

    SciTech Connect

    Oh, Se-Jin; Oh, Seung-Ju; Chung, Chin-Wook

    2010-09-15

    A radio frequency (rf) compensation design using auxiliary double probes connected in parallel with a main measurement probe was developed for Langmuir probe diagnostics. This probe structure can reduce the sheath impedance of the main probe. In our probe design, the sheath capacitance of the probe can be increased and its sheath resistance can be decreased with increasing dc bias differential voltage between the auxiliary double probes. The I-V characteristic curve and electron energy distribution functions measured by our probe system had sufficient rf compensation performance in inductively coupled plasmas.

  4. Radio frequency-compensated Langmuir probe with auxiliary double probes.

    PubMed

    Oh, Se-Jin; Oh, Seung-Ju; Chung, Chin-Wook

    2010-09-01

    A radio frequency (rf) compensation design using auxiliary double probes connected in parallel with a main measurement probe was developed for Langmuir probe diagnostics. This probe structure can reduce the sheath impedance of the main probe. In our probe design, the sheath capacitance of the probe can be increased and its sheath resistance can be decreased with increasing dc bias differential voltage between the auxiliary double probes. The I-V characteristic curve and electron energy distribution functions measured by our probe system had sufficient rf compensation performance in inductively coupled plasmas. PMID:20886976

  5. Intermolecular Vibrations of Hydrophobic Amino Acids

    NASA Astrophysics Data System (ADS)

    Williams, Michael Roy Casselman

    Hydrophobic amino acids interact with their chemical environment through a combination of electrostatic, hydrogen bonding, dipole, induced dipole, and dispersion forces. These interactions all have their own characteristic energy scale and distance dependence. The low-frequency (0.1-5 THz, 5-150 cm-1) vibrational modes of amino acids in the solid state are a direct indicator of the interactions between the molecules, which include interactions between an amino acid functional group and its surroundings. This information is central to understanding the dynamics and morphology of proteins. The alpha-carbon is a chiral center for all of the hydrophobic amino acids, meaning that they exist in two forms, traditionally referred to as L- and D-enantiomers. This nomenclature indicates which direction the molecule rotates plane-polarized visible light (levorotory and dextrorotory). Chiral a-amino acids in proteins are exclusively the L-variety In the solid state, the crystal lattice of the pure L-enantiomer is the mirror image of the D-enantiomer crystal lattice. These solids are energetically identical. Enantiomers also have identical spectroscopic properties except when the measurement is polarization sensitive. A mixture of equal amounts D- and L-amino acid enantiomers can crystallize into a racemic (DL-) structure that is different from that of the pure enantiomers. Whether a solution of both enantiomers will crystallize into a racemic form or spontaneously resolve into a mixture of separate D- and L-crystals largely depends on the interactions between molecules available in the various possible configurations. This is an active area of research. Low-frequency vibrations with intermolecular character are very sensitive to changes in lattice geometry, and consequently the vibrational spectra of racemic crystals are usually quite distinct from the spectra of the crystals of the corresponding pure enantiomers in the far-infrared (far-IR). THz time-domain spectroscopy (THz

  6. The Effect of Electrode Coupling on Single Molecule Device Characteristics: An X-Ray Spectroscopy and Scanning Probe Microscopy Study

    NASA Astrophysics Data System (ADS)

    Batra, Arunabh

    This thesis studies electronic properties of molecular devices in the limiting cases of strong and weak electrode-molecule coupling. In these two limits, we use the complementary techniques of X-Ray spectroscopy and Scanning Tunneling Microscopy (STM) to understand the mechanisms for electrode-molecule bond formation, the energy level realignment due to metal-molecule bonds, the effect of coupling strength on single-molecule conductance in low-bias measurements, and the effect of coupling on transport under high-bias. We also introduce molecular designs with inherent asymmetries, and develop an analytical method to determine the effect of these features on high-bias conductance. This understanding of the role of electrode-molecule coupling in high-bias regimes enables us to develop a series of functional electronic devices whose properties can be predictably tuned through chemical design. First, we explore the weak electrode-molecule coupling regime by studing the interaction of two types of paracyclophane derivates that are coupled 'through-space' to underlying gold substrates. The two paracyclophane derivatives differ in the strength of their intramolecular through-space coupling. X-Ray photoemission spectroscopy (XPS) and Near-Edge X-ray Absorbance Fine Structure (NEXAFS) spectroscopy allows us to determine the orientation of both molecules; Resonant Photoemission Spectroscopy (RPES) then allows us to measure charge transfer time from molecule to metal for both molecules. This study provides a quantititative measure of charge transfer time as a function of through-space coupling strength. Next we use this understanding in STM based single-molecule current-voltage measurements of a series of molecules that couple through-space to one electrode, and through-bond to the other. We find that in the high-bias regime, these molecules respond differently depending on the direction of the applied field. This asymmetric response to electric field direction results in

  7. Interatomic (Intermolecular) Decay Processes in Clusters: Current Status and Outlook

    SciTech Connect

    Averbukh, V.; Cederbaum, L. S.

    2007-11-29

    Since their theoretical prediction a decade ago, interatomic (intermolecular) Coulombic decay (ICD) and related processes have been in the focus of intensive theoretical and experimental research. The spectacular progress in this direction has been stimulated both by the fundamental importance of the new electronic decay phenomena and by the exciting possibility of their practical application, for example in spectroscopy. We review the current status of the research of interatomic (intermolecular) decay phenomena in clusters and discuss some perspectives of this new field.

  8. Frontier orbital symmetry control of intermolecular electron transfer

    SciTech Connect

    Stevens, B.

    1990-11-01

    Research continued on the study of intermolecular electron transfer. This report discusses the following topics: fluorescence quenching by electron transfer and the modification of quenching dynamics by solvent properties and net free energy change; transient absorption measurements following selective excitation of 1:1 EDA complex isomers; selective quenching of dual fluorescence from linked EDA systems; electron-transfer sensitized cycloreversion of rubrene endoperoxide; and vibronic modification of adiabatic requirements for intermolecular electron transfer. (CBS)

  9. Coherent coupling of two dopants in a silicon nanowire probed by Landau-Zener-Stückelberg interferometry.

    PubMed

    Dupont-Ferrier, E; Roche, B; Voisin, B; Jehl, X; Wacquez, R; Vinet, M; Sanquer, M; De Franceschi, S

    2013-03-29

    We report on microwave-driven coherent electron transfer between two coupled donors embedded in a silicon nanowire. By increasing the microwave frequency we observe a transition from incoherent to coherent driving revealed by the emergence of a Landau-Zener-Stückelberg quantum interference pattern of the measured current through the donors. This interference pattern is fitted to extract characteristic parameters of the double-donor system. In particular we estimate a charge dephasing time of 0.3±0.1  ns, comparable to other types of charge-based two-level systems. The demonstrated coherent coupling between two dopants is an important step towards donor-based quantum computing devices in silicon. PMID:23581354

  10. Human Leukocyte Antigen Typing Using a Knowledge Base Coupled with a High-Throughput Oligonucleotide Probe Array Analysis

    PubMed Central

    Zhang, Guang Lan; Keskin, Derin B.; Lin, Hsin-Nan; Lin, Hong Huang; DeLuca, David S.; Leppanen, Scott; Milford, Edgar L.; Reinherz, Ellis L.; Brusic, Vladimir

