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Sample records for 1h-31p heteronuclear correlation

  1. Unique Backbone-Water Interaction Detected in Sphingomyelin Bilayers with 1H/31P and 1H/13C HETCOR MAS NMR Spectroscopy

    PubMed Central

    Holland, Gregory P.; Alam, Todd M.

    2008-01-01

    Two-dimensional 1H/31P dipolar heteronuclear correlation (HETCOR) magic-angle spinning nuclear magnetic resonance (NMR) is used to investigate the correlation of the lipid headgroup with various intra- and intermolecular proton environments. Cross-polarization NMR techniques involving 31P have not been previously pursued to a great extent in lipid bilayers due to the long 1H-31P distances and high degree of headgroup mobility that averages the dipolar coupling in the liquid crystalline phase. The results presented herein show that this approach is very promising and yields information not readily available with other experimental methods. Of particular interest is the detection of a unique lipid backbone-water intermolecular interaction in egg sphingomyelin (SM) that is not observed in lipids with glycerol backbones like phosphatidylcholines. This backbone-water interaction in SM is probed when a mixing period allowing magnetization exchange between different 1H environments via the nuclear Overhauser effect (NOE) is included in the NMR pulse sequence. The molecular information provided by these 1H/31P dipolar HETCOR experiments with NOE mixing differ from those previously obtained by conventional NOE spectroscopy and heteronuclear NOE spectroscopy NMR experiments. In addition, two-dimensional 1H/13C INEPT HETCOR experiments with NOE mixing support the 1H/31P dipolar HETCOR results and confirm the presence of a H2O environment that has nonvanishing dipolar interactions with the SM backbone. PMID:18390621

  2. Heteronuclear correlation spectroscopy in rotating solids

    NASA Astrophysics Data System (ADS)

    Caravatti, P.; Braunschweiler, L.; Ernst, R. R.

    1983-09-01

    Coherence transfer by an isotropic mixing process is used for two-dimensional heteronuclear shift correlation in magic-angle-spinning solid-state spectroscopy. Selective coherence transfer is combined with efficient homonuclear and heteronuclear dipolar decoupling to obtain well-resolved shift correlation spectra.

  3. Dynamic structures of intact chicken erythrocyte chromatins as studied by 1H-31P cross-polarization NMR.

    PubMed Central

    Akutsu, H; Nishimoto, S; Kyogoku, Y

    1994-01-01

    The dynamic properties of DNA in intact chicken erythrocyte cells, nuclei, nondigested chromatins, digested soluble chromatins, H1, H5-depleted soluble chromatins and nucleosome cores were investigated by means of single-pulse and 1H-31P cross-polarization NMR. The temperature dependence of the phosphorus chemical shift anisotropy was identical for the former three in the presence of 3 mM MgCl2, suggesting that the local higher order structure is identical for these chromatins. The intrinsic phosphorus chemical shift anisotropy of the nucleosome cores was -159 ppm. The chemical shift anisotropy of DNA in the chromatins can be further averaged by the motion of the linker DNA. The spin-lattice relaxation time in the rotating frame of the proton spins (T1p) of the nondigested chromatins was measured at various locking fields. The result was analyzed on the assumption of the isotropic motion to get a rough value of the correlation time of the motion efficient for the relaxation, which was eventually ascribed to the segmental motion of the linker DNA with restricted amplitude. The 30 nm filament structure induced by NaCl was shown to be dynamically different from that induced by MgCl2. Side-by-side compaction of 30-nm filaments was suggested to be induced in the MgCl2 concentration range higher than 0.3 mM. Biological significance of the dynamic structure was discussed in connection with the results obtained. PMID:7948693

  4. Evaluation of a New 1H/31P Dual-Tuned Birdcage Coil for 31P Spectroscopy

    PubMed Central

    Potter, WM; Wang, L; McCully, KK; Zhao, Q

    2013-01-01

    We introduce a new dual-tuned Hydrogen/Phosphorus (1H/31P) birdcage coil, referred to as split birdcage coil, and evaluate its performance using both simulations and magnetic resonance (MR) experiments on a 3 T MR scanner. The proposed coil simplifies the practical matters of tuning and matching, which makes the coil easily reproducible. Simulations were run with the Finite Difference in Time Domain (FDTD) method to evaluate the sensitivity and homogeneity of the magnetic field generated by the proposed 1H coils. Following simulations, MR experiments were conducted using both a phantom and human thigh to compare the proposed design with a currently available commercial dual-tuned flexible surface coil, referred to as flex surface coil, for signal to noise ratio (SNR) as well as homogeneity for the 31P coil. At regions deep within the human thigh, the split birdcage coil was able to acquire spectroscopic signal with a higher average SNR than the flex surface coil. For all regions except those close to the flex surface coil, the split birdcage coil matched or exceeded the performance of the flex surface coil. PMID:24039555

  5. High-resolution heteronuclear correlation spectroscopy based on spatial encoding and coherence transfer in inhomogeneous fields

    NASA Astrophysics Data System (ADS)

    Wang, Kaiyu; Zhang, Zhiyong; Chen, Hao; Cai, Shuhui; Chen, Zhong

    2015-11-01

    Two-dimensional (2D) nuclear magnetic resonance (NMR) spectroscopy has been proven to be a powerful technique for chemical, biological, and medical studies. Heteronuclear single quantum correlation (HSQC) and heteronuclear multiple bond correlation (HMBC) are two frequently used 2D NMR methods. In combination with spatially encoded techniques, a heteronuclear 2D NMR spectrum can be acquired in several seconds and may be applied to monitoring chemical reactions. However, it is difficult to obtain high-resolution NMR spectra in inhomogeneous fields. Inspired by the idea of tracing the difference of precession frequencies between two different spins to yield high-resolution spectra, we propose a method with correlation acquisition option and J-resolved-like acquisition option to ultrafast obtain high-resolution HSQC/HMBC spectra and heteronuclear J-resolved-like spectra in inhomogeneous fields.

  6. The Heteronuclear Single-Quantum Correlation (HSQC) Experiment: Vectors versus Product Operators

    ERIC Educational Resources Information Center

    de la Vega-Herna´ndez, Karen; Antuch, Manuel

    2015-01-01

    A vectorial representation of the full sequence of events occurring during the 2D-NMR heteronuclear single-quantum correlation (HSQC) experiment is presented. The proposed vectorial representation conveys an understanding of the magnetization evolution during the HSQC pulse sequence for those who have little or no quantum mechanical background.…

  7. Improving the resolution in proton-detected through-space heteronuclear multiple quantum correlation NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Shen, Ming; Trébosc, J.; Lafon, O.; Pourpoint, F.; Hu, Bingwen; Chen, Qun; Amoureux, J.-P.

    2014-08-01

    Connectivities and proximities between protons and low-gamma nuclei can be probed in solid-state NMR spectroscopy using two-dimensional (2D) proton-detected heteronuclear correlation, through Heteronuclear Multiple Quantum Correlation (HMQC) pulse sequence. The indirect detection via protons dramatically enhances the sensitivity. However, the spectra are often broadened along the indirect F1 dimension by the decay of heteronuclear multiple-quantum coherences under the strong 1H-1H dipolar couplings. This work presents a systematic comparison of the performances of various decoupling schemes during the indirect t1 evolution period of dipolar-mediated HMQC (D-HMQC) experiment. We demonstrate that 1H-1H dipolar decoupling sequences during t1, such as symmetry-based schemes, phase-modulated Lee-Goldburg (PMLG) and Decoupling Using Mind-Boggling Optimization (DUMBO), provide better resolution than continuous wave 1H irradiation. We also report that high resolution requires the preservation of 1H isotropic chemical shifts during the decoupling sequences. When observing indirectly broad spectra presenting numerous spinning sidebands, the D-HMQC sequence must be fully rotor-synchronized owing to the rotor-synchronized indirect sampling and dipolar recoupling sequence employed. In this case, we propose a solution to reduce artefact sidebands caused by the modulation of window delays before and after the decoupling application during the t1 period. Moreover, we show that 1H-1H dipolar decoupling sequence using Smooth Amplitude Modulation (SAM) minimizes the t1-noise. The performances of the various decoupling schemes are assessed via numerical simulations and compared to 2D 1H-{13C} D-HMQC experiments on [U-13C]-L-histidineṡHClṡH2O at various magnetic fields and Magic Angle spinning (MAS) frequencies. Great resolution and sensitivity enhancements resulting from decoupling during t1 period enable the detection of heteronuclear correlation between aliphatic protons and

  8. Characterization of active phosphorus surface sites at synthetic carbonate-free fluorapatite using single-pulse 1H, 31P, and 31P CP MAS NMR.

    PubMed

    Jarlbring, Mathias; Sandström, Dan E; Antzutkin, Oleg N; Forsling, Willis

    2006-05-01

    The chemically active phosphorus surface sites defined as PO(x), PO(x)H, and PO(x)H2, where x = 1, 2, or 3, and the bulk phosphorus groups of PO4(3-) at synthetic carbonate-free fluorapatite (Ca5(PO4)3F) have been studied by means of single-pulse 1H,31P, and 31P CP MAS NMR. The changes in composition and relative amounts of each surface species are evaluated as a function of pH. By combining spectra from single-pulse 1H and 31P MAS NMR and data from 31P CP MAS NMR experiments at varying contact times in the range 0.2-3.0 ms, it has been possible to distinguish between resonance lines in the NMR spectra originating from active surface sites and bulk phosphorus groups and also to assign the peaks in the NMR spectra to the specific phosphorus species. In the 31P CP MAS NMR experiments, the spinning frequency was set to 4.2 kHz; in the single-pulse 1H MAS NMR experiments, the spinning frequency was 10 kHz. The 31P CP MAS NMR spectrum of fluorapatite at pH 5.9 showed one dominating resonance line at 2.9 ppm assigned to originate from PO4(3-) groups and two weaker shoulder peaks at 5.4 and 0.8 ppm which were assigned to the unprotonated PO(x) (PO, PO2-, and PO3(2-)) and protonated PO(x)H (PO2H and PO3H-) surface sites. At pH 12.7, the intensity of the peak representing unprotonated PO(x) surface sites has increased 1.7% relative to the bulk peak, while the intensity of the peaks of the protonated species PO(x)H have decreased 1.4% relative to the bulk peak. At pH 3.5, a resonance peak at -4.5 ppm has appeared in the 31P CP MAS NMR spectrum assigned to the surface species PO(x)H2 (PO3H2). The results from the 1H MAS and 31P CP MAS NMR measurements indicated that H+, OH-, and physisorbed H2O at the surface were released during the drying process at 200 degrees C.

  9. Delineation of conformational preferences in human salivary statherin by 1H, 31P NMR and CD studies: sequential assignment and structure-function correlations.

    PubMed

    Naganagowda, G A; Gururaja, T L; Levine, M J

    1998-08-01

    Membrane-induced solution structure of human salivary statherin, a 43 amino acid residue acidic phosphoprotein, has been investigated by two-dimensional proton nuclear magnetic resonance (2D 1H NMR) spectroscopy. NMR assignments and structural analysis of this phosphoprotein was accomplished by analyzing the pattern of sequential and medium range NOEs, alphaCH chemical shift perturbations and deuterium exchange measurements of the amide proton resonances. The NMR data revealed three distinct structural motifs in the molecule: (1) an alpha-helical structure at the N-terminal domain comprising Asp1-Tyr16, (2) a polyproline type II (PPII) conformation predominantly occurring at the middle proline-rich domain spanning Gly19-Gln35, and (3) a 3(10)-helical structure at the C-terminal Pro36-Phe43 sequence. Presence of a few weak dalphaN(i,i+2) NOEs suggests that N-terminus also possesses minor population of 3(10)-helical conformation. Of the three secondary structural elements, helical structure formed by the N-terminal residues, Asp1-Ile11 appears to be more rigid as observed by the relatively very slow exchange of amide hydrogens of Glu5-Ile11. 31P NMR experiments clearly indicated that N-terminal domain of statherin exists mainly in disordered state in water whereas, upon addition of structure stabilizing co-solvent, 2,2,2-trifluorethanol (TFE), it showed a strong propensity for helical conformation. Calcium ion interaction studies suggested that the disordered N-terminal region encompassing the two vicinal phosphoserines is essential for the binding of calcium ions in vivo. Results from the circular dichroism (CD) experiments were found to be consistent with and complimentary to the NMR data and provided an evidence that non-aqueous environment such as TFE, could induce the protein to fold into helical conformation. The findings that the statherin possesses blended solvent sensitive secondary structural elements and the requirement of non-structured N-terminal region under aqueous environment in calcium ion interaction may be invaluable to understand various physiological functions of statherin in the oral fluid.

  10. Correlation effects in strong-field ionization of heteronuclear diatomic molecules

    NASA Astrophysics Data System (ADS)

    Larsson, H. R.; Bauch, S.; Sørensen, L. K.; Bonitz, M.

    2016-01-01

    We develop a time-dependent theory to investigate electron dynamics and photoionization processes of diatomic molecules interacting with strong laser fields including electron-electron correlation effects. We combine the recently formulated time-dependent generalized-active-space configuration interaction theory [D. Hochstuhl and M. Bonitz, Phys. Rev. A 86, 053424 (2012), 10.1103/PhysRevA.86.053424; S. Bauch et al., Phys. Rev. A 90, 062508 (2014), 10.1103/PhysRevA.90.062508] with a prolate spheroidal basis set including localized orbitals and continuum states to describe the bound electrons and the outgoing photoelectron. As an example, we study the strong-field ionization of the two-center four-electron lithium hydride molecule in different intensity regimes. By using single-cycle pulses, two orientations of the asymmetric heteronuclear molecule are investigated: Li-H, with the electrical field pointing from H to Li, and the opposite case of H-Li. The preferred orientation for ionization is determined and we find a transition from H-Li, for low intensity, to Li-H, for high intensity. The influence of electron correlations is studied at different levels of approximation, and we find a significant change in the preferred orientation. For certain intensity regimes, even an interchange of the preferred configuration is observed, relative to the uncorrelated simulations. Further insight is provided by detailed comparisons of photoelectron angular distributions with and without correlation effects taken into account.

  11. Proton-detected heteronuclear single quantum correlation NMR spectroscopy in rigid solids with ultra-fast MAS

    PubMed Central

    Holland, Gregory P.; Cherry, Brian R.; Jenkins, Janelle E.; Yarger, Jeffery L.

    2009-01-01

    In this article, we show the potential for utilizing proton-detected heteronuclear single quantum correlation (HSQC) NMR in rigid solids under ultra-fast magic angle spinning (MAS) conditions. The indirect detection of carbon-13 from coupled neighboring hydrogen nuclei provides a sensitivity enhancement of 3 - 4 fold in crystalline amino acids over direct-detected versions. Furthermore, the sensitivity enhancement is shown to be significantly larger for disordered solids that display inhomogeneously broadened carbon-13 spectra. Latrodectus hesperus (Black Widow) dragline silk is given as an example where the sample is mass-limited and the sensitivity enhancement for the proton-detected experiment is 8 - 13 fold. The ultra-fast MAS proton-detected HSQC solid-state NMR technique has the added advantage that no proton homonuclear decoupling is applied during the experiment. Further, well-resolved, indirectly observed carbon-13 spectra can be obtained in some cases without heteronuclear proton decoupling. PMID:19857977

  12. A different approach to multiplicity-edited heteronuclear single quantum correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Sakhaii, Peyman; Bermel, Wolfgang

    2015-10-01

    A new experiment for recording multiplicity-edited HSQC spectra is presented. In standard multiplicity-edited HSQC experiments, the amplitude of CH2 signals is negative compared to those of CH and CH3 groups. We propose to reverse the sign of 13C frequencies of CH2 groups in t1 as criteria for editing. Basically, a modified [BIRD]r,x element (Bilinear Rotation Pulses and Delays) is inserted in a standard HSQC pulse sequence with States-TPPI frequency detection in t1 for this purpose. The modified BIRD element was designed in such a way as to pass or stop the evolution of the heteronuclear 1JHC coupling. This is achieved by adding a 180° proton RF pulse in each of the 1/2J periods. Depending on their position the evolution is switched on or off. Usually, the BIRD- element is applied on real and imaginary increments of a HSQC experiment to achieve the editing between multiplicities. Here, we restrict the application of the modified BIRD element to either real or imaginary increments of the HSQC. With this new scheme for editing, changing the frequency and/or amplitude of the CH2 signals becomes available. Reversing the chemical shift axis for CH2 signals simplifies overcrowded frequency regions and thus avoids accidental signal cancellation in conventional edited HSQC experiments. The practical implementation is demonstrated on the protein Lysozyme. Advantages and limitations of the idea are discussed.

  13. Carbon-13 NMR in conformational analysis of nucleic acid fragments. Heteronuclear chemical shift correlation spectroscopy of RNA constituents.

    PubMed Central

    Lankhorst, P P; Erkelens, C; Haasnoot, C A; Altona, C

    1983-01-01

    The assignment of the non-quaternary 13C resonances by means of two-dimensional heteronuclear chemical shift correlation spectroscopy is presented for several oligoribonucleotides: The dimers m6(2)AU, m6(2)Am6(2)A and mpUm6(2)A and the trimers m6(2)AUm6(2)A and m4(2)Cm4(2)Cm6(2)A. The temperature and concentration dependency of the 13C chemical shifts are studied with emphasis on the behaviour of the dimer m6(2)AU. The present study shows that in the 5-50 mM range the concentration-dependent chemical shift changes of the ribose carbons are negligible compared to chemical shift changes due to intramolecular events. All compounds studied show a surprising correlation between the chemical shifts of the carbon atoms of the ribose ring and the sugar conformational equilibrium as expressed by the percentage N or S conformer. Thus the chemical shift data can be used to obtain the thermodynamical parameters of the two-state N/S equilibrium. Parameters deduced for m6(2)AU are Tm = 306 K and delta S = -25 cal mol-1 K-1, which values are in satisfactory agreement with results obtained earlier from 1H NMR and from Circular Dichroism. PMID:6195595

  14. Determination of size and sign of hetero-nuclear coupling constants from 2D 19F-13C correlation spectra

    NASA Astrophysics Data System (ADS)

    Ampt, Kirsten A. M.; Aspers, Ruud L. E. G.; Dvortsak, Peter; van der Werf, Ramon M.; Wijmenga, Sybren S.; Jaeger, Martin

    2012-02-01

    Fluorinated organic compounds have become increasingly important within the polymer and the pharmaceutical industry as well as for clinical applications. For the structural elucidation of such compounds, NMR experiments with fluorine detection are of great value due to the favorable NMR properties of the fluorine nucleus. For the investigation of three fluorinated compounds, triple resonance 2D HSQC and HMBC experiments were adopted to fluorine detection with carbon and/or proton decoupling to yield F-C, F-C{H}, F-C{Cacq} and F-C{H,Cacq} variants. Analysis of E.COSY type cross-peak patterns in the F-C correlation spectra led, apart from the chemical shift assignments, to determination of size and signs of the JCH, JCF, and JHF coupling constants. In addition, the fully coupled F-C HMQC spectrum of steroid 1 was interpreted in terms of E.COSY type patterns. This example shows how coupling constants due to different nuclei can be determined together with their relative signs from a single spectrum. The analysis of cross-peak patterns, as presented here, not only provides relatively straightforward routes to the determination of size and sign of hetero-nuclear J-couplings in fluorinated compounds, it also provides new and easy ways for the determination of residual dipolar couplings and thus for structure elucidation. The examples and results presented in this study may contribute to a better interpretation and understanding of various F-C correlation experiments and thereby stimulate their utilization.

  15. Studies of minute quantities of natural abundance molecules using 2D heteronuclear correlation spectroscopy under 100kHz MAS

    SciTech Connect

    Nishiyama, Y.; Kobayashi, T.; Malon, M.; Singappuli-Arachchige, D.; Slowing, I. I.; Pruski, M.

    2015-02-16

    Two-dimensional 1H{13C} heteronuclear correlation solid-state NMR spectra of naturally abundant solid materials are presented, acquired using the 0.75-mm magic angle spinning (MAS) probe at spinning rates up to 100 kHz. In spite of the miniscule sample volume (290 nL), high-quality HSQC-type spectra of bulk samples as well as surface-bound molecules can be obtained within hours of experimental time. The experiments are compared with those carried out at 40 kHz MAS using a 1.6-mm probe, which offered higher overall sensitivity due to a larger rotor volume. The benefits of ultrafast MAS in such experiments include superior resolution in 1H dimension without resorting to 1H–1H homonuclear RF decoupling, easy optimization, and applicability to mass-limited samples. As a result, the HMQC spectra of surface-bound species can be also acquired under 100 kHz MAS, although the dephasing of transverse magnetization has significant effect on the efficiency transfer under MAS alone.

  16. Studies of minute quantities of natural abundance molecules using 2D heteronuclear correlation spectroscopy under 100kHz MAS

    DOE PAGES

    Nishiyama, Y.; Kobayashi, T.; Malon, M.; Singappuli-Arachchige, D.; Slowing, I. I.; Pruski, M.

    2015-02-16

    Two-dimensional 1H{13C} heteronuclear correlation solid-state NMR spectra of naturally abundant solid materials are presented, acquired using the 0.75-mm magic angle spinning (MAS) probe at spinning rates up to 100 kHz. In spite of the miniscule sample volume (290 nL), high-quality HSQC-type spectra of bulk samples as well as surface-bound molecules can be obtained within hours of experimental time. The experiments are compared with those carried out at 40 kHz MAS using a 1.6-mm probe, which offered higher overall sensitivity due to a larger rotor volume. The benefits of ultrafast MAS in such experiments include superior resolution in 1H dimensionmore » without resorting to 1H–1H homonuclear RF decoupling, easy optimization, and applicability to mass-limited samples. As a result, the HMQC spectra of surface-bound species can be also acquired under 100 kHz MAS, although the dephasing of transverse magnetization has significant effect on the efficiency transfer under MAS alone.« less

  17. High resolution heteronuclear correlation NMR spectroscopy between quadrupolar nuclei and protons in the solid state

    NASA Astrophysics Data System (ADS)

    Goldbourt, A.; Vinogradov, E.; Goobes, G.; Vega, S.

    2004-08-01

    A high resolution two-dimensional solid state NMR experiment is presented that correlates half-integer quadrupolar spins with protons. In this experiment the quadrupolar nuclei evolve during t1 under a split-t1, FAM-enhanced MQMAS pulse scheme. After each t1 period ending at the MQMAS echo position, single quantum magnetization is transferred, via a cross polarization process in the mixing time, from the quadrupolar nuclei to the protons. High-resolution proton signals are then detected in the t2 time domain during wPMLG5* homonuclear decoupling. The experiment has been demonstrated on a powder sample of sodium citrate and 23Na- 1H 2D correlation spectra have been obtained. From the HETCOR spectra and the regular MQMAS spectrum, the three crystallographically inequivalent Na + sites in the asymmetric unit were assigned. This MQMAS- wPMLG HETCOR pulse sequence can be used for spectral editing of half-integer quadrupolar nuclei coupled to protons.

  18. Design of Heteronuclear Metalloenzymes.

    PubMed

    Bhagi-Damodaran, A; Hosseinzadeh, P; Mirts, E; Reed, J; Petrik, I D; Lu, Y

    2016-01-01

    Heteronuclear metalloenzymes catalyze some of the most fundamentally interesting and practically useful reactions in nature. However, the presence of two or more metal ions in close proximity in these enzymes makes them more difficult to prepare and study than homonuclear metalloenzymes. To meet these challenges, heteronuclear metal centers have been designed into small and stable proteins with rigid scaffolds to understand how these heteronuclear centers are constructed and the mechanism of their function. This chapter describes methods for designing heterobinuclear metal centers in a protein scaffold by giving specific examples of a few heme-nonheme bimetallic centers engineered in myoglobin and cytochrome c peroxidase. We provide step-by-step procedures on how to choose the protein scaffold, design a heterobinuclear metal center in the protein scaffold computationally, incorporate metal ions into the protein, and characterize the resulting metalloproteins, both structurally and functionally. Finally, we discuss how an initial design can be further improved by rationally tuning its secondary coordination sphere, electron/proton transfer rates, and the substrate affinity. PMID:27586347

  19. Long-range heteronuclear spin locking (HSL) and its application to peptide sequencing

    NASA Astrophysics Data System (ADS)

    Tokles, Maritherese; Hatvany, Gerard S.; Rinaldi, Peter L.

    In this paper, the utility of heteronuclear-spin-locking 2D NMR experiments for structure elucidation from long-range interactions is demonstrated. Long-range { 1H} 13C heteronuclear-shift-correlation spectra via spin locking provides peptide-sequencing information for gramicidin-S with considerably better sensitivity than was previously obtained with other long-range shift-correlation methods such as HOESY and COLOC.

  20. Enantiodiscrimination and extraction of short and long range homo- and hetero-nuclear residual dipolar couplings by a spin selective correlation experiment

    NASA Astrophysics Data System (ADS)

    Nath, Nilamoni; Suryaprakash, N.

    2010-08-01

    A two dimensional correlation experiment for the measurement of short and long range homo- and hetero- nuclear residual dipolar couplings (RDCs) from the broad and featureless proton NMR spectra including 13C satellites is proposed. The method employs a single natural abundant 13C spin as a spy nucleus to probe all the coupled protons and permits the determination of RDCs of negligible strengths. The technique has been demonstrated for the study of organic chiral molecules aligned in chiral liquid crystal, where additional challenge is to unravel the overlapped spectrum of enantiomers. The significant advantage of the method is demonstrated in better chiral discrimination using homonuclear RDCs as additional parameters.

  1. Amplitudes of protein backbone dynamics and correlated motions in a small alpha/beta protein: correspondence of dipolar coupling and heteronuclear relaxation measurements.

    PubMed

    Clore, G Marius; Schwieters, Charles D

    2004-08-24

    Backbone residual dipolar coupling (N-H, Calpha-Halpha, N-C', and Calpha-C') data collected in five different media on the B3 IgG binding domain of streptococcal protein G (GB3) have been analyzed by simultaneous refinement of the coordinates and optimization of the magnitudes and orientations of the alignment tensors using single and multiple structure representations. We show, using appropriate error analysis, that agreement between observed and calculated dipolar couplings at the level of experimental uncertainty is obtained with a two-structure (N(e) = 2) ensemble representation which represents the simplest equilibrium description of anisotropic motions. The data permit one to determine the magnitude of the anisotropic motions along the four different backbone bond vectors in terms of order parameters. The order parameters, , for the N-H bond vectors are in qualitative agreement with the generalized order parameters, S(2)NH(relaxation), derived from (15)N relaxation measurements, with a correlation coefficient of 0.84. S(2)NH(relaxation) can be regarded as the product of an anisotropic order parameter, corresponding to derived from the residual dipolar couplings, and an axially symmetric order parameter, S(2)NH(axial), corresponding to bond librations which are expected to be essentially uniform along the polypeptide chain. The current data indicate that the average value of S(2)NH(axial) is approximately 0.9. The close correspondence of and S(2)NH(relaxation) indicates that any large-scale displacements from the mean coordinate positions on time scales longer than the rotational correlation time are rare and hence do not perturb the observed dipolar couplings. Analysis of a set of 100 N(e) = 2 ensembles reveals the presence of some long-range correlated motions of N-H and Calpha-Halpha vectors involving residues far apart in the sequence but close together in space. In addition, direct evidence is

  2. Conditional rotations of heteronuclear coupled spins

    NASA Astrophysics Data System (ADS)

    O'Donnell, Lauren F.; Ridge, Clark D.; Walls, Jamie D.

    2015-01-01

    We present a new pulse sequence that conditionally excites I spin magnetization only in the presence of a nonzero heteronuclear coupling to an S spin. The pulse sequence, referred to as the reverse INEPT pathway selective pulse or RIPSP, generates a pure I spin rotation by an angle that depends upon the heteronuclear coupling constant in In S spin systems. Experimental demonstrations are shown in 13C labeled chloroform, dichloromethane, and toluene samples and in unlabeled 2,3-dibromopropionic acid and brucine samples.

  3. Photoassociative production of ultracold heteronuclear ytterbium molecules

    SciTech Connect

    Borkowski, Mateusz; Ciurylo, Roman; Yamazaki, Rekishu; Takahashi, Yoshiro; Hara, Hideaki; Taie, Shintaro; Sugawa, Seiji; Takasu, Yosuke; Enomoto, Katsunari

    2011-09-15

    We report observations of photoassociation (PA) spectra near the intercombination line in isotopic mixtures of ultracold ytterbium gases. Several heteronuclear bound states have been found for the excited {sup 170}Yb{sup 174}Yb and {sup 174}Yb{sup 176}Yb molecules. We develop a single-channel mass-scaled interaction model for the excited state molecule which well reproduces the measured bound state energies. This is an important step toward optical control of interactions in mixtures of ultracold ytterbium gases using heteronuclear optical Feshbach resonances. The model developed is applicable in collisions of other similar systems, such as cadmium and mercury.

  4. Applications of the heteronuclear Overhauser effect

    SciTech Connect

    Swiecinski, F.J.

    1986-01-01

    The nuclear Overhauser effect (NOE) is a change in the intensity of the nuclear magnetic resonance (NMR) signal of a nucleus, brought about by the saturation of the resonance of a neighboring nucleus. This phenomenon is dependent on the environment, motional dynamics, and the distance separating the two nuclei. Therefore, if enough is known about the environment and dynamics of the two nuclei, the distance between the two can be determined through measurement of the NOE. The proton homonuclear Overhauser effect experiment has become a standard means of determining relative proton-proton distances. The heteronuclear Overhauser effect, on the other hand, has been primarily used as a means of improving the signal to noise of the NMR spectra of nuclei which have gyromagnetic ratios which are the same sign as that of a proton, which is most often the saturated nucleus. The effect is also commonly used to distinguish between carbons which are bonded to hydrogen and quaternary carbons. A second application is the determination of the solution conformation of a metal cation-ionophore complex, Li-Lasalocid A, based on the results of the 2-D heteronuclear Overhauser effect experiment. Finally, the amino acid sequence of a small peptide. Gramicidin S, is determined by again making use of the 2-D heteronuclear Overhauser experiment.

  5. Ultracold Collisions Involving Heteronuclear Alkali Metal Dimers

    SciTech Connect

    Cvitas, Marko T.; Soldan, Pavel; Hutson, Jeremy M.; Honvault, Pascal; Launay, Jean-Michel

    2005-05-27

    We carry out the first quantum dynamics calculations on ultracold atom-diatom collisions in isotopic mixtures. The systems studied are spin-polarized {sup 7}Li+{sup 6}Li{sup 7}Li, {sup 7}Li+{sup 6}Li{sub 2}, {sup 6}Li+{sup 6}Li{sup 7}Li, and {sup 6}Li+{sup 7}Li{sub 2}. Reactive scattering can occur for the first two systems even when the molecules are in their ground rovibrational states, but is slower than vibrational relaxation in homonuclear systems. Implications for sympathetic cooling of heteronuclear molecules are discussed.

  6. Heteronuclear Multidimensional Protein NMR in a Teaching Laboratory

    ERIC Educational Resources Information Center

    Wright, Nathan T.

    2016-01-01

    Heteronuclear multidimensional NMR techniques are commonly used to study protein structure, function, and dynamics, yet they are rarely taught at the undergraduate level. Here, we describe a senior undergraduate laboratory where students collect, process, and analyze heteronuclear multidimensional NMR experiments using an unstudied Ig domain (Ig2…

  7. An effective field theory analysis of Efimov features in heteronuclear mixture of ultracold atomic gases

    NASA Astrophysics Data System (ADS)

    Acharya, Bijaya; Ji, Chen; Platter, Lucas

    2016-05-01

    Recent experimental studies have unveiled Efimov physics in ultracold atomic gases of heteronuclear mixtures. The recombination features of such atomic systems display universal correlations including discrete scaling invariance. We use Effective Field Theory (EFT) to study the Efimov features of the heteronuclear three-atom systems consisting of two identical bosons which interact with each other through a natural scattering length and with the third particle through a large scattering length. We compute the corrections to the universal correlations by perturbative insertions of the interspecies effective range and the intraspecies scattering length. Such an analysis is relevant for mixtures of ultracold atomic gases near the interspecies Feshbach resonance. Supported by the US Department of Energy under Contract No. DE-AC05-00OR22725 and the National Science Foundation under Grant No. PHY-1516077.

  8. Nonnuclear Attractors in Heteronuclear Diatomic Systems.

    PubMed

    Terrabuio, Luiz Alberto; Teodoro, Tiago Quevedo; Matta, Chérif F; Haiduke, Roberto Luiz Andrade

    2016-03-01

    Nonnuclear attractors (NNAs) are observed in the electron density of a variety of systems, but the factors governing their appearance and their contribution to the system's properties remain a mystery. The NNA occurring in homo- and heteronuclear diatomics of main group elements with atomic numbers up to Z = 38 is investigated computationally (at the UCCSD/cc-pVQZ level of theory) by varying internuclear separations. This was done to determine the NNA occurrence window along with the evolution of the respective pseudoatomic basin properties. Two distinct categories of NNAs were detected in the data analyzed by means of catastrophe theory. Type "a" implies electronic charge transfer between atoms mediated by a pseudoatom. Type "b" shows an initial relocation of some electronic charge to a pseudoatom, which posteriorly returns to the same atom that donated this charge in the first place. A small difference of polarizability between the atoms that compose these heteronuclear diatomics seems to favor NNA formation. We also show that the NNA arising tends to result in some perceptible effects on molecular dipole and/or quadrupole moment curves against internuclear distance. Finally, successive cationic ionization results in the fast disappearance of the NNA in Li2 indicating that its formation is mainly governed by the field generated by the quantum mechanical electronic density and only depends parametrically on the bare nuclear field/potential at a given molecular geometry. PMID:26842391

  9. Observation of Heteronuclear Atomic Efimov Resonances

    SciTech Connect

    Barontini, G.; Rabatti, F.; Thalhammer, G.; Weber, C.; Catani, J.; Inguscio, M.; Minardi, F.

    2009-07-24

    Building on the recent experimental observation with ultracold atoms, we report the first experimental evidence of Efimov physics in a heteronuclear system. A mixture of {sup 41}K and {sup 87}Rb atoms was cooled to few hundred nanokelvins and stored in an optical dipole trap. Exploiting a broad interspecies Feshbach resonance, the losses due to three-body collisions were studied as a function of the interspecies scattering length. We observe an enhancement of the three-body collisions for three distinct values of the interspecies scattering lengths, both positive and negative, where no Feshbach resonances are expected. We attribute the two features at negative scattering length to the existence of two kinds of Efimov trimers, KKRb and KRbRb.

  10. Heteronuclear compounds of arsenic and antimony

    NASA Astrophysics Data System (ADS)

    Mauser, James E.

    1982-09-01

    Volatilization of secondary metals such as arsenic, antimony, and bismuth, during the smelting of copper ores, is important because of environmental and resource considerations. The Bureau of Mines, United States Department of the Interior, has been studying copper concentrate roasting in conjunction with the volatility of these minor constituents. Some unusual vaporization behavior initiated this supplemental paper which shows that when the mixed sulfides of arsenic and antimony are heated, the volatilization of arsenic is retarded and the volatilization of antimony increased. Mixed oxides of arsenic and antimony also exhibit exceptional volatilization behavior. These anomalous vaporization behaviors are attributed to the formation of heteronuclear compounds of arsenic and antimony, but the colligative properties of solutions may also be a factor.

  11. A gradient scheme suitable for localized shimming and in vivo 1H/31P STEAM and ISIS NMR spectroscopy.

    PubMed

    Yongbi, N M; Payne, G S; Leach, M O

    1994-12-01

    A gradient scheme is presented which may be used for STEAM or ISIS localization. One application of the scheme is to perform single-shot STEAM shimming prior to data acquisition with STEAM and ISIS, using identical gradient amplitudes and durations. Using conventional STEAM to shim for ISIS can produce line-shape distortions induced by different eddy currents in the two sequences; with this gradient scheme the problem is minimized. Line-shape improvements of STEAM and ISIS localized data obtained after volume localized shimming with the proposed STEAM sequence are demonstrated. The localization performance of the STEAM and ISIS sequences are demonstrated on phantoms and in vivo for 1H and 31P metabolites. PMID:7869899

  12. Complementary shapes in columnar liquid crystals: Structural control in homo- and heteronuclear bimetallic assemblies

    SciTech Connect

    Serrette, A.G.; Lai, C.K.; Swager, T.M.

    1994-12-01

    A comprehensive study of the liquid-crystalline properties of 51 bimetallic compounds based upon 1,3,5-triketonate and 1,3,5,7-tetraketonate ligands is reported. These materials are liquid crystalline when six or more side chains are appended to the mesogenic core, and only columnar phases were observed. Most of the liquid crystals were homonuclear dicopper complexes. Schiff-base derivatives of some of the triketones allowed for the synthesis of heteronuclear bimetallic liquid crystals. The NiCu and NiPd Schiff-base complexes are the first heteronuclear liquid crystals with proximate (strongly interacting) metal centers. Other heteronuclear complexes investigated were not liquid crystalline due to the tendency to retain coordinated solvent or to form strongly associated structures in the absence of axial ligands. The use of complementary shapes was demonstrated as a means to generate average relative organizations (correlations) between the complexes. The presence of these correlated structures was shown through comparisons of the structures, phase behavior, and the immiscibility between materials having the same phase but different shapes. Correlated structures were shown which produce average rotations of 90{degrees} and 180{degrees} between nearest-neighbor molecules. A crystal structure of one compound confirmed that a similar superstructure was exhibited in the solid state. In addition, it was found that the correlated structures exhibit relatively short (3.29 {angstrom}) correlations between the mesogens, thereby allowing for strong intermolecular interactions. The ability to control the orientation and relative position of transition metal centers in liquid crystals has applications in the design of new liquid-crystalline materials with useful magnetic and electronic properties. 32 refs., 8 figs., 8 tabs.

  13. Heteronuclear ionizing collisions between laser-cooled metastable helium atoms

    SciTech Connect

    McNamara, J. M.; Stas, R. J. W.; Hogervorst, W.; Vassen, W.

    2007-06-15

    We have investigated cold ionizing heteronuclear collisions in dilute mixtures of metastable (2 {sup 3}S{sub 1}) {sup 3}He and {sup 4}He atoms, extending our previous work on the analogous homonuclear collisions [R. J. W. Stas et al., Phys. Rev. A 73, 032713 (2006)]. A simple theoretical model of such collisions enables us to calculate the heteronuclear ionization rate coefficient, for our quasiunpolarized gas, in the absence of resonant light (T=1.2 mK): K{sub 34}{sup (th)}=2.4x10{sup -10} cm{sup 3}/s. This calculation is supported by a measurement of K{sub 34} using magneto-optically trapped mixtures containing about 1x10{sup 8} atoms of each species, K{sub 34}{sup (exp)}=2.5(8)x10{sup -10} cm{sup 3}/s. Theory and experiment show good agreement.

  14. Heteronuclear Efimov Scenario with Positive Intraspecies Scattering Length

    NASA Astrophysics Data System (ADS)

    Ulmanis, Juris; Häfner, Stephan; Pires, Rico; Kuhnle, Eva D.; Wang, Yujun; Greene, Chris H.; Weidemüller, Matthias

    2016-10-01

    We investigate theoretically and experimentally the heteronuclear Efimov scenario for a three-body system that consists of two bosons and one distinguishable particle with positive intraspecies scattering lengths. The three-body parameter at the three-body scattering threshold and the scaling factor between consecutive Efimov resonances are found to be controlled by the scattering length between the two bosons, approximately independent of short-range physics. We observe two excited-state Efimov resonances in the three-body recombination spectra of an ultracold mixture of fermionic 6Li 6 and bosonic 113Cs atoms close to a Li-Cs Feshbach resonance, where the Cs-Cs interaction is positive. Deviation of the obtained scaling factor of 4.0(3) from the universal prediction of 4.9 and the absence of the ground state Efimov resonance shed new light on the interpretation of the universality and the discrete scaling behavior of heteronuclear Efimov physics.

  15. Heteronuclear DNP of protons and deuterons with TEMPOL.

    PubMed

    Kaminker, I; Shimon, D; Hovav, Y; Feintuch, A; Vega, S

    2016-04-28

    Dynamic nuclear polarization (DNP) experiments on samples with several types of magnetic nuclei sometimes exhibit "cross-talk" between the nuclei, such as different nuclei having DNP spectra with similar shapes and enhancements. In this work we demonstrate that while at 20 K the DNP spectra of (1)H and (2)H nuclei, in a sample composed of 50% v/v (1)H2O/DMSO-d6 and containing 40 mM TEMPOL, are different and can be analyzed using the indirect cross effect (iCE) model, at 6 K the DNP spectra of both (1)H and (2)H nuclei become identical. In addition we experimentally demonstrate that there exists an efficient polarization exchange between the two nuclear pools at this temperature. Both of these results are hallmark predictions of the thermal mixing (TM) formalism. However, the origin of these observations cannot, in our case, be explained using the standard TM formalism, as in our sample the electron reservoir cannot be described by a single non-Zeeman spin temperature, which is a prerequisite of TM. This conclusion follows from the analysis of the electron electron double resonance (ELDOR) experiments on our sample and is similar to the previously published results. Consequently, another mechanism must be used in order to explain these "cross-talk" effects. The heteronuclear cross effect (hnCE) DNP mechanism, previously introduced based on the simulations of the spin evolution in small model systems, results in "cross-talk" effects between two types of nuclei that are similar to the experimental ones seen in this work. In particular we show that the hnCE mechanism exhibits polarization transfer between the nuclei and that there exists a clear relationship between the steady state polarizations of the two types of nuclei which may, in the future, be correlated with the phenomenon observed in the two types of bulk nuclear signals in samples during DNP experiments. It is suggested that the hnCE electrons are a possible source for the process that equalizes the bulk

  16. Rapid screening for structural integrity of expressed proteins by heteronuclear NMR spectroscopy.

    PubMed Central

    Gronenborn, A. M.; Clore, G. M.

    1996-01-01

    A simple and rapid method based on 15N labeling and 1H-15N heteronuclear single quantum coherence spectroscopy is presented to directly assess the structural integrity of overexpressed proteins in crude Escherichia coli extracts without the need for any purification. The method is demonstrated using two different expression systems and two different proteins, the B1 immunoglobulin-binding domain of streptococcal protein G (56 residues) and human interleukin-1 beta (153 residues). It is shown that high quality 1H-15N correlation spectra, recorded in as little as 15 min and displaying only cross-peaks arising from the overexpressed protein of interest, can be obtained from crude E. coli extracts. PMID:8771212

  17. Heteronuclear J-coupling measurements in grossly inhomogeneous magnetic fields.

    PubMed

    Mandal, S; Song, Y-Q

    2015-06-01

    It is difficult to measure chemical shifts in the small and inhomogeneous magnetic fields found in ex situ and single-sided NMR systems, such as those used for well-logging. However, it is still possible to obtain chemical information from J-coupling constants, which are independent of static field strength and temperature. We describe and analyze (1)H-(13)C double-resonance pulse sequences that are suitable for measuring heteronuclear J-coupling in grossly inhomogeneous fields. We also present preliminary experimental results from a low-frequency fringe-field system. PMID:25898398

  18. Secondary structure and zinc ligation of human recombinant short-form stromelysin by multidimensional heteronuclear NMR.

    PubMed

    Gooley, P R; Johnson, B A; Marcy, A I; Cuca, G C; Salowe, S P; Hagmann, W K; Esser, C K; Springer, J P

    1993-12-01

    Stromelysin-1, a member of the matrix metalloendoprotease family, is a zinc protease involved in the degradation of connective tissue in the extracellular matrix. As a step toward determining the structure of this protein, multidimensional heteronuclear NMR experiments have been applied to an inhibited truncated form of human stromelysin-1. Extensive 1H, 13C, and 15N sequential assignments have been obtained with a combination of three- and four-dimensional experiments. On the basis of sequential and short-range NOEs and 13C alpha chemical shifts, two helices have been delineated, spanning residues Asp-111 to Val-127 and Leu-195 to Ser-206. A third helix spanning residues Asp-238 to Gly-247 is characterized by sequential NOEs and 13C alpha chemical shifts, but not short-range NOEs. The lack of the latter NOEs suggests that this helix is either distorted or mobile. Similarly, sequential and interstrand NOEs and 13C alpha chemical shifts characterize a four-stranded beta-sheet with three parallel strands (Arg-100 to Ile-101, Ile-142 to Ala-147, Asp-177 to Asp-181) and one antiparallel strand (Ala-165 to Tyr-168). Two zinc sites have been identified in stromelysin [Salowe et al. (1992) Biochemistry 31, 4535-4540]. The NMR spectral properties, including chemical shift, pH dependence, and proton coupling of the imidazole nitrogens of six histidine residues (151, 166, 179, 201, 205, and 211), invariant in the matrix metalloendoprotease family, suggest that these residues are zinc ligands. NOE data indicate that these histidines form two clusters: one ligates the catalytic zinc (His-201, -205, and -211), and the other ligates a structural zinc (His-151, -166, and -179). Heteronuclear multiple quantum correlated spectra and specific labeling experiments indicate His-151, -179, -201, -205, and -211 are in the N delta 1H tautomer and His-166 is in the N epsilon 2H tautomer. PMID:8241164

  19. Accurate determination of one-bond heteronuclear coupling constants with “pure shift” broadband proton-decoupled CLIP/CLAP-HSQC experiments

    NASA Astrophysics Data System (ADS)

    Timári, István; Kaltschnee, Lukas; Kolmer, Andreas; Adams, Ralph W.; Nilsson, Mathias; Thiele, Christina M.; Morris, Gareth A.; Kövér, Katalin E.

    2014-02-01

    We report broadband proton-decoupled CLIP/CLAP-HSQC experiments for the accurate determination of one-bond heteronuclear couplings and, by extension, for the reliable measurement of small residual dipolar coupling constants. The combination of an isotope-selective BIRD(d) filter module with a non-selective 1H inversion pulse is employed to refocus proton-proton coupling evolution prior to the acquisition of brief chunks of free induction decay that are subsequently assembled to reconstruct the fully-decoupled signal evolution. As a result, the cross-peaks obtained are split only by the heteronuclear one-bond coupling along the F2 dimension, allowing coupling constants to be extracted by measuring simple frequency differences between singlet maxima. The proton decoupling scheme presented has also been utilized in standard HSQC experiments, resulting in a fully-decoupled pure shift correlation map with significantly improved resolution.