    2014-01-01

    Human leukocyte antigens (HLA) are important biomarkers because multiple diseases, drug toxicity, and vaccine responses reveal strong HLA associations. Current clinical HLA typing is an elimination process requiring serial testing. We present an alternative in situ synthesized DNA-based microarray method that contains hundreds of thousands of probes representing a complete overlapping set covering 1,610 clinically relevant HLA class I alleles accompanied by computational tools for assigning HLA type to 4-digit resolution. Our proof-of-concept experiment included 21 blood samples, 18 cell lines, and multiple controls. The method is accurate, robust, and amenable to automation. Typing errors were restricted to homozygous samples or those with very closely related alleles from the same locus, but readily resolved by targeted DNA sequencing validation of flagged samples. High-throughput HLA typing technologies that are effective, yet inexpensive, can be used to analyze the world’s populations, benefiting both global public health and personalized health care. PMID:25505899

  11. Feasibility study of a swept frequency electromagnetic probe (SWEEP) using inductive coupling for the determination of subsurface conductivity of the earth and water prospecting in arid regions

    NASA Technical Reports Server (NTRS)

    Latorraca, G. A.; Bannister, L. H.

    1974-01-01

    Techniques developed for electromagnetic probing of the lunar interior, and techniques developed for the generation of high power audio frequencies were combined to make practical a magnetic inductive coupling system for the rapid measurement of ground conductivity profiles which are helpful when prospecting for the presence and quality of subsurface water. A system which involves the measurement of the direction, intensity, and time phase of the magnetic field observed near the surface of the earth at a distance from a horizontal coil energized so as to create a field that penetrates the earth was designed and studied to deduce the conductivity and stratification of the subsurface. Theoretical studies and a rudimentary experiment in an arid region showed that the approach is conceptually valid and that this geophysical prospecting technique can be developed for the economical exploration of subterranean water resources.

  12. Inductively coupled NMR probe for versatile dynamic nuclear polarization operation at 7 T: Observation of 61 ± 2% 1H polarization at 4 K

    NASA Astrophysics Data System (ADS)

    Siaw, Ting Ann; Walker, Shamon A.; Armstrong, Brandon D.; Han, Song-I.

    2012-08-01

    We have performed dynamic nuclear polarization (DNP) experiments at liquid helium temperatures using a low-power (<70 mW) solid-state diode microwave source at 200 GHz—the electron paramagnetic resonance frequency of stable radicals at 7 T. We employed a home-built Alderman-Grant probe for the detection of 1H NMR signal at 300 MHz, as such coils are well suited for higher frequency NMR detection. The Alderman-Grant coil is inductively coupled to the rest of the radiofrequency (rf) circuit, whose design allows probe components to be placed away from the sample area, and also enables easy switching of coils with different diameters and resonance frequencies. We have tested our DNP instrument on a frozen nitroxide model system consisting of 4-Amino TEMPO dissolved in a glycerol:water mixture. The largest nuclear spin polarization observed was 61 ± 2% with a sample containing 20 mM 4-Amino TEMPO dissolved in deuterated glycerol (d-glycerol):D2O:H2O (50:40:10), amounting to record polarization measured to date at an easily amenable temperature of 4 K.

  13. Comet-FISH with strand-specific probes reveals transcription-coupled repair of 8-oxoGuanine in human cells

    PubMed Central

    Guo, Jia; Hanawalt, Philip C.; Spivak, Graciela

    2013-01-01

    Oxidized bases in DNA have been implicated in cancer, aging and neurodegenerative disease. We have developed an approach combining single-cell gel electrophoresis (comet) with fluorescence in situ hybridization (FISH) that enables the comparative quantification of low, physiologically relevant levels of DNA lesions in the respective strands of defined nucleotide sequences and in the genome overall. We have synthesized single-stranded probes targeting the termini of DNA segments of interest using a polymerase chain reaction-based method. These probes facilitate detection of damage at the single-molecule level, as the lesions are converted to DNA strand breaks by lesion-specific endonucleases or glycosylases. To validate our method, we have documented transcription-coupled repair of cyclobutane pyrimidine dimers in the ataxia telangiectasia-mutated (ATM) gene in human fibroblasts irradiated with 254 nm ultraviolet at 0.1 J/m2, a dose ∼100-fold lower than those typically used. The high specificity and sensitivity of our approach revealed that 7,8-dihydro-8-oxoguanine (8-oxoG) at an incidence of approximately three lesions per megabase is preferentially repaired in the transcribed strand of the ATM gene. We have also demonstrated that the hOGG1, XPA, CSB and UVSSA proteins, as well as actively elongating RNA polymerase II, are required for this process, suggesting cross-talk between DNA repair pathways. PMID:23775797

  14. Comet-FISH with strand-specific probes reveals transcription-coupled repair of 8-oxoGuanine in human cells.

    PubMed

    Guo, Jia; Hanawalt, Philip C; Spivak, Graciela

    2013-09-01

    Oxidized bases in DNA have been implicated in cancer, aging and neurodegenerative disease. We have developed an approach combining single-cell gel electrophoresis (comet) with fluorescence in situ hybridization (FISH) that enables the comparative quantification of low, physiologically relevant levels of DNA lesions in the respective strands of defined nucleotide sequences and in the genome overall. We have synthesized single-stranded probes targeting the termini of DNA segments of interest using a polymerase chain reaction-based method. These probes facilitate detection of damage at the single-molecule level, as the lesions are converted to DNA strand breaks by lesion-specific endonucleases or glycosylases. To validate our method, we have documented transcription-coupled repair of cyclobutane pyrimidine dimers in the ataxia telangiectasia-mutated (ATM) gene in human fibroblasts irradiated with 254 nm ultraviolet at 0.1 J/m2, a dose ∼100-fold lower than those typically used. The high specificity and sensitivity of our approach revealed that 7,8-dihydro-8-oxoguanine (8-oxoG) at an incidence of approximately three lesions per megabase is preferentially repaired in the transcribed strand of the ATM gene. We have also demonstrated that the hOGG1, XPA, CSB and UVSSA proteins, as well as actively elongating RNA polymerase II, are required for this process, suggesting cross-talk between DNA repair pathways. PMID:23775797

  15. System for effecting underwater coupling of optical fiber cables characterized by a novel V-probe cable capture mechanism

    NASA Astrophysics Data System (ADS)

    Hillenbrand, Christopher F.; Barron, Thomas D.; Nugent, David M.

    1995-03-01

    A submarine trails one fiber optic cable and an undersea vehicle is controlled by this first cable. A missile/torpedo trails a second cable that is to be coupled to the first cable. The second cable has a segment suspended vertically underwater between a buoyant pod and a sea anchor type buoy. The undersea vehicle, or Autonomous Undersea Vehicle, (AUV) hunts for the pod by conventional homing means. A forked cable pickup device in the nose of the AUV captures the suspended cable segment directing it into a slot so a male socket in the underside of the pod mates with a female socket in the slot.

  16. The Torque of the Planet: NASA Researcher Uses NCCS Computers to Probe Atmosphere-Land-Ocean Coupling

    NASA Technical Reports Server (NTRS)

    2002-01-01

    The study of Earth science is like a giant puzzle, says Braulio Sanchez. "The more you know about the individual pieces, the easier it is to fit them together." A researcher with Goddard's Space Geodesy Branch, Sanchez has been using NCCS supercomputer and mass storage resources to show how the angular momenta of the atmosphere, the oceans, and the solid Earth are dynamically coupled. Sanchez has calculated the magnitude of atmospheric torque on the planet and has determined some of the possible effects that torque has on Earth's rotation.

  17. Probing quartic couplings through three gauge boson production at an e{sup +}e{sup {minus}} linear collider

    SciTech Connect

    Dawson, S.; Likhoded, A.; Valencia, G.; Yushchenko, O.

    1996-11-22

    We explore the capability of a 500 or 1000 GeV e{sup +} e{sup {minus}} linear collider to measure anomalous quartic gauge boson couplings. In the framework of a non-linear effective Lagrangian with a custodial SU(2) symmetry, there are only two next-to-leading order operators which contribute to quartic, but not to two- and three-gauge boson interactions. The limits on the coefficients of these operators from present and future e{sup +} e{sup {minus}} colliders are compared with those available from other sources.

  18. Detection of High Explosives Using Reflection Absorption Infrared Spectroscopy with Fiber Coupled Grazing Angle Probe/FTIR

    NASA Astrophysics Data System (ADS)

    Primera-Pedrozo, Oliva M.; Soto-Feliciano, Yadira M.; Pacheco-Londoño, Leonardo C.; Hernández-Rivera, Samuel P.

    2009-06-01

    Fiber Optic Coupled Reflection/Absorption Infrared Spectroscopy (RAIRS) has been investigated as a potential technique for developing methodologies of detection and quantification of explosive residues on metallic surfaces. TNT, DNT, HMX, PETN, and Tetryl were detected at loading concentrations less than 400 ng/cm2. Data were analyzed using Chemometrics statistical analysis routines. In particular, partial least squares multivariate analysis (PLS) was used for quantification studies. Peak areas were also used for data analysis to compare with linear multivariate analysis. The measurements resulted in intense absorption bands in the fingerprint region of the infrared spectrum that were used to quantify the target threat chemicals and to calculate the limit of detection for each compound. Micro-RAIRS vibrational imaging was also used for characterization of the distribution and form of layers of explosives deposited on stainless steel sheets. The degree of homogeneity depended strongly on the method of deposition. The images were generated by calculating the area under vibrational signals of 15 μm × 15 μm grids with a separation of 15 μm. Histograms of the maps were generated and the homogeneity was evaluated by using standard deviations, mean kurtosis, skewness, and moments of distributions obtained. Methanol solutions of High Explosives (HE) resulted in the optimum distributions on the stainless steel surfaces tested and therefore, Methanol selected as the preferred solvent for the Fiber Optics Coupled-RAIRS experiments.

  19. Mass Spectrometric and Langmuir Probe Measurements in Inductively Coupled Plasmas in Ar, CHF3/Ar and CHF3/Ar/O2 Mixtures

    NASA Technical Reports Server (NTRS)

    Kim, J. S.; Rao, M. V. V. S.; Cappelli, M. A.; Sharma, S. P.; Meyyappan, M.; Arnold, Jim (Technical Monitor)

    2000-01-01

    Absolute fluxes and energy distributions of ions in inductively coupled plasmas of Ar, CHF3/Ar, and CHF3/Ar/O2 have been measured. These plasmas were generated in a Gaseous Electronics Conference (GEC) cell modified for inductive coupling at pressures 10-50 mTorr and 100-300 W of 13.56 MHz radio frequency (RF) power in various feedgas mixtures. In pure Ar plasmas, the Ar(+) flux increases linearly with pressure as well as RF-power. Total ion flux in CHF3 mixtures decreases with increase in pressure and also CHF3 concentration. Relative ion fluxes observed in the present studies are analyzed with the help of available cross sections for electron impact ionization and charge-exchange ion-molecule reactions. Measurements of plasma potential, electron and ion number densities, electron energy distribution function, and mean electron energy have also been made in the center of the plasma with a RF compensated Langmuir probe. Plasma potential values are compared with the mean ion energies determined from the measured ion energy distributions and are consistent. Electron temperature, plasma potential, and mean ion energy vary inversely with pressure, but increase with CHF3 content in the mixture.

  20. Multiple DNA Extractions Coupled with Stable-Isotope Probing of Anthracene-Degrading Bacteria in Contaminated Soil▿†

    PubMed Central

    Jones, Maiysha D.; Singleton, David R.; Sun, Wei; Aitken, Michael D.

    2011-01-01

    In many of the DNA-based stable-isotope probing (SIP) studies published to date in which soil communities were investigated, a single DNA extraction was performed on the soil sample, usually using a commercial DNA extraction kit, prior to recovering the 13C-labeled (heavy) DNA by density-gradient ultracentrifugation. Recent evidence suggests, however, that a single extraction of a soil sample may not lead to representative recovery of DNA from all of the organisms in the sample. To determine whether multiple DNA extractions would affect the DNA yield, the eubacterial 16S rRNA gene copy number, or the identification of anthracene-degrading bacteria, we performed seven successive DNA extractions on the same aliquot of contaminated soil either untreated or enriched with [U-13C]anthracene. Multiple extractions were necessary to maximize the DNA yield and 16S rRNA gene copy number from both untreated and anthracene-enriched soil samples. Sequences within the order Sphingomonadales, but unrelated to any previously described genus, dominated the 16S rRNA gene clone libraries derived from 13C-enriched DNA and were designated “anthracene group 1.” Sequences clustering with Variovorax spp., which were also highly represented, and sequences related to the genus Pigmentiphaga were newly associated with anthracene degradation. The bacterial groups collectively identified across all seven extracts were all recovered in the first extract, although quantitative PCR analysis of SIP-identified groups revealed quantitative differences in extraction patterns. These results suggest that performing multiple DNA extractions on soil samples improves the extractable DNA yield and the number of quantifiable eubacterial 16S rRNA gene copies but have little qualitative effect on the identification of the bacterial groups associated with the degradation of a given carbon source by SIP. PMID:21398486

  1. Probing mechanical principles of focal contacts in cell–matrix adhesion with a coupled stochastic–elastic modelling framework

    PubMed Central

    Gao, Huajian; Qian, Jin; Chen, Bin

    2011-01-01

    Cell–matrix adhesion depends on the collective behaviours of clusters of receptor–ligand bonds called focal contacts between cell and extracellular matrix. While the behaviour of a single molecular bond is governed by statistical mechanics at the molecular scale, continuum mechanics should be valid at a larger scale. This paper presents an overview of a series of recent theoretical studies aimed at probing the basic mechanical principles of focal contacts in cell–matrix adhesion via stochastic–elastic models in which stochastic descriptions of molecular bonds and elastic descriptions of interfacial traction–separation are unified in a single modelling framework. The intention here is to illustrate these principles using simple analytical and numerical models. The aim of the discussions is to provide possible clues to the following questions: why does the size of focal adhesions (FAs) fall into a narrow range around the micrometre scale? How can cells sense and respond to substrates of varied stiffness via FAs? How do the magnitude and orientation of mechanical forces affect the binding dynamics of FAs? The effects of cluster size, cell–matrix elastic modulus, loading direction and cytoskeletal pretension on the lifetime of FA clusters have been investigated by theoretical arguments as well as Monte Carlo numerical simulations, with results showing that intermediate adhesion size, stiff substrate, cytoskeleton stiffening, low-angle pulling and moderate cytoskeletal pretension are factors that contribute to stable FAs. From a mechanistic point of view, these results provide possible explanations for a wide range of experimental observations and suggest multiple mechanisms by which cells can actively control adhesion and de-adhesion via cytoskeletal contractile machinery in response to mechanical properties of their surroundings. PMID:21632610

  2. Probing the coupling between proton and electron transfer in Photosystem II core complexes containing a 3-fluorotyrosine

    PubMed Central

    Rappaport, Fabrice; Boussac, Alain; Force, Dee Ann; Peloquin, Jeffrey; Brynda, Marcin; Sugiura, Miwa; Un, Sun; Britt, R. David; Diner, Bruce A.