  20. Frequency-Selective Heteronuclear Dephasing and Selective Carbonyl Labeling to Deconvolute Crowded Spectra of Membrane Proteins By Magic Angle Spinning NMR

    PubMed Central

    Traaseth, Nathaniel J.; Veglia, Gianluigi

    2011-01-01

    We present a new method that combines carbonyl-selective labeling with frequency-selective heteronuclear recoupling to resolve the spectral overlap of magic angle spinning (MAS) NMR spectra of membrane proteins in fluid lipid membranes with broad lines and high redundancy in the primary sequence. We implemented this approach in both heteronuclear 15N-13Cα and homonuclear 13C-13C dipolar assisted rotational resonance (DARR) correlation experiments. We demonstrate its efficacy for the membrane protein phospholamban reconstituted in fluid PC/PE/PA lipid bilayers. The main advantage of this method is to discriminate overlapped 13Cα resonances by strategically labeling the preceding residue. This method is highly complementary to 13C′i-1-15Ni-13Cαi and 13Cαi-1-15Ni-1-13C′i experiments to discriminate inter-residue spin systems at a minimal cost to signal-to-noise. PMID:21482162

  1. (15)N Heteronuclear Chemical Exchange Saturation Transfer MRI.

    PubMed

    Zeng, Haifeng; Xu, Jiadi; Yadav, Nirbhay N; McMahon, Michael T; Harden, Bradley; Frueh, Dominique; van Zijl, Peter C M

    2016-09-01

    A two-step heteronuclear enhancement approach was combined with chemical exchange saturation transfer (CEST) to magnify (15)N MRI signal of molecules through indirect detection via water protons. Previous CEST studies have been limited to radiofrequency (rf) saturation transfer or excitation transfer employing protons. Here, the signal of (15)N is detected indirectly through the water signal by first inverting selectively protons that are scalar-coupled to (15)N in the urea molecule, followed by chemical exchange of the amide proton to bulk water. In addition to providing a small sensitivity enhancement, this approach can be used to monitor the exchange rates and thus the pH sensitivity of the participating (15)N-bound protons. PMID:27548755

  2. Application of heteronuclear couplings to conformational analysis of oligonucleotides

    SciTech Connect

    Zhu, G.; Live, D.; Bax, A.

    1994-12-01

    The value of vicinal coupling constants extracted from NMR spectra in deducing torsion angles for conformational analysis is well recognized. Due to the abundance of protons, their couplings have been mostly widely used. In many instances, couplings between protons and other nuclei may be a valuable complement to proton-proton couplings or, in some instances, may be the only coupling available to characterize the torsion angle about a bond. Recently, heteronuclear couplings have been used to great benefit in studies of isotopically enriched proteins, and this general approach has been extended to peptides at natural abundance. The possibility of using this approach to study oligonucleotides is also attractive but has not as yet been widely exploited. With the development of strategies for labeling such molecules, particularly RNAs, this may become an important component in conformational analysis. For DNA, labeling is less accessible, but sufficient quantities of unlabeled material are readily available for measuring these couplings at natural abundance. We chose several DNA systems to explore the usefulness of heteronuclear couplings in addressing the sugar conformation and the glycosidic torsion angle. Intensities of cross peaks in long-range HMQC experiments can be related to the couplings. Crosspeaks involving H1{prime} and C1{prime} atoms have been emphasized because of the superior shift dispersion at these positions between sugar protons and carbon atoms. Results will be shown for the self-complementary Dickerson duplex dodecamer sequence d(CGCGAATTCGCG) and for d(GGTCGG), which dimerizes to form a G-tetrad structure incorporating both syn and anti base orientations. The couplings provide a clear discrimination between presence of C3{prime}-endo and C2{prime}-endo conformations of the sugars and syn and anti bases arrangements.

  3. Characterization and quantification of microstructures of a fluorinated terpolymer by both homonuclear and heteronuclear two-dimensional NMR spectroscopy.

    PubMed

    Ok, Salim

    2015-02-01

    Fluoropolymers are usually insoluble in organic solvents. Insolubility of fluoropolymers limits basic characterization such as microstructural investigations. In the family of fluoropolymers, terpolymer of tetrafluorethylene (TFE), hexafluoropropylene (HFP), and vinylidene fluoride (VDF), named THV is one of the newest members. There are nine grades of THV available. Among the nine grades, THV-221 G is an ideal model polymer for basic characterization purposes. THV-221 G is soluble in solvents such as acetone and ethyl acetate. In the current report, both homonuclear and heteronuclear 2D NMR experiments were employed in solution on THV-221 G. The homonuclear gradient correlation spectroscopy NMR measurement revealed that THV has two adjacent TFE units in addition to TFE-HFP sequence orders. The fraction of the microstructures is quantified by the analysis of 1D solution (19)F NMR spectrum. Further, the gradient heteronuclear single quantum coherence experiment helped with the clarification of chemical environments of the units TFE, HFP, and VDF. The 1D solution (13)C NMR spectrum was helpful in clarifying sequence assignments of VDF. It is concluded that THV is a random polymer with a limited fraction of TFE-TFE and TFE-HFP sequence orders in addition to head-to-tail polymerization of VDF unit.

  4. Determination of unresolved heteronuclear scalar coupling constants by J(up)-HSQMBC

    NASA Astrophysics Data System (ADS)

    Glanzer, Simon; Kunert, Olaf; Zangger, Klaus

    2016-07-01

    Long-range heteronuclear scalar coupling constants provide important structural information, which is necessary for obtaining stereospecific assignment or dihedral angle information. The measurement of small proton-carbon splittings is particularly difficult due to the low natural abundance of carbon-13 and the presence of homonuclear couplings of similar size. Here we present a real-time J-upscaled HSQMBC, which allows the measurement of heteronuclear coupling constants even if they are hidden in the signal linewidth of a regular spectrum.

  5. Equation of state for fluids of hard heteronuclear diatomic and symmetric triatomic molecules

    NASA Astrophysics Data System (ADS)

    Maeso, M. J.; Solana, J. R.

    1996-03-01

    A model previously developed for the equation of state of linear homonuclear fused hard sphere fluids is generalized to fluids with heteronuclear molecules. The model only requires two parameters, which can be determined from the geometrical characteristics of the molecules, for which analytical expressions are derived. Results for fluids with heteronuclear hard diatomic and symmetric triatomic molecules agree with simulation data within their accuracy for almost all the fluids considered.

  6. 4 T Actively detuneable double-tuned 1H/31P head volume coil and four-channel 31P phased array for human brain spectroscopy.

    PubMed

    Avdievich, N I; Hetherington, H P

    2007-06-01

    Typically 31P in vivo magnetic resonance spectroscopic studies are limited by SNR considerations. Although phased arrays can improve the SNR; to date 31P phased arrays for high-field systems have not been combined with 31P volume transmit coils. Additionally, to provide anatomical reference for the 31P studies, without removal of the coil or patient from the magnet, double-tuning (31P/1H) of the volume coil is required. In this work we describe a series of methods for active detuning and decoupling enabling use of phased arrays with double-tuned volume coils. To demonstrate these principles we have built and characterized an actively detuneable 31P/1H TEM volume transmit/four-channel 31P phased array for 4 T magnetic resonance spectroscopic imaging (MRSI) of the human brain. The coil can be used either in volume-transmit/array-receive mode or in TEM transmit/receive mode with the array detuned. Threefold SNR improvement was obtained at the periphery of the brain using the phased array as compared to the volume coil. PMID:17379554

  7. Simulating spin dynamics in organic solids under heteronuclear decoupling.

    PubMed

    Frantsuzov, Ilya; Ernst, Matthias; Brown, Steven P; Hodgkinson, Paul

    2015-09-01

    Although considerable progress has been made in simulating the dynamics of multiple coupled nuclear spins, predicting the evolution of nuclear magnetisation in the presence of radio-frequency decoupling remains challenging. We use exact numerical simulations of the spin dynamics under simultaneous magic-angle spinning and RF decoupling to determine the extent to which numerical simulations can be used to predict the experimental performance of heteronuclear decoupling for the CW, TPPM and XiX sequences, using the methylene group of glycine as a model system. The signal decay times are shown to be strongly dependent on the largest spin order simulated. Unexpectedly large differences are observed between the dynamics with and without spin echoes. Qualitative trends are well reproduced by modestly sized spin system simulations, and the effects of finite spin-system size can, in favourable cases, be mitigated by extrapolation. Quantitative prediction of the behaviour in complex parameter spaces is found, however, to be very challenging, suggesting that there are significant limits to the role of numerical simulations in RF decoupling problems, even when specialist techniques, such as state-space restriction, are used.

  8. Bruker AMX Y Channel Heteronuclear Decoupling Using a Linear Amplifier

    SciTech Connect

    Alam, Todd M.; Lang, David P.

    1999-08-02

    Under both static and common MAS conditions (< 15 kHz) the question of residual X-Y heteronuclear decoupling can become a complicating factor in the analysis of various NMR results. In our lab the impact of {sup 31}P-{sup 23}Na dipolar coupling on the observed {sup 23}Na M{sub 2} relaxation for a series of sodium phosphate glasses was recently investigated by employing continuous wave {sup 31}P decoupling during the entire pulse sequence. Initially these efforts were complicate by the inability to provide a gating pulse during the data acquisition using the standard Bruker nomenclature, go=2, for the acquisition loop. A pulse sequence to overcome these restrictions is given below. Our AMX400 instrument is configured with a 3 channel MCI, but utilizes a linear AMT amplifier on the 3rd channel (requiring gating pulse via the C4 program call during the entire time it is on). The standard acquisition loop has been replaced by direct adc and aq commands for data acquisition. Unlike the go=2 statement which does not allow a C4 gating command to be included, these individual acquisition commands can all include distinct C4 gating.

  9. Percolation of heteronuclear dimers irreversibly deposited on square lattices

    NASA Astrophysics Data System (ADS)

    Gimenez, M. C.; Ramirez-Pastor, A. J.

    2016-09-01

    The percolation problem of irreversibly deposited heteronuclear dimers on square lattices is studied. A dimer is composed of two segments, and it occupies two adjacent adsorption sites. Each segment can be either a conductive segment (segment type A ) or a nonconductive segment (segment type B ). Three types of dimers are considered: A A , B B , and A B . The connectivity analysis is carried out by accounting only for the conductive segments (segments type A ). The model offers a simplified representation of the problem of percolation of defective (nonideal) particles, where the presence of defects in the system is simulated by introducing a mixture of conductive and nonconductive segments. Different cases were investigated, according to the sequence of deposition of the particles, the types of dimers involved in the process, and the degree of alignment of the deposited objects. By means of numerical simulations and finite-size scaling analysis, the complete phase diagram separating a percolating from a nonpercolating region was determined for each case. Finally, the consistency of our results was examined by comparing with previous data in the literature for linear k -mers (particles occupying k adjacent sites) with defects.

  10. Further perspective on the theory of heteronuclear decoupling.

    PubMed

    Skinner, Thomas E

    2014-11-01

    An exact general theory of heteronuclear decoupling is presented for spin-1/2 IS systems. RF irradiation applied to the I spins both modifies and generates additional couplings between states of the system. The recently derived equivalence between the dynamics of any N-level quantum system and a system of classical coupled harmonic oscillators makes explicit the exact physical couplings between states. Decoupling is thus more properly viewed as a complex intercoupling. The sign of antiphase magnetization plays a fundamental role in decoupling. A one-to-one correspondence is demonstrated between ±2SyIz and the sense of the S-spin coupling evolution. Magnetization Sx is refocused to obtain the desired decoupled state when ∫2SyIzdt=0. The exact instantaneous coupling at any time during the decoupling sequence is readily obtained in terms of the system states, showing that the creation of two-spin coherence is crucial for reducing the effective scalar coupling, as required for refocusing to occur. Representative examples from new aperiodic sequences as well as standard cyclic, periodic composite-pulse and adiabatic decoupling sequences illustrate the decoupling mechanism. The more general aperiodic sequences, obtained using optimal control, realize the potential inherent in the theory for significantly improved decoupling.

  11. Cluster formation and phase separation in heteronuclear Janus dumbbells

    NASA Astrophysics Data System (ADS)

    Munaò, G.; O'Toole, P.; Hudson, T. S.; Costa, D.; Caccamo, C.; Sciortino, F.; Giacometti, A.

    2015-06-01

    We have recently investigated the phase behavior of model colloidal dumbbells constituted by two identical tangent hard spheres, with the first being surrounded by an attractive square-well interaction (Janus dumbbells, Munaó et al 2014 Soft Matter 10 5269). Here we extend our previous analysis by introducing in the model the size asymmetry of the hard-core diameters and study the enriched phase scenario thereby obtained. By employing standard Monte Carlo simulations we show that in such ‘heteronuclear Janus dumbbells’ a larger hard-sphere site promotes the formation of clusters, whereas in the opposite condition a gas-liquid phase separation takes place, with a narrow interval of intermediate asymmetries wherein the two phase behaviors may compete. In addition, some peculiar geometrical arrangements, such as lamellæ, are observed only around the perfectly symmetric case. A qualitative agreement is found with recent experimental results, where it is shown that the roughness of molecular surfaces in heterogeneous dimers leads to the formation of colloidal micelles.

  12. Further perspective on the theory of heteronuclear decoupling

    NASA Astrophysics Data System (ADS)

    Skinner, Thomas E.

    2014-11-01

    An exact general theory of heteronuclear decoupling is presented for spin-1/2 IS systems. RF irradiation applied to the I spins both modifies and generates additional couplings between states of the system. The recently derived equivalence between the dynamics of any N-level quantum system and a system of classical coupled harmonic oscillators makes explicit the exact physical couplings between states. Decoupling is thus more properly viewed as a complex intercoupling. The sign of antiphase magnetization plays a fundamental role in decoupling. A one-to-one correspondence is demonstrated between ± 2SyIz and the sense of the S-spin coupling evolution. Magnetization Sx is refocused to obtain the desired decoupled state when ∫ 2SyIz dt = 0 . The exact instantaneous coupling at any time during the decoupling sequence is readily obtained in terms of the system states, showing that the creation of two-spin coherence is crucial for reducing the effective scalar coupling, as required for refocusing to occur. Representative examples from new aperiodic sequences as well as standard cyclic, periodic composite-pulse and adiabatic decoupling sequences illustrate the decoupling mechanism. The more general aperiodic sequences, obtained using optimal control, realize the potential inherent in the theory for significantly improved decoupling.

  13. Determination of unresolved heteronuclear scalar coupling constants by J(up)-HSQMBC.

    PubMed

    Glanzer, Simon; Kunert, Olaf; Zangger, Klaus

    2016-07-01

    Long-range heteronuclear scalar coupling constants provide important structural information, which is necessary for obtaining stereospecific assignment or dihedral angle information. The measurement of small proton-carbon splittings is particularly difficult due to the low natural abundance of carbon-13 and the presence of homonuclear couplings of similar size. Here we present a real-time J-upscaled HSQMBC, which allows the measurement of heteronuclear coupling constants even if they are hidden in the signal linewidth of a regular spectrum. PMID:27183090

  14. Heteronuclear refocusing by nonlinear phase and amplitude modulation on a single transmitter channel

    NASA Astrophysics Data System (ADS)

    Moore, Jay; Colón, Raul D.; Tadanki, Sasidhar; Waddell, Kevin W.

    2014-08-01

    The application of low magnetic fields to heteronuclear NMR has expanded recently alongside the emergence of methods for achieving near unity polarization of spin ensembles, independent of magnetic field strength. The parahydrogen induced hyperpolarization methods in particular, often use a hybrid arrangement where a high field spectrometer is used to detect or image polarized molecules that have been conjured on a separate, dedicated polarizer instrument operating at fields in the mT regime where yields are higher. For controlling polarizer chemistry, spare TTL channels of portable NMR spectrometers can be used to pulse program reaction timings in synchrony with heteronuclear RF transformations. The use of a spectrometer as a portable polarizer control module has the advantage of allowing detection in situ, simplifying the process of optimizing polarization yields prior to in vivo experimental trials. Suitable heteronuclear spectrometers compatible with this application are becoming more common, but are still sparsely available in comparison to a large existing infrastructure of single channel NMR consoles. With the goal of expanding the range of these systems to multinuclear applications, the feasibility of rotating a pair of heteronuclear spins (13C and 1H) at 12 mT was investigated in this study. Nonlinear phase and amplitude modulated waveforms designed to simultaneously refocus magnetization at 128 kHz (13C) and 510 kHz (1H) were generated numerically with optimal control. Although precise quantitative comparisons were not attempted due to limitations of the experimental setup, signals refocused at heteronuclear frequencies with this PANORAMIC approach (Precession And Nutation for Observing Rotation At Multiple Intervals about the Carrier) yielded amplitudes comparable to signals which were refocused using traditional block pulses on heteronuclear channels. Using this PANORAMIC approach to heteronuclear NMR at low field would reduce expense as well as

  15. Characterization of heteronuclear decoupling through proton spin dynamics in solid-state nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    De Paëpe, Gaël; Eléna, Bénédicte; Emsley, Lyndon

    2004-08-01

    The work presented here aims at understanding the performance of phase modulated heteronuclear decoupling sequences such as Cosine Modulation or Two Pulse Phase Modulation. To that end we provide an analytical description of the intrinsic behavior of Cosine Modulation decoupling with respect to radio-frequency-inhomogeneity and the proton-proton dipolar coupling network. We discover through a Modulation Frame average Hamiltonian analysis that best decoupling is obtained under conditions where the heteronuclear interactions are removed but notably where homonuclear couplings are recoupled at a homonuclear Rotary Resonance (HORROR) condition in the Modulation Frame. These conclusions are supported by extensive experimental investigations, and notably through the introduction of proton nutation experiments to characterize spin dynamics in solids under decoupling conditions. The theoretical framework presented in this paper allows the prediction of the optimum parameters for a given set of experimental conditions.

  16. Long-Lived Heteronuclear Spin-Singlet States in Liquids at a Zero Magnetic field

    NASA Astrophysics Data System (ADS)

    Emondts, M.; Ledbetter, M. P.; Pustelny, S.; Theis, T.; Patton, B.; Blanchard, J. W.; Butler, M. C.; Budker, D.; Pines, A.

    2014-02-01

    We report an observation of long-lived spin-singlet states in a C-H113 spin pair in a zero magnetic field. In C13-labeled formic acid, we observe spin-singlet lifetimes as long as 37 s, about a factor of 3 longer than the T1 lifetime of dipole polarization in the triplet state. In contrast to common high-field experiments, the observed coherence is a singlet-triplet coherence with a lifetime T2 longer than the T1 lifetime of dipole polarization in the triplet manifold. Moreover, we demonstrate that heteronuclear singlet states formed between a H1 and a C13 nucleus can exhibit longer lifetimes than the respective triplet states even in the presence of additional spins that couple to the spin pair of interest. Although long-lived homonuclear spin-singlet states have been extensively studied, this is the first experimental observation of analogous singlet states in heteronuclear spin pairs.

  17. Measurement of Heteronuclear Dipolar Coupling by Transferred-Echo Double-Resonance NMR

    NASA Astrophysics Data System (ADS)

    Hing, A. W.; Vega, S.; Schaefer, J.

    A magic-angle spinning experiment called transferred-echo double resonance (TEDOR) has been introduced recently to measure the I-S dipolar coupling of heteronuclear I-S pairs of spin- {1}/{2} nuclei while eliminating unwanted background signals from uncoupled I and S spins via a coherence-transfer process. In this paper, a quantitative description of the TEDOR experiment is given in terms of the evolution of the density matrix for a pair of heteronuclear spins. The resulting equations provide a theoretical basis for evaluating the selectivity and sensitivity of TEDOR and suggest strategies for determining dipolar coupling constants directly from TEDOR data. Experimental examples illustrating these aspects of TEDOR are provided by studies performed on a range of 13C- 15N dipolar couplings found in double-labeled asparagine, alanine, glycine, and the linear peptide antibiotic, gramicidin.

  18. Long-range dispersion interactions. I. Formalism for two heteronuclear atoms

    SciTech Connect

    Zhang, J.-Y.; Mitroy, J.

    2007-08-15

    A general procedure for systematically evaluating the long-range dispersion interaction between two heteronuclear atoms in arbitrary states is outlined. The C{sub 6} dispersion parameter can always be written in terms of sum rules involving oscillator strengths only and formulas for a number of symmetry cases are given. The dispersion coefficients for excited alkali-metal atoms interacting with the ground-state H and He are tabulated.

  19. Resolution and measurement of heteronuclear dipolar couplings of a noncrystalline protein immobilized in a biological supramolecular assembly by proton-detected MAS solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Park, Sang Ho; Yang, Chen; Opella, Stanley J.; Mueller, Leonard J.

    2013-12-01

    Two-dimensional 15N chemical shift/1H chemical shift and three-dimensional 1H-15N dipolar coupling/15N chemical shift/1H chemical shift MAS solid-state NMR correlation spectra of the filamentous bacteriophage Pf1 major coat protein show single-site resolution in noncrystalline, intact-phage preparations. The high sensitivity and resolution result from 1H detection at 600 MHz under 50 kHz magic angle spinning using ∼0.5 mg of perdeuterated and uniformly 15N-labeled protein in which the exchangeable amide sites are partially or completely back-exchanged (reprotonated). Notably, the heteronuclear 1H-15N dipolar coupling frequency dimension is shown to select among 15N resonances, which will be useful in structural studies of larger proteins where the resonances exhibit a high degree of overlap in multidimensional chemical shift correlation spectra.

  20. Methodology for solid state NMR off-resonance study of molecular dynamics in heteronuclear systems.

    PubMed

    Jurga, Kazimierz; Woźniak-Braszak, Aneta; Baranowski, Mikołaj

    2015-10-01

    Methodology for the study of dynamics in heteronuclear systems in the laboratory frame was described in the previous paper [1]. Now the methodology for the study of molecular dynamics in the solid state heteronuclear systems in the rotating frame is presented. The solid state NMR off-resonance experiments were carried out on a homemade pulse spectrometer operating at the frequency of 30.2 MHz for protons. This spectrometer includes a specially designed probe which contains two independently tuned and electrically isolated coils installed in the coaxial position on the dewar. A unique probe design allows working at three slightly differing frequencies off and on resonance for protons and at the frequency of 28.411 MHz for fluorine nuclei with complete absence of their electrical interference. The probe allows simultaneously creating rf magnetic fields at off-resonance frequencies within the range of 30.2-30.6 MHz and at the frequency of 28.411 MHz. Presented heteronuclear cross-relaxation off-resonance experiments in the rotating frame provide information about molecular dynamics.

  1. A unified heteronuclear decoupling strategy for magic-angle-spinning solid-state NMR spectroscopy

    SciTech Connect

    Equbal, Asif; Bjerring, Morten; Nielsen, Niels Chr. E-mail: ncn@inano.au.dk; Madhu, P. K. E-mail: ncn@inano.au.dk

    2015-05-14

    A unified strategy of two-pulse based heteronuclear decoupling for solid-state magic-angle spinning nuclear magnetic resonance is presented. The analysis presented here shows that different decoupling sequences like two-pulse phase-modulation (TPPM), X-inverse-X (XiX), and finite pulse refocused continuous wave (rCW{sup A}) are basically specific solutions of a more generalized decoupling scheme which incorporates the concept of time-modulation along with phase-modulation. A plethora of other good decoupling conditions apart from the standard, TPPM, XiX, and rCW{sup A} decoupling conditions are available from the unified decoupling approach. The importance of combined time- and phase-modulation in order to achieve the best decoupling conditions is delineated. The consequences of different indirect dipolar interactions arising from cross terms comprising of heteronuclear and homonuclear dipolar coupling terms and also those between heteronuclear dipolar coupling and chemical-shift anisotropy terms are presented in order to unfold the effects of anisotropic interactions under different decoupling conditions. Extensive numerical simulation results are corroborated with experiments on standard amino acids.

  2. Avoiding bias effects in NMR experiments for heteronuclear dipole-dipole coupling determinations: principles and application to organic semiconductor materials.

    PubMed

    Kurz, Ricardo; Cobo, Marcio Fernando; de Azevedo, Eduardo Ribeiro; Sommer, Michael; Wicklein, André; Thelakkat, Mukundan; Hempel, Günter; Saalwächter, Kay

    2013-09-16

    Carbon-proton dipole-dipole couplings between bonded atoms represent a popular probe of molecular dynamics in soft materials or biomolecules. Their site-resolved determination, for example, by using the popular DIPSHIFT experiment, can be challenged by spectral overlap with nonbonded carbon atoms. The problem can be solved by using very short cross-polarization (CP) contact times, however, the measured modulation curves then deviate strongly from the theoretically predicted shape, which is caused by the dependence of the CP efficiency on the orientation of the CH vector, leading to an anisotropic magnetization distribution even for isotropic samples. Herein, we present a detailed demonstration and explanation of this problem, as well as providing a solution. We combine DIPSHIFT experiments with the rotor-directed exchange of orientations (RODEO) method, and modifications of it, to redistribute the magnetization and obtain undistorted modulation curves. Our strategy is general in that it can also be applied to other types of experiments for heteronuclear dipole-dipole coupling determinations that rely on dipolar polarization transfer. It is demonstrated with perylene-bisimide-based organic semiconductor materials, as an example, in which measurements of dynamic order parameters reveal correlations of the molecular dynamics with the phase structure and functional properties.

  3. Heteronuclear dipolar couplings, total spin coherence, and bilinear rotations in NMR spectroscopy

    SciTech Connect

    Garbow, J.R.

    1983-07-01

    In Chapter 1 a variety of different introductory topics are presented. The potential complexity of the nuclear magnetic resonsnace (NMR) spectra of molecules dissolved in liquid crystal solvents serves to motivate the development of multiple quantum (MQ) spectroscopy. The basics of MQ NMR are reviewed in Chapter 2. An experimental search procedure for the optimization of MQ pulse sequences is introduced. Chapter 3 discusses the application of MQ NMR techniques to the measurement of dipolar couplings in heteronuclear spin systems. The advantages of MQ methods in such systems are developed and experimental results for partially oriented (1-/sup 13/C) benzene are presented. Several pulse sequences are introduced which employ a two-step excitation of heteronuclear MQ coherence. A new multiple pulse method, involving the simultaneous irradiation of both rare and abundant spin species, is described. The problem of the broadening of MQ transitions due to magnetic field inhomogeneity is considered in Chapter 4. The method of total spin coherence transfer echo spectroscopy (TSCTES) is presented, with experimets on partially oriented acetaldehyde serving to demonstrate this new technique. TSCTES results in MQ spectra which are sensitive to all chemical shifts and spin-spin couplings and which are free of inhomogeneous broadening. In Chapter 5 the spectroscopy of spin systems of several protons and a /sup 13/C nucleus in the isotropic phase is discussed. The usefulness of the heteronuclear bilinear rotation as a calculational tool is illustrated. Compensated bilinear ..pi.. rotations, which are relatively insensitive to timing parameter missets, are presented. A new technique for homonuclear proton decoupling, Bilinear Rotation Decoupling, is described and its success in weakly coupled systems is demonstrated.

  4. Simulation of the off-resonance effect in one-dimensional heteronuclear multiple quantum coherence spectroscopy

    NASA Astrophysics Data System (ADS)

    Du, Fei; Zhou, Zhifa; Miao, Xijia; Mao, Xi-an

    2000-03-01

    When a heteronuclear multiple quantum coherence (HMQC) NMR experiment is performed in one-dimensional mode, due to the wide range in chemical shift of the indirectly detected spin and the limited strength of the radio-frequency field, the off-resonance effect on the intensity of the observed signal can be serious. In this paper, the effect is studied using the spin-density-matrix formalism and simulations of the experimental results are presented. The bilinear rotation-decoupling sequence (BIRD), which is usually used in HMQC experiments, is also discussed. It is shown that the BIRD sequence has a negative effect by virtue of narrowing the excitation band.

  5. Efficient generation of fusion neutrons from cryogenically cooled heteronuclear clusters irradiated by intense femtosecond lasers

    NASA Astrophysics Data System (ADS)

    Zhang, Hui; Lu, Haiyang; Li, Song; Xu, Yi; Guo, Xiaoyang; Leng, Yuxin; Liu, Jiansheng; Shen, Baifei; Li, Ruxin; Xu, Zhizhan

    2014-02-01

    We present experimental studies on the conversion efficiency of fusion neutrons generated from Coulomb explosion of cryogenically cooled heteronuclear deuterated methane (CD4) clusters irradiated by intense femtosecond laser pulses. A stronger nonlinear relationship between the cluster size and the stagnation temperature for CD4 clusters than that for monoatomic or diatomic clusters is revealed, resulting in marked increases in the average kinetic energy of deuterons and the fusion neutron yield. Finally, a significantly enhanced conversion efficiency of 1.9 × 107 neutrons/J of incident laser energy is achieved by lowering the stagnation temperature to 217 K under a backing pressure of 80 bars.

  6. Three Structural Roles for Water in Bone Observed by Solid-State NMR

    PubMed Central

    Wilson, Erin E.; Awonusi, Ayorinde; Morris, Michael D.; Kohn, David H.; Tecklenburg, Mary M. J.; Beck, Larry W.

    2006-01-01

    Hydrogen-bearing species in the bone mineral environment were investigated using solid-state NMR spectroscopy of powdered bone, deproteinated bone, and B-type carbonated apatite. Using magic-angle spinning and cross-polarization techniques three types of structurally-bound water were observed in these materials. Two of these water types occupy vacancies within the apatitic mineral crystal in synthetic carbonated apatite and deproteinated bone and serve to stabilize these defect-containing crystals. The third water was observed at the mineral surface in unmodified bone but not in deproteinated bone, suggesting a role for this water in mediating mineral-organic matrix interactions. Direct evidence of monohydrogen phosphate in a 1H NMR spectrum of unmodified bone is presented for the first time. We obtained clear evidence for the presence of hydroxide ion in deproteinated bone by 1H MAS NMR. A 1H-31P heteronuclear correlation experiment provided unambiguous evidence for hydroxide ion in unmodified bone as well. Hydroxide ion in both unmodified and deproteinated bone mineral was found to participate in hydrogen bonding with neighboring water molecules and ions. In unmodified bone mineral hydroxide ion was found, through a 1H-31P heteronuclear correlation experiment, to be confined to a small portion of the mineral crystal, probably the internal portion. PMID:16500963

  7. Achievement of 1 H-19 F heteronuclear experiments using the conventional spectrometer with a shared single high band amplifier.

    PubMed

    Sakuma, Chiseko; Kurita, Jun-ichi; Furihata, Kazuo; Tashiro, Mitsuru

    2015-05-01

    The (1)H-(19) F heteronuclear NMR experiments were achieved using the conventional spectrometer equipped with a single high band amplifier and a (1)H/(19)F/(13) C double-tuned probe. Although double high band amplifiers are generally required to perform such experiments, a simple modification of pathway in the conventional spectrometer was capable of acquiring various (1)H-(19)F heteronuclear spectra. The efficiency of the present technique was demonstrated in an application for (19)F{(1)H} and (1)H{(19)F} saturation transfer difference experiments. PMID:25808615

  8. Achievement of 1 H-19 F heteronuclear experiments using the conventional spectrometer with a shared single high band amplifier.

    PubMed

    Sakuma, Chiseko; Kurita, Jun-ichi; Furihata, Kazuo; Tashiro, Mitsuru

    2015-05-01

    The (1)H-(19) F heteronuclear NMR experiments were achieved using the conventional spectrometer equipped with a single high band amplifier and a (1)H/(19)F/(13) C double-tuned probe. Although double high band amplifiers are generally required to perform such experiments, a simple modification of pathway in the conventional spectrometer was capable of acquiring various (1)H-(19)F heteronuclear spectra. The efficiency of the present technique was demonstrated in an application for (19)F{(1)H} and (1)H{(19)F} saturation transfer difference experiments.

  9. Secondary structure and side-chain sup 1 H and sup 13 C resonance assignments of calmodulin in solution by heteronuclear multidimensional NMR spectroscopy

    SciTech Connect

    Ikura, Mitsuhiko; Spera, S.; Barbato, G.; Kay, L.E.; Bax, A. ); Krinks, M. )

    1991-09-24

    Heteronuclear 2D and 3D NMR experiments were carried out on recombinant Drosophila calmodulin (CaM), a protein of 148 residues and with molecular mass of 16.7 kDa, that is uniformly labeled with {sup 15}N and {sup 13}C to a level of > 95%. Nearly complete {sup 1}H and {sup 13}C side-chain assignments for all amino acid residues are obtained by using the 3D HCCH-COSY and HCCH-TOCSY experiments that rely on large heteronuclear one-bond scalar couplings to transfer magnetization and establish through-bond connectivities. The secondary structure of this protein in solution has been elucidated by a qualitative interpretation of nuclear Overhauser effects, hydrogen exchange data, and {sup 3}J{sub HNH{alpha}} coupling constants. A clear correlation between the {sup 13}C{alpha} chemical shift and secondary structure is found. The secondary structure in the two globular domains of Drosophila CaM in solution is essentially identical with that of the X-ray crystal structure of mammalian CaM which consists of two pairs of a helix-loop-helix motif in each globular domain. The existence of a short antiparallel {beta}-sheet between the two loops in each domain has been confirmed. The eight {alpha}-helix segments identified from the NMR data are located at Glu-6 to Phe-19, thr-29 to Ser-38, Glu-45 to Glu-54, Phe-65 to Lys-77, Glu-82 to Asp-93, Ala-102 to Asn-111, Asp-118 to Glu-127, and Tyr-138 to Thr-146. Although the crystal structure has a long central helix from Phe-65 to Phe-92 that connects the two globular domains, NMR data indicate that residues Asp-78 to Ser-81 of this central helix adopt a nonhelical conformation with considerable flexibility.

  10. Primitive models of chemical association. IV. Polymer Percus{endash}Yevick ideal-chain approximation for heteronuclear hard-sphere chain fluids

    SciTech Connect

    Kalyuzhnyi, Y.V. |; Lin, C.; Stell, G.

    1998-04-01

    We continue here our series of studies in which integral-equation theory is developed and used for the monomer-monomer correlation functions in a fluid of multicomponent freely jointed hard-sphere polymers. In this study our approach is based on Wertheim{close_quote}s polymer Percus{endash}Yevick (PPY) theory supplemented by the ideal-chain approximation; it can be regarded as a simplified version of Wertheim{close_quote}s four-density PPY approximation for associating fluids considered in the complete-association limit. The numerical procedure of this simplified theory is much easier than that of the original Wertheim{close_quote}s four-density PPY approximation, but the degree of accuracy is reduced. The theory can also be regarded as an extension of the PPY theory for the homonuclear polymer system proposed by Chang and Sandler [J. Chem. Phys. {bold 102}, 437 (1995)]. Their work is based upon a description of a system of hard-sphere monomers that associate into a polydisperse system of chains of prescribed mean length. Our theory instead directly describes a multicomponent system of associating monomers that form monodisperse chains of prescribed length upon complete association. An analytical solution of the PPY ideal-chain approximation for the general case of a multicomponent mixture of heteronuclear hard-sphere linear chain molecules is given. Its use is illustrated by numerical results for two models of copolymer fluids, a symmetrical diblock copolymer system, and an alternating copolymer system. The comparison with Monte Carlo simulations is given to gauge the accuracy of the theory. We find for the molecules we study here that predictions of our theory for heteronuclear chain systems have the same degree of accuracy as Chang and Sandler{close_quote}s theory for homonuclear chain systems. {copyright} {ital 1998 American Institute of Physics.}

  11. Hydrothermal liquefaction oil and hydrotreated product from pine feedstock characterized by heteronuclear two-dimensional NMR spectroscopy and FT-ICR mass spectrometry

    SciTech Connect

    Sudasinghe, Nilusha; Cort, John R.; Hallen, Richard; Olarte, Mariefel; Schmidt, Andrew; Schaub, Tanner

    2014-12-01

    Hydrothermal liquefaction (HTL) crude oil and hydrotreated product from pine tree farm waste (forest product residual, FPR) have been analyzed by direct infusion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) in both positive- and negative-ionization modes and high-resolution twodimensional heteronuclear 1H-13C NMR spectroscopy. FT-ICR MS resolves thousands of compounds in complex oils and provides unparalleled compositional details for individual molecules for identification of compound class (heteroatom content), type (number of rings plus double bonds to carbon or double bond equivalents (DBE) and carbon number (degree of alkylation). Heteronuclear 1H-13C NMR spectroscopy provides one-bond and multiple-bond correlations between pairs of 1H and 13C chemical shifts that are characteristic of different organic functional groups. Taken together this information provides a picture of the chemical composition of these oils. Pyrolysis crude oil product from pine wood was characterized for comparison. Generally, pyrolysis oil is comprised of a more diverse distribution of heteroatom classes with higher oxygen number relative to HTL oil as shown by both positive- and negative-ion ESI FT-ICR MS. A total of 300 N1, 594 O1 and 267 O2 compounds were observed as products of hydrotreatment. The relative abundance of N1O1, N1O2, N1O3, N2, N2O1, N2O2 and O3 compounds are reduced to different degrees after hydrotreatment and other higher heteroatom containing species (O4-O10, N1O4, N1O5 and N2O3) are completely removed by hydrotreatment.

  12. Band-selective heteronuclear dipolar recoupling with dual back-to-back pulses in rotating solids

    NASA Astrophysics Data System (ADS)

    Zhang, Zhengfeng; Chen, Yanke; Yang, Jun

    2016-11-01

    We propose a robust band-selective heteronuclear 15N-13C recoupling method using dual back-to-back (BABA) pulses (DBP). It contains four 90° pulses in each rotor period and corresponding phase cycling on each channel (13C and 15N). DBP aims at rapid band-selective heteronuclear magnetization transfer between 15N and 13Cα/13C‧, whose efficiency is close to that of the well-known SPECIFIC CP in membrane proteins with relatively short relaxation time in rotating frame (T1ρ). Compared to SPECIFIC CP, DBP is very simple to set up and highly robust to RF variations. Thus, it can reduce the efforts in experimental optimization, especially for low-sensitive samples, and is very suitable for long-time or quantitative experiments. The efficacy of DBP is demonstrated by the E. coli diacylglycerol kinase (DAGK) proteoliposome. We anticipate that DBP would be useful for (segments of) membrane proteins that undergo the μs-ms timescale motions in magic-angle spinning (MAS) solid-state NMR.

  13. Effective-field-theory analysis of Efimov physics in heteronuclear mixtures of ultracold atomic gases

    NASA Astrophysics Data System (ADS)

    Acharya, Bijaya; Ji, Chen; Platter, Lucas

    2016-09-01

    We use an effective-field-theory framework to analyze the Efimov effect in heteronuclear three-body systems consisting of two species of atoms with a large interspecies scattering length. In the leading-order description of this theory, various three-body observables in heteronuclear mixtures can be universally parametrized by one three-body parameter. We present the next-to-leading corrections, which include the effects of the finite interspecies effective range and the finite intraspecies scattering length, to various three-body observables. We show that only one additional three-body parameter is required to render the theory predictive at this order. By including the effective range and intraspecies scattering length corrections, we derive a set of universal relations that connect the different Efimov features near the interspecies Feshbach resonance. Furthermore, we show that these relations can be interpreted in terms of the running of the three-body counterterms that naturally emerge from proper renormalization. Finally, we make predictions for recombination observables of a number of atomic systems that are of experimental interest.

  14. Interaction-induced decay of a heteronuclear two-atom system

    PubMed Central

    Xu, Peng; Yang, Jiaheng; Liu, Min; He, Xiaodong; Zeng, Yong; Wang, Kunpeng; Wang, Jin; Papoular, D. J.; Shlyapnikov, G. V.; Zhan, Mingsheng

    2015-01-01

    Two-atom systems in small traps are of fundamental interest for understanding the role of interactions in degenerate cold gases and for the creation of quantum gates in quantum information processing with single-atom traps. One of the key quantities is the inelastic relaxation (decay) time when one of the atoms or both are in a higher hyperfine state. Here we measure this quantity in a heteronuclear system of 87Rb and 85Rb in a micro optical trap and demonstrate experimentally and theoretically the presence of both fast and slow relaxation processes, depending on the choice of the initial hyperfine states. This experimental method allows us to single out a particular relaxation process thus provides an extremely clean platform for collisional physics studies. Our results have also implications for engineering of quantum states via controlled collisions and creation of two-qubit quantum gates. PMID:26199051

  15. Equation of state for fluid mixtures of hard spheres and heteronuclear hard dumbbells

    NASA Astrophysics Data System (ADS)

    Barrio, C.; Solana, J. R.

    1999-09-01

    A theoretically founded equation of state is developed for mixtures of hard spheres with heteronuclear hard dumbbells. It is based on a model previously developed for hard-convex-body fluid mixtures, and further extended to fluid mixtures of homonuclear hard dumbbells. The equation scales the excess compressibility factor for an equivalent hard-sphere fluid mixture to obtain that corresponding to the true mixture. The equivalent mixture is one in which the averaged volume of a sphere is the same as the effective molecular volume of a molecule in the real mixture. Thus, the theory requires two parameters, namely the averaged effective molecular volume of the molecules in the mixture and the scaling factor, which is the effective nonsphericity parameter. Expressions to determine these parameters are derived in terms of the geometrical characteristics of the molecules that form the mixture. The overall results are in closer agreement with simulation data than those obtained with other theories developed for these kinds of mixtures.

  16. Energetics and Control of Ultracold Isotope-Exchange Reactions between Heteronuclear Dimers in External Fields

    NASA Astrophysics Data System (ADS)

    Tomza, Michał

    2015-08-01

    We show that isotope-exchange reactions between ground-state alkali-metal, alkaline-earth-metal, and lanthanide heteronuclear dimers consisting of two isotopes of the same atom are exothermic with an energy change in the range of 1-8000 MHz, thus resulting in cold or ultracold products. For these chemical reactions, there are only one rovibrational and at most several hyperfine possible product states. The number and energetics of open and closed reactive channels can be controlled by the laser and magnetic fields. We suggest a laser-induced isotope- and state-selective Stark shift control to tune the exothermic isotope-exchange reactions to become endothermic, thus providing the ground for testing models of the chemical reactivity. The present proposal opens the way for studying the state-to-state dynamics of ultracold chemical reactions beyond the universal limit with a meaningful control over the quantum states of both reactants and products.

  17. Heteronuclear decoupling in MAS NMR in the intermediate to fast sample spinning regime

    NASA Astrophysics Data System (ADS)

    Equbal, Asif; Bjerring, Morten; Sharma, Kshama; Madhu, P. K.; Nielsen, Niels Chr.

    2016-01-01

    Heteronuclear spin decoupling in solid-state magic-angle spinning NMR is investigated to present methods overcoming interferences between rf irradiation and sample spinning in the intermediate to fast spinning regime. We demonstrate that a recent phase-alternated variant of refocused CW irradiation (rCWApA) provides efficient and robust decoupling in this regime. An extensive experimental and numerical comparison is presented for rCWApA and PISSARRO (phase-inverted supercycled sequence for attenuation of rotary resonance), previously introduced to quench rotary-resonance recoupling effects, under conditions with spinning frequencies between 30 and 60 kHz. Simulations are used to identify the effect of decoupling for various nuclear spin interactions.

  18. Energetics and Control of Ultracold Isotope-Exchange Reactions between Heteronuclear Dimers in External Fields.

    PubMed

    Tomza, Michał

    2015-08-01

    We show that isotope-exchange reactions between ground-state alkali-metal, alkaline-earth-metal, and lanthanide heteronuclear dimers consisting of two isotopes of the same atom are exothermic with an energy change in the range of 1-8000 MHz, thus resulting in cold or ultracold products. For these chemical reactions, there are only one rovibrational and at most several hyperfine possible product states. The number and energetics of open and closed reactive channels can be controlled by the laser and magnetic fields. We suggest a laser-induced isotope- and state-selective Stark shift control to tune the exothermic isotope-exchange reactions to become endothermic, thus providing the ground for testing models of the chemical reactivity. The present proposal opens the way for studying the state-to-state dynamics of ultracold chemical reactions beyond the universal limit with a meaningful control over the quantum states of both reactants and products.