    2009-01-01

    The catalytic cycle of numerous enzymes involves the coupling between proton transfer and electron transfer. Yet, the understanding of this coordinated transfer in biological systems remains limited, likely because its characterization relies on the controlled but experimentally challenging modifications of the free energy changes associated with either the electron or proton transfer. We have performed such a study here in Photosystem II. The driving force for electron transfer from TyrZ to P680•+ has been decreased by ~ 80 meV by mutating the axial ligand of P680, and that for proton transfer upon oxidation of TyrZ by substituting a 3-fluorotyrosine (3F-TyrZ) for TyrZ. In Mn-depleted Photosystem II, the dependence upon pH of the oxidation rates of TyrZ and 3F-TyrZ were found to be similar. However, in the pH range where the phenolic hydroxyl of TyrZ is involved in a H-bond with a proton acceptor, the activation energy of the oxidation of 3F-TyrZ is decreased by 110 meV, a value which correlates with the in vitro finding of a 90 meV stabilization energy to the phenolate form of 3F-Tyr when compared to Tyr (Seyedsayamdost et al., 2006, JACS 128:1569–79). Thus, when the phenol of YZ acts as a H-bond-donor, its oxidation by P680•+ is controlled by its prior deprotonation. This contrasts with the situation prevailing at lower pH, where the proton acceptor is protonated and therefore unavailable, in which the oxidation-induced proton transfer from the phenolic hydroxyl of TyrZ has been proposed to occur concertedly with the electron transfer to P680•+. This suggests a switch between a concerted proton/electron transfer at pHs < 7.5 to a sequential one at pHs > 7.5 and illustrates the roles of the H-bond and of the likely salt-bridge existing between the phenolate and the nearby proton acceptor in determining the coupling between proton and electron transfer. PMID:19265377

  3. Intermolecular interactions between imidazole derivatives intercalated in layered solids. Substituent group effect

    SciTech Connect

    González, M.; Lemus-Santana, A.A.; Rodríguez-Hernández, J.; Aguirre-Velez, C.I.; Knobel, M.; Reguera, E.

    2013-08-15

    This study sheds light on the intermolecular interactions between imidazole derive molecules (2-methyl-imidazole, 2-ethyl-imidazole and benzimidazole) intercalated in T[Ni(CN){sub 4}] layers to form a solid of formula unit T(ImD){sub 2}[Ni(CN){sub 4}]. These hybrid inorganic–organic solids were prepared by soft chemical routes and their crystal structures solved and refined from X-ray powder diffraction data. The involved imidazole derivative molecules were found coordinated through the pyridinic N atom to the axial positions for the metal T in the T[Ni(CN){sub 4}] layer. In the interlayers region ligand molecules from neighboring layers remain stacked in a face-to-face configuration through dipole–dipole and quadrupole–quadrupole interactions. These intermolecular interactions show a pronounced dependence on the substituent group and are responsible for an ImD-pillaring concatenation of adjacent layers. This is supported by the structural information and the recorded magnetic data in the 2–300 K temperature range. The samples containing Co and Ni are characterized by presence of spin–orbit coupling and pronounced temperature dependence for the effective magnetic moment except for 2-ethyl-imidazole related to the local distortion for the metal coordination environment. For this last one ligand a weak ferromagnetic ordering ascribed to a super-exchange interaction between T metals from neighboring layers through the ligands π–π interaction was detected. - Graphical abstract: In the interlayers region imidazole derivative molecules are oriented according to their dipolar and quadrupolar interactions and minimizing the steric impediment. Highlights: • Imidazole derivatives intercalation compounds. • Intermolecular interaction between intercalated imidazole derivatives. • Hybrid inorganic–organic solids. • Pi–pi interactions and ferromagnetic coupling. • Dipolar and quadrupolar interactions between intercalated imidazole derivatives.

  4. Linking proteins with anionic nanoparticles via protamine: ultrasmall protein-coupled probes for magnetic resonance imaging of apoptosis.

    PubMed

    Schellenberger, Eyk; Schnorr, Jörg; Reutelingsperger, Chris; Ungethüm, Liset; Meyer, Wolfdietrich; Taupitz, Matthias; Hamm, Bernd

    2008-02-01

    Magnetic resonance imaging (MRI) of a target in vivo depends on the surface, size, and particle relaxivity of the target-specific nanoparticles for MRI. Here a new method for decorating very small iron oxide particles (VSOPs) with target-specific ligands is described. The method is based on the electrostatic attraction of the strongly positively charged peptide protamine to the anionic citrate shell of the electrostatically stabilized VSOPs. The protamine coat allows linkage chemistry and chimera technology to functionalize VSOPs or other negative charged surfaces with biologics. Annexin A5 (anxA5)-VSOP utilizing thiol chemistry was generated to couple biologically active anxA5 to VSOPs for in vivo MRI of apoptosis. Annexin A5-VSOP comprises five anxA5 molecules per iron oxide nanoparticle with a high R2 particle relaxivity of 180 000 mM(-1) s(-1) yet small hydrodynamic diameter of only 14.7+/-2.9 nm beneficial for in vivo MRI of extravascular targets. PMID:18203233

  5. Probing the role of interlayer coupling and coulomb interactions on electronic structure in few-layer MoSe₂ nanostructures.

    PubMed

    Bradley, Aaron J; Ugeda, Miguel M; da Jornada, Felipe H; Qiu, Diana Y; Ruan, Wei; Zhang, Yi; Wickenburg, Sebastian; Riss, Alexander; Lu, Jiong; Mo, Sung-Kwan; Hussain, Zahid; Shen, Zhi-Xun; Louie, Steven G; Crommie, Michael F

    2015-04-01

    Despite the weak nature of interlayer forces in transition metal dichalcogenide (TMD) materials, their properties are highly dependent on the number of layers in the few-layer two-dimensional (2D) limit. Here, we present a combined scanning tunneling microscopy/spectroscopy and GW theoretical study of the electronic structure of high quality single- and few-layer MoSe2 grown on bilayer graphene. We find that the electronic (quasiparticle) bandgap, a fundamental parameter for transport and optical phenomena, decreases by nearly one electronvolt when going from one layer to three due to interlayer coupling and screening effects. Our results paint a clear picture of the evolution of the electronic wave function hybridization in the valleys of both the valence and conduction bands as the number of layers is changed. This demonstrates the importance of layer number and electron-electron interactions on van der Waals heterostructures and helps to clarify how their electronic properties might be tuned in future 2D nanodevices. PMID:25775022

  6. Analysis of cytochrome P450 metabolites of arachidonic acid by stable isotope probe labeling coupled with ultra high-performance liquid chromatography/mass spectrometry.

    PubMed

    Zhu, Quan-Fei; Hao, Yan-Hong; Liu, Ming-Zhou; Yue, Jiang; Ni, Jian; Yuan, Bi-Feng; Feng, Yu-Qi

    2015-09-01

    Cytochrome P450 metabolites of arachidonic acid (AA) belong to eicosanoids and are potent lipid mediators of inflammation. It is well-known that eicosanoids play an important role in numerous pathophysiological processes. Therefore, quantitative analysis of cytochrome P450 metabolites of AA, including hydroxyeicosatetraenoic acids (HETEs), epoxyeicosatreinoic acids (EETs), and dihydroxyeicosatrienoic acids (DHETs) can provide crucial information to uncover underlying mechanisms of cytochrome P450 metabolites of AA related diseases. Herein, we developed a highly sensitive method to identify and quantify HETEs, EETs, and DHETs in lipid extracts of biological samples based on stable isotope probe labeling coupled with ultra high-performance liquid chromatography/mass spectrometry. To this end, a pair of stable isotope probes, 2-dimethylaminoethylamine (DMED) and d4-2-dimethylaminoethylamine (d4-DMED), were utilized to facilely label eicosanoids. The heavy labeled eicosanoid standards were prepared and used as internal standards for quantification to minimize the matrix and ion suppression effects in mass spectrometry analysis. In addition, the detection sensitivities of DMED labeled eicosanoids improved by 3-104 folds in standard solution and 5-138 folds in serum matrix compared with unlabeled analytes. Moreover, a good separation of eicosanoids isomers was achieved upon DMED labeling. The established method provided substantial sensitivity (limit of quantification at sub-picogram), high specificity, and broad linear dynamics range (3 orders of magnitude). We further quantified cytochrome P450 metabolites of AA in rat liver, heart, brain tissues and human serum using the developed method. The results showed that 19 eicosanoids could be distinctly detected and the contents of 11-, 15-, 16-, 20-HETE, 5,6-EET, and 14,15-EET in type 2 diabetes mellitus patients and 5-, 11-, 12-, 15-, 16-, 20-HETE, 8,9-EET, and 5,6-DHET in myeloid leukemia patients had significant changes

  7. Qualitative change of character of dispersive interaction with intermolecular distance.

    PubMed

    Haslmayr, Johannes; Renger, Thomas

    2013-07-28

    The dispersive interaction between molecules results from Coulomb-correlated fluctuations of electrons and for large intermolecular distances it can be related to the molecular polarizabilities as in London's theory (F. London, Trans. Faraday Soc. 33, 8-26 (1937)). Here, we investigate the interaction between molecules with anisotropic polarizabilities at arbitrary distances using symmetry adapted perturbation theory, which allows us to analyze the different parts of the intermolecular potential separately. Whereas at large distances, in accordance with London's theory, there is no way to describe the dispersive interaction by a sum over pairwise isotropic atom-centered energy terms, at short distances such a description becomes possible. This surprising result has consequences for the development of molecular mechanics force fields, supports the dispersion energy terms applied in dispersion corrected density functional theory, and indicates that there is a qualitative change in electron correlation with distance. Apparently, at short distances intermolecular electron correlation is less influenced by intramolecular electron delocalization. PMID:23901956

  8. Intermolecular Vibrational Modes Speed Up Singlet Fission in Perylenediimide Crystals.

    PubMed

    Renaud, Nicolas; Grozema, Ferdinand C

    2015-02-01

    We report numerical simulations based on a non-Markovian density matrix propagation scheme of singlet fission (SF) in molecular crystals. Ab initio electronic structure calculations were used to parametrize the exciton and phonon Hamiltonian as well as the interactions between the exciton and the intramolecular and intermolecular vibrational modes. We demonstrate that the interactions of the exciton with intermolecular vibrational modes are highly sensitive to the stacking geometry of the crystal and can, in certain cases, significantly accelerate SF. This result may help in understanding the fast SF experimentally observed in a broad range of molecular crystals and offers a new direction for the engineering of efficient SF sensitizers. PMID:26261948

  9. Intermolecular exciton-exciton annihilation in phospholipid vesicles doped with [Ru(bpy)2dppz]2+

    NASA Astrophysics Data System (ADS)

    De la Cadena, Alejandro; Pascher, Torbjörn; Davydova, Dar'ya; Akimov, Denis; Herrmann, Felix; Presselt, Martin; Wächtler, Maria; Dietzek, Benjamin

    2016-01-01

    The ultrafast photophysics of [Ru(bpy)2dppz]2+ (dppz = dipyrido[3,2-a:2‧,3‧-c]-phenazine) embedded into the walls of phospholipid vesicles has been studied by femtosecond time-resolved pump-probe spectroscopy. While [Ru(bpy)2dppz]2+ has been studied intensively with respect to its intramolecular charge transfer processes, which are associated with the well known light-switch effect, this study focuses on intermolecular energy transfer processes taking place upon dense packing of the complexes into a phospholipid membrane composed of dipalmitoyl-L-α-phosphatidylglycerol, which can be thought of as a simplistic model of a cellular membrane. The data indicate additional quenching of excited [Ru(bpy)2dppz]2+ upon increasing the pump-pulse intensity. Hence, the observed photophysics, which is assigned to the presence of intermolecular exciton-exciton annihilation at high pump-intensities, might be related to the ultrafast photophysics of [Ru(bpy)2dppz]2+ when used as a chromophore to stain cells, an effect that may be taken into account during the employment of novel cellular markers based on Ru polypyridine complexes.

  10. Mixed Quantum-Classical Simulations of Transient Absorption Pump-Probe Signals for a Photo-Induced Electron Transfer Reaction Coupled to an Inner-Sphere Vibrational Mode.

    PubMed

    Martinez, Franz; Hanna, Gabriel

    2016-05-19

    In a previous study (Martinez, F.; Hanna, G. Chem. Phys. Lett. 2013, 573, 77-83), we demonstrated the ability of two approximate solutions of the quantum-classical Liouville equation (QCLE) for qualitatively capturing the electronic dynamics in the pump-probe transient absorption (TA) signal of a model of a condensed phase photoinduced electron transfer reaction whose ground and excited donor states have the same equilibrium geometry. However, the question remained as to the ability of these solutions to treat the more complex situation in which the electronic states are coupled to a low-frequency inner-sphere harmonic vibrational mode (representing an intramolecular mode of the donor-acceptor complex) that shifts their equilibrium geometries with respect to each other and thereby gives rise to signatures of vibrational dynamics in the TA signal. Thus, in this study, we investigated this situation by treating the vibrational mode both quantum mechanically and classically within the context of the approximate Poisson bracket mapping equation (PBME) and forward-backward trajectory solutions (FBTS) of the QCLE. Depending on the definition of the quantum subsystem, both PBME and FBTS are capable of qualitatively capturing several of the main features in the exact TA signal and quantitatively capturing the characteristic time scale of the vibrational dynamics, despite the moderately strong subsystem-bath coupling in this model. Particularly, we found that treating the vibrational mode quantum mechanically using either PBME or FBTS better captures the signatures of the vibrational dynamics, while treating it classically using FBTS better captures the decay in the signal. These findings underscore the utility of the PBME and FBTS approaches for efficiently modeling and interpreting TA signals. PMID:26766568

  11. Cavity Photons as a Probe for Charge Relaxation Resistance and Photon Emission in a Quantum Dot Coupled to Normal and Superconducting Continua

    NASA Astrophysics Data System (ADS)

    Bruhat, L. E.; Viennot, J. J.; Dartiailh, M. C.; Desjardins, M. M.; Kontos, T.; Cottet, A.