  19. Spatially selective heteronuclear multiple-quantum coherence (HMQC) spectroscopy for bio-molecular NMR studies

    PubMed Central

    Sathyamoorthy, Bharathwaj; Parish, David M.; Montelione, Gaetano T.; Xiao, Rong; Szyperski, Thomas

    2014-01-01

    Spatially selective heteronuclear multiple-quantum coherence (SS HMQC) NMR spectroscopy was devised for solution studies of proteins. Due to ‘time-staggered’ acquisition of free induction decays (FIDs) in different slices, SS HMQC allows one to employ long delays for longitudinal nuclear spin relaxation at high repetition rates for the acquisition of the FIDs. To also achieve high intrinsic sensitivity, SS HMQC was implemented by combing a single spatially selective 1H excitation pulse with non-selective 1H 180° pulses. High-quality spectra could be obtained within 66 seconds for a 7.6 kDa uniformly 13C,15N-labeled protein, and within 45 and 90 seconds for, respectively, two uniformly 2H,13C,15N-labeled but isoleucine, leucine and valine methyl group protonated proteins with molecular weights of 7.5 and 43 kDa. PMID:24789578

  20. Epitope mapping of antigenic MUC1 peptides to breast cancer antibody fragment B27.29: a heteronuclear NMR study.

    PubMed

    Grinstead, Jeffrey S; Schuman, Jason T; Campbell, A Patricia

    2003-12-01

    MUC1 mucin is a breast cancer-associated transmembrane glycoprotein, of which the extracellular domain is formed by the repeating 20-amino acid sequence GVTSAPDTRPAPGSTAPPAH. In neoplastic breast tissue, the highly immunogenic sequence PDTRPAP (in bold above) is exposed. Antibodies raised directly against MUC1-expressing tumors offer unique access to this neoplastic state, as they represent immunologically relevant "reverse templates" of the tumor-associated mucin. In a previous study [Grinstead, J. S., et al. (2002) Biochemistry 41, 9946-9961], (1)H NMR methods were used to correlate the effects of cryptic glycosylation outside of the PDTRPAP core epitope sequence on the recognition and binding of Mab B27.29, a monoclonal antibody raised against breast tumor cells. In the study presented here, isotope-edited NMR methods, including (15)N and (13)C relaxation measurements, were used to probe the recognition and binding of the PDTRPAP epitope sequence to Fab B27.29. Two peptides were studied: a one-repeat MUC1 16mer peptide of the sequence GVTSAPDTRPAPGSTA and a two-repeat MUC1 40mer peptide of the sequence (VTSAPDTRPAPGSTAPPAHG)(2). (15)N and (13)C NMR relaxation parameters were measured for both peptides free in solution and bound to Fab B27.29. The (13)C(alpha) T(1) values best represent changes in the local correlation time of the peptide epitope upon binding antibody, and demonstrate that the PDTRPAP sequence is immobilized in the antibody-combining site. This result is also reflected in the appearance of the (15)N- and (13)C-edited HSQC spectra, where line broadening of the same peptide epitope resonances is observed. The PDTRPAP peptide epitope expands upon the peptide epitope identified previously in our group as PDTRP by homonuclear NMR experiments [Grinstead, J. S., et al. (2002) Biochemistry 41, 9946-9961], and illustrates the usefulness of the heteronuclear NMR experiments. The implications of these results are discussed within the context of MUC1 breast

  1. Accurate heteronuclear J-coupling measurements in dilute spin systems using the multiple-quantum filtered J-resolved experiment.

    PubMed

    Martineau, Charlotte; Fayon, Franck; Legein, Christophe; Buzaré, Jean-Yves; Silly, Gilles; Massiot, Dominique

    2007-07-14

    A new solid-state MAS NMR experiment is proposed to accurately measure heteronuclear (19)F-(207)Pb J-coupling constants, even though these couplings are not visible on high speed (19)F 1D MAS spectra; in particular, we demonstrate that the J-resolved experiment combined with scalar multiple-quantum filtering considerably improves the resolution of J-multiplet patterns for dilute spin systems. PMID:17594032

  2. Cyclometalated heteronuclear Pt/Ag and Pt/Tl complexes: a structural and photophysical study.

    PubMed

    Jamali, Sirous; Ghazfar, Reza; Lalinde, Elena; Jamshidi, Zahra; Samouei, Hamidreza; Shahsavari, Hamid R; Moreno, M Teresa; Escudero-Adán, Eduardo; Benet-Buchholz, Jordi; Milic, Dalibor

    2014-01-21

    To investigate the factors influencing the luminescent properties of polymetallic cycloplatinated complexes a detailed study of the photophysical and structural properties of the heteronuclear complexes [Pt2Me2(bhq)2(μ-dppy)2Ag2(μ-acetone)](BF4)2, 2, [PtMe(bhq)(dppy)Tl]PF6, 3, and [Pt2Me2(bhq)2(dppy)2Tl]PF6, 4, [bhq = benzo[h]quinoline, dppy = 2-(diphenylphosphino)pyridine] was conducted. Complexes 3 and 4 synthesized by the reaction of [PtMe(bhq)(dppy)], 1, with TlPF6 (1 or 1/2 equiv.) and stabilized by unsupported Pt-Tl bonds as revealed by multinuclear NMR spectroscopy and confirmed by X-ray crystallography for 3. DFT calculations for the previously reported butterfly Pt2Ag2 cluster 2 reveal that in the optimized geometry the bridging acetone molecule is removed and the metal core displays a planar-shaped geometry in which according to a QTAIM calculation and natural bond orbital (NBO) analysis the Ag···Ag metallophilic interaction is strengthened. In contrast to the precursor 1, which is only emissive in glassy solutions ((3)MLCT 485 nm), all 2-4 heteropolynuclear complexes display intense emissions in the solid state and in glassy solutions. Time-dependent density functional theory (TD-DFT) is used to elucidate the origin of the electronic transitions in the heteronuclear complexes 2 and 3. The low energy absorption and intense orange emission for cluster 2 (solid 77 K and glass) are attributed to metal-metal to ligand charge transfer (MM'LCT) with a minor L'LCT contribution. For 3 and 4 two different bands are developed: the high energy band (602-630 nm) observed for 4 at 77 K (solid, glass) and in diluted glasses for 3 is ascribed to emission from discrete Pt2Tl units of mixed (3)L'LCT/(3)LM'CT origin. However, the low energy band (670-690 nm) observed at room temperature (solid) for both complexes and also in concentrated glasses for 3 is assigned to (3)ππ excited states arising from intermolecular interactions. PMID:24165802

  3. Dressed-bound-state molecular strong-field approximation: Application to above-threshold ionization of heteronuclear diatomic molecules

    SciTech Connect

    Hasovic, E.; Busuladzic, M.; Becker, W.; Milosevic, D. B.

    2011-12-15

    The molecular strong-field approximation (MSFA), which includes dressing of the molecular bound state, is introduced and applied to above-threshold ionization of heteronuclear diatomic molecules. Expressions for the laser-induced molecular dipole and polarizability as functions of the laser parameters (intensity and frequency) and molecular parameters [molecular orientation, dipole, and parallel and perpendicular polarizabilities of the highest occupied molecular orbital (HOMO)] are presented. Our previous MSFA theory, which incorporates the rescattering effects, is generalized from homonuclear to heteronuclear diatomic molecules. Angle- and energy-resolved high-order above-threshold ionization spectra of oriented heteronuclear diatomic molecules, exemplified by the carbon monoxide (CO) molecule, exhibit pronounced minima, which can be related to the shape of their HOMO-electron-density distribution. For the CO molecule we have found an analytical condition for the positions of these minima. We have also shown that the effect of the dressing of the HOMO is twofold: (i) the laser-induced Stark shift decreases the ionization yield and (ii) the laser-induced time-dependent dipole and polarizability change the oscillatory structure of the spectra.

  4. Heteronuclear Cross-Relaxation Effects in the NMR Spectroscopy of Hyperpolarized Targets

    PubMed Central

    Donovan, Kevin J.; Lupulescu, Adonis; Frydman, Lucio

    2016-01-01

    Dissolution DNP enables high-sensitivity solution phase NMR experiments on long-lived nuclear spin species such as 15N and 13C. This report explores certain features arising in solution-state 1H NMR, upon polarizing low-γ nuclear species. Following solid state hyperpolarization of both 13C and 1H, solution-phase 1H NMR experiments on dissolved samples revealed transient effects whereby peaks arising from protons bonded to the naturally-occurring 13C nuclei, appeared larger than the typically dominant 12C-bonded 1H resonances. This enhancement of the satellite-peaks was examined in detail, with respect to a variety of mechanisms that could potentially originate it. Both two- and three-spin phenomena active in the solid state could lead to this kind of effect; still, experimental observations revealed that the enhancement originates from 13C→1H polarization transfer processes active in the liquid state. Kinetic equations based on modified heteronuclear cross-relaxation models were examined, and found to describe well the distinct patterns of growth and decay shown by the 13C-bound 1H NMR satellite resonances. The dynamics of these novel cross-relaxation phenomena were determined, and their potential usefulness as tools for investigating hyperpolarized ensembles and for obtaining enhanced-sensitivity 1H NMR traces, is explored. PMID:24403222

  5. Solution structure of pleckstrin homology domain of dynamin by heteronuclear NMR spectroscopy.

    PubMed Central

    Fushman, D; Cahill, S; Lemmon, M A; Schlessinger, J; Cowburn, D

    1995-01-01

    The pleckstrin homology (PH) domain is a recognition motif thought to be involved in signal-transduction pathways controlled by a variety of cytoplasmic proteins. Assignments of nearly all 1H, 13C, and 15N resonances of the PH domain from dynamin have been obtained from homonuclear and heteronuclear NMR experiments. The secondary structure has been elucidated from the pattern of nuclear Overhauser enhancements, from 13C chemical shift deviations, and from observation of slowly exchanging amide hydrogens. The secondary structure contains one alpha-helix and eight beta-strands, seven of which are arranged in two contiguous, antiparallel beta-sheets. The structure is monomeric, in contrast to the well-defined intimate dimerization of the crystal structure of this molecule. Residues possibly involved in ligand binding are in apparently flexible loops. Steady-state 15N(1H) nuclear Overhauser effect measurements indicate unequivocally the boundaries of this PH domain, and the structured portion of the domain appears to be more extended to the C terminus than previously suggested for other PH domains. Images Fig. 3 PMID:7846058

  6. NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning

    NASA Astrophysics Data System (ADS)

    Shmyreva, Anna A.; Safdari, Majid; Furó, István; Dvinskikh, Sergey V.

    2016-06-01

    Orders of magnitude decrease of 207Pb and 199Hg NMR longitudinal relaxation times T1 upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX2 (Me = Pb, Hg and X = Cl, Br, I). In lead(ii) halides, the most dramatic decrease of T1 relative to that in a static sample is in PbI2, while it is smaller but still significant in PbBr2, and not detectable in PbCl2. The effect is magnetic-field dependent but independent of the spinning speed in the range 200-15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.

  7. NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning.

    PubMed

    Shmyreva, Anna A; Safdari, Majid; Furó, István; Dvinskikh, Sergey V

    2016-06-14

    Orders of magnitude decrease of (207)Pb and (199)Hg NMR longitudinal relaxation times T1 upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX2 (Me = Pb, Hg and X = Cl, Br, I). In lead(ii) halides, the most dramatic decrease of T1 relative to that in a static sample is in PbI2, while it is smaller but still significant in PbBr2, and not detectable in PbCl2. The effect is magnetic-field dependent but independent of the spinning speed in the range 200-15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.

  8. Observation of Resonant Effects in Ultracold Collisions between Heteronuclear Feshbach Molecules

    NASA Astrophysics Data System (ADS)

    Ye, Xin; Wang, Fudong; Zhu, Bing; Guo, Mingyang; Lu, Bo; Wang, Dajun

    2016-05-01

    Magnetic field dependent dimer-dimer collisional losses are studied with ultracold 23 Na87 Rb Feshbach molecules. By ramping the magnetic field across the 347.8 G inter-species Feshbach resonance and removing residual atoms with a magnetic field gradient, ~ 8000 pure NaRb Feshbach molecules with a temperature below 1 μK are produced. By holding the pure molecule sample in a crossed optical dipole trap and measuring the time-dependent loss curves under different magnetic fields near the Feshbach resonance, the dimer-dimer loss rates with respect to the atomic scattering length a are mapped out. We observe a resonant feature at around a = 600a0 and a rising tail at above a = 1600a0 . This behavior resembles previous theoretical works on homonuclear Feshbach molecule, where resonant effects between dimer-dimer collisions tied to tetramer bound states were predicted. Our work shows the possibility of exploring four-body physics within a heteronuclear system. We are supported by Hong Kong RGC General Research Fund no. CUHK403813.

  9. Heteronuclear Adiabatic Relaxation Dispersion (HARD) for quantitative analysis of conformational dynamics in proteins

    NASA Astrophysics Data System (ADS)

    Traaseth, Nathaniel J.; Chao, Fa-An; Masterson, Larry R.; Mangia, Silvia; Garwood, Michael; Michaeli, Shalom; Seelig, Burckhard; Veglia, Gianluigi

    2012-06-01

    NMR relaxation methods probe biomolecular motions over a wide range of timescales. In particular, the rotating frame spin-lock R1ρ and Carr-Purcell-Meiboom-Gill (CPMG) R2 experiments are commonly used to characterize μs to ms dynamics, which play a critical role in enzyme folding and catalysis. In an effort to complement these approaches, we introduced the Heteronuclear Adiabatic Relaxation Dispersion (HARD) method, where dispersion in rotating frame relaxation rate constants (longitudinal R1ρ and transverse R2ρ) is created by modulating the shape and duration of adiabatic full passage (AFP) pulses. Previously, we showed the ability of the HARD method to detect chemical exchange dynamics in the fast exchange regime (kex ˜ 104-105 s-1). In this article, we show the sensitivity of the HARD method to slower exchange processes by measuring R1ρ and R2ρ relaxation rates for two soluble proteins (ubiquitin and 10C RNA ligase). One advantage of the HARD method is its nominal dependence on the applied radio frequency field, which can be leveraged to modulate the dispersion in the relaxation rate constants. In addition, we also include product operator simulations to define the dynamic range of adiabatic R1ρ and R2ρ that is valid under all exchange regimes. We conclude from both experimental observations and simulations that this method is complementary to CPMG-based and rotating frame spin-lock R1ρ experiments to probe conformational exchange dynamics for biomolecules. Finally, this approach is germane to several NMR-active nuclei, where relaxation rates are frequency-offset independent.

  10. Heteronuclear cross-polarization in multinuclear multidimensional NMR: Prospects for triple-resonance CP

    SciTech Connect

    Majumdar, A.; Zuiderweg, E.R.P.

    1994-12-01

    Heteronuclear multiple-pulse-based Cross Polarization (HECP) between scalar coupled spins is gaining an important role in high-resolution multidimensional NMR of isotopically labeled biomolecules, especially in experiments involving net magnetization transfer. It has generally been observed that in these situations, the performance of HECP is superior to that of INEPT-based sequences. In particular, HECP-based three-dimensional HCCH spectroscopy is more efficient than the INEPT version of the same experiment. Differences in sensitivity have been intuitively attributed to relaxation effects and technical factors such as radiofrequency (rf) inhomogeneity We present theoretical analyses and computer simulations to probe the effects of these factors. Relaxation effects were treated phenomenologically; we found that relaxation differences are relatively small (up to 25%) between pulsed-free-precession (INEPT) and HECP-although always in favor of HECP. We explored the rf effects by employing a Gaussian distribution of rf amplitude over sample volume. We found that inhomogeneity effects significantly favor HECP over INEPT, especially under conditions of {open_quotes}matched {close_quotes} inhomogeneity in the two rf coils. The differences in favor of HECP indicate that an extension of HECP to triple resonance experiments (TRCP) in I -> S -> Q net transfers might yield better results relative to analogous INEPT-based net transfers. We theoretically analyze the possibilities of TRCP and find that transfer functions are critically dependent on the ratio J{sub IS}/J{sub SQ}. When J{sub IS} equals J{sub SQ}, we find that 100% transfer is possible for truly simultaneous TRCP and this transfer is obtained in a time 1.41 /J. The TRCP time requirement compares favorably with optimally concatenated INEPT-transfers, where net transfer I -> S -> Q is complete at 1.5 /J.

  11. Structural studies of the activation of the two component receiver domain NTRC by multidimensional heteronuclear NMR

    SciTech Connect

    Nohaile, M J

    1996-05-01

    Multidimensional heteronuclear NMR spectroscopy was used to investigate the N-terminal domain of the transcriptional enhancer NTRC (NiTrogen Regulatory protein C). This domain belongs to the family of receiver domains of two-component regulatory systems involved in signal transduction. Phosphorylation of NTRC at D54 leads to an activated form of the molecule which stimulates transcription of genes involved in nitrogen regulation. Three and four dimensional NMR techniques were used to determine an intermediate resolution structure of the unphosphorylated, inactive form of the N-terminal domain of NTRC. The structure is comprised of five {alpha}-helices and a five-stranded {beta}-sheet in a ({beta}/{alpha}){sub 5} topology. Analysis of the backbone dynamics of NTRC indicate that helix 4 and strand 5 are significantly more flexible than the rest of the secondary structure of the protein and that the loops making up the active site are flexible. The short lifetime of phospho-NTRC hampers the study of this form. However, conditions for determining the resonance assignments and, possibly, the three dimensional structure of phosphorylated NTRC have been obtained. Tentative assignments of the phosphorylated form indicate that the majority of the changes that NTRC experiences upon phosphorylation occur in helix 3, strand 4, helix 4, strand 5, and the loop between strand 5 and helix 5 (the 3445 face of NTRC) as well as near the site of phosphorylation. In order to examine a stable, activated form of the protein, constitutively active mutants of NTRC were investigated.

  12. Efficient heteronuclear decoupling in MAS solid-state NMR using non-rotor-synchronized rCW irradiation.

    PubMed

    Equbal, Asif; Paul, Subhradip; Mithu, Venus Singh; Madhu, P K; Nielsen, Niels Chr

    2014-09-01

    We present new non-rotor-synchronized variants of the recently introduced refocused continuous wave (rCW) heteronuclear decoupling method significantly improving the performance relative to the original rotor-synchronized variants. Under non-rotor-synchronized conditions the rCW decoupling sequences provide more efficient decoupling, are easier to setup, and prove more robust towards experimental parameters such as radio frequency (rf) field amplitude and spinning frequency. This is demonstrated through numerical simulations substantiated with experimental results under different sample spinning and rf field amplitude conditions for powder samples of U-(13)C-glycine and U-(13)C-L-histidine·HCl·H2O. PMID:25123538

  13. ELECTRONIC AND CHEMICAL PROPERTIES OF PD IN BIMETALLIC SYSTEMS: HOW MUCH DO WE KNOW ABOUT HETERONUCLEAR METAL-METAL BONDING?

    SciTech Connect

    RODRIGUEZ,J.A.

    2001-09-27

    The experimental and theoretical studies described above illustrate the complex nature of the heteronuclear metal-metal bond. In many cases, bimetallic bonding induces a significant redistribution of charge around the bonded metals. This redistribution of charge is usually linked to the strength of the bimetallic bond, affects the position of the core and valence levels of the metals, and can determine the chemical reactivity of the system under study. New concepts are emerging [22,23,34,36] and eventually the coupling of experiment and theory can be useful for designing more efficient bimetallic catalysts [98,106,107].

  14. Tautomeric states of the active-site histidines of phosphorylated and unphosphorylated IIIGlc, a signal-transducing protein from Escherichia coli, using two-dimensional heteronuclear NMR techniques.

    PubMed Central

    Pelton, J. G.; Torchia, D. A.; Meadow, N. D.; Roseman, S.

    1993-01-01

    IIIGlc is an 18.1-kDa signal-transducing phosphocarrier protein of the phosphoenolpyruvate:glycose phosphotransferase system from Escherichia coli. The 1H, 15N, and 13C histidine ring NMR signals of both the phosphorylated and unphosphorylated forms of IIIGlc have been assigned using two-dimensional 1H-15N and 1H-13C heteronuclear multiple-quantum coherence (HMQC) experiments and a two-dimensional 13C-13C-1H correlation spectroscopy via JCC coupling experiment. The data were acquired on uniformly 15N-labeled and uniformly 15N/13C-labeled protein samples. The experiments rely on one-bond and two-bond J couplings that allowed for assignment of the signals without the need for the analysis of through-space (nuclear Overhauser effect spectroscopy) correlations. The 15N and 13C chemical shifts were used to determine that His-75 exists predominantly in the N epsilon 2-H tautomeric state in both the phosphorylated and unphosphorylated forms of IIIGlc, and that His-90 exists primarily in the N delta 1-H state in the unphosphorylated protein. Upon phosphorylation of the N epsilon 2 nitrogen of His-90, the N delta 1 nitrogen remains protonated, resulting in the formation of a charged phospho-His-90 moiety. The 1H, 15N, and 13C signals of the phosphorylated and unphosphorylated proteins showed only minor shifts in the pH range from 6.0 to 9.0. These data indicate that the pK alpha values for both His-75 and His-90 in IIIGlc and His-75 in phospho-IIIGlc are less than 5.0, and that the pK alpha value for phospho-His-90 is greater than 10. The results are presented in relation to previously obtained structural data on IIIGlc, and implications for proposed mechanisms of phosphoryl transfer are discussed. PMID:8518729

  15. Solid-State P and H NMR Investigations of Amorphous and Crystalline Calcium Phosphates Grown Biomimetically From a Mesoporous Bioactive Glass.

    PubMed

    Mathew, Renny; Gunawidjaja, Philips N; Izquierdo-Barba, Isabel; Jansson, Kjell; García, Ana; Arcos, Daniel; Vallet-Regí, María; Edén, Mattias

    2011-10-27

    By exploiting (1)H and (31)P magic-angle spinning nuclear magnetic resonance (NMR) spectroscopy, we explore the proton and orthophosphate environments in biomimetic amorphous calcium phosphate (ACP) and hydroxy-apatite (HA), as grown in vitro at the surface of a 10CaO-85SiO(2)-5P(2)O(5) mesoporous bioactive glass (MBG) in either a simulated body fluid or buffered water. Transmission electron microscopy confirmed the presence of a calcium phosphate layer comprising nanocrystalline HA. Two-dimensional (1)H-(31)P heteronuclear correlation NMR established predominantly (1)H(2)O↔(31)PO(4) (3-) and O(1)H↔(31)PO(4) (3-) contacts in the amorphous and crystalline component, respectively, of the MBG surface-layer; these two pairs exhibit distinctly different (1)H→(31)P cross-polarization dynamics, revealing a twice as large squared effective (1)H-(31)P dipolar coupling constant in ACP compared with HA. These respective observations are mirrored in synthetic (well-crystalline) HA, and the amorphous calcium orthophosphate (CaP) clusters that are present in the pristine MBG pore walls: besides highlighting very similar local (1)H and (31)P environments in synthetic and biomimetic HA, our findings evidence closely related NMR characteristics, and thereby similar local structures, of the CaP clusters in the pristine MBG relative to biomimetic ACP.

  16. Homonuclear and Heteronuclear NMR Studies of a Statherin Fragment Bound to Hydroxyapatite Crystals

    SciTech Connect

    Raghunathan, Vinodhkumar; Gibson, James M.; Goobes, Gil; Popham, Jennifer M.; Louie, Elizabeth; Stayton, Patrick; Drobny, Gary P.

    2006-05-11

    Acidic proteins found in mineralized tissues act as nature's crystal engineers, where they play a key role in promoting or inhibiting the growth of minerals such as hydroxyapatite (HAP), Ca10(PO4)6(OH)2, the main mineral component of bone and teeth. Key to understanding the structural basis of protein-crystal recognition and protein control of hard tissue growth is the nature of interactions between the protein side chains and the crystal surface. In an earlier work we have measured the proximity of the lysine (K6) side chain in an SN-15 peptide fragment of the salivary protein statherin adsorbed to the Phosphorus-rich surface of HAP using solid-state NMR recoupling experiments. 15N(31P) rotational echo double resonance (REDOR) NMR data on the side-chain nitrogen in K6 gave rise to three different models of protein-surface interaction to explain the experimental data acquired. In this work we extend the analysis of the REDOR data by examining the contribution of interactions between surface phosphorus atoms to the observed 15N REDOR decay. We performed 31P-31P recoupling experiments in HAP and (NH4)2HPO4 (DHP) to explore the nature of dipolar coupled 31P spin networks. These studies indicate that extensive networks of dipolar coupled 31P spins can be represented as stronger effective dipolar couplings, the existence of which must be included in the analysis of REDOR data. We carried out 15N(31P) REDOR in the case of DHP to determine how the size of the dephasing spin network influences the interpretation of the REDOR data. Although use of an extended 31P coupled spin network simulates the REDOR data well, a simplified 31P dephasing system composed of two spins with a larger dipolar coupling also simulates the REDOR data and only perturbs the heteronuclear couplings very slightly. The 31P-31P dipolar couplings between phosphorus nuclei in HAP can be replaced by an effective dipolar interaction of 600 Hz between two 31P spins. We incorporated this coupling and

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

    PubMed

    Basse, Kristoffer; Shankar, Ravi; Bjerring, Morten; Vosegaard, Thomas; Nielsen, Niels Chr; Nielsen, Anders B

    2016-09-01

    We present a theoretical analysis of the influence of chemical shifts on amplitude-modulated heteronuclear dipolar recoupling experiments in solid-state NMR spectroscopy. The method is demonstrated using the Rotor Echo Short Pulse IRrAdiaTION mediated Cross-Polarization ((RESPIRATION)CP) experiment as an example. By going into the pulse sequence rf interaction frame and employing a quintuple-mode operator-based Floquet approach, we describe how chemical shift offset and anisotropic chemical shift affect the efficiency of heteronuclear polarization transfer. In this description, it becomes transparent that the main attribute leading to non-ideal performance is a fictitious field along the rf field axis, which is generated from second-order cross terms arising mainly between chemical shift tensors and themselves. This insight is useful for the development of improved recoupling experiments. We discuss the validity of this approach and present quaternion calculations to determine the effective resonance conditions in a combined rf field and chemical shift offset interaction frame transformation. Based on this, we derive a broad-banded version of the (RESPIRATION)CP experiment. The new sequence is experimentally verified using SNNFGAILSS amyloid fibrils where simultaneous (15)N → (13)CO and (15)N → (13)Cα coherence transfer is demonstrated on high-field NMR instrumentation, requiring great offset stability. PMID:27608995

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

    NASA Astrophysics Data System (ADS)

    Basse, Kristoffer; Shankar, Ravi; Bjerring, Morten; Vosegaard, Thomas; Nielsen, Niels Chr.; Nielsen, Anders B.

    2016-09-01

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

  19. Directly and indirectly detected through-bond heteronuclear correlation solid-state NMR spectroscopy under fast MAS

    SciTech Connect

    Mao, Kanmi; Pruski, Marek

    2009-09-10

    Two-dimensional through-bond {sup 1}H({sup 13}C) solid-state NMR experiments utilizing fast magic angle spinning (MAS) and homonuclear multipulse {sup 1}H decoupling are presented. Remarkable efficiency of polarization transfer can be achieved at MAS rates exceeding 40 kHz, which is instrumental in these measurements. Schemes utilizing direct and indirect detection of heteronuclei are compared in terms of resolution and sensitivity. A simple procedure for optimization of {sup 1}H homonuclear decoupling sequences under these conditions is proposed. The capabilities of these techniques were confirmed on two naturally abundant solids, tripeptide N-formyl-l-methionyl-l-leucyl-l-phenylalanine (f-MLF-OH) and brown coal.

  20. Solid-state NMR heteronuclear coherence transfer using phase and amplitude modulated rf irradiation at the Hartmann Hahn sideband conditions

    NASA Astrophysics Data System (ADS)

    Bjerring, Morten; Nielsen, Niels Chr.

    2003-12-01

    An improved variant of the popular double cross-polarization (DCP) experiment for heteronuclear dipolar recoupling in solid-state NMR spectroscopy under magic-angle-spinning is introduced. By simple phase and amplitude modulation of the rf irradiation at the Hartman-Hahn sideband conditions, the new pulse sequence, dubbed iDCP, enables broadband excitation with the high efficiency of γ-encoded coherence transfer. The efficiency and robustness of iDCP toward isotropic chemical shift variations and chemical shift anisotropies, in the order typically applying for the backbone atoms in uniformly 13C, 15N-labeled proteins, is demonstrated numerically and experimentally by 15N to 13C coherence transfer for 15N-labeled N-Ac- L-valyl- L-leucine and 13C, 15N-labeled- L-threonine.

  1. IPAP-HSQMBC: measurement of long-range heteronuclear coupling constants from spin-state selective multiplets.

    PubMed

    Gil, Sergi; Espinosa, Juan Félix; Parella, Teodor

    2010-12-01

    A new NMR approach is proposed for the measurement of long-range heteronuclear coupling constants ((n)J(XH), n>1) in natural abundance molecules. Two complementary in-phase (IP) and anti-phase (AP) data are separately recorded from a modified HSQMBC experiment and then added/subtracted to provide spin-state-selective α/β-HSQMBC spectra. The magnitude of (n)J(XH) can be directly determined by simple analysis of the relative displacement between α- and β-cross-peaks. The robustness of this IPAP-HSQMBC experiment is evaluated experimentally and by simulation using a variety of different conditions. Important aspects such as signal intensity dependence and presence of unwanted cross-talk effects are discussed and examples on the measurement of small proton-carbon ((n)J(CH)) and proton-nitrogen ((n)J(NH)) coupling constants are provided. PMID:20952232

  2. Young Investigator Award Lecture. Structures of larger proteins, protein-ligand and protein-DNA complexes by multidimensional heteronuclear NMR.

    PubMed Central

    Clore, G. M.; Gronenborn, A. M.

    1994-01-01

    The recent development of a whole panoply of multidimensional heteronuclear-edited and -filtered NMR experiments has revolutionized the field of protein structure determination by NMR, making it possible to extend the methodology from the 10-kDa limit of conventional 2-dimensional NMR to systems up to potentially 35-40 kDa. The basic strategy for solving 3-dimensional structures of larger proteins and protein-ligand complexes in solution using 3- and 4-dimensional NMR spectroscopy is summarized, and the power of these methods is illustrated using 3 examples: interleukin-1 beta, the complex of calmodulin with a target peptide, and the specific complex of the transcription factor GATA-1 with its cognate DNA target site. PMID:8019409

  3. Correlation consistent basis sets for the atoms In–Xe

    SciTech Connect

    Mahler, Andrew; Wilson, Angela K.

    2015-02-28

    In this work, the correlation consistent family of Gaussian basis sets has been expanded to include all-electron basis sets for In–Xe. The methodology for developing these basis sets is described, and several examples of the performance and utility of the new sets have been provided. Dissociation energies and bond lengths for both homonuclear and heteronuclear diatomics demonstrate the systematic convergence behavior with respect to increasing basis set quality expected by the family of correlation consistent basis sets in describing molecular properties. Comparison with recently developed correlation consistent sets designed for use with the Douglas-Kroll Hamiltonian is provided.

  4. Fluorine detected 2D NMR experiments for the practical determination of size and sign of homonuclear F-F and heteronuclear C-F multiple bond J-coupling constants in multiple fluorinated compounds

    NASA Astrophysics Data System (ADS)

    Aspers, Ruud L. E. G.; Ampt, Kirsten A. M.; Dvortsak, Peter; Jaeger, Martin; Wijmenga, Sybren S.

    2013-06-01

    The use of fluorine in molecules obtained from chemical synthesis has become increasingly important within the pharmaceutical and agricultural industry. NMR characterization of these compounds is of great value with respect to their structure elucidation, their screening in metabolomics investigations and binding studies. The favorable NMR properties of the fluorine nucleus make NMR with fluorine detection of great value in this respect. A suite of NMR 2D F-F- and F-C-correlation experiments with fluorine detection was applied to the assignment of resonances, nJCF- and nJFF-couplings as well as the determination of their size and sign. The utilization of this experiment suite was exemplarily demonstrated for a highly fluorinated vinyl alkyl ether. Especially F-C HSQC and J-scaled F-C HMBC experiments allowed determining the size of the J-couplings of this compound. The relative sign of its homo- and heteronuclear couplings was achieved by different combinations of 2D NMR experiments, including non-selective and F2-selective F-C XLOC, F2-selective F-C HMQC, and F-F COSY. The F2-one/two-site selective F-C XLOC versions were found highly useful, as they led to simplifications of the common E.COSY patterns and resulted in a higher confidence level of the assignment by using selective excitation. The combination of F2-one/two-site selective F-C XLOC experiments with a F2-one-site selective F-C HMQC experiment provided the signs of all nJCF- and nJFF-couplings in the vinyl moiety of the test compound. Other combinations of experiments were found useful as well for special purposes when focusing for example on homonuclear couplings a combination of F-F COSY-10 with a F2-one-site selective F-C HMQC could be used. The E.COSY patterns in the spectra demonstrated were analyzed by use of the spin-selective displacement vectors, and in case of the XLOC also by use of the DQ- and ZQ-displacement vectors. The variety of experiments presented shall contribute to facilitate the

  5. Determination of glucan phosphorylation using heteronuclear 1H, 13C double and 1H, 13C, 31P triple-resonance NMR spectra.

    PubMed

    Schmieder, Peter; Nitschke, Felix; Steup, Martin; Mallow, Keven; Specker, Edgar

    2013-10-01

    Phosphorylation and dephosphorylation of starch and glycogen are important for their physicochemical properties and also their physiological functions. It is therefore desirable to reliably determine the phosphorylation sites. Heteronuclear multidimensional NMR-spectroscopy is in principle a straightforward analytical approach even for complex carbohydrate molecules. With heterogeneous samples from natural sources, however, the task becomes more difficult because a full assignment of the resonances of the carbohydrates is impossible to obtain. Here, we show that the combination of heteronuclear (1) H,(13) C and (1) H,(13) C,(31) P techniques and information derived from spectra of a set of reference compounds can lead to an unambiguous determination of the phosphorylation sites even in heterogeneous samples. PMID:23913630

  6. Determination of glucan phosphorylation using heteronuclear 1H, 13C double and 1H, 13C, 31P triple-resonance NMR spectra.

    PubMed

    Schmieder, Peter; Nitschke, Felix; Steup, Martin; Mallow, Keven; Specker, Edgar

    2013-10-01

    Phosphorylation and dephosphorylation of starch and glycogen are important for their physicochemical properties and also their physiological functions. It is therefore desirable to reliably determine the phosphorylation sites. Heteronuclear multidimensional NMR-spectroscopy is in principle a straightforward analytical approach even for complex carbohydrate molecules. With heterogeneous samples from natural sources, however, the task becomes more difficult because a full assignment of the resonances of the carbohydrates is impossible to obtain. Here, we show that the combination of heteronuclear (1) H,(13) C and (1) H,(13) C,(31) P techniques and information derived from spectra of a set of reference compounds can lead to an unambiguous determination of the phosphorylation sites even in heterogeneous samples.

  7. Heteronuclear Cross Polarization for Enhanced Sensitivity of in Vivo13C MR Spectroscopy on a Clinical 1.5 T MR System

    NASA Astrophysics Data System (ADS)

    van den Bergh, Adrianus J.; van den Boogert, Hendrikus J.; Heerschap, Arend

    1998-11-01

    The potential of heteronuclear {1H-13C} cross polarization was studied for optimization of the signal-to-noise ratio inin vivo13C MR spectroscopy at the clinical field strength of 1.5 T. Experiments on the human calf showed a significant chemical-shift selective signal enhancement on triglyceride signals of 3.9 by heteronuclear cross polarization, compared to a standard pulse-acquire sequence. Studies on a neonatal piglet brain showed an enhancement by cross polarization of 2.2 for the detection of13C-1-glucose. This enhancement allowed a fourfold improvement in time resolution in dynamic13C MR of13C-1-glucose inflow in piglet brain. Phantom experiments demonstrated the efficiency of this technique for interleaved detection of two spectral regions. Tests with a volume coil showed the feasibility of signal enhancement by cross polarization over a large volume of interest.

  8. Relative merits of rCW(A) and XiX heteronuclear spin decoupling in solid-state magic-angle-spinning NMR spectroscopy: A bimodal Floquet analysis.

    PubMed

    Equbal, Asif; Leskes, Michal; Nielsen, Niels Chr; Madhu, P K; Vega, Shimon

    2016-02-01

    We present a bimodal Floquet analysis of the recently introduced refocused continuous wave (rCW) solid-state NMR heteronuclear dipolar decoupling method and compare it with the similar looking X-inverse X (XiX) scheme. The description is formulated in the rf interaction frame and is valid for both finite and ideal π pulse rCW irradiation that forms the refocusing element in the rCW scheme. The effective heteronuclear dipolar coupling Hamiltonian up to first order is described. The analysis delineates the difference between the two sequences to different orders of their Hamiltonians for both diagonal and off-diagonal parts. All the resonance conditions observed in experiments and simulations have been characterised and their influence on residual line broadening is highlighted. The theoretical comparison substantiates the numerical simulations and experimental results to a large extent.

  9. Isotope-detected 1H NMR studies of proteins: a general strategy for editing interproton nuclear Overhauser effects by heteronuclear decoupling, with application to phage lambda repressor.

    PubMed Central

    Weiss, M A; Redfield, A G; Griffey, R H

    1986-01-01

    A strategy for editing interproton nuclear Overhauser effects (NOEs) in proteins is proposed and illustrated. Selective incorporation of 13C- (or 15N)-labeled amino acids into a protein permits NOEs involving the labeled residues to be identified by heteronuclear difference decoupling. Such heteronuclear editing simplifies the NOE difference spectrum and avoids ambiguities due to spin diffusion. Isotope-detected 1H NMR thus opens to study proteins too large for conventional one- and two-dimensional NMR methods (20-75 kDa). We have applied this strategy to the N-terminal domain of phage lambda repressor, a protein of dimer molecular mass 23 kDa. A tertiary NOE from an internal aromatic ring (Phe-51) to a beta-13C-labeled alanine residue (Ala-62) is demonstrated. PMID:3006046

  10. A comparison of the pH, urea, and temperature-denatured states of barnase by heteronuclear NMR: implications for the initiation of protein folding.

    PubMed

    Arcus, V L; Vuilleumier, S; Freund, S M; Bycroft, M; Fersht, A R

    1995-11-24

    The denatured states of barnase that are induced by urea, acid, and high temperature and acid have been assigned and characterised by high resolution heteronuclear NMR. The assignment was completed using a combination of triple-resonance and magnetisation-transfer methods. The latter was facilitated by selecting a suitable mutant of barnase (Ile-->Val51) which has an appropriate rate of interconversion between native and denatured states in urea. 3J NH-C alpha H coupling constants were determined for pH and urea-denatured barnase and intrinsic "random coil" coupling constants are shown to be different for different residue types. All the denatured states are highly unfolded. But, a consistent series of weak correlations in chemical shift, NOESY and coupling constant data provides evidence that the acid-denatured state has some residual structure in regions that form the first and second helices and the central strands of beta-sheet in the native protein. The acid/temperature-denatured states has less structure in these regions, and the urea-denatured state, less still. These observations may be combined with detailed analyses of the folding pathway of barnase from kinetic studies to illuminate the relevance of residual structure in the denatured states of proteins to the mechanism of protein folding. First, the folding of barnase is known to proceed in its later stages through structures in which the first helix and centre of the beta-sheet are extensively formed. Thus, embryonic initiation sites for these do exist in the denatured states and so could well develop into true nuclei. Second, it has been clearly established that the second helix is unfolded in these later states, and so residual structure in this region of the protein is non-productive. These data fit a model of protein folding in which local nucleation sites are latent in the denatured state and develop only when they make interactions elsewhere in the protein that stabilise them during the folding

  11. Na/Ca Intermixing around Silicate and Phosphate Groups in Bioactive Phosphosilicate Glasses Revealed by Heteronuclear Solid-State NMR and Molecular Dynamics Simulations.

    PubMed

    Mathew, Renny; Stevensson, Baltzar; Edén, Mattias

    2015-04-30

    We characterize the intermixing of network-modifying Na(+)/Ca(2+) ions around the silicate (QSi(n)) and phosphate (QP(n)) tetrahedra in a series of 16 Na2O–CaO–SiO2–P2O5 glasses, whose P content and silicate network connectivity were varied independently. The set includes both bioactive and bioinactive compositions and also encompasses two soda-lime-silicate members devoid of P, as well as two CaO–SiO2 glasses and one Na2O–SiO2–P2O5 glass. The various Si/P↔Na/Ca contacts were probed by molecular dynamics (MD) simulations together with heteronuclear magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) experimentation utilizing (23)Na{(31)P} and (23)Na{(29)Si} REDOR, as well as (31)P{ (23)Na} and (29)Si{(23)Na} REAPDOR. We introduce an approach for quantifying the extent of Na(+)/Ca(2+) ordering around a given QP(n) or QSi(n) group, encoded by the preference factor 0⩽ PM ⩽ 1 conveying the relative weights of a random cation intermixing (PM = 0) and complete preference/ordering (PM = 1) for one of the species M, which represents either Na(+) or Ca(2+). The MD-derived preference factors reveal phosphate and silicate species surrounded by Na(+)/Ca(2+) ions intermixed nearly randomly (PM ≲ 0.15), except for the QSi(4) and QSi(1) groups, which manifest more significant cation ordering with preference for Na+ and Ca2+, respectively. The overall weak preferences are essentially independent of the Si and P contents of the glass, whereas PM primarily correlates with the total amount of network modifiers: as the latter is increased, the Na/Ca distribution around the {QP(0), QSi(1), QSi(2)} groups with preference for Ca2(+ )tend to randomize (i.e., PCa decreases), while the PNa-values grow slightly for the {QP(1), QSi(3), QSi(4)} species already preferring coordination of Na. The set of experimental preference factors {PCa} for the orthophosphate (QP(0)) groups extracted from (31)P{(23)Na} REAPDOR NMR-derived M2(P–Na) dipolar second moments agrees

  12. Heteronuclear relayed E.COSY revisited: determination of 3J(H(alpha),C(gamma)) couplings in Asx and aromatic residues in proteins.

    PubMed

    Löhr, F; Pérez, C; Köhler, R; Rüterjans, H; Schmidt, J M

    2000-09-01

    Constant-time 3D heteronuclear relayed E.COSY [Schmidt et al. (1996) J. Biomol. NMR, 7, 142-152], as based on generic 2D small-flip-angle HMQC-COSY [Schmidt et al. (1995) J. Biomol. NMR, 6, 95-105], has been modified to allow for quantitative determination of heteronuclear three-bond 3J(H(alpha),C(gamma)) couplings. The method is applicable to amino acid spin topologies with carbons in the gamma position which lack attached protons, i.e. to asparagine, aspartate, and aromatic residues in uniformly 13C-enriched proteins. The pulse sequence critically exploits heteronuclear triple-quantum coherence (HTQC) of CH2 moieties involving geminal H(beta) proton pairs, taking advantage of improved multiple-quantum relaxation properties, at the same time avoiding scalar couplings between those spins involved in multiple-quantum coherence, thus yielding E.COSY-type multiplets with a splitting structure that is simpler than with the original scheme. Numerical least-squares 2D line-shape simulation is used to extract 3J(H(alpha),C(gamma)) coupling constants which are of relevance to side-chain chi1 dihedral-angle conformations in polypeptides. Methods are demonstrated with recombinant 15N,13C-enriched ribonuclease T1 and Desulfovibrio vulgaris flavodoxin with bound oxidized FMN.

  13. Synthesis, crystal structures and Hirshfeld surface analyses of two new Salen type nickel/sodium heteronuclear complexes

    NASA Astrophysics Data System (ADS)

    Mahlooji, Niloofar; Behzad, Mahdi; Tarahhomi, Atekeh; Maroney, Michael; Rudbari, Hadi Amiri; Bruno, Giuseppe; Ghanbari, Bahram

    2016-04-01

    Two new heteronuclear Nickel(II)/Sodium(I) complexes of a side-off compartmental Schiff base ligand were synthesized and characterized by spectroscopic methods. Crystal structures of both of the complexes were also obtained. The Schiff base ligand was synthesized from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with 2-hydroxy-3-methoxybenzaldehyde. In both of the complexes the Ni(II) ion is coordinated to the inner N2O2 coordination sphere with square-planar geometry and the Na(I) ion is coordinated to the outer O2 O2‧ coordination sphere. In Complex (1) with general formula [Ni(L)Na(CH3OH)(ClO4)] the sodium ion is seven coordinated while in (2) with general formula [{Ni(L)Na(OH2)}2(μ-Ni(CN)4)] the sodium ion is six coordinated. Intermolecular interactions in two studied complexes were analyzed using 3D Hirshfeld surfaces and corresponding 2D fingerprint plots. This analysis showed that the H … H and C … H/H … C contacts for both structures (altogether 67.5% of total Hirshfeld surface area for (1) and 77.6% for (2)) and the O … H/H … O (24.2%) for (1) and the N … H/H … N (8.1%) contacts for (2) were the characteristic intermolecular contacts in the related crystal structures.

  14. Adiabatic fast passage application in solid state NMR study of cross relaxation and molecular dynamics in heteronuclear systems.

    PubMed

    Baranowski, M; Woźniak-Braszak, A; Jurga, K

    2016-01-01

    The paper presents the benefits of using fast adiabatic passage for the study of molecular dynamics in the solid state heteronuclear systems in the laboratory frame. A homemade pulse spectrometer operating at the frequency of 30.2MHz and 28.411MHz for protons and fluorines, respectively, has been enhanced with microcontroller direct digital synthesizer DDS controller [1-4]. This work briefly describes how to construct a low-cost and easy-to-assemble adiabatic extension set for homemade and commercial spectrometers based on recently very popular Arduino shields. The described set was designed for fast adiabatic generation. Timing and synchronization problems are discussed. The cross-relaxation experiments with different initial states of the two spin systems have been performed. Contrary to our previous work [5] where the steady-state NOE experiments were conducted now proton spins (1)H are polarized in the magnetic field B0 while fluorine spins (19)F are perturbed by selective saturation for a short time and then the system is allowed to evolve for a period in the absence of a saturating field. The adiabatic passage application leads to a reversal of magnetization of fluorine spins and increases the amplitude of the signal. PMID:26705906

  15. De novo design of an endohedral heteronuclear dimetallofullerene (U-Gd)@C60 with exceptional structural and electronic properties.

    PubMed

    Dai, Xing; Han, Jie; Gao, Yang; Wang, Zhigang

    2014-12-01

    Ever since the first synthesis of La@C82 and U@C28 , there has been a growing interest in the study of endohedral metallofullerenes (EMFs) because of their great potential in various applications. Here we design a novel heteronuclear EMF (U-Gd)@C60 , by using density functional theory (DFT), which shows an encapsulation energy of about -5.53 eV, comparable to that of U2 @C60, La2 @C80 , and Lu2 @C76 . (U-Gd)@C60 is found to have a surprising twofold, single-electron UGd bond that results from the strong nanoconfinement of the fullerene, dominated by uranium's 5f and 6d and gadolinium's 5d atomic orbitals. The ground state shows an 11-et high spin state, and the net spins distributed on the U-pole carbons are relatively scattered, while they are highly concentrated on the Gd-pole carbons. The exceptional electronic characteristics of this novel EMF, containing both uranium and gadolinium atoms encapsulated, might prove useful for future applications in nuclear energy and biomedicine.

  16. Direct writing of CoFe alloy nanostructures by focused electron beam induced deposition from a heteronuclear precursor

    NASA Astrophysics Data System (ADS)

    Porrati, F.; Pohlit, M.; Müller, J.; Barth, S.; Biegger, F.; Gspan, C.; Plank, H.; Huth, M.

    2015-11-01

    Recently, focused electron beam-induced deposition has been employed to prepare functional magnetic nanostructures with potential in nanomagnetic logic and sensing applications by using homonuclear precursor gases like Fe(CO)5 or Co2(CO)8. Here we show that an extension towards the fabrication of bi-metallic compounds is possible by using a single-source heteronuclear precursor gas. We have grown CoFe alloy magnetic nanostructures from the HFeCo3(CO)12 metal carbonyl precursor. The compositional analysis indicates that the samples contain about 80 at% of metal and 10 at% of carbon and oxygen. Four-probe magnetotransport measurements are carried out on nanowires of various sizes down to a width of 50 nm, for which a room temperature resistivity of 43 μΩcm is found. Micro-Hall magnetometry reveals that 50 nm × 250 nm nanobars of the material are ferromagnetic up to the highest measured temperature of 250 K. Finally, the transmission electron microscopy (TEM) microstructural investigation shows that the deposits consist of a bcc Co-Fe phase mixed with a FeCo2 O4 spinel oxide phase with nanograins of about 5 nm diameter.

  17. Adiabatic fast passage application in solid state NMR study of cross relaxation and molecular dynamics in heteronuclear systems

    NASA Astrophysics Data System (ADS)

    Baranowski, M.; Woźniak-Braszak, A.; Jurga, K.

    2016-01-01

    The paper presents the benefits of using fast adiabatic passage for the study of molecular dynamics in the solid state heteronuclear systems in the laboratory frame. A homemade pulse spectrometer operating at the frequency of 30.2 MHz and 28.411 MHz for protons and fluorines, respectively, has been enhanced with microcontroller direct digital synthesizer DDS controller [1-4]. This work briefly describes how to construct a low-cost and easy-to-assemble adiabatic extension set for homemade and commercial spectrometers based on recently very popular Arduino shields. The described set was designed for fast adiabatic generation. Timing and synchronization problems are discussed. The cross-relaxation experiments with different initial states of the two spin systems have been performed. Contrary to our previous work [5] where the steady-state NOE experiments were conducted now proton spins 1H are polarized in the magnetic field B0 while fluorine spins 19F are perturbed by selective saturation for a short time and then the system is allowed to evolve for a period in the absence of a saturating field. The adiabatic passage application leads to a reversal of magnetization of fluorine spins and increases the amplitude of the signal.

  18. Adiabatic fast passage application in solid state NMR study of cross relaxation and molecular dynamics in heteronuclear systems.

    PubMed

    Baranowski, M; Woźniak-Braszak, A; Jurga, K

    2016-01-01

    The paper presents the benefits of using fast adiabatic passage for the study of molecular dynamics in the solid state heteronuclear systems in the laboratory frame. A homemade pulse spectrometer operating at the frequency of 30.2MHz and 28.411MHz for protons and fluorines, respectively, has been enhanced with microcontroller direct digital synthesizer DDS controller [1-4]. This work briefly describes how to construct a low-cost and easy-to-assemble adiabatic extension set for homemade and commercial spectrometers based on recently very popular Arduino shields. The described set was designed for fast adiabatic generation. Timing and synchronization problems are discussed. The cross-relaxation experiments with different initial states of the two spin systems have been performed. Contrary to our previous work [5] where the steady-state NOE experiments were conducted now proton spins (1)H are polarized in the magnetic field B0 while fluorine spins (19)F are perturbed by selective saturation for a short time and then the system is allowed to evolve for a period in the absence of a saturating field. The adiabatic passage application leads to a reversal of magnetization of fluorine spins and increases the amplitude of the signal.

  19. Photoelectron velocity-map imaging and theoretical studies of heteronuclear metal carbonyls MNi(CO)3- (M = Mg, Ca, Al)

    NASA Astrophysics Data System (ADS)

    Xie, Hua; Zou, Jinghan; Yuan, Qinqin; Fan, Hongjun; Tang, Zichao; Jiang, Ling

    2016-03-01

    The heteronuclear metal carbonyl anions MNi(CO)3- (M = Mg, Ca, Al) have been investigated using photoelectron velocity-map imaging spectroscopy. Electron affinities of neutral MNi(CO)3 (M = Mg, Ca, Al) are measured from the photoelectron spectra to be 1.064 ± 0.063, 1.050 ± 0.064, and 1.541 ± 0.040 eV, respectively. The C-O stretching mode in these three clusters is observed and the vibrational frequency is determined to be 2049, 2000, and 2041 cm-1 for MgNi(CO)3, CaNi(CO)3, and AlNi(CO)3, respectively. Density functional theory calculations are carried out to elucidate the geometric and electronic structures and to aid the experimental assignments. It has been found that three terminal carbonyls are preferentially bonded to the nickel atom in these heterobinuclear nickel carbonyls MNi(CO)3-1/0, resulting in the formation of the Ni(CO)3 motif. Ni remains the 18-electron configuration for MgNi(CO)3 and CaNi(CO)3 neutrals, but not for AlNi(CO)3. This is different from the homobinuclear nickel carbonyl Ni-Ni(CO)3 with the involvement of three bridging ligands. Present findings would be helpful for understanding CO adsorption on alloy surfaces.

  20. Homo- and heteronuclear compounds with a symmetrical bis-hydrazone ligand: synthesis, structural studies, and luminescent properties.

    PubMed

    Rodríguez-Hermida, Sabina; Lago, Ana B; Carballo, Rosa; Fabelo, Oscar; Vázquez-López, Ezequiel M

    2015-04-20

    Nine new coordination compounds have been synthesized by the reaction of salts of bivalent metal ions (a=Zn(II) , b=Cu(II) , c=Ni(II) , d=Co(II) ) with the bis(benzoylhydrazone) derivative of 4,6-diacetylresorcinol (H4 L). Three kinds of complexes have been obtained: homodinuclear compounds [M2 (H2 L)2 ]⋅nH2 O (1 a, 1 b, 1 c, and 1 d), homotetranuclear compounds [M4 (L)2 ]⋅n(solv) (2 a and 2 c), and heterotetranuclear compounds [Zn2 M2 (L)2 ]⋅n(solv) (2 ab, 2 ac, and 2 ad). The structures of the free ligand H4 L⋅2 DMSO and its complexes [Zn2 (H2 L)2 (DMSO)2 ] (1 a*), [Zn4 (L)2 (DMSO)6 ] (2 a*), and [Zn0.45 Cu3.55 (L)2 (DMSO)6 ]⋅2 DMSO (2 ab*) were elucidated by single-crystal X-ray diffraction. The ligand shows luminescence properties and its fluorimetric behavior towards M(II) metals (M=Zn, Cu, Ni and Co) has been studied. Furthermore, the solid-state luminescence properties of the ligand and compounds have been determined at room temperature. (1) H NMR spectroscopic monitoring of the reaction of H4 L with Zn(II) showed the deprotonation sequence of the OH/NH groups upon metal coordination. Heteronuclear reactions have also been monitored by using ESI-MS and spectrofluorimetric techniques.

  1. Broadband cross-polarization-based heteronuclear dipolar recoupling for structural and dynamic NMR studies of rigid and soft solids.

    PubMed

    Kharkov, B B; Chizhik, V I; Dvinskikh, S V

    2016-01-21

    Dipolar recoupling is an essential part of current solid-state NMR methodology for probing atomic-resolution structure and dynamics in solids and soft matter. Recently described magic-echo amplitude- and phase-modulated cross-polarization heteronuclear recoupling strategy aims at efficient and robust recoupling in the entire range of coupling constants both in rigid and highly dynamic molecules. In the present study, the properties of this recoupling technique are investigated by theoretical analysis, spin-dynamics simulation, and experimentally. The resonance conditions and the efficiency of suppressing the rf field errors are examined and compared to those for other recoupling sequences based on similar principles. The experimental data obtained in a variety of rigid and soft solids illustrate the scope of the method and corroborate the results of analytical and numerical calculations. The technique benefits from the dipolar resolution over a wider range of coupling constants compared to that in other state-of-the-art methods and thus is advantageous in studies of complex solids with a broad range of dynamic processes and molecular mobility degrees. PMID:26801025

  2. Accurate determination of small one-bond heteronuclear residual dipolar couplings by F1 coupled HSQC modified with a G-BIRD (r) module

    NASA Astrophysics Data System (ADS)

    Fehér, Krisztina; Berger, Stefan; Kövér, Katalin E.

    2003-08-01

    We report a G-BIRD (r) modified coupled HSQC experiment for the accurate determination of one-bond heteronuclear residual dipolar couplings. The G-BIRD (r) module has been employed to refocus the long-range coupling evolution of the heteronucleus during the t1 frequency labeling period. As a result, the crosspeaks obtained are split by only the direct one-bond coupling that can be extracted by measuring simple frequency differences between singlet maxima. Additionally the decoupling of long-range multiple bond splittings leads to considerable sensitivity enhancement. The modification also has been applied in a TROSY sequence resulting in a significant sensitivity and resolution improvement.

  3. Investigation of the backbone dynamics of the IgG-binding domain of streptococcal protein G by heteronuclear two-dimensional 1H-15N nuclear magnetic resonance spectroscopy.

    PubMed

    Barchi, J J; Grasberger, B; Gronenborn, A M; Clore, G M

    1994-01-01

    The backbone dynamics of the immunoglobulin-binding domain (B1) of streptococcal protein G, uniformly labeled with 15N, have been investigated by two-dimensional inverse detected heteronuclear 1H-15N NMR spectroscopy at 500 and 600 MHz. 15N T1, T2, and nuclear Overhauser enhancement data were obtained for all 55 backbone NH vectors of the B1 domain at both field strengths. The overall correlation time obtained from an analysis of the T1/T2 ratios was 3.3 ns at 26 degrees C. Overall, the B1 domain is a relatively rigid protein, consistent with the fact that over 95% of the residues participate in secondary structure, comprising a four-stranded sheet arranged in a -1, +3x, -1 topology, on top of which lies a single helix. Residues in the turns and loops connecting the elements of secondary structure tend to exhibit a higher degree of mobility on the picosecond time scale, as manifested by lower values of the overall order parameter. A number of residues at the ends of the secondary structure elements display two distinct internal motions that are faster than the overall rotational correlation time: one is fast (< 20 ps) and lies in the extreme narrowing limit, whereas the other is one to two orders of magnitude slower (1-3 ns) and lies outside the extreme narrowing limit. The slower motion can be explained by large-amplitude (20-40 degrees) jumps in the N-H vectors between states with well-defined orientations that are stabilized by hydrogen bonds.(ABSTRACT TRUNCATED AT 250 WORDS)

  4. The Mineral Phase of Calcified Cartilage: Its Molecular Structure and Interface with the Organic Matrix

    PubMed Central

    Duer, Melinda J.; Friščić, Tomislav; Murray, Rachel C.; Reid, David G.; Wise, Erica R.

    2009-01-01

    Abstract We have studied the atomic level structure of mineralized articular cartilage with heteronuclear solid-state NMR, our aims being to identify the inorganic species present at the surfaces of the mineral crystals which may interact with the surrounding organic matrix and to determine which components of the organic matrix are most closely involved with the mineral crystals. One-dimensional 1H and 31P and two-dimensional 1H-31P heteronuclear correlation NMR experiments show that the mineral component is very similar to that in bone with regard to its surface structure. 13C{31P} rotational echo double resonance experiments identify the organic molecules at the mineral surface as glycosaminoglycans, which concurs with our recent finding in bone. There is also evidence of γ-carboxyglutamic acid residues interacting with the mineral. However, other matrix components appear more distant from the mineral compared with bone. This may be due to a larger hydration layer on the mineral crystal surfaces in calcified cartilage. PMID:19383480

  5. Group contribution methodology based on the statistical associating fluid theory for heteronuclear molecules formed from Mie segments.

    PubMed

    Papaioannou, Vasileios; Lafitte, Thomas; Avendaño, Carlos; Adjiman, Claire S; Jackson, George; Müller, Erich A; Galindo, Amparo

    2014-02-01

    A generalization of the recent version of the statistical associating fluid theory for variable range Mie potentials [Lafitte et al., J. Chem. Phys. 139, 154504 (2013)] is formulated within the framework of a group contribution approach (SAFT-γ Mie). Molecules are represented as comprising distinct functional (chemical) groups based on a fused heteronuclear molecular model, where the interactions between segments are described with the Mie (generalized Lennard-Jonesium) potential of variable attractive and repulsive range. A key feature of the new theory is the accurate description of the monomeric group-group interactions by application of a high-temperature perturbation expansion up to third order. The capabilities of the SAFT-γ Mie approach are exemplified by studying the thermodynamic properties of two chemical families, the n-alkanes and the n-alkyl esters, by developing parameters for the methyl, methylene, and carboxylate functional groups (CH3, CH2, and COO). The approach is shown to describe accurately the fluid-phase behavior of the compounds considered with absolute average deviations of 1.20% and 0.42% for the vapor pressure and saturated liquid density, respectively, which represents a clear improvement over other existing SAFT-based group contribution approaches. The use of Mie potentials to describe the group-group interaction is shown to allow accurate simultaneous descriptions of the fluid-phase behavior and second-order thermodynamic derivative properties of the pure fluids based on a single set of group parameters. Furthermore, the application of the perturbation expansion to third order for the description of the reference monomeric fluid improves the predictions of the theory for the fluid-phase behavior of pure components in the near-critical region. The predictive capabilities of the approach stem from its formulation within a group-contribution formalism: predictions of the fluid-phase behavior and thermodynamic derivative properties of

  6. Systematic evaluation of heteronuclear spin decoupling in solid-state NMR at the rotary-resonance conditions in the regime of fast magic-angle spinning

    NASA Astrophysics Data System (ADS)

    Sharma, Kshama; Madhu, P. K.; Agarwal, Vipin

    2016-09-01

    The performance of heteronuclear spin decoupling sequences in solid-state NMR severely degrades when the proton radiofrequency (RF) nutation frequencies (ν1) are close to or at multiples of magic-angle spinning (MAS) frequency (νr) that are referred to as rotary-resonance recoupling conditions (ν1 = n · νr). Recently, two schemes, namely, PISSARRO and rCWApA, have been shown to be less affected by the problem of MAS and RF interference, specifically at the n = 2 rotary-resonance recoupling condition, especially in the fast MAS regime. Here, we systematically evaluate the loss in intensity of several heteronuclear spin decoupling sequences at the n = 1, 2 conditions compared to high-power decoupling in the fast-MAS regime. We propose that in the fast-MAS regime (above 40 kHz) the entire discussion about RF and MAS interference can be avoided by using appropriate low-power decoupling sequences which give comparable performance to decoupling sequences with high-power 1H irradiation of ca.195 kHz.

  7. Systematic evaluation of heteronuclear spin decoupling in solid-state NMR at the rotary-resonance conditions in the regime of fast magic-angle spinning.

    PubMed

    Sharma, Kshama; Madhu, P K; Agarwal, Vipin

    2016-09-01

    The performance of heteronuclear spin decoupling sequences in solid-state NMR severely degrades when the proton radiofrequency (RF) nutation frequencies (ν1) are close to or at multiples of magic-angle spinning (MAS) frequency (νr) that are referred to as rotary-resonance recoupling conditions (ν1=n·νr). Recently, two schemes, namely, PISSARRO and rCW(ApA), have been shown to be less affected by the problem of MAS and RF interference, specifically at the n=2 rotary-resonance recoupling condition, especially in the fast MAS regime. Here, we systematically evaluate the loss in intensity of several heteronuclear spin decoupling sequences at the n=1, 2 conditions compared to high-power decoupling in the fast-MAS regime. We propose that in the fast-MAS regime (above 40kHz) the entire discussion about RF and MAS interference can be avoided by using appropriate low-power decoupling sequences which give comparable performance to decoupling sequences with high-power (1)H irradiation of ca.195kHz. PMID:27472380

  8. Systematic evaluation of heteronuclear spin decoupling in solid-state NMR at the rotary-resonance conditions in the regime of fast magic-angle spinning.

    PubMed

    Sharma, Kshama; Madhu, P K; Agarwal, Vipin

    2016-09-01

    The performance of heteronuclear spin decoupling sequences in solid-state NMR severely degrades when the proton radiofrequency (RF) nutation frequencies (ν1) are close to or at multiples of magic-angle spinning (MAS) frequency (νr) that are referred to as rotary-resonance recoupling conditions (ν1=n·νr). Recently, two schemes, namely, PISSARRO and rCW(ApA), have been shown to be less affected by the problem of MAS and RF interference, specifically at the n=2 rotary-resonance recoupling condition, especially in the fast MAS regime. Here, we systematically evaluate the loss in intensity of several heteronuclear spin decoupling sequences at the n=1, 2 conditions compared to high-power decoupling in the fast-MAS regime. We propose that in the fast-MAS regime (above 40kHz) the entire discussion about RF and MAS interference can be avoided by using appropriate low-power decoupling sequences which give comparable performance to decoupling sequences with high-power (1)H irradiation of ca.195kHz.

  9. Primitive models of chemical association. III. Totally flexible sticky two-point model for multicomponent heteronuclear fixed-chain-length polymerization

    SciTech Connect

    Lin, C.; Kalyuzhnyi, Y.V. |; Stell, G.

    1998-04-01

    A multidensity integral-equation theory for polymerization into freely jointed hard-sphere homonuclear chain fluids proposed earlier [J. Chem. Phys. {bold 106}, 1940 (1997)] is extended to the case of multicomponent heteronuclear chain polymerization. The theory is based on the analytical solution of the polymer Percus{endash}Yevick (PPY) approximation for the totally flexible sticky two-point (S2P) model of associating fluids. The model consists of an n-component mixture of hard spheres of different sizes with species 2,{hor_ellipsis},n{minus}1 bearing two sticky sites A and B, randomly distributed on its surface, and species 1 and n with only one B and A site per particle, respectively. Due to some specific restrictions imposed on the possibility of forming bonds between particles of various species, the present version of the S2P model represents an associating fluid that is able to polymerize into a mixture of heteronuclear chain macromolecules. The structural properties of such a model are studied in the complete-association limit and compared with computer-simulation results for homonuclear hard-sphere chain mixtures, symmetrical diblock copolymers, alternating copolymers, and homonuclear hard-sphere chains in a hard-sphere solvent. Some results for the case of partial association are also presented. The PPY theory represents a quantitatively successful theory for the mixtures of short homonuclear chains and the short copolymer systems studied here. We also expect that the theory will prove to be of the same order of accuracy in investigating the case of partial association. {copyright} {ital 1998 American Institute of Physics.}

  10. Structures and standard molar enthalpies of formation of a series of Ln(III)–Cu(II) heteronuclear compounds with pyrazine-2,3-dicarboxylic acid

    SciTech Connect

    Yang, Qi; Xie, Gang; Wei, Qing; Chen, Sanping Gao, Shengli

    2014-07-01

    Fifteen lanthanide–copper heteronuclear compounds, formulated as [CuLn{sub 2}(pzdc){sub 4}(H{sub 2}O){sub 6}]·xH{sub 2}O (1–6(x=2), 8(x=3), 9–10(x=4)); [CuLn{sub 2}(pzdc){sub 4}(H{sub 2}O){sub 4}]·xH{sub 2}O (7, 12–13, 15(x=4), 14(x=5), 11(x=8)) (Ln(III)=La(1); Ce(2); Pr(3); Nd(4); Sm(5); Eu(6); Gd(7); Tb(8); Dy(9); Ho(10); Er(11); Tm(12); Yb(13); Lu(14); Y(15); H{sub 2}pzdc (C{sub 6}H{sub 4}N{sub 2}O{sub 4})=pyrazine-2,3-dicarboxylic acid) have been hydrothermally synthesized. All compounds were characterized by element analysis, IR spectroscopy, single-crystal X-ray diffraction and thermal analysis. X-ray diffraction analyses confirm that all compounds are isostructural and feature a 3D brick-like framework structure with (4.6{sup 2}){sub 2}(4{sup 2}.6{sup 2}.8{sup 2})(6{sup 3}){sup 2}(6{sup 5}.8){sub 2} topology. Using 1 mol cm{sup −3} HCl(aq) as calorimetric solvent, with an isoperibol solution–reaction calorimeter, the standard molar enthalpies of formation of all compounds were determined by a designed thermochemical cycle. In addition, solid state luminescence properties of compounds 5, 6, 8 and 9 were studied in the solid state. - Graphical abstract: According to Hess' rule, the standard molar enthalpies of formation of Ln–Cu heterometallic coordination compounds were determined by a designed thermochemical cycle. - Highlights: • Fifteen lanthanide–copper heteronuclear isostructural compounds. • Structurally characterization by IR, X-ray diffraction and thermal analysis. • The standard molar enthalpy of formation. • Isoperibol solution–reaction calorimetry.

  11. Coupled long-range carbon-hydrogen correlation experiment without refocusing delay

    NASA Astrophysics Data System (ADS)

    Krishnamurthy, V. V.; Nunlist, Rudi

    In long-range carbon-hydrogen correlation experiments with standard heteronuclear shift correlation sequences cross-peak intensities can be severely attenuated due to modulation by "interfering" long-range couplings with other protons. Often cross peaks, even if the polarization transfer delay, Δ1, is optimized, can be missed due to the wrong choice of the refocusing delay, Δ2. A useful improvement is to eliminate the Δ2 delay and acquire without proton decoupling. A one-step low-pass J filter is introduced before evolution to suppress one-bond correlations and this sequence is compared to decoupled versions (the standard heteronuclear shift correlation sequence and the COLOC sequence with one-step low-pass J filter before evolution and a BIRD pulse midway through Δ2). Using rotenone as an example we show the advantages of removing the "refocusing" ("defocusing") delay and retaining 1H coupling in the F2 dimension. It is suggested that the decrease in S/ N (by a factor of 2 or less) is often not very significant compared to the danger of accidental missing of cross peaks due to the wrong choice of Δ2.

  12. Structure and chemistry of the heteronuclear oxo-cluster [VPO4]•+: a model system for the gas-phase oxidation of small hydrocarbons.

    PubMed

    Dietl, Nicolas; Wende, Torsten; Chen, Kai; Jiang, Ling; Schlangen, Maria; Zhang, Xinhao; Asmis, Knut R; Schwarz, Helmut

    2013-03-01

    The heteronuclear oxo-cluster [VPO4](•+) is generated via electrospray ionization and investigated with respect to both its electronic structure as well as its gas-phase reactivity toward small hydrocarbons, thus permitting a comparison to the well-known vanadium-oxide cation [V2O4](•+). As described in previous studies, the latter oxide exhibits no or just minor reactivity toward small hydrocarbons, such as CH4, C2H6, C3H8, n-C4H10, and C2H4, while substitution of one vanadium by a phosphorus atom yields the reactive [VPO4](•+) ion; the latter brings about oxidative dehydrogenation (ODH) of saturated hydrocarbons, e.g., propane and butane as well as oxygen-atom transfer (OAT) to unsaturated hydrocarbons, e.g. ethene, at thermal conditions. Further, the gas-phase structure of [VPO4](•+) is determined by IR photodissociation spectroscopy and compared to that of [V2O4](•+). DFT calculations help to elucidate the reaction mechanism. The results underline the crucial role of phosphorus in terms of C-H bond activation of hydrocarbons by mixed VPO clusters.

  13. pH-Dependent two novel heteronuclear Cu(II)/Sr(II) coordination polymers constructed from 1,3,5-benzenetricarboxylic acid: Synthesis, crystal structures and properties

    NASA Astrophysics Data System (ADS)

    Sun, Qiao-Zhen; Yin, Yi-Biao; Pan, Jun-Qiao; Chai, Li-Yuan; Su, Nan; Liu, Hui; Zhao, Yi-Lin; Liu, Xing-Tao

    2016-02-01

    Two novel heteronuclear coordination polymers, namely, [CuSr2(BTC)2]·10H2O (1) and [Cu2Sr(H4TMA)2]·4H2O (2) (H3BTC = 1,3,5-benzenetricarboxylic acid, H4TMA = 2-hydroxytrimesic acid) were hydrothermally synthesized as pH-dependent products and characterized by elemental analysis (EA), infrared spectroscopy (IR) and single crystal X-ray diffraction. For compound 1, it displays a 3D structure with (2,5,6)-connected net topology. For 2, the H3BTC ligand is oxidized into H4TMA and compound 2 features a 2D layer structure, which is further linked by Cu⋯Cu and Cu⋯O supramolecular interactions into a 3D structure. The results show that the pH plays a crucial role in determining the structure of the compounds. In addition, thermalgravimetric analysis of compounds 1-2 and luminescence property of 1 are also investigated.

  14. Structure and chemistry of the heteronuclear oxo-cluster [VPO4]•+: a model system for the gas-phase oxidation of small hydrocarbons.

    PubMed

    Dietl, Nicolas; Wende, Torsten; Chen, Kai; Jiang, Ling; Schlangen, Maria; Zhang, Xinhao; Asmis, Knut R; Schwarz, Helmut

    2013-03-01

    The heteronuclear oxo-cluster [VPO4](•+) is generated via electrospray ionization and investigated with respect to both its electronic structure as well as its gas-phase reactivity toward small hydrocarbons, thus permitting a comparison to the well-known vanadium-oxide cation [V2O4](•+). As described in previous studies, the latter oxide exhibits no or just minor reactivity toward small hydrocarbons, such as CH4, C2H6, C3H8, n-C4H10, and C2H4, while substitution of one vanadium by a phosphorus atom yields the reactive [VPO4](•+) ion; the latter brings about oxidative dehydrogenation (ODH) of saturated hydrocarbons, e.g., propane and butane as well as oxygen-atom transfer (OAT) to unsaturated hydrocarbons, e.g. ethene, at thermal conditions. Further, the gas-phase structure of [VPO4](•+) is determined by IR photodissociation spectroscopy and compared to that of [V2O4](•+). DFT calculations help to elucidate the reaction mechanism. The results underline the crucial role of phosphorus in terms of C-H bond activation of hydrocarbons by mixed VPO clusters. PMID:23432112

  15. Two heteronuclear dipolar results at the price of one: Quantifying Na/P contacts in phosphosilicate glasses and biomimetic hydroxy-apatite

    NASA Astrophysics Data System (ADS)

    Stevensson, Baltzar; Mathew, Renny; Yu, Yang; Edén, Mattias

    2015-02-01

    The analysis of S{I} recoupling experiments applied to amorphous solids yields a heteronuclear second moment M2 (S-I) that represents the effective through-space dipolar interaction between the detected S spins and the neighboring I-spin species. We show that both M2 (S-I) and M2 (I-S) values are readily accessible from a sole S{I} or I{S} experiment, which may involve either S or I detection, and is naturally selected as the most favorable option under the given experimental conditions. For the common case where I has half-integer spin, an I{S} REDOR implementation is preferred to the S{I} REAPDOR counterpart. We verify the procedure by 23Na{31P} REDOR and 31P{23Na} REAPDOR NMR applied to Na2O-CaO-SiO2-P2O5 glasses and biomimetic hydroxyapatite, where the M2 (P-Na) values directly determined by REAPDOR agree very well with those derived from the corresponding M2 (Na-P) results measured by REDOR. Moreover, we show that dipolar second moments are readily extracted from the REAPDOR NMR protocol by a straightforward numerical fitting of the initial dephasing data, in direct analogy with the well-established procedure to determine M2 (S-I) values from REDOR NMR experiments applied to amorphous materials; this avoids the problems with time-consuming numerically exact simulations whose accuracy is limited for describing the dynamics of a priori unknown multi-spin systems in disordered structures.

  16. The role of interleukin-6 in mitogenic T-cell activation: detection of interleukin-2 heteronuclear RNA by polymerase chain reaction.

    PubMed

    Walz, G; Stevens, C; Zanker, B; Melton, L B; Clark, S C; Suthanthiran, M; Strom, T B

    1991-05-01

    It has been documented that interleukin-6 (IL-6) supports the proliferation of purified, anti-CD3-stimulated murine T cells. We found that stimulation of human peripheral blood mononuclear cells (PBMCs) with anti-CD3 induced a significant accumulation of IL-6 mRNA, indicating that antigen-mediated T-cell activation may involve IL-6 release from accessory cells. Phytohemagglutinin (PHA) had little effect upon IL-6 gene expression. In keeping with these findings, anti-IL-6 reduced but did not abolish anti-CD3-mediated proliferation of PBMCs, but had no significant effect upon PHA-stimulated proliferation. The addition of recombinant (r) IL-6 enhanced the proliferation of anti-CD3-stimulated PBMCs and increased the accumulation of IL-2 mRNA in PHA-stimulated PBMCs during the first 5 hr of culture. Nuclear run-off experiments did not reveal significant changes in IL-2 transcription in PHA plus rIL-6-treated PBMCs attempting to assume that IL-6 mediates stabilization of IL-2 mRNA. However, monitoring of partially spliced IL-2 mRNA by polymerase chain reaction revealed a clear increase in IL-2 heteronuclear RNA. Thus IL-6 increases the rate of IL-2 transcription which was not detectable by conventional in vitro transcription assays. We conclude that anti-CD3 triggers T-cell proliferation through a process that is partially but not entirely dependent upon release of IL-6. IL-6, in turn, supports IL-2 transcription. Insofar as anti-CD3 mimics antigen-triggered activation of the T-cell receptor complex, IL-6 appears to support the early immune response by augmenting antigen-triggered IL-2 gene expression. PMID:1827050

  17. Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy

    SciTech Connect

    Hou, Guangjin E-mail: tpolenov@udel.edu; Lu, Xingyu E-mail: lexvega@comcast.net; Vega, Alexander J. E-mail: lexvega@comcast.net; Polenova, Tatyana E-mail: tpolenov@udel.edu

    2014-09-14

    We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear {sup 1}H-X (X = {sup 13}C, {sup 15}N, {sup 31}P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the {sup 1}H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the {sup 1}H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from {sup 1}H chemical shift anisotropy, while keeping the {sup 1}H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [{sup 15}N]-N-acetyl-valine and [U-{sup 13}C,{sup 15}N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate {sup 1}H-{sup 15}N dipolar couplings in the context of 3D experiments is presented on U-{sup 13}C,{sup 15}N-enriched dynein light chain protein LC8.

  18. Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Hou, Guangjin; Lu, Xingyu; Vega, Alexander J.; Polenova, Tatyana

    2014-09-01

    We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear 1H-X (X = 13C, 15N, 31P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the 1H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the 1H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from 1H chemical shift anisotropy, while keeping the 1H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [15N]-N-acetyl-valine and [U-13C,15N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate 1H-15N dipolar couplings in the context of 3D experiments is presented on U-13C,15N-enriched dynein light chain protein LC8.

  19. Structural characterization of d(CAACCCGTTG) and d(CAACGGGTTG) mini-hairpin loops by heteronuclear NMR: the effects of purines versus pyrimidines in DNA hairpins.

    PubMed Central

    Avizonis, D Z; Kearns, D R

    1995-01-01

    The DNA decamers, d(CAACCCGTTG) and d(CAACGGGTTG) were studied in solution by proton and heteronuclear NMR. Under appropriate conditions of pH, temperature, salt concentration and DNA concentration, both decamers form hairpin conformations with similar stabilities [Avizonis and Kearns (1995) Biopolymers, 35, 187-200]. Both decamers adopt mini-hairpin loops, where the first and last four nucleotides are involved in Watson-Crick hydrogen bonding and the central two nucleotides, CC or GG respectively, form the loop. Through the use of proton-proton, proton-phosphorus and natural abundance proton-carbon NMR experiments, backbone torsion angles (beta, gamma and epsilon), sugar puckers and interproton distances were measured. The nucleotides forming the loops of these decamers were found to stack upon one another in an L1 type of loop conformation. Both show gamma tr and unusual beta torsion angles in the loop-closing nucleotide G7, as expected for mini-hairpin loop formation. Our results indicate that the beta and epsilon torsion angles of the fifth and sixth nucleotides that form the loop and the loop-closing nucleotide G7 are not in the standard trans conformation as found in B-DNA. Although the loop structures calculated from NMR-derived constraints are not well defined, the stacking of the bases in the two different hairpins is different. This difference in the base stacking of the loop may provide an explanation as to why the cytosine-containing hairpin is thermodynamically more stable than the guanine-containing hairpin. PMID:7739905

  20. Dependence of in vivo glutamine synthetase activity on ammonia concentration in rat brain studied by 1H - 15N heteronuclear multiple-quantum coherence-transfer NMR.

    PubMed Central

    Kanamori, K; Ross, B D; Kuo, E L

    1995-01-01

    The dependence of the in vivo rate of glutamine synthesis on the substrate ammonia concentration was studied in rat brain by 1H-15N heteronuclear multiple-quantum coherence-transfer NMR in combination with biochemical techniques. In vivo rates were measured at various steady-state blood and brain ammonia concentrations within the ranges 0.4-0.55 mumol/g and 0.86-0.98 mumol/g respectively, after low-rate intravenous 15NH4+ infusion (isotope chase). The rate of glutamine synthesis at steady state was determined from the change in brain [5-15N]glutamine levels during isotope chase, observed selectively through the amide proton by NMR, and 15N enrichments of brain glutamine and of blood and brain ammonia measured byN gas chromatography-MS. The in vivo rate (v) was 3.3-4.5 mumol/h per g of brain at blood ammonia concentrations (s) of 0.40-0.55 mumol/g. A linear increase of 1/v with 1/s permitted estimation of the in vivo glutamine synthetase (GS) activity at a physiological blood ammonia concentration to be 0.4-2.1 mumol/h per g. The observed ammonia-dependence strongly suggests that, under physiological conditions, in vivo GS activity is kinetically limited by sub-optimal in situ concentrations of ammonia as well as glutamate and ATP. Comparison of the observed in vivo GS activity with the reported in vivo rates of glutaminase and of gamma-aminobutyrate (GABA) synthesis suggests that, under mildly hyperammonaemic conditions, glutamine is synthesized at a sufficiently high rate to serve as a precursor of GABA, but glutaminase-catalysed hydrolysis of glutamine is too slow to be the sole provider of glutamate used for GABA synthesis. PMID:7487913

  1. Characterization of the phosphatic mineral of the barnacle Ibla cumingi at atomic level by solid-state nuclear magnetic resonance: comparison with other phosphatic biominerals.

    PubMed

    Reid, David G; Mason, Matthew J; Chan, Benny K K; Duer, Melinda J

    2012-07-01

    Ibliform barnacles are among the few invertebrate animals harnessing calcium phosphate to construct hard tissue. The (31)P solid-state NMR (SSNMR) signal from the shell plates of Ibla cumingi (Iblidae) is broader than that of bone, and shifted by ca 1 ppm to low frequency. (1)H-(31)P heteronuclear correlation (HETCOR) experiments show a continuum of different phosphorus/phosphate atomic environments, close to hydrogen populations with resonance frequencies between ca 10 and 20 ppm. Associated (1)H and (31)P chemical shifts argue the coexistence of weakly (high (31)P frequency, low (1)H frequency) to more strongly (lower (31)P frequency, higher (1)H frequency) hydrogen-bonded hydrogen phosphate-like molecular/ionic species. There is no resolved signal from discrete OH(-) ions. (13)C SSNMR shows chitin, protein and other organic biomolecules but, unlike bone, there are no significant atomic scale organic matrix-mineral contacts. The poorly ordered hydrogen phosphate-like iblid mineral is strikingly different, structurally and compositionally, from both vertebrate bone mineral and the more crystalline fluoroapatite of the linguliform brachiopods. It probably represents a previously poorly characterized calcium phosphate biomineral, the evolution of which may have reflected either the chemical conditions of ancestral seas or the mechanical advantages of phosphatic biomineralization over a calcium carbonate equivalent.

  2. Overcoming the overlap problem in the assignment of 1H NMR spectra of larger proteins by use of three-dimensional heteronuclear 1H-15N Hartmann-Hahn-multiple quantum coherence and nuclear Overhauser-multiple quantum coherence spectroscopy: application to interleukin 1 beta.

    PubMed

    Marion, D; Driscoll, P C; Kay, L E; Wingfield, P T; Bax, A; Gronenborn, A M; Clore, G M

    1989-07-25

    The application of three-dimensional (3D) heteronuclear NMR spectroscopy to the sequential assignment of the 1H NMR spectra of larger proteins is presented, using uniformly labeled (approximately 95%) [15N]interleukin 1 beta, a protein of 153 residues and molecular mass of 17.4 kDa, as an example. The two-dimensional (2D) 600-MHz spectra of interleukin 1 beta are too complex for complete analysis, owing to extensive cross-peak overlap and chemical shift degeneracy. We show that the combined use of 3D 1H-15N Hartmann-Hahn-multiple quantum coherence (HOHAHA-HMQC) and nuclear Overhauser-multiple quantum coherence (NOESY-HMQC) spectroscopy, designed to provide the necessary through-bond and through-space correlations for sequential assignment, provides a practical general-purpose method for resolving ambiguities which severely limit the analysis of conventional 2D NMR spectra. The absence of overlapping cross-peaks in these 3D spectra allows the unambiguous identification of C alpha H(i)-NH(i+1) and NH(i)-NH(i+1) through-space nuclear Overhauser connectivities necessary for connecting a particular C alpha H(i)-NH(i) through-bond correlation with its associated through-space sequential cross-peak The problem of amide NH chemical shift degeneracy in the 1H NMR spectrum is therefore effectively removed, and the assignment procedure simply involves inspecting a series of 2D 1H-1H slices edited by the chemical shift of the directly bonded 15N atom. Connections between residues can be identified almost without any knowledge of the spin system types involved, though this type of information is clearly required for the eventual placement of the connected residues within the primary sequence.

  3. Solution secondary structure of a bacterially expressed peptide from the receptor binding domain of Pseudomonas aeruginosa pili strain PAK: A heteronuclear multidimensional NMR study.

    PubMed

    Campbell, A P; Bautista, D L; Tripet, B; Wong, W Y; Irvin, R T; Hodges, R S; Sykes, B D

    1997-10-21

    The C-terminal receptor binding region of Pseudomonas aeruginosa pilin protein strain PAK (residues 128-144) has recently been the target for the design of a synthetic peptide vaccine effective against multiple strains of P. aeruginosa infection. We have successfully cloned and bacterially expressed a 15N-labeled PAK pilin peptide spanning residues 128-144 of the intact PAK pilin protein, PAK 128-144(Hs145), and have determined the solution secondary structure of this peptide using heteronuclear multidimensional NMR spectroscopy. The oxidized recombinant peptide exists as a major (trans) and minor (cis) species in solution, arising from isomerization around the Ile138-Pro139 peptide bond. The pattern of NOEs, temperature coefficients, and coupling constants observed for the trans isomer demonstrate the presence of a type I beta-turn and a type II beta-turn spanning Asp134-Glu-Gln-Phe137 and Pro139-Lys-Gly-Cys142, respectively. This is in agreement with the NMR solution structure of the trans isomer of a synthetic PAK 128-144 peptide which showed a type I and a type II beta-turn in these same regions of the sequence [McInnes, C., Sönnichsen, F. D., Kay, C. M., Hodges, R. S., and Sykes, B. D. (1993) Biochemistry 32, 13432-13440; Campbell, A. P., McInnes, C., Hodges, R. S., and Sykes, B. D. (1995) Biochemistry 34, 16255-16268]. The pattern of NOEs, temperature coefficients, and coupling constants observed for the cis isomer also demonstrate a type II beta-turn spanning Pro139-Lys-Gly-Cys142, but suggest a second beta-turn spanning Asp132-Gln-Asp-Glu135. Thus, the cis isomer may also possess a double-turn motif (like the trans isomer), but with different spacing between the turns and a different placement of the first turn in the sequence. The discovery of a double-turn motif in the trans (and cis) recombinant PAK pilin peptide is an extremely important result since the double turn has been implicated as a structural requirement for the recognition of both receptor

  4. Heteronuclear Micro-Helmholtz Coil Facilitates µm-Range Spatial and Sub-Hz Spectral Resolution NMR of nL-Volume Samples on Customisable Microfluidic Chips

    PubMed Central

    Spengler, Nils; Höfflin, Jens; Moazenzadeh, Ali; Mager, Dario; MacKinnon, Neil; Badilita, Vlad; Wallrabe, Ulrike; Korvink, Jan G.

    2016-01-01

    We present a completely revised generation of a modular micro-NMR detector, featuring an active sample volume of ∼ 100 nL, and an improvement of 87% in probe efficiency. The detector is capable of rapidly screening different samples using exchangeable, application-specific, MEMS-fabricated, microfluidic sample containers. In contrast to our previous design, the sample holder chips can be simply sealed with adhesive tape, with excellent adhesion due to the smooth surfaces surrounding the fluidic ports, and so withstand pressures of ∼2.5 bar, while simultaneously enabling high spectral resolution up to 0.62 Hz for H2O, due to its optimised geometry. We have additionally reworked the coil design and fabrication processes, replacing liquid photoresists by dry film stock, whose final thickness does not depend on accurate volume dispensing or precise levelling during curing. We further introduced mechanical alignment structures to avoid time-intensive optical alignment of the chip stacks during assembly, while we exchanged the laser-cut, PMMA spacers by diced glass spacers, which are not susceptible to melting during cutting. Doing so led to an overall simplification of the entire fabrication chain, while simultaneously increasing the yield, due to an improved uniformity of thickness of the individual layers, and in addition, due to more accurate vertical positioning of the wirebonded coils, now delimited by a post base plateau. We demonstrate the capability of the design by acquiring a 1H spectrum of ∼ 11 nmol sucrose dissolved in D2O, where we achieved a linewidth of 1.25 Hz for the TSP reference peak. Chemical shift imaging experiments were further recorded from voxel volumes of only ∼ 1.5nL, which corresponded to amounts of just 1.5 nmol per voxel for a 1 M concentration. To extend the micro-detector to other nuclei of interest, we have implemented a trap circuit, enabling heteronuclear spectroscopy, demonstrated by two 1H/13C 2D HSQC experiments. PMID

  5. Heteronuclear Micro-Helmholtz Coil Facilitates µm-Range Spatial and Sub-Hz Spectral Resolution NMR of nL-Volume Samples on Customisable Microfluidic Chips.

    PubMed

    Spengler, Nils; Höfflin, Jens; Moazenzadeh, Ali; Mager, Dario; MacKinnon, Neil; Badilita, Vlad; Wallrabe, Ulrike; Korvink, Jan G

    2016-01-01

    We present a completely revised generation of a modular micro-NMR detector, featuring an active sample volume of ∼ 100 nL, and an improvement of 87% in probe efficiency. The detector is capable of rapidly screening different samples using exchangeable, application-specific, MEMS-fabricated, microfluidic sample containers. In contrast to our previous design, the sample holder chips can be simply sealed with adhesive tape, with excellent adhesion due to the smooth surfaces surrounding the fluidic ports, and so withstand pressures of ∼2.5 bar, while simultaneously enabling high spectral resolution up to 0.62 Hz for H2O, due to its optimised geometry. We have additionally reworked the coil design and fabrication processes, replacing liquid photoresists by dry film stock, whose final thickness does not depend on accurate volume dispensing or precise levelling during curing. We further introduced mechanical alignment structures to avoid time-intensive optical alignment of the chip stacks during assembly, while we exchanged the laser-cut, PMMA spacers by diced glass spacers, which are not susceptible to melting during cutting. Doing so led to an overall simplification of the entire fabrication chain, while simultaneously increasing the yield, due to an improved uniformity of thickness of the individual layers, and in addition, due to more accurate vertical positioning of the wirebonded coils, now delimited by a post base plateau. We demonstrate the capability of the design by acquiring a 1H spectrum of ∼ 11 nmol sucrose dissolved in D2O, where we achieved a linewidth of 1.25 Hz for the TSP reference peak. Chemical shift imaging experiments were further recorded from voxel volumes of only ∼ 1.5 nL, which corresponded to amounts of just 1.5 nmol per voxel for a 1 M concentration. To extend the micro-detector to other nuclei of interest, we have implemented a trap circuit, enabling heteronuclear spectroscopy, demonstrated by two 1H/13C 2D HSQC experiments. PMID

  6. Heteronuclear Micro-Helmholtz Coil Facilitates µm-Range Spatial and Sub-Hz Spectral Resolution NMR of nL-Volume Samples on Customisable Microfluidic Chips.

    PubMed

    Spengler, Nils; Höfflin, Jens; Moazenzadeh, Ali; Mager, Dario; MacKinnon, Neil; Badilita, Vlad; Wallrabe, Ulrike; Korvink, Jan G

    2016-01-01

    We present a completely revised generation of a modular micro-NMR detector, featuring an active sample volume of ∼ 100 nL, and an improvement of 87% in probe efficiency. The detector is capable of rapidly screening different samples using exchangeable, application-specific, MEMS-fabricated, microfluidic sample containers. In contrast to our previous design, the sample holder chips can be simply sealed with adhesive tape, with excellent adhesion due to the smooth surfaces surrounding the fluidic ports, and so withstand pressures of ∼2.5 bar, while simultaneously enabling high spectral resolution up to 0.62 Hz for H2O, due to its optimised geometry. We have additionally reworked the coil design and fabrication processes, replacing liquid photoresists by dry film stock, whose final thickness does not depend on accurate volume dispensing or precise levelling during curing. We further introduced mechanical alignment structures to avoid time-intensive optical alignment of the chip stacks during assembly, while we exchanged the laser-cut, PMMA spacers by diced glass spacers, which are not susceptible to melting during cutting. Doing so led to an overall simplification of the entire fabrication chain, while simultaneously increasing the yield, due to an improved uniformity of thickness of the individual layers, and in addition, due to more accurate vertical positioning of the wirebonded coils, now delimited by a post base plateau. We demonstrate the capability of the design by acquiring a 1H spectrum of ∼ 11 nmol sucrose dissolved in D2O, where we achieved a linewidth of 1.25 Hz for the TSP reference peak. Chemical shift imaging experiments were further recorded from voxel volumes of only ∼ 1.5 nL, which corresponded to amounts of just 1.5 nmol per voxel for a 1 M concentration. To extend the micro-detector to other nuclei of interest, we have implemented a trap circuit, enabling heteronuclear spectroscopy, demonstrated by two 1H/13C 2D HSQC experiments.