    2016-04-01

    Microwave cavities have been widely used to investigate the behavior of closed few-level systems. Here, we show that they also represent a powerful probe for the dynamics of charge transfer between a discrete electronic level and fermionic continua. We have combined experiment and theory for a carbon nanotube quantum dot coupled to normal metal and superconducting contacts. In equilibrium conditions, where our device behaves as an effective quantum dot-normal metal junction, we approach a universal photon dissipation regime governed by a quantum charge relaxation effect. We observe how photon dissipation is modified when the dot admittance turns from capacitive to inductive. When the fermionic reservoirs are voltage biased, the dot can even cause photon emission due to inelastic tunneling to/from a Bardeen-Cooper-Schrieffer peak in the density of states of the superconducting contact. We can model these numerous effects quantitatively in terms of the charge susceptibility of the quantum dot circuit. This validates an approach that could be used to study a wide class of mesoscopic QED devices.

  12. Synergy between measurements of gravitational waves and the triple-Higgs coupling in probing the first-order electroweak phase transition

    NASA Astrophysics Data System (ADS)

    Hashino, Katsuya; Kakizaki, Mitsuru; Kanemura, Shinya; Matsui, Toshinori

    2016-07-01

    Probing the Higgs potential and new physics behind the electroweak symmetry breaking is one of the most important issues of particle physics. In particular, the nature of the electroweak phase transition is essential for understanding the physics of the early Universe, such that the strongly first-order phase transition is required for a successful scenario of electroweak baryogenesis. The strongly first-order phase transition is expected to be tested by precisely measuring the triple Higgs boson coupling at future colliders like the International Linear Collider. It can also be explored via the spectrum of stochastic gravitational waves to be measured at future space-based interferometers such as eLISA and DECIGO. We discuss the complementarity of both the methods in testing the strongly first-order phase transition of the electroweak symmetry in models with additional isospin singlet scalar fields with and without classical scale invariance. We find that they are synergetic in identifying specific models of electroweak symmetry breaking in more detail.

  13. Design of a scanning probe microscope with advanced sample treatment capabilities: An atomic force microscope combined with a miniaturized inductively coupled plasma source

    SciTech Connect

    Hund, Markus; Herold, Hans

    2007-06-15

    We describe the design and performance of an atomic force microscope (AFM) combined with a miniaturized inductively coupled plasma source working at a radio frequency of 27.12 MHz. State-of-the-art scanning probe microscopes (SPMs) have limited in situ sample treatment capabilities. Aggressive treatments such as plasma etching or harsh treatments such as etching in aggressive liquids typically require the removal of the sample from the microscope. Consequently, time consuming procedures are required if the same sample spot has to be imaged after successive processing steps. We have developed a first prototype of a SPM which features a quasi in situ sample treatment using a modified commercial atomic force microscope. A sample holder is positioned in a special reactor chamber; the AFM tip can be retracted by several millimeters so that the chamber can be closed for a treatment procedure. Most importantly, after the treatment, the tip is moved back to the sample with a lateral drift per process step in the 20 nm regime. The performance of the prototype is characterized by consecutive plasma etching of a nanostructured polymer film.

  14. Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host-Guest Systems.

    PubMed

    Zhang, Dawei; Chatelet, Bastien; Serrano, Eloisa; Perraud, Olivier; Dutasta, Jean-Pierre; Robert, Vincent; Martinez, Alexandre

    2015-10-01

    The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation-π and anion-π interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron-poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion-pair recognition. Wavefunction calculations highlight how short- and long-range interactions interfere in this recognition process, suggesting that a disruption of anion-π interactions can occur in the presence of a co-bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions. PMID:26401973

  15. Intramolecular and intermolecular vibrational energy relaxation of CH 2I 2 dissolved in supercritical fluid

    NASA Astrophysics Data System (ADS)

    Sekiguchi, K.; Shimojima, A.; Kajimoto, O.

    2002-04-01

    A pump-probe experiment was performed to examine vibrational population relaxation of diiodomethane (CH 2I 2) molecule dissolved in supercritical CO 2. Using an apparatus with femtosecond time resolution, we observed the contributions of intramolecular vibrational energy redistribution (IVR) and intermolecular vibrational energy transfer (VET) separately. IVR and VET rates were measured with varying solvent densities at a constant temperature. It is shown that the IVR rate is not density dependent while the VET rate increases with increasing density from 0.4 to 0.8 g cm-3. This observation suggests that the rate of the VET process is determined by solute-solvent collisions whereas the IVR rate is not much affected by solute-solvent interaction.

  16. Fast acquisition of high-resolution NMR spectra in inhomogeneous fields via intermolecular double-quantum coherences

    PubMed Central

    Chen, Zhong; Cai, Shuhui; Chen, Zhiwei; Zhong, Jianhui

    2009-01-01

    A pulse sequence, IDEAL-II, is proposed based on the concept of intermolecular dipolar-interaction enhanced all lines [Z. Chen et al., J. Am. Chem. Soc. 126, 446 (2004)] for obtaining one-dimensional (1D) high-resolution liquid NMR spectra in inhomogeneous fields via two-dimensional acquisitions. With the new acquisition scheme, the range of magnetic field inhomogeneity rather than chemical shift is sampled in the indirect dimension. This enables a great reduction in acquisition time and amount of data, much improved over the original IDEAL implementation. It is applicable to both isolated and J-coupled spin systems in liquid. For the latter, apparent J coupling constants are magnified threefold in spectra obtained with this sequence. This allows a more accurate measurement of J coupling constants in the cases of small J coupling constants or large inhomogeneous fields. Analytical expression was derived based on intermolecular multiple-quantum coherence treatments. Solution samples that were purposely deshimmed and biological samples with intrinsic field inhomogeneities were tested. Experimental results demonstrate that this sequence retains useful structural information including chemical shifts, relative peak areas, and multiplet patterns of J coupling even when the field inhomogeneity is severe enough to almost erase all spectroscopic information with conventional 1D single-quantum coherence techniques. This sequence is more applicable to weakly coupled and uncoupled spin systems, potentially useful for studying metabolites in in vivo NMR spectroscopy and for characterizing technologically important new materials in combinatorial chemistry. PMID:19256612

  17. Intermolecular energy-band dispersion in PTCDA multilayers

    NASA Astrophysics Data System (ADS)

    Yamane, Hiroyuki; Kera, Satoshi; Okudaira, Koji K.; Yoshimura, Daisuke; Seki, Kazuhiko; Ueno, Nobuo

    2003-07-01

    The electronic structure of a well-oriented perylene-3,4,9,10-tetracarboxylic acid-dianhydride multilayer prepared on MoS2 single crystal surface were studied by angle-resolved ultraviolet photoemission spectroscopy using synchrotron radiation. From the photon energy dependence of normal emission spectra, we observed an intermolecular energy-band dispersion of about 0.2 eV for the highest occupied molecular orbital (HOMO) band of single π character. The observed energy-band dispersion showed a cosine curve, which originates from the intermolecular π-π interaction. Analyses using the tight-binding model gave that the transfer integral of about 0.05 eV for the π-π interaction, the effective mass of HOMO hole m*h=5.28m0, and the hole mobility μh>3.8 cm2/V s. This is the first observation of the intermolecular energy-band dispersion of a conventional single-component organic semiconductor only with the weak intermolecular van der Waals interaction.