  7. Electron-correlation effects in enhanced ionization of molecules: A time-dependent generalized-active-space configuration-interaction study

    NASA Astrophysics Data System (ADS)

    Chattopadhyay, S.; Bauch, S.; Madsen, L. B.

    2015-12-01

    We numerically study models of H2 and LiH molecules, aligned collinearly with the linear polarization of the external field, to elucidate the possible role of correlation in the enhanced-ionization (EI) phenomena. Correlation is considered at different levels of approximation with the time-dependent generalized-active-space configuration-interaction method. The results of our studies show that enhanced ionization occurs in multielectron molecules and that correlation is important, and they also demonstrate significant deviations between the results of the single-active-electron approximation and more accurate configuration-interaction methods. We further investigate the role of low-lying excited states in the EI phenomena. With the inclusion of correlation we show strong carrier-envelope-phase effects in the enhanced ionization of the asymmetric heteronuclear LiH -like molecule. The correlated calculation shows an intriguing feature of crossover in enhanced ionization with two carrier-envelope phases at critical internuclear separation.

  8. Synthesis, crystal structure and catalytic behavior of homo- and heteronuclear coordination polymers [M(tdc)(bpy)] (M2+ = Fe2+, Co2+, Zn2+, Cd2+; tdc2- = 2,5-thiophenedicarboxylate).

    PubMed

    Kettner, Florian; Worch, Christian; Moellmer, Jens; Gläser, Roger; Staudt, Reiner; Krautscheid, Harald

    2013-08-01

    A series of isostructural 3D coordination polymers (3)∞[M(tdc)(bpy)] (M(2+) = Zn(2+), Cd(2+), Co(2+), Fe(2+); tdc(2-) = 2,5-thiophenedicarboxylate; bpy = 4,4'-bipyridine) was synthesized and characterized by X-ray diffraction, thermal analysis, and gas adsorption measurements. The materials show high thermal stability up to approximately 400 °C and a solvent induced phase transition. Single crystal X-ray structure determination was successfully performed for all compounds after the phase transition. In the zinc-based coordination polymer, various amounts of a second type of metal ions such as Co(2+) or Fe(2+) could be incorporated. Furthermore, the catalytic behavior of the homo- and heteronuclear 3D coordination polymers in an oxidation model reaction was investigated.

  9. Electronic Origins of the Variable Efficiency of Room-Temperature Methane Activation by Homo- and Heteronuclear Cluster Oxide Cations [XYO2](+) (X, Y = Al, Si, Mg): Competition between Proton-Coupled Electron Transfer and Hydrogen-Atom Transfer.

    PubMed

    Li, Jilai; Zhou, Shaodong; Zhang, Jun; Schlangen, Maria; Weiske, Thomas; Usharani, Dandamudi; Shaik, Sason; Schwarz, Helmut

    2016-06-29

    The reactivity of the homo- and heteronuclear oxide clusters [XYO2](+) (X, Y = Al, Si, Mg) toward methane was studied using Fourier transform ion cyclotron resonance mass spectrometry, in conjunction with high-level quantum mechanical calculations. The most reactive cluster by both experiment and theory is [Al2O2](•+). In its favorable pathway, this cluster abstracts a hydrogen atom by means of proton-coupled electron transfer (PCET) instead of following the conventional hydrogen-atom transfer (HAT) route. This mechanistic choice originates in the strong Lewis acidity of the aluminum site of [Al2O2](•+), which cleaves the C-H bond heterolytically to form an Al-CH3 entity, while the proton is transferred to the bridging oxygen atom of the cluster ion. In addition, a comparison of the reactivity of heteronuclear and homonuclear oxide clusters [XYO2](+) (X, Y = Al, Si, Mg) reveals a striking doping effect by aluminum. Thus, the vacant s-p hybrid orbital on Al acts as an acceptor of the electron pair from methyl anion (CH3(-)) and is therefore eminently important for bringing about thermal methane activation by PCET. For the Al-doped cluster ions, the spin density at an oxygen atom, which is crucial for the HAT mechanism, acts here as a spectator during the course of the PCET mediated C-H bond cleavage. A diagnostic plot of the deformation energy vis-à-vis the barrier shows the different HAT/PCET reactivity map for the entire series. This is a strong connection to the recently discussed mechanism of oxidative coupling of methane on magnesium oxide surfaces proceeding through Grignard-type intermediates. PMID:27241233

  10. Electronic Origins of the Variable Efficiency of Room-Temperature Methane Activation by Homo- and Heteronuclear Cluster Oxide Cations [XYO2](+) (X, Y = Al, Si, Mg): Competition between Proton-Coupled Electron Transfer and Hydrogen-Atom Transfer.

    PubMed

    Li, Jilai; Zhou, Shaodong; Zhang, Jun; Schlangen, Maria; Weiske, Thomas; Usharani, Dandamudi; Shaik, Sason; Schwarz, Helmut

    2016-06-29

    The reactivity of the homo- and heteronuclear oxide clusters [XYO2](+) (X, Y = Al, Si, Mg) toward methane was studied using Fourier transform ion cyclotron resonance mass spectrometry, in conjunction with high-level quantum mechanical calculations. The most reactive cluster by both experiment and theory is [Al2O2](•+). In its favorable pathway, this cluster abstracts a hydrogen atom by means of proton-coupled electron transfer (PCET) instead of following the conventional hydrogen-atom transfer (HAT) route. This mechanistic choice originates in the strong Lewis acidity of the aluminum site of [Al2O2](•+), which cleaves the C-H bond heterolytically to form an Al-CH3 entity, while the proton is transferred to the bridging oxygen atom of the cluster ion. In addition, a comparison of the reactivity of heteronuclear and homonuclear oxide clusters [XYO2](+) (X, Y = Al, Si, Mg) reveals a striking doping effect by aluminum. Thus, the vacant s-p hybrid orbital on Al acts as an acceptor of the electron pair from methyl anion (CH3(-)) and is therefore eminently important for bringing about thermal methane activation by PCET. For the Al-doped cluster ions, the spin density at an oxygen atom, which is crucial for the HAT mechanism, acts here as a spectator during the course of the PCET mediated C-H bond cleavage. A diagnostic plot of the deformation energy vis-à-vis the barrier shows the different HAT/PCET reactivity map for the entire series. This is a strong connection to the recently discussed mechanism of oxidative coupling of methane on magnesium oxide surfaces proceeding through Grignard-type intermediates.

  11. Exploring Chromophore-Binding Pocket: High-Resolution Solid-State H-C Interfacial Correlation NMR Spectra with Windowed PMLG Scheme.

    PubMed

    Song, Chen; Lang, Christina; Mailliet, Jo; Hughes, Jon; Gärtner, Wolfgang; Matysik, Jörg

    2012-02-01

    High-resolution two-dimensional (2D) (1)H-(13)C heteronuclear correlation spectra are recorded for selective observation of interfacial 3-5.5 Å contacts of the uniformly (13)C-labeled phycocyanobilin (PCB) chromophore with its unlabeled binding pocket. The experiment is based on a medium- and long-distance heteronuclear correlation (MELODI-HETCOR) method. For improving (1)H spectral resolution, a windowed phase-modulated Lee-Goldburg (wPMLG) decoupling scheme is applied during the t(1) evolution period. Our approach allows for identification of chromophore-protein interactions, in particular for elucidation of the hydrogen-bonding networks and charge distributions within the chromophore-binding pocket. The resulting pulse sequence is tested on the cyanobacterial (Cph1) phytochrome sensory module (residues 1-514, Cph1Δ2) containing uniformly (13)C- and (15)N-labeled PCB chromophore (u-[(13)C,(15)N]-PCB-Cph1Δ2) at 17.6 T. PMID:22303079

  12. Superadditive correlation.

    PubMed

    Giraud, B G; Heumann, J M; Lapedes, A S

    1999-05-01

    The fact that correlation does not imply causation is well known. Correlation between variables at two sites does not imply that the two sites directly interact, because, e.g., correlation between distant sites may be induced by chaining of correlation between a set of intervening, directly interacting sites. Such "noncausal correlation" is well understood in statistical physics: an example is long-range order in spin systems, where spins which have only short-range direct interactions, e.g., the Ising model, display correlation at a distance. It is less well recognized that such long-range "noncausal" correlations can in fact be stronger than the magnitude of any causal correlation induced by direct interactions. We call this phenomenon superadditive correlation (SAC). We demonstrate this counterintuitive phenomenon by explicit examples in (i) a model spin system and (ii) a model continuous variable system, where both models are such that two variables have multiple intervening pathways of indirect interaction. We apply the technique known as decimation to explain SAC as an additive, constructive interference phenomenon between the multiple pathways of indirect interaction. We also explain the effect using a definition of the collective mode describing the intervening spin variables. Finally, we show that the SAC effect is mirrored in information theory, and is true for mutual information measures in addition to correlation measures. Generic complex systems typically exhibit multiple pathways of indirect interaction, making SAC a potentially widespread phenomenon. This affects, e.g., attempts to deduce interactions by examination of correlations, as well as, e.g., hierarchical approximation methods for multivariate probability distributions, which introduce parameters based on successive orders of correlation. PMID:11969452

  13. 1H-13C/1H-15N Heteronuclear Dipolar Recoupling by R-Symmetry Sequences Under Fast Magic Angle Spinning for Dynamics Analysis of Biological and Organic Solids

    PubMed Central

    Hou, Guangjin; Byeon, In-Ja L.; Ahn, Jinwoo; Gronenborn, Angela M.; Polenova, Tatyana

    2011-01-01

    Fast magic angle spinning (MAS) NMR spectroscopy is becoming increasingly important in structural and dynamics studies of biological systems and inorganic materials. Superior spectral resolution due to the efficient averaging of the dipolar couplings can be attained at MAS frequencies of 40 kHz and higher with appropriate decoupling techniques, while proton detection gives rise to significant sensitivity gains, therefore making fast MAS conditions advantageous across the board compared with the conventional slow- and moderate-MAS approaches. At the same time, many of the dipolar recoupling approaches that currently constitute the basis for structural and dynamics studies of solid materials and that are designed for MAS frequencies of 20 kHz and below, fail above 30 kHz. In this report, we present an approach for 1H-13C/1H-15N heteronuclear dipolar recoupling under fast MAS conditions using R-type symmetry sequences, which is suitable even for fully protonated systems. A series of rotor-synchronized R-type symmetry pulse schemes are explored for the determination of structure and dynamics in biological and organic systems. The investigations of the performance of the various RNnv-symmetry sequences at the MAS frequency of 40 kHz experimentally and by numerical simulations on [U-13C,15N]-alanine and [U-13C,15N]-N-acetyl-valine, revealed excellent performance for sequences with high symmetry number ratio (N/2n > 2.5). Further applications of this approach are presented for two proteins, sparsely 13C/uniformly 15N enriched CAP-Gly domain of dynactin and U-13C,15N-Tyr enriched C-terminal domain of HIV-1 CA protein. 2D and 3D R1632-based DIPSHIFT experiments carried out at the MAS frequency of 40 kHz, yielded site-specific 1H-13C/1H-15N heteronuclear dipolar coupling constants for CAP-Gly and CTD CA, reporting on the dynamic behavior of these proteins on time scales of nano- to microseconds. The R-symmetry based dipolar recoupling under fast MAS is expected to find

  14. Determination of Relative Tensor Orientations by γ-encoded Chemical Shift Anisotropy/Heteronuclear Dipolar Coupling 3D NMR Spectroscopy in Biological Solids

    PubMed Central

    Hou, Guangjin; Paramasivam, Sivakumar; Byeon, In-Ja L.; Gronenborn, Angela M.

    2011-01-01

    In this paper, we present 3D chemical shift anisotropy (CSA)/dipolar coupling correlation experiments, based on γ-encoded R-type symmetry sequences. The γ-encoded correlation spectra are exquisitely sensitive to the relative orientation of the CSA and dipolar tensors and can provide important structural and dynamic information in peptides and proteins. We show that the first-order (m = ±1) and second-order (m = ±2) Hamiltonians in the R-symmetry recoupling sequences give rise to different correlation patterns due to their different dependencies on the crystallite orientation. The relative orientation between CSA and dipolar tensors can be determined by fitting the corresponding correlation patterns. The orientation of 15N CSA tensor in the quasi-molecular frame is determined by the relative Euler angles, αNH and βNH, when the combined symmetry schemes are applied for orientational studies of 1H-15N dipolar and 15N CSA tensors. The correlation experiments introduced here work at moderate magic angle spinning frequencies (10-20 kHz) and allow for simultaneous measurement of multiple sites of interest. We studied the orientational sensitivity of γ-encoded symmetry-based recoupling techniques numerically and experimentally. The results are demonstrated on [15N]-N-acetyl-valine (NAV) and N-formyl-Met-Leu-Phe (MLF) tripeptide. PMID:20936218

  15. Fluorine-Decoupled Carbon Spectroscopy for the Determination of Configuration at Fully Substituted, Trifluoromethyl- and Perfluoroalkyl-Bearing Carbons: Comparison with 19F–1H Heteronuclear Overhauser Effect Spectroscopy

    PubMed Central

    2016-01-01

    The synthesis of a series of α-trifluoromethylcyclohexanols and analogous trimethylsilyl ethers by addition of the Ruppert–Prakash reagent to substituted cyclohexanones is presented. A method for the assignment of configuration of such compounds, of related α-trifluoromethylcyclohexylamines and of quaternary trifluoromethyl-substituted carbons is described based on the determination of the 3JCH coupling constant between the fluorine-decoupled 13CF3 resonance and the vicinal hydrogens. This method is dubbed fluorine-decoupled carbon spectroscopy and abbreviated FDCS. The method is also applied to the configurational assignment of substances bearing mono-, di-, and perfluoroalkyl rather than trifluoromethyl groups. The configuration of all substances was verified by either 19F−1H heteronuclear Overhauser spectroscopy (HOESY) or X-ray crystallography. The relative merits of FDCS and HOESY are compared and contrasted. 2JCH, 3JCH, and 4JCH coupling constants to 19F decoupled CF3 groups in alkenes and arenes have also been determined and should prove to be useful in the structural assignment of trifluoromethylated alkenes and arenes. PMID:25561269

  16. Fluorine-decoupled carbon spectroscopy for the determination of configuration at fully substituted, trifluoromethyl- and perfluoroalkyl-bearing carbons: comparison with 19F-1H heteronuclear Overhauser effect spectroscopy.

    PubMed

    Mandhapati, Appi Reddy; Kato, Takayuki; Matsushita, Takahiko; Ksebati, Bashar; Vasella, Andrea; Böttger, Erik C; Crich, David

    2015-02-01

    The synthesis of a series of α-trifluoromethylcyclohexanols and analogous trimethylsilyl ethers by addition of the Ruppert-Prakash reagent to substituted cyclohexanones is presented. A method for the assignment of configuration of such compounds, of related α-trifluoromethylcyclohexylamines and of quaternary trifluoromethyl-substituted carbons is described based on the determination of the (3)J(CH) coupling constant between the fluorine-decoupled (13)CF3 resonance and the vicinal hydrogens. This method is dubbed fluorine-decoupled carbon spectroscopy and abbreviated FDCS. The method is also applied to the configurational assignment of substances bearing mono-, di-, and perfluoroalkyl rather than trifluoromethyl groups. The configuration of all substances was verified by either (19)F-(1)H heteronuclear Overhauser spectroscopy (HOESY) or X-ray crystallography. The relative merits of FDCS and HOESY are compared and contrasted. (2)J(CH), (3)J(CH), and (4)J(CH) coupling constants to (19)F decoupled CF3 groups in alkenes and arenes have also been determined and should prove to be useful in the structural assignment of trifluoromethylated alkenes and arenes.

  17. Determination of the Structural Parameters of Heteronuclear (Phthalocyaninato)bis(crownphthalocyaninato)lanthanide(III) Triple-Deckers in Solution by Simultaneous Analysis of NMR and Single-Crystal X-ray Data.

    PubMed

    Polovkova, Marina A; Martynov, Alexander G; Birin, Kirill P; Nefedov, Sergey E; Gorbunova, Yulia G; Tsivadze, Aslan Yu

    2016-09-19

    Application of a general and convenient approach to the synthesis of heteronuclear crown-substituted triple-decker phthalocyaninates afforded two series of complexes containing one dia- and one paramagnetic Ln(III) ion (for Y and almost the whole lanthanide family), [(15C5)4Pc]M*[(15C5)4Pc]M(Pc) (or [M*,M] for brevity sake), where (15C5) is 15-crown-5; (Pc(2-)) is phthalocyaninato dianion; and M ≠ M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This approach consists of using LaPc2 as an efficient Pc(2-) source. The solid-state structures of two complexes ([Tm*,Y] and [Yb*,Y]) were studied by single-crystal X-ray diffraction analysis, providing therefore a structural model for the assignment and analysis of (1)H NMR spectra of the complexes, which is strongly affected by the presence of paramagnetic lanthanide ions. Model validation was performed on complexes containing two different paramagnetic ions-[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm] and [Tm*,Tb]-synthesized by the above-mentioned method.

  18. A theoretical study on the molecular structure and vibrational (FT-IR and Raman) spectra of cyano-bridged heteronuclear polymeric complex of triethylenetetramine

    NASA Astrophysics Data System (ADS)

    Kürkçüoğlu, Güneş Süheyla; Çetinkaya, Fulya; Arslan, Taner

    The cyano bridged complex of triethylenetetramine was characterized by FT-IR, Raman spectroscopy and X-ray single crystal diffraction analysis. The molecular geometry and vibrational frequencies of the complex in the ground state have been calculated by using B3LYP density functional method with LANL2DZ basis set. A good correlation was found via comparison of the experimental and theoretical vibrational frequencies of complex. The complex of the type [Zn(teta)Ni(μ-CN)2(CN)2]n has been studied in the 4000-250 cm-1 region and assignment of all the observed bands were made. The analysis of the FT-IR and Raman spectra indicates that there are some structure spectra correlations.

  19. Correlative Tomography

    PubMed Central

    Burnett, T. L.; McDonald, S. A.; Gholinia, A.; Geurts, R.; Janus, M.; Slater, T.; Haigh, S. J.; Ornek, C.; Almuaili, F.; Engelberg, D. L.; Thompson, G. E.; Withers, P. J.

    2014-01-01

    Increasingly researchers are looking to bring together perspectives across multiple scales, or to combine insights from different techniques, for the same region of interest. To this end, correlative microscopy has already yielded substantial new insights in two dimensions (2D). Here we develop correlative tomography where the correlative task is somewhat more challenging because the volume of interest is typically hidden beneath the sample surface. We have threaded together x-ray computed tomography, serial section FIB-SEM tomography, electron backscatter diffraction and finally TEM elemental analysis all for the same 3D region. This has allowed observation of the competition between pitting corrosion and intergranular corrosion at multiple scales revealing the structural hierarchy, crystallography and chemistry of veiled corrosion pits in stainless steel. With automated correlative workflows and co-visualization of the multi-scale or multi-modal datasets the technique promises to provide insights across biological, geological and materials science that are impossible using either individual or multiple uncorrelated techniques. PMID:24736640

  20. Correlative Tomography

    NASA Astrophysics Data System (ADS)

    Burnett, T. L.; McDonald, S. A.; Gholinia, A.; Geurts, R.; Janus, M.; Slater, T.; Haigh, S. J.; Ornek, C.; Almuaili, F.; Engelberg, D. L.; Thompson, G. E.; Withers, P. J.

    2014-04-01

    Increasingly researchers are looking to bring together perspectives across multiple scales, or to combine insights from different techniques, for the same region of interest. To this end, correlative microscopy has already yielded substantial new insights in two dimensions (2D). Here we develop correlative tomography where the correlative task is somewhat more challenging because the volume of interest is typically hidden beneath the sample surface. We have threaded together x-ray computed tomography, serial section FIB-SEM tomography, electron backscatter diffraction and finally TEM elemental analysis all for the same 3D region. This has allowed observation of the competition between pitting corrosion and intergranular corrosion at multiple scales revealing the structural hierarchy, crystallography and chemistry of veiled corrosion pits in stainless steel. With automated correlative workflows and co-visualization of the multi-scale or multi-modal datasets the technique promises to provide insights across biological, geological and materials science that are impossible using either individual or multiple uncorrelated techniques.

  1. NMR-based Structural Analysis of the Complete Rough-type Lipopolysaccharide Isolated from Capnocytophaga canimorsus*

    PubMed Central

    Zähringer, Ulrich; Ittig, Simon; Lindner, Buko; Moll, Hermann; Schombel, Ursula; Gisch, Nicolas; Cornelis, Guy R.

    2014-01-01

    We here describe the NMR analysis of an intact lipopolysaccharide (LPS, endotoxin) in water with 1,2-dihexanoyl-sn-glycero-3-phosphocholine as detergent. When HPLC-purified rough-type LPS of Capnocytophaga canimorsus was prepared, 13C,15N labeling could be avoided. The intact LPS was analyzed by homonuclear (1H) and heteronuclear (1H,13C, and 1H,31P) correlated one- and two-dimensional NMR techniques as well as by mass spectrometry. It consists of a penta-acylated lipid A with an α-linked phosphoethanolamine attached to C-1 of GlcN (I) in the hybrid backbone, lacking the 4′-phosphate. The hydrophilic core oligosaccharide was found to be a complex hexasaccharide with two mannose (Man) and one each of 3-deoxy-d-manno-oct-2-ulosonic acid (Kdo), Gal, GalN, and l-rhamnose residues. Position 4 of Kdo is substituted by phosphoethanolamine, also present in position 6 of the branched ManI residue. This rough-type LPS is exceptional in that all three negative phosphate residues are “masked” by positively charged ethanolamine substituents, leading to an overall zero net charge, which has so far not been observed for any other LPS. In biological assays, the corresponding isolated lipid A was found to be endotoxically almost inactive. By contrast, the intact rough-type LPS described here expressed a 20,000-fold increased endotoxicity, indicating that the core oligosaccharide significantly contributes to the endotoxic potency of the whole rough-type C. canimorsus LPS molecule. Based on these findings, the strict view that lipid A alone represents the toxic center of LPS needs to be reassessed. PMID:24993825

  2. Changes to the Disordered Phase and Apatite Crystallite Morphology during Mineralization by an Acidic Mineral Binding Peptide from Osteonectin.

    PubMed

    Iline-Vul, Taly; Matlahov, Irina; Grinblat, Judith; Keinan-Adamsky, Keren; Goobes, Gil

    2015-09-14

    Noncollagenous proteins regulate the formation of the mineral constituent in hard tissue. The mineral formed contains apatite crystals coated by a functional disordered calcium phosphate phase. Although the crystalline phase of bone mineral was extensively investigated, little is known about the disordered layer's composition and structure, and less is known regarding the function of noncollagenous proteins in the context of this layer. In the current study, apatite was prepared with an acidic peptide (ON29) derived from the bone/dentin protein osteonectin. The mineral formed comprises needle-shaped hydroxyapatite crystals like in dentin and a stable disordered phase coating the apatitic crystals as shown using X-ray diffraction, transmission electron microscopy, and solid-state NMR techniques. The peptide, embedded between the mineral particles, reduces the overall phosphate content in the mineral formed as inferred from inductively coupled plasma and elemental analysis results. Magnetization transfers between disordered phase species and apatitic phase species are observed for the first time using 2D (1)H-(31)P heteronuclear correlation NMR measurements. The dynamics of phosphate magnetization transfers reveal that ON29 decreases significantly the amount of water molecules in the disordered phase and increases slightly their content at the ordered-disordered interface. The peptide decreases hydroxyl to disordered phosphate transfers within the surface layer but does not influence transfer within the bulk crystalline mineral. Overall, these results indicate that control of crystallite morphology and properties of the inorganic component in hard tissue by biomolecules is more involved than just direct interaction between protein functional groups and mineral crystal faces. Subtler mechanisms such as modulation of the disordered phase composition and structural changes at the ordered-disordered interface may be involved. PMID:26207448

  3. Correlative microscopy.

    PubMed

    Loussert Fonta, Céline; Humbel, Bruno M

    2015-09-01

    In recent years correlative microscopy, combining the power and advantages of different imaging system, e.g., light, electrons, X-ray, NMR, etc., has become an important tool for biomedical research. Among all the possible combinations of techniques, light and electron microscopy, have made an especially big step forward and are being implemented in more and more research labs. Electron microscopy profits from the high spatial resolution, the direct recognition of the cellular ultrastructure and identification of the organelles. It, however, has two severe limitations: the restricted field of view and the fact that no live imaging can be done. On the other hand light microscopy has the advantage of live imaging, following a fluorescently tagged molecule in real time and at lower magnifications the large field of view facilitates the identification and location of sparse individual cells in a large context, e.g., tissue. The combination of these two imaging techniques appears to be a valuable approach to dissect biological events at a submicrometer level. Light microscopy can be used to follow a labelled protein of interest, or a visible organelle such as mitochondria, in time, then the sample is fixed and the exactly same region is investigated by electron microscopy. The time resolution is dependent on the speed of penetration and fixation when chemical fixatives are used and on the reaction time of the operator for cryo-fixation. Light microscopy can also be used to identify cells of interest, e.g., a special cell type in tissue or cells that have been modified by either transfections or RNAi, in a large population of non-modified cells. A further application is to find fluorescence labels in cells on a large section to reduce searching time in the electron microscope. Multiple fluorescence labelling of a series of sections can be correlated with the ultrastructure of the individual sections to get 3D information of the distribution of the marked proteins: array

  4. Correlation spectrometer

    DOEpatents

    Sinclair, Michael B.; Pfeifer, Kent B.; Flemming, Jeb H.; Jones, Gary D.; Tigges, Chris P.

    2010-04-13

    A correlation spectrometer can detect a large number of gaseous compounds, or chemical species, with a species-specific mask wheel. In this mode, the spectrometer is optimized for the direct measurement of individual target compounds. Additionally, the spectrometer can measure the transmission spectrum from a given sample of gas. In this mode, infrared light is passed through a gas sample and the infrared transmission signature of the gasses present is recorded and measured using Hadamard encoding techniques. The spectrometer can detect the transmission or emission spectra in any system where multiple species are present in a generally known volume.

  5. Correlative microscopy.

    PubMed

    Loussert Fonta, Céline; Humbel, Bruno M

    2015-09-01

    In recent years correlative microscopy, combining the power and advantages of different imaging system, e.g., light, electrons, X-ray, NMR, etc., has become an important tool for biomedical research. Among all the possible combinations of techniques, light and electron microscopy, have made an especially big step forward and are being implemented in more and more research labs. Electron microscopy profits from the high spatial resolution, the direct recognition of the cellular ultrastructure and identification of the organelles. It, however, has two severe limitations: the restricted field of view and the fact that no live imaging can be done. On the other hand light microscopy has the advantage of live imaging, following a fluorescently tagged molecule in real time and at lower magnifications the large field of view facilitates the identification and location of sparse individual cells in a large context, e.g., tissue. The combination of these two imaging techniques appears to be a valuable approach to dissect biological events at a submicrometer level. Light microscopy can be used to follow a labelled protein of interest, or a visible organelle such as mitochondria, in time, then the sample is fixed and the exactly same region is investigated by electron microscopy. The time resolution is dependent on the speed of penetration and fixation when chemical fixatives are used and on the reaction time of the operator for cryo-fixation. Light microscopy can also be used to identify cells of interest, e.g., a special cell type in tissue or cells that have been modified by either transfections or RNAi, in a large population of non-modified cells. A further application is to find fluorescence labels in cells on a large section to reduce searching time in the electron microscope. Multiple fluorescence labelling of a series of sections can be correlated with the ultrastructure of the individual sections to get 3D information of the distribution of the marked proteins: array

  6. Site-resolved multiple-quantum filtered correlations and distance measurements by magic-angle spinning NMR: Theory and applications to spins with weak to vanishing quadrupolar couplings.

    PubMed

    Eliav, U; Haimovich, A; Goldbourt, A

    2016-01-14

    We discuss and analyze four magic-angle spinning solid-state NMR methods that can be used to measure internuclear distances and to obtain correlation spectra between a spin I = 1/2 and a half-integer spin S > 1/2 having a small quadrupolar coupling constant. Three of the methods are based on the heteronuclear multiple-quantum and single-quantum correlation experiments, that is, high rank tensors that involve the half spin and the quadrupolar spin are generated. Here, both zero and single-quantum coherence of the half spins are allowed and various coherence orders of the quadrupolar spin are generated, and filtered, via active recoupling of the dipolar interaction. As a result of generating coherence orders larger than one, the spectral resolution for the quadrupolar nucleus increases linearly with the coherence order. Since the formation of high rank tensors is independent of the existence of a finite quadrupolar interaction, these experiments are also suitable to materials in which there is high symmetry around the quadrupolar spin. A fourth experiment is based on the initial quadrupolar-driven excitation of symmetric high order coherences (up to p = 2S, where S is the spin number) and subsequently generating by the heteronuclear dipolar interaction higher rank (l + 1 or higher) tensors that involve also the half spins. Due to the nature of this technique, it also provides information on the relative orientations of the quadrupolar and dipolar interaction tensors. For the ideal case in which the pulses are sufficiently strong with respect to other interactions, we derive analytical expressions for all experiments as well as for the transferred echo double resonance experiment involving a quadrupolar spin. We show by comparison of the fitting of simulations and the analytical expressions to experimental data that the analytical expressions are sufficiently accurate to provide experimental (7)Li-(13)C distances in a complex of lithium, glycine, and water. Discussion

  7. Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2016-01-01

    Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D 1H/13C/1H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t1 and t3 periods, respectively. In addition to through-space and through-bond 13C/1H and 13C/13C chemical shift correlations, the 3D 1H/13C/1H experiment also provides a COSY-type 1H/1H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices (1H/1H chemical shift correlation spectrum) at different 13C chemical shift frequencies from the 3D 1H/13C/1H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D 1H/13C/1H experiment would be useful to study the structure and dynamics of a variety of chemical and biological

  8. Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2016-01-21

    Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D (1)H/(13)C/(1)H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t1 and t3 periods, respectively. In addition to through-space and through-bond (13)C/(1)H and (13)C/(13)C chemical shift correlations, the 3D (1)H/(13)C/(1)H experiment also provides a COSY-type (1)H/(1)H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices ((1)H/(1)H chemical shift correlation spectrum) at different (13)C chemical shift frequencies from the 3D (1)H/(13)C/(1)H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D (1)H/(13)C/(1)H experiment would be useful to study the structure and dynamics of

  9. Multidimensional J-driven NMR correlations by single-scan offset-encoded recoupling.

    PubMed

    Lin, Yulan; Lupulescu, Adonis; Frydman, Lucio

    2016-04-01

    Two-dimensional (2D) correlations between bonded heteroatoms, lie at the cornerstone of many uses given to contemporary nuclear magnetic resonance (NMR). Improving the efficiency with which these correlations are established is an important topic in modern NMR, with potential applications in rapid chemical analysis and dynamic biophysical studies. Alternatives have been developed over the last decade to speed up these experiments, based among others on reducing the number of data points that need to be sampled, and/or shortening the inter-scan delays. Approaches have also been proposed to forfeit multi-scan schemes altogether, and complete full 2D correlations in a single shot. Here we explore and discuss a new alternative enabling the collection of such very fast - in principle, single-scan - acquisitions of 2D heteronuclear correlations among bonded species, which operates on the basis of a partial reintroduction of J couplings. Similar approaches had been proposed in the past based on collecting coupled spectra for arrays of off-resonance decoupling values; the proposal that is here introduced operates on the basis of suitably incorporating frequency-swept pulses, into spin-echo sequences. Thanks to the offset-dependent amplitude modulations of the in- and anti-phase components that such sequences impart, chemical shifts of coupled but otherwise unobserved nuclear species, can be extracted from the relative intensities and phases of J-coupled multiplets observed in one-dimensional acquisitions. A description of the steps needed to implement this rapid acquisition approach in a quantitative fashion, as well as applications of the ensuing sequences, are presented. PMID:26852416

  10. Multidimensional J-driven NMR correlations by single-scan offset-encoded recoupling

    NASA Astrophysics Data System (ADS)

    Lin, Yulan; Lupulescu, Adonis; Frydman, Lucio

    2016-04-01

    Two-dimensional (2D) correlations between bonded heteroatoms, lie at the cornerstone of many uses given to contemporary nuclear magnetic resonance (NMR). Improving the efficiency with which these correlations are established is an important topic in modern NMR, with potential applications in rapid chemical analysis and dynamic biophysical studies. Alternatives have been developed over the last decade to speed up these experiments, based among others on reducing the number of data points that need to be sampled, and/or shortening the inter-scan delays. Approaches have also been proposed to forfeit multi-scan schemes altogether, and complete full 2D correlations in a single shot. Here we explore and discuss a new alternative enabling the collection of such very fast - in principle, single-scan - acquisitions of 2D heteronuclear correlations among bonded species, which operates on the basis of a partial reintroduction of J couplings. Similar approaches had been proposed in the past based on collecting coupled spectra for arrays of off-resonance decoupling values; the proposal that is here introduced operates on the basis of suitably incorporating frequency-swept pulses, into spin-echo sequences. Thanks to the offset-dependent amplitude modulations of the in- and anti-phase components that such sequences impart, chemical shifts of coupled but otherwise unobserved nuclear species, can be extracted from the relative intensities and phases of J-coupled multiplets observed in one-dimensional acquisitions. A description of the steps needed to implement this rapid acquisition approach in a quantitative fashion, as well as applications of the ensuing sequences, are presented.

  11. Correlation in instruments - Cross correlation flowmeters

    NASA Astrophysics Data System (ADS)

    Beck, M. S.

    1981-01-01

    The principles of cross-correlation flowmeters are presented demonstrating methods of identifying dynamic properties of telecommunication, structural, and process systems. The flowmeters are designed for measurements of the transit time of a tagging signal such as turbulence or clumps of particles in the flow between two axially separated sensors; the transit time is measured by a cross-correlator. Cross-correlation flowmeters can reduce large scale integrated circuit costs and will be applied to environmental and industrial measurement problems.

  12. HyperSPASM NMR: A New Approach to Single-Shot 2D Correlations on DNP-Enhanced Samples

    PubMed Central

    Donovan, Kevin J.; Frydman, Lucio

    2016-01-01

    Dissolution DNP experiments are limited to a single or at most a few scan, before the non-Boltzmann magnetization has been. This makes it impractical to record 2D NMR data by conventional, t1-incremented schemes. Here a new approach termed HyperSPASM to establish 2D heteronuclear correlations in a single scan is reported, aimed at dealing with this kind of challenge. The HyperSPASM experiment relies on imposing an amplitude-modulation of the data by a single Δt1 indirect-domain evolution time, and subsequently monitoring the imparted encoding on separate echo and the anti-echo pathway signals within a single continuous acquisition. This is implemented via the use of alternating, switching, coherence selection gradients. As a result of these manipulations the phase imparted by a heteronucleus over its indirect domain evolution can be accurately extracted, and 2D data unambiguously reconstructed with a single-shot excitation. The nature of this sequence makes the resulting experiment particularly well suited for the collecting indirectly-detected HSQC data on hyperpolarized samples. The potential of the ensuing “HyperSPASM” method is exemplified with natural-abundance hyperpolarized correlations on model systems. PMID:23159821

  13. Correlation of tryptophan fluorescence intensity decay parameters with sup 1 H NMR-determined rotamer conformations: (tryptophan sup 2 )oxytocin

    SciTech Connect

    Ross, J.B.A.; Schwartz, G.P.; Laws, W.R. ); Wyssbrod, H.R.; Porter, R.A. ); Michaels, C.A. )

    1992-02-18

    While the fluorescence decay kinetics of tyrosine model compounds can be explained in terms of heterogeneity derived from the three ground-state {chi}{sup 1} rotamers, a similar correlation has yet to be directly observed for a tryptophan residue. In addition, the asymmetric indole ring might also lead to heterogeneity from {chi}{sup 2} rotations. In this paper, the time-resolved and steady-state fluorescence properties of (tryptophan{sup 2})oxytocin at pH 3 are presented and compared with {sup 1}H NMR results. According to the unrestricted analyses of individual fluorescence decay curves taken as a function of emission wavelength-independent decay constants, only three exponential terms are required. In addition, the preexponential weighting factors (amplitudes) have the same relative relationship (weights) as the {sup 1}H NMR-determined {chi}{sup 1} rotamer populations of the indole side chain. {sup 15}N was used in heteronuclear coupling experiments to confirm the rotamer assignments. Inclusion of a linked function restricting the decay amplitudes to the {chi}{sup 1} rotamer populations in the individual decay curve analyses and in the global analysis confirms this correlation. According to qualitative nuclear Overhauser data, there are two {chi}{sup 2} populations.

  14. Pursuing structure in microcrystalline solids with independent molecules in the unit cell using 1H–13C correlation data

    PubMed Central

    Harper, James K.; Strohmeier, Mark; Grant, David M.

    2007-01-01

    The 1H–13C solid-state NMR heteronuclear correlation (HETCOR) experiment is demonstrated to provide shift assignments in certain powders that have two or more structurally independent molecules in the unit cell (i.e. multiple molecules per asymmetric unit). Although this class of solids is often difficult to characterize using other methods, HETCOR provides both the conventional assignment of shifts to molecular positions and associates many resonances with specific molecules in the asymmetric unit. Such assignments facilitate conformational characterization of the individual molecules of the asymmetric unit and the first such characterization solely from solid-state NMR data is described. HETCOR offers advantages in sensitivity over prior methods that assign resonances in the asymmetric unit by 13C–13C correlations and therefore allows shorter average analysis times in natural abundance materials. The 1H–13C analysis is demonstrated first on materials with known shift assignments from INADEQUATE data (santonin and Ca(OAc)2 phase I) to verify the technique and subsequently is extended to a pair of unknown solids: (+)-catechin and Ca(OAc)2 phase II. Sufficient sensitivity and resolution is achieved in the spectra to provide assignments to one of the specific molecules of the asymmetric unit at over 54% of the sites. PMID:17869558

  15. Fast robust correlation.

    PubMed

    Fitch, Alistair J; Kadyrov, Alexander; Christmas, William J; Kittler, Josef

    2005-08-01

    A new, fast, statistically robust, exhaustive, translational image-matching technique is presented: fast robust correlation. Existing methods are either slow or non-robust, or rely on optimization. Fast robust correlation works by expressing a robust matching surface as a series of correlations. Speed is obtained by computing correlations in the frequency domain. Computational cost is analyzed and the method is shown to be fast. Speed is comparable to conventional correlation and, for large images, thousands of times faster than direct robust matching. Three experiments demonstrate the advantage of the technique over standard correlation.

  16. IAA Correlator Center

    NASA Technical Reports Server (NTRS)

    Surkis, Igor; Ken, Voitsekh; Melnikov, Alexey; Mishin, Vladimir; Sokolova, Nadezda; Shantyr, Violet; Zimovsky, Vladimir

    2013-01-01

    The activities of the six-station IAA RAS correlator include regular processing of national geodetic VLBI programs Ru-E, Ru-U, and Ru-F. The Ru-U sessions have been transferred in e-VLBI mode and correlated in the IAA Correlator Center automatically since 2011. The DiFX software correlator is used at the IAA in some astrophysical experiments.

  17. What Is Strong Correlation?

    ERIC Educational Resources Information Center

    Kozak, Marcin

    2009-01-01

    Interpretation of correlation is often based on rules of thumb in which some boundary values are given to help decide whether correlation is non-important, weak, strong or very strong. This article shows that such rules of thumb may do more harm than good, and instead of supporting interpretation of correlation--which is their aim--they teach a…

  18. Lipid-Protein Correlations in Nanoscale Phospholipid Bilayers by Solid-State NMR

    PubMed Central

    Kijac, Aleksandra; Shih, Amy Y.; Nieuwkoop, Andrew J.; Schulten, Klaus; Sligar, Stephen G.; Rienstra, Chad M.

    2011-01-01

    Nanodiscs are an example of discoidal nanoscale lipid/protein particles that have been extremely useful for the biochemical and biophysical characterization of membrane proteins. They are discoidal lipid bilayer fragments encircled and stabilized by two amphipathic helical proteins named membrane scaffolding protein (MSP), ~10 nm in size. Nanodiscs are homogeneous, easily prepared with reproducible success, amenable to preparations with a variety of lipids, and stable under a range of temperatures. Here we present solid-state NMR (SSNMR) studies on lyophilized, rehydrated POPC Nanodiscs prepared with uniformly 13C, 15N-labeled MSP1D1 (Δ1-11 truncated MSP). Under these conditions, by SSNMR we directly determine the gel-to-liquid crystal lipid phase transition to be at 3 ± 2 °C. Above this phase transition, the lipid 1H signals have slow transverse relaxation, enabling filtering experiments as previously demonstrated for lipid vesicles. We incorporate this approach into two- and three-dimensional heteronuclear SSNMR experiments to examine the MSP1D1 residues interfacing with the lipid bilayer. These 1H-13C and 1H-13C-13C correlation spectra are used to identify and quantify the number of lipid-correlated and solvent-exposed residues by amino acid type, which furthermore is compared with molecular dynamics studies of MSP1D1 in Nanodiscs. This study demonstrates the utility of SSNMR experiments with Nanodiscs for examining lipid-protein interfaces and has important applications for future structural studies of membrane proteins in physiologically relevant formulations. PMID:20804175

  19. Optical correlator tracking nonlinearity

    NASA Astrophysics Data System (ADS)

    Gregory, Don A.; Kirsch, James C.; Johnson, John L.

    1987-01-01

    A limitation observed in the tracking ability of optical correlators is reported. It is shown by calculations that an inherent nonlinearity exists in many optical correlator configurations, with the problem manifesting itself in a mismatch of the input scene with the position of the correlation signal. Results indicate that some care must be given to the selection of components and their configuration in constructing an optical correlator which exhibits true translational invariance. An input test scene is shown along with the correlation spot and cross hairs from a contrast detector; the offset is apparent.

  20. Correlations in Werner States

    NASA Astrophysics Data System (ADS)

    Luo, Shun-Long; Li, Nan

    2008-02-01

    Werner states are paradigmatic examples of quantum states and play an innovative role in quantum information theory. In investigating the correlating capability of Werner states, we find the curious phenomenon that quantum correlations, as quantified by the entanglement of formation, may exceed the total correlations, as measured by the quantum mutual information. Consequently, though the entanglement of formation is so widely used in quantifying entanglement, it cannot be interpreted as a consistent measure of quantum correlations per se if we accept the folklore that total correlations are measured (or rather upper bounded) by the quantum mutual information.

  1. High-resolution correlation

    NASA Astrophysics Data System (ADS)

    Nelson, D. J.

    2007-09-01

    In the basic correlation process a sequence of time-lag-indexed correlation coefficients are computed as the inner or dot product of segments of two signals. The time-lag(s) for which the magnitude of the correlation coefficient sequence is maximized is the estimated relative time delay of the two signals. For discrete sampled signals, the delay estimated in this manner is quantized with the same relative accuracy as the clock used in sampling the signals. In addition, the correlation coefficients are real if the input signals are real. There have been many methods proposed to estimate signal delay to more accuracy than the sample interval of the digitizer clock, with some success. These methods include interpolation of the correlation coefficients, estimation of the signal delay from the group delay function, and beam forming techniques, such as the MUSIC algorithm. For spectral estimation, techniques based on phase differentiation have been popular, but these techniques have apparently not been applied to the correlation problem . We propose a phase based delay estimation method (PBDEM) based on the phase of the correlation function that provides a significant improvement of the accuracy of time delay estimation. In the process, the standard correlation function is first calculated. A time lag error function is then calculated from the correlation phase and is used to interpolate the correlation function. The signal delay is shown to be accurately estimated as the zero crossing of the correlation phase near the index of the peak correlation magnitude. This process is nearly as fast as the conventional correlation function on which it is based. For real valued signals, a simple modification is provided, which results in the same correlation accuracy as is obtained for complex valued signals.

  2. RHIC DATA CORRELATION METHODOLOGY.

    SciTech Connect

    MICHNOFF,R.; D'OTTAVIO,T.; HOFF,L.; MACKAY,W.; SATOGATA,T.

    1999-03-29

    A requirement for RHIC data plotting software and physics analysis is the correlation of data from all accelerator data gathering systems. Data correlation provides the capability for a user to request a plot of multiple data channels vs. time, and to make meaningful time-correlated data comparisons. The task of data correlation for RHIC requires careful consideration because data acquisition triggers are generated from various asynchronous sources including events from the RHIC Event Link, events from the two Beam Sync Links, and other unrelated clocks. In order to correlate data from asynchronous acquisition systems a common time reference is required. The RHIC data correlation methodology will allow all RHIC data to be converted to a common wall clock time, while still preserving native acquisition trigger information. A data correlation task force team, composed of the authors of this paper, has been formed to develop data correlation design details and provide guidelines for software developers. The overall data correlation methodology will be presented in this paper.

  3. ALMA correlator computer systems

    NASA Astrophysics Data System (ADS)

    Pisano, Jim; Amestica, Rodrigo; Perez, Jesus

    2004-09-01

    We present a design for the computer systems which control, configure, and monitor the Atacama Large Millimeter Array (ALMA) correlator and process its output. Two distinct computer systems implement this functionality: a rack- mounted PC controls and monitors the correlator, and a cluster of 17 PCs process the correlator output into raw spectral results. The correlator computer systems interface to other ALMA computers via gigabit Ethernet networks utilizing CORBA and raw socket connections. ALMA Common Software provides the software infrastructure for this distributed computer environment. The control computer interfaces to the correlator via multiple CAN busses and the data processing computer cluster interfaces to the correlator via sixteen dedicated high speed data ports. An independent array-wide hardware timing bus connects to the computer systems and the correlator hardware ensuring synchronous behavior and imposing hard deadlines on the control and data processor computers. An aggregate correlator output of 1 gigabyte per second with 16 millisecond periods and computational data rates of approximately 1 billion floating point operations per second define other hard deadlines for the data processing computer cluster.

  4. Explorations in Statistics: Correlation

    ERIC Educational Resources Information Center

    Curran-Everett, Douglas

    2010-01-01

    Learning about statistics is a lot like learning about science: the learning is more meaningful if you can actively explore. This sixth installment of "Explorations in Statistics" explores correlation, a familiar technique that estimates the magnitude of a straight-line relationship between two variables. Correlation is meaningful only when the…

  5. Haystack Observatory VLBI Correlator

    NASA Technical Reports Server (NTRS)

    Titus, Mike; Cappallo, Roger; Corey, Brian; Dudevoir, Kevin; Niell, Arthur; Whitney, Alan

    2013-01-01

    This report summarizes the activities of the Haystack Correlator during 2012. Highlights include finding a solution to the DiFX InfiniBand timeout problem and other DiFX software development, conducting a DBE comparison test following the First International VLBI Technology Workshop, conducting a Mark IV and DiFX correlator comparison, more broadband delay experiments, more u- VLBI Galactic Center observations, and conversion of RDV session processing to the Mark IV/HOPS path. Non-real-time e-VLBI transfers and engineering support of other correlators continued.

  6. Correlation Plenoptic Imaging.

    PubMed

    D'Angelo, Milena; Pepe, Francesco V; Garuccio, Augusto; Scarcelli, Giuliano

    2016-06-01

    Plenoptic imaging is a promising optical modality that simultaneously captures the location and the propagation direction of light in order to enable three-dimensional imaging in a single shot. However, in standard plenoptic imaging systems, the maximum spatial and angular resolutions are fundamentally linked; thereby, the maximum achievable depth of field is inversely proportional to the spatial resolution. We propose to take advantage of the second-order correlation properties of light to overcome this fundamental limitation. In this Letter, we demonstrate that the correlation in both momentum and position of chaotic light leads to the enhanced refocusing power of correlation plenoptic imaging with respect to standard plenoptic imaging. PMID:27314718

  7. Correlation Plenoptic Imaging.

    PubMed

    D'Angelo, Milena; Pepe, Francesco V; Garuccio, Augusto; Scarcelli, Giuliano

    2016-06-01

    Plenoptic imaging is a promising optical modality that simultaneously captures the location and the propagation direction of light in order to enable three-dimensional imaging in a single shot. However, in standard plenoptic imaging systems, the maximum spatial and angular resolutions are fundamentally linked; thereby, the maximum achievable depth of field is inversely proportional to the spatial resolution. We propose to take advantage of the second-order correlation properties of light to overcome this fundamental limitation. In this Letter, we demonstrate that the correlation in both momentum and position of chaotic light leads to the enhanced refocusing power of correlation plenoptic imaging with respect to standard plenoptic imaging.

  8. Ozone Correlative Measurements Workshop

    NASA Technical Reports Server (NTRS)

    Hilsenrath, E. (Editor)

    1985-01-01

    A study was conducted to determine the necessary parameters for the correlation of data on Earth ozone. Topics considered were: (1) measurement accuracy; (2) equipment considerations (SBUV); and (3) ground based measurements to support satellite data.

  9. Extractable Work from Correlations

    NASA Astrophysics Data System (ADS)

    Perarnau-Llobet, Martí; Hovhannisyan, Karen V.; Huber, Marcus; Skrzypczyk, Paul; Brunner, Nicolas; Acín, Antonio

    2015-10-01

    Work and quantum correlations are two fundamental resources in thermodynamics and quantum information theory. In this work, we study how to use correlations among quantum systems to optimally store work. We analyze this question for isolated quantum ensembles, where the work can be naturally divided into two contributions: a local contribution from each system and a global contribution originating from correlations among systems. We focus on the latter and consider quantum systems that are locally thermal, thus from which any extractable work can only come from correlations. We compute the maximum extractable work for general entangled states, separable states, and states with fixed entropy. Our results show that while entanglement gives an advantage for small quantum ensembles, this gain vanishes for a large number of systems.

  10. Photothermal absorption correlation spectroscopy.

    PubMed

    Octeau, Vivien; Cognet, Laurent; Duchesne, Laurence; Lasne, David; Schaeffer, Nicolas; Fernig, David G; Lounis, Brahim

    2009-02-24

    Fluorescence correlation spectroscopy (FCS) is a popular technique, complementary to cell imaging for the investigation of dynamic processes in living cells. Based on fluorescence, this single molecule method suffers from artifacts originating from the poor fluorophore photophysics: photobleaching, blinking, and saturation. To circumvent these limitations we present here a new correlation method called photothermal absorption correlation spectroscopy (PhACS) which relies on the absorption properties of tiny nano-objects. PhACS is based on the photothermal heterodyne detection technique and measures akin FCS, the time correlation function of the detected signals. Application of this technique to the precise determination of the hydrodynamic sizes of different functionalized gold nanoparticles are presented, highlighting the potential of this method. PMID:19236070

  11. Personality correlates of homophobia.

    PubMed

    Johnson, M E; Brems, C; Alford-Keating, P

    1997-01-01

    This study explored the relationship between homophobia and several personality traits (empathy, religiosity, and coping style) in the context of respondents' gender and age. The sample consisted of 714 college students who responded to the Homophobia Attitude Scale (HAS) and personality trait scales. Results revealed that women endorsed fewer homophobic attitudes, beliefs, and behaviors than men and that age was negatively correlated with homophobia. Empathic concern and perspective taking were significantly correlated with lower overall homophobic attitudes, less affect discomfort in regard to gays, and less likelihood to abridge the human rights of gays. Religiosity was significantly correlated with more biased beliefs about the origins of homophobia, greater affective discomfort around gays, less endorsement of human rights for gays, and greater homophobia. Use of denial and isolation as coping styles were positively related to homophobia and use of turning against style was negatively correlated.

  12. Tsukuba VLBI Correlator

    NASA Technical Reports Server (NTRS)

    Kurihara, Shinobu; Nozawa, Kentaro

    2013-01-01

    The K5/VSSP software correlator (Figure 1), located in Tsukuba, Japan, is operated by the Geospatial Information Authority of Japan (GSI). It is fully dedicated to processing the geodetic VLBI sessions of the International VLBI Service for Geodesy and Astrometry. All of the weekend IVS Intensives (INT2) and the Japanese domestic VLBI observations organized by GSI were processed at the Tsukuba VLBI Correlator.

  13. Cross-correlation beamforming

    NASA Astrophysics Data System (ADS)

    Ruigrok, Elmer; Gibbons, Steven; Wapenaar, Kees

    2016-10-01

    An areal distribution of sensors can be used for estimating the direction of incoming waves through beamforming. Beamforming may be implemented as a phase-shifting and stacking of data recorded on the different sensors (i.e., conventional beamforming). Alternatively, beamforming can be applied to cross-correlations between the waveforms on the different sensors. We derive a kernel for beamforming cross-correlated data and call it cross-correlation beamforming (CCBF). We point out that CCBF has slightly better resolution and aliasing characteristics than conventional beamforming. When auto-correlations are added to CCBF, the array response functions are the same as for conventional beamforming. We show numerically that CCBF is more resilient to non-coherent noise. Furthermore, we illustrate that with CCBF individual receiver-pairs can be removed to improve mapping to the slowness domain. An additional flexibility of CCBF is that cross-correlations can be time-windowed prior to beamforming, e.g., to remove the directionality of a scattered wavefield. The observations on synthetic data are confirmed with field data from the SPITS array (Svalbard). Both when beamforming an earthquake arrival and when beamforming ambient noise, CCBF focuses more of the energy to a central beam. Overall, the main advantage of CCBF is noise suppression and its flexibility to remove station pairs that deteriorate the signal-related beampower.

  14. Geometrically representing spin correlations

    NASA Astrophysics Data System (ADS)

    White, Ian G.; Mirasola, Anthony; Hollingsworth, Jacob; Mukherjee, Rick; Hazzard, Kaden R. A.

    2016-05-01

    We develop a general method to visualize spin correlations, and we demonstrate its usefulness in ultracold matter from fermions in lattices to trapped ions and ultracold molecules. Correlations are of fundamental interest in many-body physics: they characterize phases in condensed matter and AMO, and are required for quantum sensing and computing. However, it is often difficult to understand even the simplest correlations - for example between two spin-1/2's - directly from the components Cab = - for { a , b } ∈ { x , y , z } . Not only are the nine independent Cab unwieldy, but considering the components also obscures the natural geometric structure. For example, simple spin rotations lead to complex transformations among the nine Cab. We provide a one-to-one map between the spin correlations and certain three-dimensional objects, analogous to the map between single spins and Bloch vectors. This object makes the geometric structure of the correlations manifest. Moreover, much as one can reason geometrically about dynamics using a Bloch vector - e.g. a magnetic field causes it to precess and dephasing causes it to shrink - we show that analogous reasoning holds for our visualization method.

  15. Correlation-Peak Imaging

    NASA Astrophysics Data System (ADS)

    Ziegler, A.; Metzler, A.; Köckenberger, W.; Izquierdo, M.; Komor, E.; Haase, A.; Décorps, M.; von Kienlin, M.

    1996-08-01

    Identification and quantitation in conventional1H spectroscopic imagingin vivois often hampered by the small chemical-shift range. To improve the spectral resolution of spectroscopic imaging, homonuclear two-dimensional correlation spectroscopy has been combined with phase encoding of the spatial dimensions. From the theoretical description of the coherence-transfer signal in the Fourier-transform domain, a comprehensive acquisition and processing strategy is presented that includes optimization of the width and the position of the acquisition windows, matched filtering of the signal envelope, and graphical presentation of the cross peak of interest. The procedure has been applied to image the spatial distribution of the correlation peaks from specific spin systems in the hypocotyl of castor bean (Ricinus communis) seedlings. Despite the overlap of many resonances, correlation-peak imaging made it possible to observe a number of proton resonances, such as those of sucrose, β-glucose, glutamine/glutamate, lysine, and arginine.

  16. Advanced quantum noise correlations

    NASA Astrophysics Data System (ADS)

    Vogl, Ulrich; Glasser, Ryan T.; Clark, Jeremy B.; Glorieux, Quentin; Li, Tian; Corzo, Neil V.; Lett, Paul D.

    2014-01-01

    We use the quantum correlations of twin beams of light to investigate the fundamental addition of noise when one of the beams propagates through a fast-light medium based on phase-insensitive gain. The experiment is based on two successive four-wave mixing processes in rubidium vapor, which allow for the generation of bright two-mode-squeezed twin beams followed by a controlled advancement while maintaining the shared quantum correlations between the beams. The demonstrated effect allows the study of irreversible decoherence in a medium exhibiting anomalous dispersion, and for the first time shows the advancement of a bright nonclassical state of light. The advancement and corresponding degradation of the quantum correlations are found to be operating near the fundamental quantum limit imposed by using a phase-insensitive amplifier.

  17. The VLBA Correlator

    NASA Astrophysics Data System (ADS)

    Romney, J. D.

    1995-05-01

    The VLBA correlator has been operational for somewhat more than a year. Since the beginning of 1995, it has operated at 54% efficiency (i.e., that fraction of scheduled production time leads directly to finished results). After correcting for effects of the playback speedup and the part-time production schedule, this corresponds to a 39% net operational efficiency of the VLBA instrument over the same interval. The current operational system includes most of the capabilities originally planned for the correlator's initial configuration. Two important exceptions could not be included: narrowband (less than 250 kHz bandwidth) spectroscopy, and various forms of sub-arraying. On the other hand, two capabilities not planned until later have been achieved: cross-polarized correlation and an extremely accurate fringe model. Parts of the real-time control software are currently being rewritten. The goals of this effort are both scientific, including support for narrowband and sub-arrayed observations, and technical, providing a more secure basis for development of additional capabilities in future phases. Among the most promising of these later features is a frequency-dependent signal gate, which will enable gated, de-dispersed interferometry of pulsars. The correlator is a 20-station system, capable of processing data rates up to the VLBA's maximicrons of 512 Mbit/s, with spectral resolution up to 2048 points per baseline. Its design is based on an ``FX'' architecture, performing a fast Fourier transform operation on segmented input signal streams, followed by a pointwise cross-multiplication operation and subsequent integration. This approach makes possible a relatively inexpensive, flexible yet simple hardware organization, and in turn a fairly simple structure of the control software. It provides several enhancements of sensitivity relative to a conventional lag correlator. Facilities included in the VLBA array and correlator for dealing with the less favorable aspects

  18. Correlation ion mobility spectroscopy

    DOEpatents

    Pfeifer, Kent B.; Rohde, Steven B.

    2008-08-26

    Correlation ion mobility spectrometry (CIMS) uses gating modulation and correlation signal processing to improve IMS instrument performance. Closely spaced ion peaks can be resolved by adding discriminating codes to the gate and matched filtering for the received ion current signal, thereby improving sensitivity and resolution of an ion mobility spectrometer. CIMS can be used to improve the signal-to-noise ratio even for transient chemical samples. CIMS is especially advantageous for small geometry IMS drift tubes that can otherwise have poor resolution due to their small size.

  19. FONO: a difficult case for theory. The ELF and ELI-D topological studies on the chemical bonding using correlated wavefunctions.

    PubMed

    Berski, Slawomir; Gordon, Agnieszka J; Latajka, Zdzislaw

    2013-04-01

    The complicated nature of the chemical bonding in cis and trans isomers of F-O-N=O is discussed based on the results obtained from the topological analysis of electron localization function (η) (ELF), electron localizability index (Y(D)(σ)), and electron density (ρ). The calculations have been performed for correlated wavefunctions using the CCSD and CASSCF methods. The F-O1 bond with non-bonding basins, V(F) and V(')(O1), belongs to the protocovalent type (η,Y(D)(σ)) and its total population ranges between 0.2 and 0.4e. The central N-O1 bond in the cis form is protocovalent (η, Y(D)(σ)) with two basins, V(N) and V(O1). The total population oscillates between 0.7 and 0.9e. In the trans isomer, topology of ELF depends on used method. At the CCSD level only one non-bonding basin, V(N), is observed (η). Its population is about 0.5e. According to the definition of a heteronuclear charge-shift (CS) bond, only N-O1 bond in trans-FONO belongs to the CS class. A relation between η- and ρ-topology and N-O1 bond length is discussed.

  20. FONO: A difficult case for theory. The ELF and ELI-D topological studies on the chemical bonding using correlated wavefunctions

    NASA Astrophysics Data System (ADS)

    Berski, Slawomir; Gordon, Agnieszka J.; Latajka, Zdzislaw

    2013-04-01

    The complicated nature of the chemical bonding in cis and trans isomers of F-O-N=O is discussed based on the results obtained from the topological analysis of electron localization function (η) (ELF), electron localizability index (Y_D^σ), and electron density (ρ). The calculations have been performed for correlated wavefunctions using the CCSD and CASSCF methods. The F-O1 bond with non-bonding basins, V(F) and V'(O1), belongs to the protocovalent type (η,Y_D^σ) and its total population ranges between 0.2 and 0.4e. The central N-O1 bond in the cis form is protocovalent (η, Y_D^σ) with two basins, V(N) and V(O1). The total population oscillates between 0.7 and 0.9e. In the trans isomer, topology of ELF depends on used method. At the CCSD level only one non-bonding basin, V(N), is observed (η). Its population is about 0.5e. According to the definition of a heteronuclear charge-shift (CS) bond, only N-O1 bond in trans-FONO belongs to the CS class. A relation between η- and ρ-topology and N-O1 bond length is discussed.

  1. Cross-Correlated Relaxation of Dipolar Coupling and Chemical-Shift Anisotropy in Magic-Angle Spinning R1ρ NMR Measurements: Application to Protein Backbone Dynamics Measurements.

    PubMed

    Kurauskas, Vilius; Weber, Emmanuelle; Hessel, Audrey; Ayala, Isabel; Marion, Dominique; Schanda, Paul

    2016-09-01

    Transverse relaxation rate measurements in magic-angle spinning solid-state nuclear magnetic resonance provide information about molecular motions occurring on nanosecond-to-millisecond (ns-ms) time scales. The measurement of heteronuclear ((13)C, (15)N) relaxation rate constants in the presence of a spin-lock radiofrequency field (R1ρ relaxation) provides access to such motions, and an increasing number of studies involving R1ρ relaxation in proteins have been reported. However, two factors that influence the observed relaxation rate constants have so far been neglected, namely, (1) the role of CSA/dipolar cross-correlated relaxation (CCR) and (2) the impact of fast proton spin flips (i.e., proton spin diffusion and relaxation). We show that CSA/D CCR in R1ρ experiments is measurable and that the CCR rate constant depends on ns-ms motions; it can thus provide insight into dynamics. We find that proton spin diffusion attenuates this CCR due to its decoupling effect on the doublet components. For measurements of dynamics, the use of R1ρ rate constants has practical advantages over the use of CCR rates, and this article reveals factors that have so far been disregarded and which are important for accurate measurements and interpretation. PMID:27500976

  2. Cross-Correlated Relaxation of Dipolar Coupling and Chemical-Shift Anisotropy in Magic-Angle Spinning R1ρ NMR Measurements: Application to Protein Backbone Dynamics Measurements.

    PubMed

    Kurauskas, Vilius; Weber, Emmanuelle; Hessel, Audrey; Ayala, Isabel; Marion, Dominique; Schanda, Paul

    2016-09-01

    Transverse relaxation rate measurements in magic-angle spinning solid-state nuclear magnetic resonance provide information about molecular motions occurring on nanosecond-to-millisecond (ns-ms) time scales. The measurement of heteronuclear ((13)C, (15)N) relaxation rate constants in the presence of a spin-lock radiofrequency field (R1ρ relaxation) provides access to such motions, and an increasing number of studies involving R1ρ relaxation in proteins have been reported. However, two factors that influence the observed relaxation rate constants have so far been neglected, namely, (1) the role of CSA/dipolar cross-correlated relaxation (CCR) and (2) the impact of fast proton spin flips (i.e., proton spin diffusion and relaxation). We show that CSA/D CCR in R1ρ experiments is measurable and that the CCR rate constant depends on ns-ms motions; it can thus provide insight into dynamics. We find that proton spin diffusion attenuates this CCR due to its decoupling effect on the doublet components. For measurements of dynamics, the use of R1ρ rate constants has practical advantages over the use of CCR rates, and this article reveals factors that have so far been disregarded and which are important for accurate measurements and interpretation.

  3. Correlates of School Stress.

    ERIC Educational Resources Information Center

    Matthews, Doris B.

    As part of a continuing series of research studies on stress in schools, this study examined the construct validity of peripheral temperature at the fingertips as a measure of school stress. Measurements were made in classes selected at random from 11 volunteer schools in South Carolina. Three types of correlational studies were undertaken: (1)…

  4. Neuroanatomical Correlates of Intelligence

    ERIC Educational Resources Information Center

    Luders, Eileen; Narr, Katherine L.; Thompson, Paul M.; Toga, Arthur W.

    2009-01-01

    With the advancement of image acquisition and analysis methods in recent decades, unique opportunities have emerged to study the neuroanatomical correlates of intelligence. Traditional approaches examining global measures have been complemented by insights from more regional analyses based on pre-defined areas. Newer state-of-the-art approaches…

  5. Correlational Comparison in English

    ERIC Educational Resources Information Center

    Smith, Elizabeth Allyn

    2011-01-01

    This dissertation proposes a novel analysis of the syntax and semantics of Comparative Correlative sentences in English such as "the bigger they are, the harder they fall or the faster we drive, the sooner we'll get there." The analysis is cast in a framework that distinguishes between argument structure and word order, called…

  6. CMB Lensing Cross Correlations

    NASA Astrophysics Data System (ADS)

    Bleem, Lindsey

    2014-03-01

    A new generation of experiments designed to conduct high-resolution, low-noise observations of the Cosmic Microwave Background (CMB)--including ACTpol, Planck, POLARBEAR and SPTpol--are producing exquisite measurements of the gravitational lensing of the CMB. Such measurements, covering large fractions of the sky, provide detailed maps of the projected mass distribution extending to the surface of the CMB's last scattering. Concurrently, a large number of deep, wide-area imaging and spectroscopic surveys (e.g., the Dark Energy Survey (DES),WISE all-sky survey, Subaru HyperSuprimeCam Survey, LSST, MS-DESI, BigBoss, etc.) are, or will soon be, providing maps of the distribution of galaxies in the Universe. Correlations of such tracer populations with lensing data allows new probes of where and how galaxies form in the dark matter skeleton of the Universe. Recent correlations of maps of galaxy and quasar densities with lensing convergence maps have produced significant measurements of galaxy bias. The near-term prospect for improvements in such measurements is notable as more precise lensing data from CMB polarization experiments will help to break cosmological and astrophysical parameter degeneracies. Work by the Planck, SPT, and POLARBEAR collaborations has also focused on the correlation of the Cosmic Infrared Background (CIB) with CMB lensing convergence maps. This correlation is particularly strong as the redshifts of the CIB and CMB lensing kernel are well matched. Such correlations probe high-redshift structure, constraining models of star-formation and the characteristic mass scale for halos hosting CIB galaxies and have also been used to demonstrate the first detection of CMB B-mode polarization--an important milestone in CMB observations. Finally, combining galaxy number density, cosmic shear and CMB lensing maps has the potential to provide valuable systematic tests for upcoming cosmological results from large optical surveys such as LSST.

  7. From micro-correlations to macro-correlations

    NASA Astrophysics Data System (ADS)

    Eliazar, Iddo

    2016-11-01

    Random vectors with a symmetric correlation structure share a common value of pair-wise correlation between their different components. The symmetric correlation structure appears in a multitude of settings, e.g. mixture models. In a mixture model the components of the random vector are drawn independently from a general probability distribution that is determined by an underlying parameter, and the parameter itself is randomized. In this paper we study the overall correlation of high-dimensional random vectors with a symmetric correlation structure. Considering such a random vector, and terming its pair-wise correlation "micro-correlation", we use an asymptotic analysis to derive the random vector's "macro-correlation" : a score that takes values in the unit interval, and that quantifies the random vector's overall correlation. The method of obtaining macro-correlations from micro-correlations is then applied to a diverse collection of frameworks that demonstrate the method's wide applicability.

  8. Correlates of financial satisfaction.

    PubMed

    Hsieh, C M

    2001-01-01

    The objectives of this study are to 1) assess the effects of major correlates of global subjective well-being on financial satisfaction, and 2) use empirical data to present the consequences of violating basic regression assumptions. Analyzing data from the General Social Surveys, 1972-1996 (Davis & Smith, 1996a) this study found that among Americans age forty-five and above, most of the major correlates of global subjective well-being show similar effects on financial satisfaction. The study's findings confirm a nonlinear effect of income on financial satisfaction. Comparing results from different analytical methods, this study also alerts researchers to the importance of taking into account the level of measurements of study variables, which have tended to be overlooked by previous subjective well-being research.

  9. Digital demodulator-correlator

    NASA Technical Reports Server (NTRS)

    Layland, J. W.; Martin, W. L.; Zygielbaum, A. I.; Goldstein, R. M.; Hubbard, W. P. (Inventor)

    1978-01-01

    An apparatus for demodulation and correlation of a code modulated 10 MHz signal is presented. The apparatus is comprised of a sample and hold analog-to-digital converter synchronized by a frequency coherent 40 MHz pulse to obtain four evenly spaced samples of each of the signal. Each sample is added or subtracted to or from one of four accumulators to or from the separate sums. The correlation functions are then computed. As a further feature of the invention, multipliers are each multiplied by a squarewave chopper signal having a period that is long relative to the period of the received signal to foreclose contamination of the received signal by leakage from either of the other two terms of the multipliers.

  10. Correlators in nontrivial backgrounds

    SciTech Connect

    Mello Koch, Robert de; Ives, Norman; Stephanou, Michael

    2009-01-15

    Operators in N=4 super Yang-Mills theory with an R-charge of O(N{sup 2}) are dual to backgrounds which are asymtotically AdS{sub 5}xS{sup 5}. In this article we develop efficient techniques that allow the computation of correlation functions in these backgrounds. We find that (i) contractions between fields in the string words and fields in the operator creating the background are the field theory accounting of the new geometry, (ii) correlation functions of probes in these backgrounds are given by the free field theory contractions but with rescaled propagators and (iii) in these backgrounds there are no open string excitations with their special end point interactions; we have only closed string excitations.

  11. Correlation, coherence and context

    NASA Astrophysics Data System (ADS)

    Eberly, J. H.

    2016-08-01

    The modern theory of coherence is based on correlation functions. A generic example could be written < {{V}\\ast}≤ft({{t}1}\\right)V≤ft({{t}2}\\right)> , denoting an average of products of the values of a signal V(t) at two specified times. Here we infer that t is a degree of freedom that the signal depends on. Typically, physical variables depend on more than one degree of freedom, and recognition of this has prompted attention to some interesting questions for the correlation functions and the several coherences that can be attributed to the same optical field. We examine some of the questions arising from the standpoint of experimental contexts. Degree of polarizability and degree of entanglement (classical non-separability) can serve as starting points for quantitative assignments.

  12. DD correlations in photoproduction

    NASA Astrophysics Data System (ADS)

    Alvarez, M. P.; Barate, R.; Bloch, D.; Bonamy, P.; Borgeaud, P.; Burchell, M.; Burmeister, H.; Brunet, J. M.; Calvino, F.; Cattaneo, M.; Crespo, J. M.; D'Almagne, B.; David, M.; di Ciaccio, L.; Dixon, J.; Druet, P.; Duane, A.; Engel, J. P.; Ferrer, A.; Filippas, T. A.; Fokitis, E.; Forty, R. W.; Foucault, P.; Gazis, E. N.; Gerber, J. P.; Giomataris, Y.; Hofmokl, T.; Katsoufis, E. C.; Koratzinos, M.; Krafft, C.; Lefievre, B.; Lemoigne, Y.; Lopez, A.; Lui, W. K.; Magneville, C.; Maltezos, A.; McEwen, J. G.; Papadopoulou, T.; Pattison, B.; Poutot, D.; Primout, M.; Rahmani, H.; Roudeau, P.; Seez, C.; Six, J.; Strub, R.; Treille, D.; Triscos, P.; Tristram, G.; Villet, G.; Volte, A.; Wayne, M.; Websdale, D. M.; Wormser, G.; Zolnierowski, Y.

    1992-03-01

    Kinematic correlations between the charmed D and D mesons produced by a photon beam of mean energy 100 GeV/c have been measured by the NA14/2 experiment at CERN using a sample of almost background-free fully reconstructed DD events. The observed D and DD distributions are compared to the predictions of production models using different parameters for the charm fragmentation function and for the intrinsic transverse momentum of the partons.

  13. Neural correlates of gratitude.

    PubMed

    Fox, Glenn R; Kaplan, Jonas; Damasio, Hanna; Damasio, Antonio

    2015-01-01

    Gratitude is an important aspect of human sociality, and is valued by religions and moral philosophies. It has been established that gratitude leads to benefits for both mental health and interpersonal relationships. It is thus important to elucidate the neurobiological correlates of gratitude, which are only now beginning to be investigated. To this end, we conducted an experiment during which we induced gratitude in participants while they underwent functional magnetic resonance imaging. We hypothesized that gratitude ratings would correlate with activity in brain regions associated with moral cognition, value judgment and theory of mind. The stimuli used to elicit gratitude were drawn from stories of survivors of the Holocaust, as many survivors report being sheltered by strangers or receiving lifesaving food and clothing, and having strong feelings of gratitude for such gifts. The participants were asked to place themselves in the context of the Holocaust and imagine what their own experience would feel like if they received such gifts. For each gift, they rated how grateful they felt. The results revealed that ratings of gratitude correlated with brain activity in the anterior cingulate cortex and medial prefrontal cortex, in support of our hypotheses. The results provide a window into the brain circuitry for moral cognition and positive emotion that accompanies the experience of benefitting from the goodwill of others.

  14. Correlation Algorithm Library

    SciTech Connect

    2013-08-02

    CorAL is a software Library designed to aid in the analysis of femtoscipic data. Femtoscopic data are a class of measured quantities used in heavy-ion collisions to characterize particle emitting source sizes. The most common type of this data is two-particle correleations induced by the Hanbury-Brown/Twiss (HBT) Effect, but can also include correlations induced by final-state interactions between pairs of emitted particles in a heavy-ion collision. Because heavy-ion collisions are complex many particle systems, modeling hydrodynamical models or hybrid techniques. Using the CRAB module, CorAL can turn the output from these models into something that can be directley compared to experimental data. CorAL can also take the raw experimentally measured correlation functions and image them by inverting the Koonin-Pratt equation to extract the space-time emission profile of the particle emitting source. This source function can be further analyzed or directly compared to theoretical calculations.

  15. Neural correlates of gratitude

    PubMed Central

    Fox, Glenn R.; Kaplan, Jonas; Damasio, Hanna; Damasio, Antonio

    2015-01-01

    Gratitude is an important aspect of human sociality, and is valued by religions and moral philosophies. It has been established that gratitude leads to benefits for both mental health and interpersonal relationships. It is thus important to elucidate the neurobiological correlates of gratitude, which are only now beginning to be investigated. To this end, we conducted an experiment during which we induced gratitude in participants while they underwent functional magnetic resonance imaging. We hypothesized that gratitude ratings would correlate with activity in brain regions associated with moral cognition, value judgment and theory of mind. The stimuli used to elicit gratitude were drawn from stories of survivors of the Holocaust, as many survivors report being sheltered by strangers or receiving lifesaving food and clothing, and having strong feelings of gratitude for such gifts. The participants were asked to place themselves in the context of the Holocaust and imagine what their own experience would feel like if they received such gifts. For each gift, they rated how grateful they felt. The results revealed that ratings of gratitude correlated with brain activity in the anterior cingulate cortex and medial prefrontal cortex, in support of our hypotheses. The results provide a window into the brain circuitry for moral cognition and positive emotion that accompanies the experience of benefitting from the goodwill of others. PMID:26483740

  16. Neural correlates of gratitude.

    PubMed

    Fox, Glenn R; Kaplan, Jonas; Damasio, Hanna; Damasio, Antonio

    2015-01-01

    Gratitude is an important aspect of human sociality, and is valued by religions and moral philosophies. It has been established that gratitude leads to benefits for both mental health and interpersonal relationships. It is thus important to elucidate the neurobiological correlates of gratitude, which are only now beginning to be investigated. To this end, we conducted an experiment during which we induced gratitude in participants while they underwent functional magnetic resonance imaging. We hypothesized that gratitude ratings would correlate with activity in brain regions associated with moral cognition, value judgment and theory of mind. The stimuli used to elicit gratitude were drawn from stories of survivors of the Holocaust, as many survivors report being sheltered by strangers or receiving lifesaving food and clothing, and having strong feelings of gratitude for such gifts. The participants were asked to place themselves in the context of the Holocaust and imagine what their own experience would feel like if they received such gifts. For each gift, they rated how grateful they felt. The results revealed that ratings of gratitude correlated with brain activity in the anterior cingulate cortex and medial prefrontal cortex, in support of our hypotheses. The results provide a window into the brain circuitry for moral cognition and positive emotion that accompanies the experience of benefitting from the goodwill of others. PMID:26483740

  17. Variable angle correlation spectroscopy

    SciTech Connect

    Lee, Y K

    1994-05-01

    In this dissertation, a novel nuclear magnetic resonance (NMR) technique, variable angle correlation spectroscopy (VACSY) is described and demonstrated with {sup 13}C nuclei in rapidly rotating samples. These experiments focus on one of the basic problems in solid state NMR: how to extract the wealth of information contained in the anisotropic component of the NMR signal while still maintaining spectral resolution. Analysis of the anisotropic spectral patterns from poly-crystalline systems reveal information concerning molecular structure and dynamics, yet in all but the simplest of systems, the overlap of spectral patterns from chemically distinct sites renders the spectral analysis difficult if not impossible. One solution to this problem is to perform multi-dimensional experiments where the high-resolution, isotropic spectrum in one dimension is correlated with the anisotropic spectral patterns in the other dimensions. The VACSY technique incorporates the angle between the spinner axis and the static magnetic field as an experimental parameter that may be incremented during the course of the experiment to help correlate the isotropic and anisotropic components of the spectrum. The two-dimensional version of the VACSY experiments is used to extract the chemical shift anisotropy tensor values from multi-site organic molecules, study molecular dynamics in the intermediate time regime, and to examine the ordering properties of partially oriented samples. The VACSY technique is then extended to three-dimensional experiments to study slow molecular reorientations in a multi-site polymer system.

  18. Correlation Algorithm Library

    2013-08-02

    CorAL is a software Library designed to aid in the analysis of femtoscipic data. Femtoscopic data are a class of measured quantities used in heavy-ion collisions to characterize particle emitting source sizes. The most common type of this data is two-particle correleations induced by the Hanbury-Brown/Twiss (HBT) Effect, but can also include correlations induced by final-state interactions between pairs of emitted particles in a heavy-ion collision. Because heavy-ion collisions are complex many particle systems, modelingmore » hydrodynamical models or hybrid techniques. Using the CRAB module, CorAL can turn the output from these models into something that can be directley compared to experimental data. CorAL can also take the raw experimentally measured correlation functions and image them by inverting the Koonin-Pratt equation to extract the space-time emission profile of the particle emitting source. This source function can be further analyzed or directly compared to theoretical calculations.« less

  19. Bootstrapped Deattenuated Correlation: Nonnormal Distributions

    ERIC Educational Resources Information Center

    Padilla, Miguel A.; Veprinsky, Anna

    2014-01-01

    Correlation attenuation due to measurement error and a corresponding correction, the deattenuated correlation, have been known for over a century. Nevertheless, the deattenuated correlation remains underutilized. A few studies in recent years have investigated factors affecting the deattenuated correlation, and a couple of them provide alternative…

  20. Proton-detected 3D 1H/13C/1H correlation experiment for structural analysis in rigid solids under ultrafast-MAS above 60 kHz

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy

    2015-10-01

    A proton-detected 3D 1H/13C/1H chemical shift correlation experiment is proposed for the assignment of chemical shift resonances, identification of 13C-1H connectivities, and proximities of 13C-1H and 1H-1H nuclei under ultrafast magic-angle-spinning (ultrafast-MAS) conditions. Ultrafast-MAS is used to suppress all anisotropic interactions including 1H-1H dipolar couplings, while the finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used to recouple dipolar couplings among protons and the insensitive nuclei enhanced by polarization transfer technique is used to transfer magnetization between heteronuclear spins. The 3D experiment eliminates signals from non-carbon-bonded protons and non-proton-bonded carbons to enhance spectral resolution. The 2D (F1/F3) 1H/1H and 2D 13C/1H (F2/F3) chemical shift correlation spectra extracted from the 3D spectrum enable the identification of 1H-1H proximity and 13C-1H connectivity. In addition, the 2D (F1/F2) 1H/13C chemical shift correlation spectrum, incorporated with proton magnetization exchange via the fp-RFDR recoupling of 1H-1H dipolar couplings, enables the measurement of proximities between 13C and even the remote non-carbon-bonded protons. The 3D experiment also gives three-spin proximities of 1H-1H-13C chains. Experimental results obtained from powder samples of L-alanine and L-histidine ṡ H2O ṡ HCl demonstrate the efficiency of the 3D experiment.

  1. Proton-detected 3D (1)H/(13)C/(1)H correlation experiment for structural analysis in rigid solids under ultrafast-MAS above 60 kHz.

    PubMed

    Zhang, Rongchun; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy

    2015-10-28

    A proton-detected 3D (1)H/(13)C/(1)H chemical shift correlation experiment is proposed for the assignment of chemical shift resonances, identification of (13)C-(1)H connectivities, and proximities of (13)C-(1)H and (1)H-(1)H nuclei under ultrafast magic-angle-spinning (ultrafast-MAS) conditions. Ultrafast-MAS is used to suppress all anisotropic interactions including (1)H-(1)H dipolar couplings, while the finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used to recouple dipolar couplings among protons and the insensitive nuclei enhanced by polarization transfer technique is used to transfer magnetization between heteronuclear spins. The 3D experiment eliminates signals from non-carbon-bonded protons and non-proton-bonded carbons to enhance spectral resolution. The 2D (F1/F3) (1)H/(1)H and 2D (13)C/(1)H (F2/F3) chemical shift correlation spectra extracted from the 3D spectrum enable the identification of (1)H-(1)H proximity and (13)C-(1)H connectivity. In addition, the 2D (F1/F2) (1)H/(13)C chemical shift correlation spectrum, incorporated with proton magnetization exchange via the fp-RFDR recoupling of (1)H-(1)H dipolar couplings, enables the measurement of proximities between (13)C and even the remote non-carbon-bonded protons. The 3D experiment also gives three-spin proximities of (1)H-(1)H-(13)C chains. Experimental results obtained from powder samples of L-alanine and L-histidine ⋅ H2O ⋅ HCl demonstrate the efficiency of the 3D experiment.

  2. Strongly correlated Bose gases

    NASA Astrophysics Data System (ADS)

    Chevy, F.; Salomon, C.

    2016-10-01

    The strongly interacting Bose gas is one of the most fundamental paradigms of quantum many-body physics and the subject of many experimental and theoretical investigations. We review recent progress on strongly correlated Bose gases, starting with a description of beyond mean-field corrections. We show that the Efimov effect leads to non universal phenomena and to a metastability of the low temperature Bose gas through three-body recombination to deeply bound molecular states. We outline differences and similarities with ultracold Fermi gases, discuss recent experiments on the unitary Bose gas, and finally present a few perspectives for future research.

  3. Digital Image Correlation Engine

    SciTech Connect

    Turner, Dan; Crozier, Paul; Reu, Phil

    2015-10-06

    DICe is an open source digital image correlation (DIC) tool intended for use as a module in an external application or as a standalone analysis code. It's primary capability is computing full –field displacements and strains from sequences of digital These images are typically of a material sample undergoing a materials characterization experiment, but DICe is also useful for other applications (for example, trajectory tracking). DICe is machine portable (Windows, Linux and Mac) and can be effectively deployed on a high performance computing platform. Capabilities from DICe can be invoked through a library interface, via source code integration of DICe classes or through a graphical user interface.

  4. Vibrational Echo Correlation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Asbury, John B.; Steinel, Tobias; Fayer, M. D.

    Multidimensional vibrational echo correlation spectroscopy with full phase resolution is used to measure hydrogen bond dynamics in water and methanol. The OD hydroxyl stretches of methanol-OD oligomers in CCl4 and HOD inH2O are studied using the shortest mid-IR pulses (< 45 fs, < 4 cycles of light) produced to date. The pulses have sufficient spectral bandwidth to span the very broad (> 400 cm-1) spectrum of the 0-1 and 1-2 vibrational transitions. Hydrogen bond population dynamics are extricated with exceptional detail in MeOD oligomers because the different hydrogen-bonded species are spectrally distinct. The experimental results along with detailed calculations indicate the strongest hydrogen bonds are selectively broken through a non-equilibrium relaxation pathway following vibrational relaxation of the hydroxyl stretch. Following hydrogen bond breaking, the broken MeOD oligomers retain a detailed structural memory of the prior intact hydrogen bond network. The correlation spectra are also a sensitive probe of the structural fluctuations in water and provide a stringent test of water models that are widely used in simulations of aqueous systems. The analysis of the 2D band shapes demonstrates that different hydrogen-bonded species are subject to distinct (wavelength-dependent) ultrafast (˜ 100 fs) local fluctuations and essentially identical slower (0.4 ps and ˜ 2 ps) structural rearrangements. Observation of wavelength-dependent dynamics demonstrates that standard theoretical approaches assuming Gaussian fluctuations cannot adequately describe water dynamics.

  5. CONDITIONAL DISTANCE CORRELATION

    PubMed Central

    Wang, Xueqin; Pan, Wenliang; Hu, Wenhao; Tian, Yuan; Zhang, Heping

    2015-01-01

    Statistical inference on conditional dependence is essential in many fields including genetic association studies and graphical models. The classic measures focus on linear conditional correlations, and are incapable of characterizing non-linear conditional relationship including non-monotonic relationship. To overcome this limitation, we introduces a nonparametric measure of conditional dependence for multivariate random variables with arbitrary dimensions. Our measure possesses the necessary and intuitive properties as a correlation index. Briefly, it is zero almost surely if and only if two multivariate random variables are conditionally independent given a third random variable. More importantly, the sample version of this measure can be expressed elegantly as the root of a V or U-process with random kernels and has desirable theoretical properties. Based on the sample version, we propose a test for conditional independence, which is proven to be more powerful than some recently developed tests through our numerical simulations. The advantage of our test is even greater when the relationship between the multivariate random variables given the third random variable cannot be expressed in a linear or monotonic function of one random variable versus the other. We also show that the sample measure is consistent and weakly convergent, and the test statistic is asymptotically normal. By applying our test in a real data analysis, we are able to identify two conditionally associated gene expressions, which otherwise cannot be revealed. Thus, our measure of conditional dependence is not only an ideal concept, but also has important practical utility. PMID:26877569

  6. PREFACE: Correlated Electrons (Japan)

    NASA Astrophysics Data System (ADS)

    Miyake, Kazumasa

    2007-03-01

    This issue of Journal of Physics: Condensed Matter is dedicated to results in the field of strongly correlated electron systems under multiple-environment. The physics of strongly correlated electron systems (SCES) has attracted much attention since the discovery of superconductivity in CeCu_2 Si_2 by Steglich and his co-workers a quater-century ago. Its interest has been intensified by the discovery of high-Tc superconductivity in a series of cuprates with layered perovskite structure which are still under active debate. The present issue of Journal of Physics: Condensed Matter present some aspects of SCES physics on the basis of activities of a late project "Centre-Of-Excellence" supported by MEXT (Ministry of Education, Sports, Science, Culture and Technology of the Japanese Government). This project has been performed by a condensed matter physics group in the faculties of science and engineering science of Osaka University. Although this project also covers correlated phenomena in optics and nano-scale systems, we focus here on the issues of SCES related to superconductivity, mainly unconventional. The present issue covers the discussions on a new mechanism of superconductivity with electronic origin (critical valence fluctuation mechanism), interplay and unification of magnetism and superconductivity in SCES based on a systematic study of NQR under pressure, varieties of Fermi surface of Ce- and U-based SCES probed by the de Haas-van Alphen effect, electronic states probed by a bulk sensitive photoemission spectroscopy with soft X-ray, pressure induced superconductivity of heavy electron materials, pressure dependence of superconducting transition temperature based on a first-principle calculation, and new superconductors under very high-pressure. Some papers offer readers' reviews of the relevant fields and/or include new developments of this intriguing research field of SCES. Altogether, the papers within this issue outline some aspects of electronic states

  7. Correlated motions in DNA

    SciTech Connect

    Sundaralingam, M.; Westhof, E.

    1980-10-01

    The furanose ring of nucleic acids plays a key role in detrmining the conformations of nucleic acids because it shares a common bond C3'-C4'(psi') with the sugar-phosphate backbone. This structural feature enables the transmission of conformational changes between the side-chain base and the backbone through conformational correlations between the base and sugar. Thermally-induced local fluctuations of P can be transmitted along the backbone through psi', particularly when the sugar is in the C2'-endo domain. The sugar pucker-dependent flexibility of DNA is further exemplified by studies that have shown that due to steric interactions, absence of the 2'-OH group in deoxyribose tends to increase the conformational flexibility about the internucleotide phosphodiester (..omega.., ..omega..') especially when the sugar assumes the C2'-endo pucker.

  8. Neural correlates of frustration.

    PubMed

    Abler, Birgit; Walter, Henrik; Erk, Susanne

    2005-05-12

    Psychological considerations suggest that the omission of rewards in humans comprises two effects: first, an allocentric effect triggering learning and behavioural changes potentially processed by dopaminergic neurons according to the prediction error theory; second, an egocentric effect representing the individual's emotional reaction, commonly called frustration. We investigated this second effect in the context of omission of monetary reward with functional magnetic resonance imaging. As expected, the contrast omission relative to receipt of reward led to a decrease in ventral striatal activation consistent with prediction error theory. Increased activation for this contrast was found in areas previously related to emotional pain: the right anterior insula and the right ventral prefrontal cortex. We interpreted this as a neural correlate of the egocentric effect.

  9. Digital Image Correlation Engine

    2015-10-06

    DICe is an open source digital image correlation (DIC) tool intended for use as a module in an external application or as a standalone analysis code. It's primary capability is computing full –field displacements and strains from sequences of digital These images are typically of a material sample undergoing a materials characterization experiment, but DICe is also useful for other applications (for example, trajectory tracking). DICe is machine portable (Windows, Linux and Mac) and canmore » be effectively deployed on a high performance computing platform. Capabilities from DICe can be invoked through a library interface, via source code integration of DICe classes or through a graphical user interface.« less

  10. Some correlates of trust.

    PubMed

    Frost, T; Stimpson, D V; Maughan, M R

    1978-05-01

    Trust has been variously defined by behavioral scientists and not very thoroughly investigated. In this study trust was defined as an expectancy held by an individual that the behavior of another person or a group would be altruistic and personally beneficial. An attempt was made, using this conceptual definition, to identify some personality and behavioral correlates of trust. Seven interpersonal relations groups with approximately 10 male and female undergraduates per group were studied with use of the Janis and Field self-esteem inventory, Schutz's FIRO-B scale, and the Rotter internal-external scale. It was discovered that a trusted person is one who is highly influential, has an internal locus of control, a low need to control others, high self-esteem, and is open to being influenced by others.

  11. EEG correlates of submovements.

    PubMed

    Dipietro, L; Poizner, H; Krebs, H I

    2011-01-01

    Numerous studies on motor control in humans and primates have suggested that the Central Nervous System (CNS) generates and controls continuous movement via discrete, elementary units of movement or submovements. While most studies are based on analysis of kinematic data, investigations of neural correlates have been lacking. To fill this gap we recorded and analyzed kinematic and high-density electroencephalographic (64-channel EEG) data from three right-handed normal adults during a reaching task that required online movement corrections. Each kinematic submovement was accompanied by stereotyped scalp maps. Furthermore, the peaks of event-related potentials (ERP) recorded at electrode C1 (over contralateral motor cortex) were time-locked to kinematic submovement peaks. These results provide further evidence for the hypothesis that the CNS generates and controls continuous movement via discrete submovements. Applications include design of quantitative outcome metrics for motor disorders of neurological origin such as stroke and Parkinson's disease. PMID:22256056

  12. Correlation monitor materials

    SciTech Connect

    Corwin, W.R.