  18. Spin radical enhanced magnetocapacitance effect in intermolecular excited states.

    PubMed

    Zang, Huidong; Wang, Jianguo; Li, Mingxing; He, Lei; Liu, Zitong; Zhang, Deqing; Hu, Bin

    2013-11-14

    This article reports the magnetocapacitance effect (MFC) based on both pristine polymer MEH-PPV and its composite system doped with spin radicals (6R-BDTSCSB). We observed that a photoexcitation leads to a significant positive MFC in the pristine MEH-PPV. Moreover, we found that a low doping of spin radicals in polymer MEH-PPV causes a significant change on the MFC signal: an amplitude increase and a line-shape narrowing under light illumination at room temperature. However, no MFC signal was observed under dark conditions in either the pristine MEH-PPV or the radical-doped MEH-PPV. Furthermore, the magnitude increase and line-shape narrowing caused by the doped spin radicals are very similar to the phenomena induced by increasing the photoexcitation intensity. Our studies suggest that the MFC is essentially originated from the intermolecular excited states, namely, intermolecular electron-hole pairs, generated by a photoexcitation in the MEH-PPV. More importantly, by comparing the effects of spin radicals and electrically polar molecules on the MFC magnitude and line shape, we concluded that the doped spin radicals can have the spin interaction with intermolecular excited states and consequently affect the internal spin-exchange interaction within intermolecular excited states in the development of MFC. Clearly, our experimental results indicate that dispersing spin radicals forms a convenient method to enhance the magnetocapacitance effect in organic semiconducting materials. PMID:24144347

  19. Learning about Intermolecular Interactions from the Cambridge Structural Database

    ERIC Educational Resources Information Center

    Battle, Gary M.; Allen, Frank H.

    2012-01-01

    A clear understanding and appreciation of noncovalent interactions, especially hydrogen bonding, are vitally important to students of chemistry and the life sciences, including biochemistry, molecular biology, pharmacology, and medicine. The opportunities afforded by the IsoStar knowledge base of intermolecular interactions to enhance the…

  20. Morphology and the Strength of Intermolecular Contact in Protein Crystals

    NASA Technical Reports Server (NTRS)

    Matsuura, Yoshiki; Chernov, Alexander A.

    2002-01-01

    The strengths of intermolecular contacts (macrobonds) in four lysozyme crystals were estimated based on the strengths of individual intermolecular interatomic interaction pairs. The periodic bond chain of these macrobonds accounts for the morphology of protein crystals as shown previously. Further in this paper, the surface area of contact, polar coordinate representation of contact site, Coulombic contribution on the macrobond strength, and the surface energy of the crystal have been evaluated. Comparing location of intermolecular contacts in different polymorphic crystal modifications, we show that these contacts can form a wide variety of patches on the molecular surface. The patches are located practically everywhere on this surface except for the concave active site. The contacts frequently include water molecules, with specific intermolecular hydrogen-bonds on the background of non-specific attractive interactions. The strengths of macrobonds are also compared to those of other protein complex systems. Making use of the contact strengths and taking into account bond hydration we also estimated crystal-water interfacial energies for different crystal faces.

  1. Intermolecular potentials from shock structure experiments. [for monatomic gases

    NASA Technical Reports Server (NTRS)

    Sturtevant, B.; Steinhilper, E. A.

    1974-01-01

    Ground-state intermolecular interaction potentials determined from shock structure experiments with four monatomic gases are reported. These potentials are assessed for self-consistency, using the law of corresponding states, and their suitability for engineering applications in rarefied gas dynamics is discussed.

  2. Intermolecular Silacarbonyl Ylide Cycloadditions: A Direct Pathway to Oxasilacyclopentenes

    PubMed Central

    Bourque, Laura E.; Woerpel, K. A.

    2009-01-01

    Silacarbonyl ylides, generated by metal-catalyzed silylene transfer to carbonyls, participate in formal intermolecular 1,3-dipolar cycloaddition reactions with carbonyl compounds and alkynes to form dioxasilacyclopentane acetals and oxasilacyclopentenes in an efficient, one-step process. PMID:18922005

  3. Dancing Crystals: A Dramatic Illustration of Intermolecular Forces

    ERIC Educational Resources Information Center

    Mundell, Donald W.

    2007-01-01

    Crystals of naphthalene form on the surface of an acetone solution and dance about in an animated fashion illustrating surface tension, crystallization, and intermolecular forces. Additional experiments reveal the properties of the solution. Flows within the solutions can be visualized by various means. Previous demonstrations of surface motion…

  4. Student Understanding of Intermolecular Forces: A Multimodal Study

    ERIC Educational Resources Information Center

    Cooper, Melanie M.; Williams, Leah C.; Underwood, Sonia M.

    2015-01-01

    The ability to use representations of molecular structure to predict the macroscopic properties of a substance is central to the development of a robust understanding of chemistry. Intermolecular forces (IMFs) play an important role in this process because they provide a mechanism for how and why molecules interact. In this study, we investigate…

  5. Hydrogen-hydrogen intermolecular structure of polyethylene in the melt

    NASA Astrophysics Data System (ADS)

    Londono, J. D.; Annis, B. K.; Habenschuss, A.; Smith, G. D.; Borodin, O.; Tso, C.; Hsieh, E. T.; Soper, A. K.

    1999-05-01

    Three polyethylene samples, which differed in their degree of deuteration, were studied in neutron diffraction isotopic substitution (NDIS) experiments at 428 K. These results were complemented at small wavevectors by small angle neutron measurements. The intermolecular hydrogen-hydrogen (HH) structure function, hHH(Q), was obtained without recourse to intramolecular structure models, as demonstrated in a prior report. The PE experimental results are compared to computer simulation results for the alkanes C100 at 509 K and C44 at 350, 400, and 450 K. The small temperature dependence of the HH intermolecular radial distribution functions, gHH(r) for C44 indicates that the differences observed between the PE, C100, and C44 (450 K) results are, for the most part, not due to just temperature differences. It is shown that the string model, an analytic result from an integral equation theory of polymers (PRISM), can account approximately for the overall shape of the gHH(r) functions, and that this overall shape is dependent on the radius of gyration of the molecule. Further analysis shows that there are two other contributions to gHH(r), both of which are independent of chain length to first order. The first is due to chain-chain packing, and the second is due to local HH intermolecular correlations. These results are significant because they demonstrate that hHH(Q) is a useful function for studying intermolecular polymer structure, which has been shown to underpin phase behavior in polyolefin blends.