    1995-10-01

    This task has been established with the explicit purpose of ensuring the continued availability of the pedigreed and extremely well-characterized material now required for inclusion in all additional and future surveillance capsules in commercial light-water reactors. During this reporting period, concrete was poured and pallets storage racks were installed to provide adequate room for the storage of the correlation monitor material being transferred from its location at the Y-12 Plant to its archival storage location at ORNL. The racks came from surplus material storage at ORNL and hence were obtained at no cost to the HSSI Program. Inquiries into cost-effective means of sheltering the blocks of correlation monitor materials from further weather-related deteriorization were initiated. The most likely approach would be to procure a turn-key sheet metal building installed over the storage racks by an outside contractor to minimize costs. Most of the material has now been transferred from Y-12 to the ORNL storage area. It has been repositioned on new storage pallets and placed into the storage racks, An update of the detailed material inventory was initiated to ascertain the revised location of all blocks. Pieces of HSST plate O3 were distributed to participants in the ASTM cross-comparison exercise on subsize specimen testing technology. The use of the HSST O3 will provide for data from the many varieties of tests to be performed to be compared with the standardized data previously developed. The testing techniques will focus on ways to measure transition temperature and fracture toughness.

  13. Sensitivity enhanced (14)N/(14)N correlations to probe inter-beta-sheet interactions using fast magic angle spinning solid-state NMR in biological solids.

    PubMed

    Pandey, Manoj Kumar; Amoureux, Jean-Paul; Asakura, Tetsuo; Nishiyama, Yusuke

    2016-08-10

    (14)N/(14)N correlations are vital for structural studies of solid samples, especially those in which (15)N isotopic enrichment is challenging, time-consuming and expensive. Although (14)N nuclei have high isotopic abundance (99.6%), there are inherent difficulties in observing (14)N/(14)N correlations due to limited resolution and sensitivity related to: (i) low (14)N gyromagnetic ratio (γ), (ii) large (14)N quadrupolar couplings, (iii) integer (14)N spin quantum number (I = 1), and (iv) very weak (14)N-(14)N dipolar couplings. Previously, we demonstrated a proton-detected 3D (14)N/(14)N/(1)H correlation experiment at fast magic angle spinning (MAS) on l-histidine·HCl·H2O utilizing a through-bond (J) and residual dipolar-splitting (RDS) based heteronuclear multiple quantum correlation (J-HMQC) sequence mediated through (1)H/(1)H radio-frequency driven recoupling (RFDR). As an extension of our previous work, in this study we show the utility of dipolar-based HMQC (D-HMQC) in combination with (1)H/(1)H RFDR mixing to obtain sensitivity enhanced (14)N/(14)N correlations in more complex biological solids such as a glycyl-l-alanine (Gly-l-Ala) dipeptide, and parallel (P) and antiparallel (AP) β-strand alanine tripeptides (P-(Ala)3 and AP-(Ala)3, respectively). These systems highlight the mandatory necessity of 3D (14)N/(14)N/(1)H measurements to get (14)N/(14)N correlations when the amide proton resonances are overlapped. Moreover, the application of long selective (14)N pulses, instead of short hard ones, is shown to improve the sensitivity. Globally, we demonstrate that replacing J-scalar with dipolar interaction and hard- with selective-(14)N pulses allows gaining a factor of ca. 360 in experimental time. On the basis of intermolecular NH/NH distances and (14)N quadrupolar tensor orientations, (14)N/(14)N correlations are effectively utilized to make a clear distinction between the parallel and antiparallel arrangements of the β-strands in (Ala)3 through the

  14. Sensitivity enhanced (14)N/(14)N correlations to probe inter-beta-sheet interactions using fast magic angle spinning solid-state NMR in biological solids.

    PubMed

    Pandey, Manoj Kumar; Amoureux, Jean-Paul; Asakura, Tetsuo; Nishiyama, Yusuke

    2016-08-10

    (14)N/(14)N correlations are vital for structural studies of solid samples, especially those in which (15)N isotopic enrichment is challenging, time-consuming and expensive. Although (14)N nuclei have high isotopic abundance (99.6%), there are inherent difficulties in observing (14)N/(14)N correlations due to limited resolution and sensitivity related to: (i) low (14)N gyromagnetic ratio (γ), (ii) large (14)N quadrupolar couplings, (iii) integer (14)N spin quantum number (I = 1), and (iv) very weak (14)N-(14)N dipolar couplings. Previously, we demonstrated a proton-detected 3D (14)N/(14)N/(1)H correlation experiment at fast magic angle spinning (MAS) on l-histidine·HCl·H2O utilizing a through-bond (J) and residual dipolar-splitting (RDS) based heteronuclear multiple quantum correlation (J-HMQC) sequence mediated through (1)H/(1)H radio-frequency driven recoupling (RFDR). As an extension of our previous work, in this study we show the utility of dipolar-based HMQC (D-HMQC) in combination with (1)H/(1)H RFDR mixing to obtain sensitivity enhanced (14)N/(14)N correlations in more complex biological solids such as a glycyl-l-alanine (Gly-l-Ala) dipeptide, and parallel (P) and antiparallel (AP) β-strand alanine tripeptides (P-(Ala)3 and AP-(Ala)3, respectively). These systems highlight the mandatory necessity of 3D (14)N/(14)N/(1)H measurements to get (14)N/(14)N correlations when the amide proton resonances are overlapped. Moreover, the application of long selective (14)N pulses, instead of short hard ones, is shown to improve the sensitivity. Globally, we demonstrate that replacing J-scalar with dipolar interaction and hard- with selective-(14)N pulses allows gaining a factor of ca. 360 in experimental time. On the basis of intermolecular NH/NH distances and (14)N quadrupolar tensor orientations, (14)N/(14)N correlations are effectively utilized to make a clear distinction between the parallel and antiparallel arrangements of the β-strands in (Ala)3 through the

  15. Magnitude correlations in global seismicity

    SciTech Connect

    Sarlis, N. V.

    2011-08-15

    By employing natural time analysis, we analyze the worldwide seismicity and study the existence of correlations between earthquake magnitudes. We find that global seismicity exhibits nontrivial magnitude correlations for earthquake magnitudes greater than M{sub w}6.5.

  16. Lagged correlation networks

    NASA Astrophysics Data System (ADS)

    Curme, Chester

    Technological advances have provided scientists with large high-dimensional datasets that describe the behaviors of complex systems: from the statistics of energy levels in complex quantum systems, to the time-dependent transcription of genes, to price fluctuations among assets in a financial market. In this environment, where it may be difficult to infer the joint distribution of the data, network science has flourished as a way to gain insight into the structure and organization of such systems by focusing on pairwise interactions. This work focuses on a particular setting, in which a system is described by multivariate time series data. We consider time-lagged correlations among elements in this system, in such a way that the measured interactions among elements are asymmetric. Finally, we allow these interactions to be characteristically weak, so that statistical uncertainties may be important to consider when inferring the structure of the system. We introduce a methodology for constructing statistically validated networks to describe such a system, extend the methodology to accommodate interactions with a periodic component, and show how consideration of bipartite community structures in these networks can aid in the construction of robust statistical models. An example of such a system is a financial market, in which high frequency returns data may be used to describe contagion, or the spreading of shocks in price among assets. These data provide the experimental testing ground for our methodology. We study NYSE data from both the present day and one decade ago, examine the time scales over which the validated lagged correlation networks exist, and relate differences in the topological properties of the networks to an increasing economic efficiency. We uncover daily periodicities in the validated interactions, and relate our findings to explanations of the Epps Effect, an empirical phenomenon of financial time series. We also study bipartite community

  17. Estimating the Polyserial Correlation Coefficient.

    ERIC Educational Resources Information Center

    Bedrick, Edward J.; Breslin, Frederick C.

    1996-01-01

    Simple noniterative estimators of the polyserial correlation coefficient are developed by exploiting a general relationship between the polyserial correlation and the point polyserial correlation to give extensions of the biserial estimators of K. Pearson (1909), H. E. Brogden (1949), and F. M. Lord (1963) to the multicategory setting. (SLD)

  18. The 512-channel correlator controller

    NASA Technical Reports Server (NTRS)

    Brokl, S. S.

    1976-01-01

    A high-speed correlator for radio and radar observations was developed and a controller was designed so that the correlator could run automatically without computer intervention. The correlator controller assumes the role of bus master and keeps track of data and properly interrupts the computer at the end of the observation.

  19. Liquid-Crystal Optical Correlator

    NASA Technical Reports Server (NTRS)

    Liu, Hua-Kuang

    1989-01-01

    Optical correlator uses commercially-available liquid-crystal television (LCTV) screen as spatial light modulator. Correlations with this device done at video frame rates, making such operations as bar-code recognition possible at reasonable cost. With further development, such correlator useful in automation, robotic vision, and optical image processing.

  20. Facile Separation of Regioisomeric Compounds by a Heteronuclear Organometallic Capsule.

    PubMed

    Zhang, Wen-Ying; Lin, Yue-Jian; Han, Ying-Feng; Jin, Guo-Xin

    2016-08-24

    Owing to the often-similar physical and chemical properties of structural isomers of organic molecules, large efforts have been made to develop efficient strategies to isolate specific isomers. However, facile separation of regioisomeric compounds remains difficult. Here we demonstrate a universal organometallic capsule in which two silver centers are rigidly separated from each other by two tetranuclear [Rh4] pyramidal frustums, which selectively encapsulate a specific isomer from mixtures. Not only is the present heterometallic capsule suitable as a host for the encapsulation of a series of aromatic compounds, but also the receptor shows widely differing specificity for the various isomers. Direct experimental evidence is provided for the selective encapsulation of a series of para (p)-disubstituted benzene derivatives, such as p-xylene, p-dichlorobenzene, p-dibromobenzene, and p-diiodobenzene. The size and shape matching, as well as the Ag-π interactions, are the main forces governing the extent of molecular recognition. The encapsulated guest p-xylene can be released by using the solid-liquid solvent washing strategy, and the other guest molecules are easily liberated by using light stimulus. PMID:27463561

  1. Allowing for Correlations between Correlations in Random-Effects Meta-Analysis of Correlation Matrices

    ERIC Educational Resources Information Center

    Prevost, A. Toby; Mason, Dan; Griffin, Simon; Kinmonth, Ann-Louise; Sutton, Stephen; Spiegelhalter, David

    2007-01-01

    Practical meta-analysis of correlation matrices generally ignores covariances (and hence correlations) between correlation estimates. The authors consider various methods for allowing for covariances, including generalized least squares, maximum marginal likelihood, and Bayesian approaches, illustrated using a 6-dimensional response in a series of…

  2. Correlation Structures of Correlated Binomial Models and Implied Default Distribution

    NASA Astrophysics Data System (ADS)

    Mori, Shintaro; Kitsukawa, Kenji; Hisakado, Masato

    2008-11-01

    We show how to analyze and interpret the correlation structures, the conditional expectation values and correlation coefficients of exchangeable Bernoulli random variables. We study implied default distributions for the iTraxx-CJ tranches and some popular probabilistic models, including the Gaussian copula model, Beta binomial distribution model and long-range Ising model. We interpret the differences in their profiles in terms of the correlation structures. The implied default distribution has singular correlation structures, reflecting the credit market implications. We point out two possible origins of the singular behavior.

  3. SAW correlator spread spectrum receiver

    DOEpatents

    Brocato, Robert W

    2014-04-01

    A surface acoustic wave (SAW) correlator spread-spectrum (SS) receiver is disclosed which utilizes a first demodulation stage with a chip length n and a second demodulation stage with a chip length m to decode a transmitted SS signal having a code length l=n.times.m which can be very long (e.g. up to 2000 chips or more). The first demodulation stage utilizes a pair of SAW correlators which demodulate the SS signal to generate an appropriate code sequence at an intermediate frequency which can then be fed into the second demodulation stage which can be formed from another SAW correlator, or by a digital correlator. A compound SAW correlator comprising two input transducers and a single output transducer is also disclosed which can be used to form the SAW correlator SS receiver, or for use in processing long code length signals.

  4. Waveform correlation by tree matching.

    PubMed

    Cheng, Y C; Lu, S Y

    1985-03-01

    A waveform correlation scheme is presented. The scheme consists of four parts: 1) the representation of waveforms by trees, 2) the definition of basic operations on tree nodes and tree distance, 3) a tree matching algorithm, and 4) a backtracking procedure to find the best node-to-node correlation. This correlation scheme has been implemented. Results show that the scheme has the capability of handling distortions that result from stretching or shrinking of intervals or from missing intervals.

  5. Image correlation and sampling study

    NASA Technical Reports Server (NTRS)

    Popp, D. J.; Mccormack, D. S.; Sedwick, J. L.

    1972-01-01

    The development of analytical approaches for solving image correlation and image sampling of multispectral data is discussed. Relevant multispectral image statistics which are applicable to image correlation and sampling are identified. The general image statistics include intensity mean, variance, amplitude histogram, power spectral density function, and autocorrelation function. The translation problem associated with digital image registration and the analytical means for comparing commonly used correlation techniques are considered. General expressions for determining the reconstruction error for specific image sampling strategies are developed.

  6. Producing and Detecting Correlated Atoms

    SciTech Connect

    Westbrook, C. I.; Schellekens, M.; Perrin, A.; Krachmalnicoff, V.; Viana Gomes, J.; Trebbia, J.-B.; Esteve, J.; Chang, H.; Bouchoule, I.; Boiron, D.; Aspect, A.; Jeltes, T.; McNamara, J.; Hogervorst, W.; Vassen, W.

    2006-11-07

    We discuss experiments to produce and detect atom correlations in a degenerate or nearly degenerate gas of neutral atoms. First we treat the atomic analog of the celebrated Hanbury Brown Twiss experiment, in which atom correlations result simply from interference effects without any atom interactions. We have performed this experiment for both bosons and fermions. Next we show how atom interactions produce correlated atoms using the atomic analog of spontaneous four-wave mixing. Finally, we briefly mention experiments on a one dimensional gas on an atom chip in which correlation effects due to both interference and interactions have been observed.

  7. Regularized Generalized Canonical Correlation Analysis

    ERIC Educational Resources Information Center

    Tenenhaus, Arthur; Tenenhaus, Michel

    2011-01-01

    Regularized generalized canonical correlation analysis (RGCCA) is a generalization of regularized canonical correlation analysis to three or more sets of variables. It constitutes a general framework for many multi-block data analysis methods. It combines the power of multi-block data analysis methods (maximization of well identified criteria) and…

  8. Psychophysical correlations, synchronicity and meaning.

    PubMed

    Atmanspacher, Harald

    2014-04-01

    The dual-aspect framework which Jung developed with Wolfgang Pauli implies that psychophysical phenomena are neither reducible to physical processes nor to conscious mental activity. Rather, they constitute a radically novel kind of phenomena, deriving from correlations between the physical and the mental. In synchronistic events, a particular subclass of psychophysical phenomena, these correlations are explicated as experienced meaning.

  9. Correlation Weights in Multiple Regression

    ERIC Educational Resources Information Center

    Waller, Niels G.; Jones, Jeff A.

    2010-01-01

    A general theory on the use of correlation weights in linear prediction has yet to be proposed. In this paper we take initial steps in developing such a theory by describing the conditions under which correlation weights perform well in population regression models. Using OLS weights as a comparison, we define cases in which the two weighting…

  10. Personality Correlates of Polydrug Abuse.

    ERIC Educational Resources Information Center

    Kilpatrick, Dean G.; And Others

    Although the personality correlates of heroin addiction, LSD use, and marijuana smoking have been frequently investigated, relatively few data are available to describe the personality or lifestyle variables correlated with the pattern of polydrug abuse. In an attempt to gather such information, 17 polydrug users, selected from a group of 224…

  11. Optical Correlator Performs Novelty Filtering

    NASA Technical Reports Server (NTRS)

    Liu, Duncan Tsuen-Hsi; Chao, Tien-Hsin; Cheng, Li-Jen

    1994-01-01

    Experimental real-time optical correlator performs correlation and novelty filtering in photorefractive crystal. Crystal oriented enabling cross-polarization diffraction: together with polarizing beam splitter, increases signal-to-noise ratio. Laser and optical components expand, collimate, and divide laser beam.

  12. Polarization correlations of Dirac particles

    SciTech Connect

    Caban, Pawel; Dziegielewska, Agnieszka; Karmazyn, Anna; Okrasa, Malgorzata

    2010-03-15

    We calculate the polarization correlation function in the Einstein-Podolsky-Rosen-type experiments with relativistic spin-1/2 particles. This function depends monotonically on the particle momenta. Moreover, we also show that the polarization correlation function violates the Clauser-Horn-Shimony-Holt inequality and the degree of this violation can depend on the particle momenta and the motion of observers.

  13. Squeezed Particle-Antiparticle Correlations

    NASA Astrophysics Data System (ADS)

    Padula, S. S.; Dudek, D. M.; Socolowski, O., Jr.

    2009-04-01

    A novel type of correlation involving particle-antiparticle pairs was found out in the 1990's. Currently known as squeezed or Back-to-Back Correlations (BBC), they should be present if the hadronic masses are modified in the hot and dense medium formed in high energy heavy ion collisions. Although well-established theoretically, such hadronic correlations have not yet been observed experimentally. In this phenomenological study we suggest a promising way to search for the BBC signal, by looking into the squeezed correlation function of phi phi and K+ K- pairs at RHIC energies, as function of the pair average momentum, K12=(@BOLD@ k1+@BOLD@ k2)/2. The effects of in-medium mass-shift on the identical particle correlations (Hanbury-Brown and Twiss effect) are also discussed.

  14. Cross-correlation of long-range correlated series

    NASA Astrophysics Data System (ADS)

    Arianos, Sergio; Carbone, Anna

    2009-03-01

    A method for estimating the cross-correlation Cxy(τ) of long-range correlated series x(t) and y(t), at varying lags τ and scales n, is proposed. For fractional Brownian motions with Hurst exponents H1 and H2, the asymptotic expression for Cxy(τ) depends only on the lag τ (wide-sense stationarity) and scales as a power of n with exponent H1+H2 for \\tau \\rightarrow 0 . The method is illustrated on: (i) financial series, to show the leverage effect; (ii) genomic sequences, to estimate the correlations between structural parameters along the chromosomes.

  15. Proton-detected 3D {sup 1}H/{sup 13}C/{sup 1}H correlation experiment for structural analysis in rigid solids under ultrafast-MAS above 60 kHz

    SciTech Connect

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke

    2015-10-28

    A proton-detected 3D {sup 1}H/{sup 13}C/{sup 1}H chemical shift correlation experiment is proposed for the assignment of chemical shift resonances, identification of {sup 13}C-{sup 1}H connectivities, and proximities of {sup 13}C-{sup 1}H and {sup 1}H-{sup 1}H nuclei under ultrafast magic-angle-spinning (ultrafast-MAS) conditions. Ultrafast-MAS is used to suppress all anisotropic interactions including {sup 1}H-{sup 1}H dipolar couplings, while the finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used to recouple dipolar couplings among protons and the insensitive nuclei enhanced by polarization transfer technique is used to transfer magnetization between heteronuclear spins. The 3D experiment eliminates signals from non-carbon-bonded protons and non-proton-bonded carbons to enhance spectral resolution. The 2D (F1/F3) {sup 1}H/{sup 1}H and 2D {sup 13}C/{sup 1}H (F2/F3) chemical shift correlation spectra extracted from the 3D spectrum enable the identification of {sup 1}H-{sup 1}H proximity and {sup 13}C-{sup 1}H connectivity. In addition, the 2D (F1/F2) {sup 1}H/{sup 13}C chemical shift correlation spectrum, incorporated with proton magnetization exchange via the fp-RFDR recoupling of {sup 1}H-{sup 1}H dipolar couplings, enables the measurement of proximities between {sup 13}C and even the remote non-carbon-bonded protons. The 3D experiment also gives three-spin proximities of {sup 1}H-{sup 1}H-{sup 13}C chains. Experimental results obtained from powder samples of L-alanine and L-histidine ⋅ H{sub 2}O ⋅ HCl demonstrate the efficiency of the 3D experiment.

  16. New structural information on a humic acid from two-dimensional 1H-13C correlation solid-state nuclear magnetic resonance.

    PubMed

    Mao, J D; Xing, B; Schmidt-Rohr, K

    2001-05-15

    New information on the chemical structure of a peat humic acid has been obtained using a series of two-dimensional 1H-13C heteronuclear correlation solid-state NMR (HETCOR) experiments with different contact times and with spectral editing by dipolar dephasing and 13C transverse relaxation filtering. Carbon-bonded methyl groups (C-CH3) are found to be near both aliphatic and O-alkyl but not aromatic groups. The spectra prove that most OCH3 groups are connected directly with the aromatic rings, as is typical in lignin. As a result, about one-third of the aromatic C-O groups is not phenolic C-OH but C-OCH3. Both protonated and unprotonated anomeric O-C-O carbons are identified in the one- and two-dimensional spectra. COO groups are found predominantly in OCHn-COO environments, but some are also bonded to aromatic rings and aliphatic groups. All models of humic acids in the literature lack at least some of the features observed here. Compositional heterogeneity was studied by introducing 1H spin diffusion into the HETCOR experiment. Comparison with data for a synthetic polymer, polycarbonate, indicates that the separation between O-alkyl and aromatic groups in the humic acid is less than 1.5 nm. However, transverse 13C relaxation filtering under 1H decoupling reveals heterogeneity on a nanometer scale, with the slow-relaxing component being rich in lignin-like aromatic-C-O-CH3 moieties and poor in COO groups.

  17. Cluster identification based on correlations

    NASA Astrophysics Data System (ADS)

    Schulman, L. S.

    2012-04-01

    The problem addressed is the identification of cooperating agents based on correlations created as a result of the joint action of these and other agents. A systematic method for using correlations beyond second moments is developed. The technique is applied to a didactic example, the identification of alphabet letters based on correlations among the pixels used in an image of the letter. As in this example, agents can belong to more than one cluster. Moreover, the identification scheme does not require that the patterns be known ahead of time.

  18. Pseudopotentials for correlated electron systems

    NASA Astrophysics Data System (ADS)

    Trail, J. R.; Needs, R. J.

    2013-07-01

    A scheme is developed for creating pseudopotentials for use in correlated-electron calculations. Pseudopotentials for the light elements H, Li, Be, B, C, N, O, and F, are reported, based on data from high-level quantum chemical calculations. Results obtained with these correlated electron pseudopotentials (CEPPs) are compared with data for atomic energy levels and the dissociation energies, molecular geometries, and zero-point vibrational energies of small molecules obtained from coupled cluster single double triple calculations with large basis sets. The CEPPs give better results in correlated-electron calculations than Hartree-Fock-based pseudopotentials available in the literature.

  19. Correlation, Cost Risk, and Geometry

    NASA Technical Reports Server (NTRS)

    Dean, Edwin B.

    1992-01-01

    The geometric viewpoint identifies the choice of a correlation matrix for the simulation of cost risk with the pairwise choice of data vectors corresponding to the parameters used to obtain cost risk. The correlation coefficient is the cosine of the angle between the data vectors after translation to an origin at the mean and normalization for magnitude. Thus correlation is equivalent to expressing the data in terms of a non orthogonal basis. To understand the many resulting phenomena requires the use of the tensor concept of raising the index to transform the measured and observed covariant components into contravariant components before vector addition can be applied. The geometric viewpoint also demonstrates that correlation and covariance are geometric properties, as opposed to purely statistical properties, of the variates. Thus, variates from different distributions may be correlated, as desired, after selection from independent distributions. By determining the principal components of the correlation matrix, variates with the desired mean, magnitude, and correlation can be generated through linear transforms which include the eigenvalues and the eigenvectors of the correlation matrix. The conversion of the data to a non orthogonal basis uses a compound linear transformation which distorts or stretches the data space. Hence, the correlated data does not have the same properties as the uncorrelated data used to generate it. This phenomena is responsible for seemingly strange observations such as the fact that the marginal distributions of the correlated data can be quite different from the distributions used to generate the data. The joint effect of statistical distributions and correlation remains a fertile area for further research. In terms of application to cost estimating, the geometric approach demonstrates that the estimator must have data and must understand that data in order to properly choose the correlation matrix appropriate for a given estimate

  20. Modernizing the JPL VLBI Correlator

    NASA Astrophysics Data System (ADS)

    Rogstad, S.; Goodhart, C. E.; Clark, J. E.; Finley, S.; Lanyi, G. E.; White, L. A.; Jacobs, Christopher S.>

    This poster will present the current capabilities of the JPL VLBI Correlator (JVC) and the general architecture of the equipment. In addition, the scientific and navigation uses of the JVC will be enumerated for background purposes. The JVC is a software correlator based on a Beowulf cluster of computers. It replaces a thirty year old correlator based on custom designed digital hardware. General comparisons between the old and new equipment will be made. The JVC makes use of a separate program, SoftC, to do the actual correlations. The JVC manages the sending of data to multiple machines in a Beowulf cluster each running SoftC in parallel on small chunks of the data. The basic architecture of SoftC will also be described.

  1. Digital correlator with fewer IC's

    NASA Technical Reports Server (NTRS)

    Apple, G. G.; Rubin, L.

    1979-01-01

    Digital correlator requires only few integrated circuits to determine synchronization of two 24-bit digital words. Circuit is easily reduced or expanded to accommodate shorter or longer words and can be utilized in industrial and commercial data processing and telecommunications.

  2. Glassy correlations in nematic elastomers

    NASA Astrophysics Data System (ADS)

    Lu, Bing; Goldbart, Paul; Mao, Xiaoming

    2009-03-01

    We address the physical properties of an isotropic melt or solution of nematogenic polymers that is then cross-linked beyond the vulcanization point. To do this, we construct a replica Landau theory involving a coupled pair of order- parameter fields: one describing vulcanization, the other describing local nematic order. Thermal nematic fluctuations, present at the time of cross-linking, are trapped by cross- linking into the vulcanized network. The resulting glassy nematic fluctuations are analyzed in the Gaussian approximation in two regimes. When the localization length is shorter than the thermal nematic correlation length, the nematic correlations are well captured as glassy correlations. In the opposite regime, fluctuations in the positions of the localized polymers partially wash out the glassy nematic correlations.

  3. Correlations and Neuronal Population Information.

    PubMed

    Kohn, Adam; Coen-Cagli, Ruben; Kanitscheider, Ingmar; Pouget, Alexandre

    2016-07-01

    Brain function involves the activity of neuronal populations. Much recent effort has been devoted to measuring the activity of neuronal populations in different parts of the brain under various experimental conditions. Population activity patterns contain rich structure, yet many studies have focused on measuring pairwise relationships between members of a larger population-termed noise correlations. Here we review recent progress in understanding how these correlations affect population information, how information should be quantified, and what mechanisms may give rise to correlations. As population coding theory has improved, it has made clear that some forms of correlation are more important for information than others. We argue that this is a critical lesson for those interested in neuronal population responses more generally: Descriptions of population responses should be motivated by and linked to well-specified function. Within this context, we offer suggestions of where current theoretical frameworks fall short.

  4. Electronic correlations in the ironpnictides

    SciTech Connect

    Qazilbash, M. M.; Hamlin, J. J.; Baumbach, R. E.; Zhang, Lijun; Singh, David J; Maple, M. B.; Basov, D. N.

    2009-01-01

    In correlated metals derived from Mott insulators, the motion of an electron is impeded by Coulomb repulsion due to other electrons. This phenomenon causes a substantial reduction in the electron's kinetic energy, leading to remarkable experimental manifestations in optical spectroscopy. The high-transition-temperature (Tc) superconducting cuprates are perhaps the most studied examples of such correlated metals. The occurrence of high-Tc superconductivity in the iron pnictides puts a spotlight on the relevance of correlation effects in these materials. Here, we present an infrared and optical study on single crystals of the iron pnictide superconductor LaFePO. We find clear evidence of electronic correlations in metallic LaFePO with the kinetic energy of the electrons reduced to half of that predicted by band theory of nearly free electrons. We deduce that electronic many-body effects are important in the iron pnictides despite the absence of a Mott transition.

  5. Local Realism of Macroscopic Correlations

    NASA Astrophysics Data System (ADS)

    Ramanathan, R.; Paterek, T.; Kay, A.; Kurzyński, P.; Kaszlikowski, D.

    2011-08-01

    We identify conditions under which correlations resulting from quantum measurements performed on macroscopic systems (systems composed of a number of particles of the order of the Avogadro number) can be described by local realism. We argue that the emergence of local realism at the macroscopic level is caused by an interplay between the monogamous nature of quantum correlations and the fact that macroscopic measurements do not reveal properties of individual particles.

  6. Intraclass correlations of periodontal measurements.

    PubMed

    Haffajee, A D; Socransky, S S; Goodson, J M; Lindhe, J

    1985-03-01

    Components of variance and intraclass correlation coefficients were computed for changes in attachment level, pocket depth, gingival and plaque index scores for 5 groups of treated periodontal disease patients and 1 group of untreated subjects with periodontal disease. The intraclass correlation coefficients for attachment level change ranged from 0.011 to 0.165 (median 0.067), while intraclass correlation coefficients for pocket depth changes ranged from -0.009 to 0.178 (median 0.071). These intraclass correlation coefficients were much lower than those computed for changes in measurements of plaque which ranged from 0.086 to 0.568 (median 0.268) or gingival inflammation which ranged from 0.119 to 0.522 (median 0.264). Intraclass correlation coefficients at baseline for pocket depths ranged from 0.000 to 0.199 (median 0.053), for plaque accumulation from 0.121 to 0.531 (median 0.222) and for gingival inflammation from 0.229 to 0.596 (median 0.391). The differences in the intraclass correlation coefficients between pocket depth and attachment level on the one hand and plaque accumulation or gingival inflammation on the other could not be explained on the basis of differences in the measurement scale employed, since collapsing measurement scales had little effect on the intraclass correlation coefficients. The observed larger intraclass correlation coefficients for changes in plaque and gingival indices suggest a larger rôle for host contribution to these measurements. In contrast, the data suggest that the major but by no means the sole factor determining the variability of attachment level or pocket depth changes is the nature of the local factors.

  7. Correlated imaging through atmospheric turbulence

    SciTech Connect

    Zhang Pengli; Gong Wenlin; Shen Xia; Han Shensheng

    2010-09-15

    Correlated imaging through atmospheric turbulence is studied, and the analytical expressions describing turbulence effects on image resolution are derived. Compared with direct imaging, correlated imaging can reduce the influence of turbulence to a certain extent and reconstruct high-resolution images. The result is backed up by numerical simulations, in which turbulence-induced phase perturbations are simulated by random-phase screens inserted into propagation paths.

  8. Why Waveform Correlation Sometimes Fails

    NASA Astrophysics Data System (ADS)

    Carmichael, J.

    2015-12-01

    Waveform correlation detectors used in explosion monitoring scan noisy geophysical data to test two competing hypotheses: either (1) an amplitude-scaled version of a template waveform is present, or, (2) no signal is present at all. In reality, geophysical wavefields that are monitored for explosion signatures include waveforms produced by non-target sources that are partially correlated with the waveform template. Such signals can falsely trigger correlation detectors, particularly at low thresholds required to monitor for smaller target explosions. This challenge is particularly formidable when monitoring known test sites for seismic disturbances, since uncatalogued natural seismicity is (generally) more prevalent at lower magnitudes, and could be mistaken for small explosions. To address these challenges, we identify real examples in which correlation detectors targeting explosions falsely trigger on both site-proximal earthquakes (Figure 1, below) and microseismic "noise". Motivated by these examples, we quantify performance loss when applying these detectors, and re-evaluate the correlation-detector's hypothesis test. We thereby derive new detectors from more general hypotheses that admit unknown background seismicity, and apply these to real data. From our treatment, we derive "rules of thumb'' for proper template and threshold selection in heavily cluttered signal environments. Last, we answer the question "what is the probability of falsely detecting an earthquake collocated at a test site?", using correlation detectors that include explosion-triggered templates. Figure Top: An eight-channel data stream (black) recorded from an earthquake near a mine. Red markers indicate a detection. Middle: The correlation statistic computed by scanning the template against the data stream at top. The red line indicates the threshold for event declaration, determined by a false-alarm on noise probability constraint, as computed from the signal-absent distribution using

  9. Nonglobal correlations in collider physics

    DOE PAGES

    Moult, Ian; Larkoski, Andrew J.

    2016-01-13

    Despite their importance for precision QCD calculations, correlations between in- and out-of-jet regions of phase space have never directly been observed. These so-called non-global effects are present generically whenever a collider physics measurement is not explicitly dependent on radiation throughout the entire phase space. In this paper, we introduce a novel procedure based on mutual information, which allows us to isolate these non-global correlations between measurements made in different regions of phase space. We study this procedure both analytically and in Monte Carlo simulations in the context of observables measured on hadronic final states produced in e+e- collisions, though itmore » is more widely applicable.The procedure exploits the sensitivity of soft radiation at large angles to non-global correlations, and we calculate these correlations through next-to-leading logarithmic accuracy. The bulk of these non-global correlations are found to be described in Monte Carlo simulation. They increase by the inclusion of non-perturbative effects, which we show can be incorporated in our calculation through the use of a model shape function. As a result, this procedure illuminates the source of non-global correlations and has connections more broadly to fundamental quantities in quantum field theory.« less

  10. A scalable correlator for multichannel diffuse correlation spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  11. Recirculating cross-correlation detector

    DOEpatents

    Andrews, W.H. Jr.; Roberts, M.J.

    1985-01-18

    A digital cross-correlation detector is provided in which two time-varying signals are correlated by repetitively comparing data samples stored in digital form to detect correlation between the two signals. The signals are sampled at a selected rate converted to digital form, and stored in separate locations in separate memories. When the memories are filled, the data samples from each memory are first fed word-by-word through a multiplier and summing circuit and each result is compared to the last in a peak memory circuit and if larger than the last is retained in the peak memory. Then the address line to leading signal memory is offset by one byte to affect one sample period delay of a known amount in that memory and the data in the two memories are then multiplied word-by-word once again and summed. If a new result is larger than a former sum, it is saved in the peak memory together with the time delay. The recirculating process continues with the address of the one memory being offset one additional byte each cycle until the address is shifted through the length of the memory. The correlation between the two signals is indicated by the peak signal stored in the peak memory together with the delay time at which the peak occurred. The circuit is faster and considerably less expensive than comparable accuracy correlation detectors.

  12. Community Detection for Correlation Matrices

    NASA Astrophysics Data System (ADS)

    MacMahon, Mel; Garlaschelli, Diego

    2015-04-01

    A challenging problem in the study of complex systems is that of resolving, without prior information, the emergent, mesoscopic organization determined by groups of units whose dynamical activity is more strongly correlated internally than with the rest of the system. The existing techniques to filter correlations are not explicitly oriented towards identifying such modules and can suffer from an unavoidable information loss. A promising alternative is that of employing community detection techniques developed in network theory. Unfortunately, this approach has focused predominantly on replacing network data with correlation matrices, a procedure that we show to be intrinsically biased because of its inconsistency with the null hypotheses underlying the existing algorithms. Here, we introduce, via a consistent redefinition of null models based on random matrix theory, the appropriate correlation-based counterparts of the most popular community detection techniques. Our methods can filter out both unit-specific noise and system-wide dependencies, and the resulting communities are internally correlated and mutually anticorrelated. We also implement multiresolution and multifrequency approaches revealing hierarchically nested subcommunities with "hard" cores and "soft" peripheries. We apply our techniques to several financial time series and identify mesoscopic groups of stocks which are irreducible to a standard, sectorial taxonomy; detect "soft stocks" that alternate between communities; and discuss implications for portfolio optimization and risk management.

  13. Broadband finite-pulse radio-frequency-driven recoupling (fp-RFDR) with (XY8)4(1) super-cycling for homo-nuclear correlations in very high magnetic fields at fast and ultra-fast MAS frequencies.

    PubMed

    Shen, Ming; Hu, Bingwen; Lafon, Oliver; Trébosc, Julien; Chen, Qun; Amoureux, Jean-Paul

    2012-10-01

    We demonstrate that inter-residue (13)C-(13)C proximities (of about 380 pm) in uniformly (13)C-labeled proteins can be probed by applying robust first-order recoupling during several milliseconds in single-quantum single-quantum dipolar homo-nuclear correlation (SQ-SQ D-HOMCOR) 2D experiments. We show that the intensity of medium-range homo-nuclear correlations in these experiments is enhanced using broadband first-order finite-pulse radio-frequency-driven recoupling (fp-RFDR) NMR sequence with a nested (XY8)4(1) super-cycling. The robustness and the efficiency of the fp-RFDR-(XY8)4(1) method is demonstrated at high magnetic field (21.1T) and high Magic-Angle Spinning (MAS) speeds (up to 60 kHz). The introduced super-cycling, formed by combining phase inversion and a global four-quantum phase cycle, improves the robustness of fp-RFDR to (i) chemical shift anisotropy (CSA), (ii) spread in isotropic chemical shifts, (iii) rf-inhomogeneity and (iv) hetero-nuclear dipolar couplings for long recoupling times. We show that fp-RFDR-(XY8)4(1) is efficient sans (1)H decoupling, which is beneficial for temperature-sensitive biomolecules. The efficiency and the robustness of fp-RFDR-(XY8)4(1) is investigated by spin dynamics numerical simulations as well as solid-state NMR experiments on [U-(13)C]-L-histidine·HCl, a tetra-peptide (Fmoc-[U-(13)C,(15)N]-Val-[U-(13)C,(15)N]-Ala-[U-(13)C,(15)N]-Phe-Gly-t-Boc) and Al(PO(3))(3).

  14. Biometric verification with correlation filters.

    PubMed

    Vijaya Kumar, B V K; Savvides, Marios; Xie, Chunyan; Venkataramani, Krithika; Thornton, Jason; Mahalanobis, Abhijit

    2004-01-10

    Using biometrics for subject verification can significantly improve security over that of approaches based on passwords and personal identification numbers, both of which people tend to lose or forget. In biometric verification the system tries to match an input biometric (such as a fingerprint, face image, or iris image) to a stored biometric template. Thus correlation filter techniques are attractive candidates for the matching precision needed in biometric verification. In particular, advanced correlation filters, such as synthetic discriminant function filters, can offer very good matching performance in the presence of variability in these biometric images (e.g., facial expressions, illumination changes, etc.). We investigate the performance of advanced correlation filters for face, fingerprint, and iris biometric verification. PMID:14735958

  15. Correlative Fluorescence and Electron Microscopy

    PubMed Central

    Schirra, Randall T.; Zhang, Peijun

    2014-01-01

    Correlative fluorescence and electron microscopy (CFEM) is a multimodal technique that combines dynamic and localization information from fluorescence methods with ultrastructural data from electron microscopy, to give new information about how cellular components change relative to the spatiotemporal dynamics within their environment. In this review, we will discuss some of the basic techniques and tools of the trade for utilizing this attractive research method, which is becoming a very powerful tool for biology labs. The information obtained from correlative methods has proven to be invaluable in creating consensus between the two types of microscopy, extending the capability of each, and cutting the time and expense associate with using each method separately for comparative analysis. The realization of the advantages of these methods in cell biology have led to rapid improvement in the protocols and have ushered in a new generation of instruments to reach the next level of correlation – integration. PMID:25271959

  16. Softc: An Operational Software Correlator

    NASA Technical Reports Server (NTRS)

    Lowe, Stephen T.

    2004-01-01

    Softc has been used operationally for spacecraft navigation at JPL for over 2 years and will be JPL's Mark 5 correlator next year. Softc was written to be as close to an ideal correlator as possible, making approximations only below 10(exp -13) seconds. The program can correlate real USB, real LSB, or complex I/Q data sampled with 1, 2, 4. or 8-bit resolution, and was developed with strong debugging tools that made final debugging relatively quick. Softc's algorithms and program structure are fully documented. Timing tests on a recent Intel CPU show Softc processes 8 lags of 1-bit sampled data at 10 MSamples/sec, independent of sample rate.

  17. Correlated optical and isotopic nanoscopy

    PubMed Central

    Saka, Sinem K.; Vogts, Angela; Kröhnert, Katharina; Hillion, François; Rizzoli, Silvio O; Wessels, Johannes T.

    2014-01-01

    The isotopic composition of different materials can be imaged by secondary ion mass spectrometry. In biology, this method is mainly used to study cellular metabolism and turnover, by pulsing the cells with marker molecules such as amino acids labelled with stable isotopes (15N, 13C). The incorporation of the markers is then imaged with a lateral resolution that can surpass 100 nm. However, secondary ion mass spectrometry cannot identify specific subcellular structures like organelles, and needs to be correlated with a second technique, such as fluorescence imaging. Here, we present a method based on stimulated emission depletion microscopy that provides correlated optical and isotopic nanoscopy (COIN) images. We use this approach to study the protein turnover in different organelles from cultured hippocampal neurons. Correlated optical and isotopic nanoscopy can be applied to a variety of biological samples, and should therefore enable the investigation of the isotopic composition of many organelles and subcellular structures. PMID:24718107

  18. Converting Coherence to Quantum Correlations

    NASA Astrophysics Data System (ADS)

    Ma, Jiajun; Yadin, Benjamin; Girolami, Davide; Vedral, Vlatko; Gu, Mile

    2016-04-01

    Recent results in quantum information theory characterize quantum coherence in the context of resource theories. Here, we study the relation between quantum coherence and quantum discord, a kind of quantum correlation which appears even in nonentangled states. We prove that the creation of quantum discord with multipartite incoherent operations is bounded by the amount of quantum coherence consumed in its subsystems during the process. We show how the interplay between quantum coherence consumption and creation of quantum discord works in the preparation of multipartite quantum correlated states and in the model of deterministic quantum computation with one qubit.

  19. Correlation properties of loose groups

    SciTech Connect

    Maia, M.A.G.; Da Costa, L.N. )

    1990-02-01

    The two-point spatial correlation function for loose groups of galaxies is computed, using the recently compiled catalog of groups in the southern hemisphere. It is found that the correlation function for groups has a similar slope to that of galaxies but with a smaller amplitude, confirming an earlier result obtained from a similar analysis of the CfA group catalog. This implies that groups of galaxies are more randomly distributed than galaxies, which may be consistent with the predictions of Kashlinsky (1987) for a gravitational clustering scenario for the formation of large-scale structures. 21 refs.

  20. Converting Coherence to Quantum Correlations.

    PubMed

    Ma, Jiajun; Yadin, Benjamin; Girolami, Davide; Vedral, Vlatko; Gu, Mile

    2016-04-22

    Recent results in quantum information theory characterize quantum coherence in the context of resource theories. Here, we study the relation between quantum coherence and quantum discord, a kind of quantum correlation which appears even in nonentangled states. We prove that the creation of quantum discord with multipartite incoherent operations is bounded by the amount of quantum coherence consumed in its subsystems during the process. We show how the interplay between quantum coherence consumption and creation of quantum discord works in the preparation of multipartite quantum correlated states and in the model of deterministic quantum computation with one qubit.

  1. Defect Detection in Correlated Noise

    NASA Astrophysics Data System (ADS)

    Dogandžić, Aleksandar; Eua-Anant, Nawanat

    2004-02-01

    We present methods for detecting NDE defect signals in correlated noise having unknown covariance. The proposed detectors are derived using the statistical theory of generalized likelihood ratio (GLR) tests and multivariate analysis of variance (MANOVA). We consider both real and complex data models. To allow accurate estimation of the noise covariance, we incorporate secondary data containing only noise into detector design. Probability distributions of the GLR test statistics are derived under the null hypothesis, i.e. assuming that the signal is absent, and used for detector design. We apply the proposed methods to simulated and experimental data and demonstrate their superior performance compared with the detectors that neglect noise correlation.

  2. PREFACE: Strongly correlated electron systems Strongly correlated electron systems

    NASA Astrophysics Data System (ADS)

    Saxena, Siddharth S.; Littlewood, P. B.

    2012-07-01

    This special section is dedicated to the Strongly Correlated Electron Systems Conference (SCES) 2011, which was held from 29 August-3 September 2011, in Cambridge, UK. SCES'2011 is dedicated to 100 years of superconductivity and covers a range of topics in the area of strongly correlated systems. The correlated electronic and magnetic materials featured include f-electron based heavy fermion intermetallics and d-electron based transition metal compounds. The selected papers derived from invited presentations seek to deepen our understanding of the rich physical phenomena that arise from correlation effects. The focus is on quantum phase transitions, non-Fermi liquid phenomena, quantum magnetism, unconventional superconductivity and metal-insulator transitions. Both experimental and theoretical work is presented. Based on fundamental advances in the understanding of electronic materials, much of 20th century materials physics was driven by miniaturisation and integration in the electronics industry to the current generation of nanometre scale devices. The achievements of this industry have brought unprecedented advances to society and well-being, and no doubt there is much further to go—note that this progress is founded on investments and studies in the fundamentals of condensed matter physics from more than 50 years ago. Nevertheless, the defining challenges for the 21st century will lie in the discovery in science, and deployment through engineering, of technologies that can deliver the scale needed to have an impact on the sustainability agenda. Thus the big developments in nanotechnology may lie not in the pursuit of yet smaller transistors, but in the design of new structures that can revolutionise the performance of solar cells, batteries, fuel cells, light-weight structural materials, refrigeration, water purification, etc. The science presented in the papers of this special section also highlights the underlying interest in energy-dense materials, which

  3. EDITORIAL: Strongly correlated electron systems Strongly correlated electron systems

    NASA Astrophysics Data System (ADS)

    Ronning, Filip; Batista, Cristian

    2011-03-01

    Strongly correlated electrons is an exciting and diverse field in condensed matter physics. This special issue aims to capture some of that excitement and recent developments in the field. Given that this issue was inspired by the 2010 International Conference on Strongly Correlated Electron Systems (SCES 2010), we briefly give some history in order to place this issue in context. The 2010 International Conference on Strongly Correlated Electron Systems was held in Santa Fe, New Mexico, a reunion of sorts from the 1989 International Conference on the Physics of Highly Correlated Electron Systems that also convened in Santa Fe. SCES 2010—co-chaired by John Sarrao and Joe Thompson—followed the tradition of earlier conferences, in this century, hosted by Buzios (2008), Houston (2007), Vienna (2005), Karlsruhe (2004), Krakow (2002) and Ann Arbor (2001). Every three years since 1997, SCES has joined the International Conference on Magnetism (ICM), held in Recife (2000), Rome (2003), Kyoto (2006) and Karlsruhe (2009). Like its predecessors, SCES 2010 topics included strongly correlated f- and d-electron systems, heavy-fermion behaviors, quantum-phase transitions, non-Fermi liquid phenomena, unconventional superconductivity, and emergent states that arise from electronic correlations. Recent developments from studies of quantum magnetism and cold atoms complemented the traditional subjects and were included in SCES 2010. 2010 celebrated the 400th anniversary of Santa Fe as well as the birth of astronomy. So what's the connection to SCES? The Dutch invention of the first practical telescope and its use by Galileo in 1610 and subsequent years overturned dogma that the sun revolved about the earth. This revolutionary, and at the time heretical, conclusion required innovative combinations of new instrumentation, observation and mathematics. These same combinations are just as important 400 years later and are the foundation of scientific discoveries that were discussed

  4. Tetrachoric Correlation: A Permutation Alternative

    ERIC Educational Resources Information Center

    Long, Michael A.; Berry, Kenneth J.; Mielke, Paul W., Jr.