  6. Copper-catalyzed intermolecular asymmetric propargylic dearomatization of indoles.

    PubMed

    Shao, Wen; Li, He; Liu, Chuan; Liu, Chen-Jiang; You, Shu-Li

    2015-06-22

    The first copper-catalyzed intermolecular dearomatization of indoles by an asymmetric propargylic substitution reaction was developed. This method provides a highly efficient synthesis of versatile furoindoline and pyrroloindoline derivatives containing a quaternary carbon stereogenic center and a terminal alkyne moiety with up to 86 % yield and 98 % ee. PMID:25968474

  7. Probing Spin and Spin-Orbit Coupling effects in Narrow-gap Semiconductor Nano-structures by THz Magneto-photoresponse Spectroscopy and Magneto-transport Measurements

    NASA Astrophysics Data System (ADS)

    Pakmehr, Mehdi

    Using the spin degree of freedom in a emergent field Known as Spintronics has motivated scientist in different disciplines including physicist within last 10 years. Due to different interaction mechanisms which affects the physical behavior of spin (eg its state and transport properties) within solid medium (Semiconductors in our case), one needs to distinguish these mechanisms and their importance for making any practical spin based devices. For example the idea of making spin based transistors with electrons being transported within InGaAs and their spin state is being controlled by Rashba type field has been around for around 25 years but injection of spin polarized currents from a source into the channel has not been solved yet. Spin orbit coupling (SOC) is one of the mechanisms which changes the spin state of electrons and avoid the existence of pure spin state as a favorable one from device point of view. SOC could have a different origin depending on material type or structure of device. One method of measuring and quantifying this mechanisms within semiconductor nanostructures is through measuring the parameters known as Lande g-factor. This parameters turns out to be a promising one to probe different effects on electronic band structure including quantum confinement, strain, electric filed, etc. We probe a combination of these effects (SOC, Strain, band mixing, etc) by measuring different g-factor tensor components of narrow gap Zinc blend semiconductor nanostructures which we hope finally serve to the purpose of making reliable spin based devices* (Spintronics). To reach this goal we have developed and implemented THz magneto-Photoresponse spectroscopy in conjunction with magneto-transport measurements at cryogenic temperatures. The samples include InAs and HgTe based Quantum wells as well as InAs based quantum point contact. Our findings clarify the situation where the combination of SOC, Strain, quantum confinements as well as many body electron effect

  8. Dynamics of intermolecular interactions in CCl4via the isotope effect by femtosecond time-resolved spectroscopy.

    PubMed

    Konarska, Jadwiga; Gadomski, Wojciech; Ratajska-Gadomska, Bożena; Polok, Kamil; Pudłowski, Grzegorz; Kardaś, Tomasz M

    2016-06-21

    We report our study on the ultrafast dynamics of intermolecular interactions in liquid CCl4. A transient transmission time domain signal, obtained in the 40 ps delay range, exhibits beating at the difference frequency of the totally symmetric stretching vibrations of the tetrachloride isotopologues. We show that the spectra obtained as the windowed Fourier transform of different parts of the time domain signal in the range of this totally symmetric vibration, split due to the isotope effect, carry the information about the dynamics of the coherently excited, coupled molecules. We use a simple theoretical model in order to prove that the intermolecular interaction influences the relative amplitudes of the isotopologue peaks in the spectrum. Moreover, we demonstrate that the pump induced coherence in the system leads to additional strengthening of the interaction, which can be observed in the spectra obtained from the experimental time domain signal. PMID:27244535

  9. Use of urea and glycine betaine to quantify coupled folding and probe the burial of DNA phosphates in lac repressor-lac operator binding.

    PubMed

    Hong, Jiang; Capp, Mike W; Saecker, Ruth M; Record, M Thomas

    2005-12-27

    Thermodynamic analysis of urea-biopolymer interactions and effects of urea on folding of proteins and alpha-helical peptides shows that urea interacts primarily with polar amide surface. Urea is therefore predicted to be a quantitative probe of coupled folding, remodeling, and other large-scale changes in the amount of water-accessible polar amide surface in protein processes. A parallel analysis indicates that glycine betaine [N,N,N-trimethylglycine (GB)] can be used to detect burial or exposure of anionic (carboxylate, phosphate) biopolymer surface. To test these predictions, we have investigated the effects of these solutes (0-3 m) on the formation of 1:1 complexes between lac repressor (LacI) and its symmetric operator site (SymL) at a constant KCl molality. Urea reduces the binding constant K(TO) [initial slope dlnK(TO)/dm(urea) = -1.7 +/- 0.2], and GB increases K(TO) [initial slope dlnK(TO)/dm(GB) = 2.1 +/- 0.2]. For both solutes, this derivative decreases with an increase in solute concentration. Analysis of these initial slopes predicts that (1.5 +/- 0.3) x 10(3) A2 of polar amide surface and (4.5 +/- 1.0) x 10(2) A2 of anionic surface are buried in the association process. Analysis of published structural data, together with modeling of unfolded regions of free LacI as extended chains, indicates that 1.5 x 10(3) A2 of polar amide surface and 6.3 x 10(2) A2 of anionic surface are buried in complexation. Quantitative agreement between structural and thermodynamic results is obtained for amide surface (urea); for anionic surface (GB), the experimental value is approximately 70% of the structural value. For LacI-SymL binding, two-thirds of the structurally predicted change in amide surface (1.0 x 10(3) A2) occurs outside the protein-DNA interface in protein-protein interfaces formed by folding of the hinge helices and interactions of the DNA binding domain (DBD) with the core of the repressor. Since urea interacts principally with amide surface, it is

  10. Small molecular probes for G-protein-coupled C5a receptors: conformationally constrained antagonists derived from the C terminus of the human plasma protein C5a.

    PubMed

    Wong, A K; Finch, A M; Pierens, G K; Craik, D J; Taylor, S M; Fairlie, D P

    1998-08-27

    Activation of the human complement system of plasma proteins in response to infection or injury produces a 4-helix bundle glycoprotein (74 amino acids) known as C5a. C5a binds to G-protein-coupled receptors on cell surfaces triggering receptor-ligand internalization, signal transduction, and powerful inflammatory responses. Since excessive levels of C5a are associated with autoimmune and chronic inflammatory disorders, inhibitors of receptor activation may have therapeutic potential. We now report solution structures and receptor-binding and antagonist activities for some of the first small molecule antagonists of C5a derived from its hexapeptide C terminus. The antagonist NMe-Phe-Lys-Pro-D-Cha-Trp-D-Arg-CO2H (1) surprisingly shows an unusually well-defined solution structure as determined by 1H NMR spectroscopy. This is one of the smallest acyclic peptides found to possess a defined solution conformation, which can be explained by the constraining role of intramolecular hydrogen bonding. NOE and coupling constant data, slow deuterium exchange, and a low dependence on temperature for the chemical shift of the D-Cha-NH strongly indicate an inverse gamma turn stabilized by a D-Cha-NH. OC-Lys hydrogen bond. Smaller conformational populations are associated with a hydrogen bond between Trp-NH.OC-Lys, defining a type II beta turn distorted by the inverse gamma turn incorporated within it. An excellent correlation between receptor-affinity and antagonist activity is indicated for a limited set of synthetic peptides. Conversion of the C-terminal carboxylate of 1 to an amide decreases antagonist potency 5-fold, but potency is increased up to 10-fold over 1 if the amide bond is made between the C-terminal carboxylate and a Lys/Orn side chain to form a cyclic analogue. The solution structure of cycle 6 also shows gamma and beta turns; however, the latter occurs in a different position, and there are clear conformational changes in 6 vs 1 that result in enhanced activity