    2009-01-01

    An exact permutation test is provided for the tetrachoric correlation coefficient. Comparisons with the conventional test employing Student's t distribution demonstrate the necessity of using the permutation approach for small sample sizes and/or disproportionate marginal frequency totals. (Contains 4 tables.)

  5. Octupole correlation effects in nuclei

    SciTech Connect

    Chasman, R.R.

    1992-01-01

    Octupole correlation effects in nuclei are discussed from the point of view of many-body wavefunctions as well as mean-field methods. The light actinides, where octupole effects are largest, are considered in detail. Comparisons of theory and experiment are made for energy splittings of parity doublets; E1 transition matrix elements and one-nucleon transfer reactions.

  6. Sample Size and Correlational Inference

    ERIC Educational Resources Information Center

    Anderson, Richard B.; Doherty, Michael E.; Friedrich, Jeff C.

    2008-01-01

    In 4 studies, the authors examined the hypothesis that the structure of the informational environment makes small samples more informative than large ones for drawing inferences about population correlations. The specific purpose of the studies was to test predictions arising from the signal detection simulations of R. B. Anderson, M. E. Doherty,…

  7. Octupole correlation effects in nuclei

    SciTech Connect

    Chasman, R.R.

    1992-08-01

    Octupole correlation effects in nuclei are discussed from the point of view of many-body wavefunctions as well as mean-field methods. The light actinides, where octupole effects are largest, are considered in detail. Comparisons of theory and experiment are made for energy splittings of parity doublets; E1 transition matrix elements and one-nucleon transfer reactions.

  8. Unorthodox Uses of Correlation Coefficients.

    ERIC Educational Resources Information Center

    Kraemer, Helena Chmura

    While the potential use of correlation methods has spread to wide contexts and these uses have permeated behavioral research, their scope remains the orthodox applications: to test independence, and to measure association. It is well worth noticing that problems having no obstensible connection to dependence, independence, or association have been…

  9. Multilevel Modeling with Correlated Effects

    ERIC Educational Resources Information Center

    Kim, Jee-Seon; Frees, Edward W.

    2007-01-01

    When there exist omitted effects, measurement error, and/or simultaneity in multilevel models, explanatory variables may be correlated with random components, and standard estimation methods do not provide consistent estimates of model parameters. This paper introduces estimators that are consistent under such conditions. By employing generalized…

  10. In vivo correlation mapping microscopy

    NASA Astrophysics Data System (ADS)

    McGrath, James; Alexandrov, Sergey; Owens, Peter; Subhash, Hrebesh; Leahy, Martin

    2016-04-01

    To facilitate regular assessment of the microcirculation in vivo, noninvasive imaging techniques such as nailfold capillaroscopy are required in clinics. Recently, a correlation mapping technique has been applied to optical coherence tomography (OCT), which extends the capabilities of OCT to microcirculation morphology imaging. This technique, known as correlation mapping optical coherence tomography, has been shown to extract parameters, such as capillary density and vessel diameter, and key clinical markers associated with early changes in microvascular diseases. However, OCT has limited spatial resolution in both the transverse and depth directions. Here, we extend this correlation mapping technique to other microscopy modalities, including confocal microscopy, and take advantage of the higher spatial resolution offered by these modalities. The technique is achieved as a processing step on microscopy images and does not require any modification to the microscope hardware. Results are presented which show that this correlation mapping microscopy technique can extend the capabilities of conventional microscopy to enable mapping of vascular networks in vivo with high spatial resolution in both the transverse and depth directions.

  11. The Seduction of Correlational Data.

    ERIC Educational Resources Information Center

    Cochran, Nancy

    1979-01-01

    A dependency on correlational data allows one to avoid theory building and even to avoid defining terms. The social science community is being seduced by data and would do well to resist what is available simply because of its ease of tabulation and redundancy. (RL)

  12. Correlation Techniques for Application in Photon Correlation Spectroscopy.

    NASA Astrophysics Data System (ADS)

    Courtney, Peter R.

    Available from UMI in association with The British Library. Requires signed TDF. In this thesis the application of modern computing and electronics to the techniques used in photon correlation spectroscopy is investigated. The study leads to the development of a computer controlled full correlator system based on the TMS32010 digital signal processor, installed in a PC -type microprocessor. A suite of computer control programs are developed featuring full correlation, computer optimization of sampling frequency, dust discrimination and automatic operation. The system was fully tested both on simulated data and during the study of experimental solutions. It was shown to exhibit improved signal to noise, stability, resolution and ease of use over the existing clipping correlator, in addition to being independent of the statistics of the scattered light field. Designs for further development of the system are discussed. Polymer dynamics have been investigated in the study of diisooctylphthalate as a solvent for polystyrene. It was seen to exhibit Theta solvent behaviour at low concentrations with gelation occurring as the concentration increases. At elevated temperatures competing effects produce an initial rise in D _ c followed by a subsequent fall with increasing concentration until a stable level is reached. Dynamics of the Human Immunoglobulins 1gG were studied in solutions approximating to in-vivo conditions. Translational diffusion and bulk rotation was observed for all subclasses, and the movement of Fab arms about the hinge region was conclusively observed for 1gG1 and 1gG3. The characterisation reinforces existing structural models and facilitates further investigations which would be greatly enhanced by the application of techniques developed in this thesis.

  13. In Vivo Fluorescence Correlation and Cross-Correlation Spectroscopy

    NASA Astrophysics Data System (ADS)

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

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

  14. Separating Spike Count Correlation from Firing Rate Correlation.

    PubMed

    Vinci, Giuseppe; Ventura, Valérie; Smith, Matthew A; Kass, Robert E

    2016-05-01

    Populations of cortical neurons exhibit shared fluctuations in spiking activity over time. When measured for a pair of neurons over multiple repetitions of an identical stimulus, this phenomenon emerges as correlated trial-to-trial response variability via spike count correlation (SCC). However, spike counts can be viewed as noisy versions of firing rates, which can vary from trial to trial. From this perspective, the SCC for a pair of neurons becomes a noisy version of the corresponding firing rate correlation (FRC). Furthermore, the magnitude of the SCC is generally smaller than that of the FRC and is likely to be less sensitive to experimental manipulation. We provide statistical methods for disambiguating time-averaged drive from within-trial noise, thereby separating FRC from SCC. We study these methods to document their reliability, and we apply them to neurons recorded in vivo from area V4 in an alert animal. We show how the various effects we describe are reflected in the data: within-trial effects are largely negligible, while attenuation due to trial-to-trial variation dominates and frequently produces comparisons in SCC that, because of noise, do not accurately reflect those based on the underlying FRC.

  15. Identification and structure determination of a third cyclobutane photodimer of thymidylyl-(3'-->5')-thymidine: the trans-syn-II product.

    PubMed

    Kao, J L; Nadji, S; Taylor, J S

    1993-01-01

    Photolysis of thymidylyl-(3'-->5')-thymidine (TpT) has been previously reported by many workers to lead to only two cyclobutane dimers, the cis-syn and trans-syn-I dimers. This is curious in light of the fact that photolysis of thymidylyl-(3'-->5')-deoxyuridine (TpdU), which has a hydrogen in place of a methyl group at C6 of the 3'-thymidine, produces two trans-syn diastereomers. Recently, we discovered by way of X-ray crystallography that photolysis of the (Rp)-methyl phosphate ester of TpT leads to two trans-syn diastereomers, prompting us to reexamine the photochemistry of TpT. In this paper we show that sensitized photolysis of TpT also leads to the hitherto unknown trans-syn-II diastereomer in 2% yield. We also report the solution-state 1H NMR assignment of the trans-syn-II photodimer of TpT and its (Rp)-methyl phosphate ester by way of 2D homonuclear Hartmann--Hahn experiment, rotating frame nuclear Overhauser effect spectroscopy, and proton-detected 1H-31P correlation spectroscopy. Conformational analysis of three-bond 1H-1H, 1H-31P, and 13C-31P coupling constant data established a close similarity between the solution-state structures of the trans-syn-II photodimer of TpT and its (Rp)-methyl phosphate ester, with the crystal structure of the methyl phosphate ester.

  16. CMS results on multijet correlations

    SciTech Connect

    Safronov, Grigory

    2015-04-10

    We present recent CMS measurements on multijet correlations using forward and low-p{sub T} jets, focusing on searches for BFKL and saturation phenomena. In pp collisions at √(s)=7 TeV, azimuthal correlations in dijets separated in rapidity by up to 9.4 units were measured. The results are compared to BFKL- and DGLAP-based predictions. In pp collisions at √(s)=8 TeV, cross sections for jets with p{sub T} > 21 GeV and |y| < 4.7, and for track-jets with p{sub T} > 1 GeV (minijets) are presented. The minijet results are sensitive to the bound imposed by the total inelastic cross section, and are compared to various models for taming the growth of the 2 → 2 cross section at low p{sub T}.

  17. Softness Correlations Across Length Scales

    NASA Astrophysics Data System (ADS)

    Ivancic, Robert; Shavit, Amit; Rieser, Jennifer; Schoenholz, Samuel; Cubuk, Ekin; Durian, Douglas; Liu, Andrea; Riggleman, Robert

    In disordered systems, it is believed that mechanical failure begins with localized particle rearrangements. Recently, a machine learning method has been introduced to identify how likely a particle is to rearrange given its local structural environment, quantified by softness. We calculate the softness of particles in simulations of atomic Lennard-Jones mixtures, molecular Lennard-Jones oligomers, colloidal systems and granular systems. In each case, we find that the length scale characterizing spatial correlations of softness is approximately a particle diameter. These results provide a rationale for why localized rearrangements--whose size is presumably set by the scale of softness correlations--might occur in disordered systems across many length scales. Supported by DOE DE-FG02-05ER46199.

  18. CMS results on multijet correlations

    NASA Astrophysics Data System (ADS)

    Safronov, Grigory

    2015-04-01

    We present recent CMS measurements on multijet correlations using forward and low-pT jets, focusing on searches for BFKL and saturation phenomena. In pp collisions at √{s }=7 TeV, azimuthal correlations in dijets separated in rapidity by up to 9.4 units were measured. The results are compared to BFKL- and DGLAP-based predictions. In pp collisions at √{s }=8 TeV, cross sections for jets with pT > 21 GeV and |y| < 4.7, and for track-jets with pT > 1 GeV (minijets) are presented. The minijet results are sensitive to the bound imposed by the total inelastic cross section, and are compared to various models for taming the growth of the 2 → 2 cross section at low pT.

  19. Correlated Electrons in Reduced Dimensions

    SciTech Connect

    Bonesteel, Nicholas E

    2015-01-31

    This report summarizes the work accomplished under the support of US DOE grant # DE-FG02-97ER45639, "Correlated Electrons in Reduced Dimensions." The underlying hypothesis of the research supported by this grant has been that studying the unique behavior of correlated electrons in reduced dimensions can lead to new ways of understanding how matter can order and how it can potentially be used. The systems under study have included i) fractional quantum Hall matter, which is realized when electrons are confined to two-dimensions and placed in a strong magnetic field at low temperature, ii) one-dimensional chains of spins and exotic quasiparticle excitations of topologically ordered matter, and iii) electrons confined in effectively ``zero-dimensional" semiconductor quantum dots.

  20. Ultraviolet divergences in cosmological correlations

    SciTech Connect

    Weinberg, Steven

    2011-03-15

    A method is developed for dealing with ultraviolet divergences in calculations of cosmological correlations, which does not depend on dimensional regularization. An extended version of the WKB approximation is used to analyze the divergences in these calculations, and these divergences are controlled by the introduction of Pauli-Villars regulator fields. This approach is illustrated in the theory of a scalar field with arbitrary self-interactions in a fixed flat-space Robertson-Walker metric with arbitrary scale factor a(t). Explicit formulas are given for the counterterms needed to cancel all dependence on the regulator properties, and an explicit prescription is given for calculating finite regulator-independent correlation functions. The possibility of infrared divergences in this theory is briefly considered.

  1. Bootstrapping N=2 chiral correlators

    NASA Astrophysics Data System (ADS)

    Lemos, Madalena; Liendo, Pedro

    2016-01-01

    We apply the numerical bootstrap program to chiral operators in four-dimensional N=2 SCFTs. In the first part of this work we study four-point functions in which all fields have the same conformal dimension. We give special emphasis to bootstrapping a specific theory: the simplest Argyres-Douglas fixed point with no flavor symmetry. In the second part we generalize our setup and consider correlators of fields with unequal dimension. This is an example of a mixed correlator and allows us to probe new regions in the parameter space of N=2 SCFTs. In particular, our results put constraints on relations in the Coulomb branch chiral ring and on the curvature of the Zamolodchikov metric.

  2. Electron correlation energies in atoms

    NASA Astrophysics Data System (ADS)

    McCarthy, Shane Patrick

    This dissertation is a study of electron correlation energies Ec in atoms. (1) Accurate values of E c are computed for isoelectronic sequences of "Coulomb-Hooke" atoms with varying mixtures of Coulombic and Hooke character. (2) Coupled-cluster calculations in carefully designed basis sets are combined with fully converged second-order Moller-Plesset perturbation theory (MP2) computations to obtain fairly accurate, non-relativistic Ec values for the 12 closed-shell atoms from Ar to Rn. The complete basis-set (CBS) limits of MP2 energies are obtained for open-shell atoms by computations in very large basis sets combined with a knowledge of the MP2/CBS limit for the next larger closed-shell atom with the same valence shell structure. Then higher-order correlation corrections are found by coupled-cluster calculations using basis sets that are not quite as large. The method is validated for the open-shell atoms from Al to Cl and then applied to get E c values, probably accurate to 3%, for the 4th-period open-shell atoms: K, Sc-Cu, and Ga-Br. (3) The results show that, contrary to quantum chemical folklore, MP2 overestimates |Ec| for atoms beyond Fe. Spin-component scaling arguments are used to provide a simple explanation for this overestimation. (4) Eleven non-relativistic density functionals, including some of the most widely-used ones, are tested on their ability to predict non-relativistic, electron correlation energies for atoms and their cations. They all lead to relatively poor predictions for the heavier atoms. Several novel, few-parameter, density functionals for the correlation energy are developed heuristically. Four new functionals lead to improved predictions for the 4th-period atoms without unreasonably compromising accuracy for the lighter atoms. (5) Simple models describing the variation of E c with atomic number are developed.

  3. Neural correlates and causal mechanisms.

    PubMed

    Hohwy, Jakob

    2012-06-01

    What Joseph Neisser calls for is exactly right: more philosophy of science will help us better understand and refine the idea of neural correlates of consciousness (NCC). But (i) the key bit of philosophy of science Neisser appeals to is itself in need of clarification; (ii) the orthodox NCC definition is more resourceful than Neisser allows, and (iii) it is possible to resist the phenomenological conception of conscious experience that fuels some of Neisser's argument.

  4. Quantum correlations beyond Tsirelson's bound

    NASA Astrophysics Data System (ADS)

    Berry, Dominic; Ringbauer, Martin; Fedrizzi, Alessandro; White, Andrew

    2014-03-01

    Violations of Bell inequalities show that there are correlations that cannot explained by any classical theory. Further violation, beyond Tsirelson's bound, shows that there are correlations that are not explained by quantum mechanics. Such super-quantum correlations would enable violation of information causality, where communication of one bit provides more than one bit of information [Nature 461, 1101 (2009)]. An unavoidable feature of all realistic Bell inequality experiments is loss. If one postselects on successful measurements, unentangled states can violate Bell inequalities. On the other hand, loss can be used to enhance the violation of Bell inequalities for entangled states. This can improve the ability to distinguish between entangled and unentangled states, despite loss. Here we report an optical experiment providing maximal violation of the CHSH-Bell inequality with entangled states. Due to loss and postselection, Tsirelson's bound is also violated. This enables us to more easily distinguish between entangled and unentangled states. In addition, it provides violation of information causality for the postselected data.

  5. Correlated Temporal and Spectral Variability

    NASA Technical Reports Server (NTRS)

    Swank, Jean H.

    2007-01-01

    The variability of neutron star and black hole X-ray sources has several dimensions, because of the roles played by different important time-scales. The variations on time scales of hours, weeks, and months, ranging from 50% to orders of magnitude, arise out of changes in the flow in the disk. The most important driving forces for those changes are probably various possible instabilities in the disk, though there may be effects with other dominant causes. The changes in the rate of flow appear to be associated with changes in the flow's configuration, as the accreting material approaches the compact object, for there are generally correlated changes in both the Xray spectra and the character of the faster temporal variability. There has been a lot of progress in tracking these correlations, both for Z and Atoll neutron star low-mass X-ray binaries, and for black hole binaries. I will discuss these correlations and review briefly what they tell us about the physical states of the systems.

  6. Sequential backbone assignment of uniformly 13C-labeled RNAs by a two-dimensional P(CC)H-TOCSY triple resonance NMR experiment.

    PubMed

    Wijmenga, S S; Heus, H A; Leeuw, H A; Hoppe, H; van der Graaf, M; Hilbers, C W

    1995-01-01

    A new 1H-13C-31P triple resonance experiment is described which allows unambiguous sequential backbone assignment in 13C-labeled oligonucleotides via through-bond coherence transfer from 31P via 13C to 1H. The approach employs INEPT to transfer coherence from 31P to 13C and homonuclear TOCSY to transfer the 13C coherence through the ribose ring, followed by 13C to 1H J-cross-polarisation. The efficiencies of the various possible transfer pathways are discussed. The most efficient route involves transfer of 31Pi coherence via C4'i and C4'i-1, because of the relatively large JPC4' couplings involved. Via the homonuclear and heteronuclear mixing periods, the C4'i and C4'i-1 coherences are subsequently transferred to, amongst others, H1'i and H1'i-1, respectively, leading to a 2D 1H-31P spectrum which allows a sequential assignment in the 31P-1H1' region of the spectrum, i.e. in the region where the proton resonances overlap least. The experiment is demonstrated on a 13C-labeled RNA hairpin with the sequence 5'(GGGC-CAAA-GCCU)3'.

  7. High-resolution 2D NMR spectroscopy of bicelles to measure the membrane interaction of ligands.

    PubMed

    Dvinskikh, Sergey V; Dürr, Ulrich H N; Yamamoto, Kazutoshi; Ramamoorthy, Ayyalusamy

    2007-01-31

    Magnetically aligned bicelles are increasingly being used as model membranes in solution- and solid-state NMR studies of the structure, dynamics, topology, and interaction of membrane-associated peptides and proteins. These studies commonly utilize the PISEMA pulse sequence to measure dipolar coupling and chemical shift, the two key parameters used in subsequent structural analysis. In the present study, we demonstrate that the PISEMA and other rotating-frame pulse sequences are not suitable for the measurement of long-range heteronuclear dipolar couplings, and that they provide inaccurate values when multiple protons are coupled to a 13C nucleus. Furthermore, we demonstrate that a laboratory-frame separated-local-field experiment is capable of overcoming these difficulties in magnetically aligned bicelles. An extension of this approach to accurately measure 13C-31P and 1H-31P couplings from phospholipids, which are useful to understand the interaction of molecules with the membrane, is also described. In these 2D experiments, natural abundance 13C was observed from bicelles containing DMPC and DHPC lipid molecules. As a first application, these solid-state NMR approaches were utilized to probe the membrane interaction of an antidepressant molecule, desipramine, and its location in the membrane.

  8. PREFACE: Strongly correlated electron systems Strongly correlated electron systems

    NASA Astrophysics Data System (ADS)

    Saxena, Siddharth S.; Littlewood, P. B.

    2012-07-01

    This special section is dedicated to the Strongly Correlated Electron Systems Conference (SCES) 2011, which was held from 29 August-3 September 2011, in Cambridge, UK. SCES'2011 is dedicated to 100 years of superconductivity and covers a range of topics in the area of strongly correlated systems. The correlated electronic and magnetic materials featured include f-electron based heavy fermion intermetallics and d-electron based transition metal compounds. The selected papers derived from invited presentations seek to deepen our understanding of the rich physical phenomena that arise from correlation effects. The focus is on quantum phase transitions, non-Fermi liquid phenomena, quantum magnetism, unconventional superconductivity and metal-insulator transitions. Both experimental and theoretical work is presented. Based on fundamental advances in the understanding of electronic materials, much of 20th century materials physics was driven by miniaturisation and integration in the electronics industry to the current generation of nanometre scale devices. The achievements of this industry have brought unprecedented advances to society and well-being, and no doubt there is much further to go—note that this progress is founded on investments and studies in the fundamentals of condensed matter physics from more than 50 years ago. Nevertheless, the defining challenges for the 21st century will lie in the discovery in science, and deployment through engineering, of technologies that can deliver the scale needed to have an impact on the sustainability agenda. Thus the big developments in nanotechnology may lie not in the pursuit of yet smaller transistors, but in the design of new structures that can revolutionise the performance of solar cells, batteries, fuel cells, light-weight structural materials, refrigeration, water purification, etc. The science presented in the papers of this special section also highlights the underlying interest in energy-dense materials, which

  9. Measures and models for angular correlation and angular-linear correlation. [correlation of random variables

    NASA Technical Reports Server (NTRS)

    Johnson, R. A.; Wehrly, T.

    1976-01-01

    Population models for dependence between two angular measurements and for dependence between an angular and a linear observation are proposed. The method of canonical correlations first leads to new population and sample measures of dependence in this latter situation. An example relating wind direction to the level of a pollutant is given. Next, applied to pairs of angular measurements, the method yields previously proposed sample measures in some special cases and a new sample measure in general.

  10. Correlation, functional analysis and optical pattern recognition

    SciTech Connect

    Dickey, F.M.; Lee, M.L.; Stalker, K.T.

    1994-03-01

    Correlation integrals have played a central role in optical pattern recognition. The success of correlation, however, has been limited. What is needed is a mathematical operation more complex than correlation. Suitably complex operations are the functionals defined on the Hilbert space of Lebesgue square integrable functions. Correlation is a linear functional of a parameter. In this paper, we develop a representation of functionals in terms of inner products or equivalently correlation functions. We also discuss the role of functionals in neutral networks. Having established a broad relation of correlation to pattern recognition, we discuss the computation of correlation functions using acousto-optics.

  11. Iterative method for generating correlated binary sequences

    NASA Astrophysics Data System (ADS)

    Usatenko, O. V.; Melnik, S. S.; Apostolov, S. S.; Makarov, N. M.; Krokhin, A. A.

    2014-11-01

    We propose an efficient iterative method for generating random correlated binary sequences with a prescribed correlation function. The method is based on consecutive linear modulations of an initially uncorrelated sequence into a correlated one. Each step of modulation increases the correlations until the desired level has been reached. The robustness and efficiency of the proposed algorithm are tested by generating sequences with inverse power-law correlations. The substantial increase in the strength of correlation in the iterative method with respect to single-step filtering generation is shown for all studied correlation functions. Our results can be used for design of disordered superlattices, waveguides, and surfaces with selective transport properties.

  12. Variable Selection through Correlation Sifting

    NASA Astrophysics Data System (ADS)

    Huang, Jim C.; Jojic, Nebojsa

    Many applications of computational biology require a variable selection procedure to sift through a large number of input variables and select some smaller number that influence a target variable of interest. For example, in virology, only some small number of viral protein fragments influence the nature of the immune response during viral infection. Due to the large number of variables to be considered, a brute-force search for the subset of variables is in general intractable. To approximate this, methods based on ℓ1-regularized linear regression have been proposed and have been found to be particularly successful. It is well understood however that such methods fail to choose the correct subset of variables if these are highly correlated with other "decoy" variables. We present a method for sifting through sets of highly correlated variables which leads to higher accuracy in selecting the correct variables. The main innovation is a filtering step that reduces correlations among variables to be selected, making the ℓ1-regularization effective for datasets on which many methods for variable selection fail. The filtering step changes both the values of the predictor variables and output values by projections onto components obtained through a computationally-inexpensive principal components analysis. In this paper we demonstrate the usefulness of our method on synthetic datasets and on novel applications in virology. These include HIV viral load analysis based on patients' HIV sequences and immune types, as well as the analysis of seasonal variation in influenza death rates based on the regions of the influenza genome that undergo diversifying selection in the previous season.

  13. The crystallography of correlated disorder

    NASA Astrophysics Data System (ADS)

    Keen, David A.; Goodwin, Andrew L.

    2015-05-01

    Classical crystallography can determine structures as complicated as multi-component ribosomal assemblies with atomic resolution, but is inadequate for disordered systems--even those as simple as water ice--that occupy the complex middle ground between liquid-like randomness and crystalline periodic order. Correlated disorder nevertheless has clear crystallographic signatures that map to the type of disorder, irrespective of the underlying physical or chemical interactions and material involved. This mapping hints at a common language for disordered states that will help us to understand, control and exploit the disorder responsible for many interesting physical properties.

  14. Speeding up local correlation methods

    SciTech Connect

    Kats, Daniel

    2014-12-28

    We present two techniques that can substantially speed up the local correlation methods. The first one allows one to avoid the expensive transformation of the electron-repulsion integrals from atomic orbitals to virtual space. The second one introduces an algorithm for the residual equations in the local perturbative treatment that, in contrast to the standard scheme, does not require holding the amplitudes or residuals in memory. It is shown that even an interpreter-based implementation of the proposed algorithm in the context of local MP2 method is faster and requires less memory than the highly optimized variants of conventional algorithms.

  15. Boundary anomalies and correlation functions

    NASA Astrophysics Data System (ADS)

    Huang, Kuo-Wei

    2016-08-01

    It was shown recently that boundary terms of conformal anomalies recover the universal contribution to the entanglement entropy and also play an important role in the boundary monotonicity theorem of odd-dimensional quantum field theories. Motivated by these results, we investigate relationships between boundary anomalies and the stress tensor correlation functions in conformal field theories. In particular, we focus on how the conformal Ward identity and the renormalization group equation are modified by boundary central charges. Renormalized stress tensors induced by boundary Weyl invariants are also discussed, with examples in spherical and cylindrical geometries.

  16. Correlation dimension of complex networks.

    PubMed

    Lacasa, Lucas; Gómez-Gardeñes, Jesús

    2013-04-19

    We propose a new measure to characterize the dimension of complex networks based on the ergodic theory of dynamical systems. This measure is derived from the correlation sum of a trajectory generated by a random walker navigating the network, and extends the classical Grassberger-Procaccia algorithm to the context of complex networks. The method is validated with reliable results for both synthetic networks and real-world networks such as the world air-transportation network or urban networks, and provides a computationally fast way for estimating the dimensionality of networks which only relies on the local information provided by the walkers.

  17. The crystallography of correlated disorder.

    PubMed

    Keen, David A; Goodwin, Andrew L

    2015-05-21

    Classical crystallography can determine structures as complicated as multi-component ribosomal assemblies with atomic resolution, but is inadequate for disordered systems--even those as simple as water ice--that occupy the complex middle ground between liquid-like randomness and crystalline periodic order. Correlated disorder nevertheless has clear crystallographic signatures that map to the type of disorder, irrespective of the underlying physical or chemical interactions and material involved. This mapping hints at a common language for disordered states that will help us to understand, control and exploit the disorder responsible for many interesting physical properties.

  18. Pairing Correlations at High Spins

    NASA Astrophysics Data System (ADS)

    Ma, Hai-Liang; Dong, Bao-Guo; Zhang, Yan; Fan, Ping; Yuan, Da-Qing; Zhu, Shen-Yun; Zhang, Huan-Qiao; Petrache, C. M.; Ragnarsson, I.; Carlsson, B. G.

    The pairing correcting energies at high spins in 161Lu and 138Nd are studied by comparing the results of the cranked-Nilsson-Strutinsky (CNS) and cranked-Nilsson-Strutinsky-Bogoliubov (CNSB) models. It is concluded that the Coriolis effect rather than the rotational alignment effect plays a major role in the reduction of the pairing correlations in the high spin region. Then we proposed an average pairing correction method which not only better reproduces the experimental data comparing with the CNS model but also enables a clean-cut tracing of the configurations thus the full-spin-range discussion on the various rotating bands.

  19. Preselected Sub-Poissonian Correlations

    NASA Technical Reports Server (NTRS)

    Pavicic, Mladen

    1996-01-01

    The simplest possible photon-number-squeezed states containing only two photons and exhibiting sub-poissonian statistics with the Fano factor approaching 0.5 have been used for a proposal of a loophole-free Bell experiment requiring only 67 percent of detection efficiency. The states are obtained by the fourth order interference first of two downconverted photons at an asymmetrical beam splitter and thereupon of two photons from two independent singlets at an asymmetrical beam splitter. In the latter set-up, the other two photons which nowhere interacted and whose paths never crossed appear entangled in a singlet-like correlated state.

  20. EDITORIAL: Strongly correlated electron systems Strongly correlated electron systems

    NASA Astrophysics Data System (ADS)

    Ronning, Filip; Batista, Cristian

    2011-03-01

    Strongly correlated electrons is an exciting and diverse field in condensed matter physics. This special issue aims to capture some of that excitement and recent developments in the field. Given that this issue was inspired by the 2010 International Conference on Strongly Correlated Electron Systems (SCES 2010), we briefly give some history in order to place this issue in context. The 2010 International Conference on Strongly Correlated Electron Systems was held in Santa Fe, New Mexico, a reunion of sorts from the 1989 International Conference on the Physics of Highly Correlated Electron Systems that also convened in Santa Fe. SCES 2010—co-chaired by John Sarrao and Joe Thompson—followed the tradition of earlier conferences, in this century, hosted by Buzios (2008), Houston (2007), Vienna (2005), Karlsruhe (2004), Krakow (2002) and Ann Arbor (2001). Every three years since 1997, SCES has joined the International Conference on Magnetism (ICM), held in Recife (2000), Rome (2003), Kyoto (2006) and Karlsruhe (2009). Like its predecessors, SCES 2010 topics included strongly correlated f- and d-electron systems, heavy-fermion behaviors, quantum-phase transitions, non-Fermi liquid phenomena, unconventional superconductivity, and emergent states that arise from electronic correlations. Recent developments from studies of quantum magnetism and cold atoms complemented the traditional subjects and were included in SCES 2010. 2010 celebrated the 400th anniversary of Santa Fe as well as the birth of astronomy. So what's the connection to SCES? The Dutch invention of the first practical telescope and its use by Galileo in 1610 and subsequent years overturned dogma that the sun revolved about the earth. This revolutionary, and at the time heretical, conclusion required innovative combinations of new instrumentation, observation and mathematics. These same combinations are just as important 400 years later and are the foundation of scientific discoveries that were discussed

  1. Novelty filtered optical correlator using photorefractive crystal

    NASA Technical Reports Server (NTRS)

    Liu, Duncan T. H.; Chao, Tien-Hsin; Cheng, Li-Jen

    1992-01-01

    We demonstrate a new optical correlator in which the correlation peak intensity is increased when the matched input object is moving. The basic configuration of the correlator is the same as a VanderLugt optical correlator consisting of a photorefractive crystal. The principal of this new correlator is based on the dynamic grating erasure property of photorefractive materials. The detail of this principle is described.

  2. ASTROCHEMICAL CORRELATIONS IN MOLECULAR CLOUDS

    SciTech Connect

    Gaches, Brandt A. L.; Offner, Stella S. R.; Rosolowsky, Erik W.; Bisbas, Thomas G. E-mail: soffner@astro.umass.edu E-mail: tb@star.ucl.ac.uk

    2015-02-01

    We investigate the spectral correlations between different species used to observe molecular clouds. We use hydrodynamic simulations and a full chemical network to study the abundances of over 150 species in typical Milky Way molecular clouds. We perform synthetic observations in order to produce emission maps of a subset of these tracers. We study the effects of different lines of sight and spatial resolution on the emission distribution and perform a robust quantitative comparison of the species to each other. We use the Spectral Correlation Function (SCF), which quantifies the root mean squared difference between spectra separated by some length scale, to characterize the structure of the simulated cloud in position-position-velocity (PPV) space. We predict the observed SCF for a broad range of observational tracers, and thus identify homologous species. In particular, we show that the pairs C and CO, C{sup +} and CN, and NH{sub 3} and H{sub 2}CS have very similar SCFs. We measure the SCF slope variation as a function of beam size for all species and demonstrate that the beam size has a distinct effect on different species emission. However, for beams of up to 10'', placing the cloud at 1 kpc, the change is not large enough to move the SCF slopes into different regions of parameter space. The results from this study provide observational guidance for choosing the best tracer to probe various cloud length scales.

  3. The dynamics of correlated novelties

    NASA Astrophysics Data System (ADS)

    Tria, F.; Loreto, V.; Servedio, V. D. P.; Strogatz, S. H.

    2014-07-01

    Novelties are a familiar part of daily life. They are also fundamental to the evolution of biological systems, human society, and technology. By opening new possibilities, one novelty can pave the way for others in a process that Kauffman has called ``expanding the adjacent possible''. The dynamics of correlated novelties, however, have yet to be quantified empirically or modeled mathematically. Here we propose a simple mathematical model that mimics the process of exploring a physical, biological, or conceptual space that enlarges whenever a novelty occurs. The model, a generalization of Polya's urn, predicts statistical laws for the rate at which novelties happen (Heaps' law) and for the probability distribution on the space explored (Zipf's law), as well as signatures of the process by which one novelty sets the stage for another. We test these predictions on four data sets of human activity: the edit events of Wikipedia pages, the emergence of tags in annotation systems, the sequence of words in texts, and listening to new songs in online music catalogues. By quantifying the dynamics of correlated novelties, our results provide a starting point for a deeper understanding of the adjacent possible and its role in biological, cultural, and technological evolution.

  4. Strongly correlated perovskite fuel cells

    NASA Astrophysics Data System (ADS)

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

    2016-06-01

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

  5. The dynamics of correlated novelties.

    PubMed

    Tria, F; Loreto, V; Servedio, V D P; Strogatz, S H

    2014-01-01

    Novelties are a familiar part of daily life. They are also fundamental to the evolution of biological systems, human society, and technology. By opening new possibilities, one novelty can pave the way for others in a process that Kauffman has called "expanding the adjacent possible". The dynamics of correlated novelties, however, have yet to be quantified empirically or modeled mathematically. Here we propose a simple mathematical model that mimics the process of exploring a physical, biological, or conceptual space that enlarges whenever a novelty occurs. The model, a generalization of Polya's urn, predicts statistical laws for the rate at which novelties happen (Heaps' law) and for the probability distribution on the space explored (Zipf's law), as well as signatures of the process by which one novelty sets the stage for another. We test these predictions on four data sets of human activity: the edit events of Wikipedia pages, the emergence of tags in annotation systems, the sequence of words in texts, and listening to new songs in online music catalogues. By quantifying the dynamics of correlated novelties, our results provide a starting point for a deeper understanding of the adjacent possible and its role in biological, cultural, and technological evolution. PMID:25080941

  6. Strongly correlated perovskite fuel cells.

    PubMed

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

    2016-05-16

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

  7. Strongly correlated perovskite fuel cells.

    PubMed

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

    2016-06-01

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations. PMID:27279218

  8. Dipolar correlations in liquid water

    SciTech Connect

    Zhang, Cui; Galli, Giulia

    2014-08-28

    We present an analysis of the dipolar correlations in water as a function of temperature and density and in the presence of simple ionic solutes, carried out using molecular dynamics simulations and empirical potentials. We show that the dipole-dipole correlation function of the liquid exhibits sizable oscillations over nanodomains of about 1.5 nm radius, with several isosbestic points as a function of temperature; the size of the nanodomains is nearly independent on temperature and density, between 240 and 400 K and 0.9 and 1.3 g/cm{sup 3}, but it is substantially affected by the presence of solvated ions. In the same range of thermodynamic conditions, the decay time (τ) of the system dipole moment varies by a factor of about 30 and 1.5, as a function of temperature and density, respectively. At 300 K, we observed a maximum in τ as a function of density, and a corresponding shallow maximum in the tetrahedral order parameter, in a range where the diffusion coefficient, the pressure and the dielectric constant increase monotonically.

  9. EEG, temporal correlations, and avalanches.

    PubMed

    Benayoun, Marc; Kohrman, Michael; Cowan, Jack; van Drongelen, Wim

    2010-12-01

    Epileptiform activity in the EEG is frequently characterized by rhythmic, correlated patterns or synchronized bursts. Long-range temporal correlations (LRTC) are described by power law scaling of the autocorrelation function and have been observed in scalp and intracranial EEG recordings. Synchronous large-amplitude bursts (also called neuronal avalanches) have been observed in local field potentials both in vitro and in vivo. This article explores the presence of neuronal avalanches in scalp and intracranial EEG in the context of LRTC. Results indicate that both scalp and intracranial EEG show LRTC, with larger scaling exponents in scalp recordings than intracranial. A subset of analyzed recordings also show avalanche behavior, indicating that avalanches may be associated with LRTC. Artificial test signals reveal a linear relationship between the scaling exponent measured by detrended fluctuation analysis and the exponent of the avalanche size distribution. Analysis and evaluation of simulated data reveal that preprocessing of EEG (squaring the signal or applying a filter) affect the ability of detrended fluctuation analysis to reliably measure LRTC.

  10. A correlated nickelate synaptic transistor.

    PubMed

    Shi, Jian; Ha, Sieu D; Zhou, You; Schoofs, Frank; Ramanathan, Shriram

    2013-01-01

    Inspired by biological neural systems, neuromorphic devices may open up new computing paradigms to explore cognition, learning and limits of parallel computation. Here we report the demonstration of a synaptic transistor with SmNiO₃, a correlated electron system with insulator-metal transition temperature at 130°C in bulk form. Non-volatile resistance and synaptic multilevel analogue states are demonstrated by control over composition in ionic liquid-gated devices on silicon platforms. The extent of the resistance modulation can be dramatically controlled by the film microstructure. By simulating the time difference between postneuron and preneuron spikes as the input parameter of a gate bias voltage pulse, synaptic spike-timing-dependent plasticity learning behaviour is realized. The extreme sensitivity of electrical properties to defects in correlated oxides may make them a particularly suitable class of materials to realize artificial biological circuits that can be operated at and above room temperature and seamlessly integrated into conventional electronic circuits. PMID:24177330

  11. The Neurogenetic Correlates of Consciousness

    NASA Astrophysics Data System (ADS)

    Grandy, John K.

    2013-09-01

    The neurogenetic correlates of consciousness (NgCC) is a new field of consciousness studies that focuses on genes that have an effect on or are involved in the continuum of neuron-based consciousness. A framework of consciousness based on the neural correlates of consciousness (NCC) has already been established by Francis Crick and Christof Kock. In this work I propose that there are NgCC underlying the NCC which are both active during the conscious experience. So how are genes involved? There are two significant connections between DNA and neurons that are involved in the conscious experience. First, any brain system can be adversely affected by underlying genetic abnormalities which can be expressed in an individual at birth, in adulthood, or later in life. Second, the DNA molecule does not lay dormant while the neuron runs on autopilot. DNA is active in translating and transcribing RNA and protein products that are utilized during neuron functioning. Without these products being continuously produced by the DNA during a conscious experience the neurons would cease to function correctly and be rendered unable to provide a continuum of human consciousness. Consequently, in addition to NCC, NgCC must be factored in when appreciating a conscious event. In this work I will discuss and explain some NgCC citing several examples.

  12. Oral health correlates of captivity.

    PubMed

    Kapoor, Varsha; Antonelli, Tyler; Parkinson, Jennifer A; Hartstone-Rose, Adam

    2016-08-01

    The predominant diet fed to captive carnivores in North America consists of ground meat formulated to provide full nutritional requirements. However, this ground meat diet completely lacks the mechanical properties (i.e., toughness and hardness) of the foods these animals would consume in the wild. The goal of this study is to evaluate the effect of captivity on oral health by comparing the prevalence of periodontal disease and dental calculus accumulation in wild and captive lions and tigers (Panthera leo and Panthera tigris), and to also correlate oral health with cranial morphology in these specimens. To achieve this, 34 adult lion and 29 adult tiger skulls were scored for the presence and extent of dental calculus and periodontal disease. These oral health scores were also compared to cranial deformations examined in a previous study. We found that the occurrence and severity of calculus buildup and periodontal disease was significantly higher in captive felids compared to their wild counterparts. Further, higher calculus accumulation occurred on the posterior teeth when compared to the anterior teeth, while an opposite trend for periodontal disease was observed. We also found a significant correlation between oral health and cranial morphology of lions and tigers. The results suggest that food mechanical properties are significant factors contributing to oral health in felids. PMID:27473998

  13. Oral health correlates of captivity.

    PubMed

    Kapoor, Varsha; Antonelli, Tyler; Parkinson, Jennifer A; Hartstone-Rose, Adam

    2016-08-01

    The predominant diet fed to captive carnivores in North America consists of ground meat formulated to provide full nutritional requirements. However, this ground meat diet completely lacks the mechanical properties (i.e., toughness and hardness) of the foods these animals would consume in the wild. The goal of this study is to evaluate the effect of captivity on oral health by comparing the prevalence of periodontal disease and dental calculus accumulation in wild and captive lions and tigers (Panthera leo and Panthera tigris), and to also correlate oral health with cranial morphology in these specimens. To achieve this, 34 adult lion and 29 adult tiger skulls were scored for the presence and extent of dental calculus and periodontal disease. These oral health scores were also compared to cranial deformations examined in a previous study. We found that the occurrence and severity of calculus buildup and periodontal disease was significantly higher in captive felids compared to their wild counterparts. Further, higher calculus accumulation occurred on the posterior teeth when compared to the anterior teeth, while an opposite trend for periodontal disease was observed. We also found a significant correlation between oral health and cranial morphology of lions and tigers. The results suggest that food mechanical properties are significant factors contributing to oral health in felids.

  14. Fiducial marker for correlating images

    DOEpatents

    Miller, Lisa Marie; Smith, Randy J.; Warren, John B.; Elliott, Donald

    2011-06-21

    The invention relates to a fiducial marker having a marking grid that is used to correlate and view images produced by different imaging modalities or different imaging and viewing modalities. More specifically, the invention relates to the fiducial marking grid that has a grid pattern for producing either a viewing image and/or a first analytical image that can be overlaid with at least one other second analytical image in order to view a light path or to image different imaging modalities. Depending on the analysis, the grid pattern has a single layer of a certain thickness or at least two layers of certain thicknesses. In either case, the grid pattern is imageable by each imaging or viewing modality used in the analysis. Further, when viewing a light path, the light path of the analytical modality cannot be visualized by viewing modality (e.g., a light microscope objective). By correlating these images, the ability to analyze a thin sample that is, for example, biological in nature but yet contains trace metal ions is enhanced. Specifically, it is desired to analyze both the organic matter of the biological sample and the trace metal ions contained within the biological sample without adding or using extrinsic labels or stains.

  15. Tunneling in strongly correlated materials

    NASA Astrophysics Data System (ADS)

    Maltseva, Marianna

    Tunneling studies of strongly correlated materials provide information about the nature of electronic correlations, which is vital for investigation of emergent materials at the microscopic level. In particular, scanning tunneling spectroscopy/microscopy (STS/STM) studies have made major contributions to understanding cuprate superconductors (66), yet there is a sense that huge STM data arrays contain much more precious information to be extracted and analyzed. One of the most pressing questions in the field is how to improve the data analysis, so as to extract more information from STM data. A dominant trend in STM data analysis has been to interpret the data within a particular microscopic model, while using only basic data analysis tools. To decrease the reliance of the STM data interpretation on particular microscopic models, further advances in data analysis methods are necessary. In Chapter 2 of this Thesis, we discuss how one can extract information about the phase of the order parameter from STM data. We show that symmetrized and anti-symmetrized correlators of local density of states give rise to observable coherence factor effects. In Chapter 3, we apply this framework to analyze the recent scanning tunneling experiments on an underdoped cuprate superconductor Ca2-xNaxCuO2Cl2 by T. Hanaguri et al. (60). In Chapter 4, we propose a model for nodal quasiparticle scattering in a disordered vortex lattice. Recently, scanning tunneling studies of a Kondo lattice material URu2Si2 became possible (117). If it proves possible to apply scanning tunneling spectroscopy to Kondo lattice materials, then remarkable new opportunities in the ongoing investigation may emerge. In Chapter 5, we examine the effect of co-tunneling to develop a theory of tunneling into a Kondo lattice. We find that the interference between the direct tunneling and the co-tunneling channels leads to a novel asymmetric lineshape, which has two peaks and a gap. The presence of the peaks suggests

  16. Vertical velocity-CCN correlations

    NASA Astrophysics Data System (ADS)

    Hudson, J. G.; Noble, S. R.

    2013-12-01

    The realization that smaller cloud droplets evaporate more readily (Xue and Feingold 2006; Jiang et al. 2002) gives rise to an anti-indirect aerosol effect (IAE); less cloudiness with pollution. The greater latent heat exchange of the greater evaporation in more polluted clouds adds TKE and buoyancy gradients that can enhance vertical velocity (W), mixing and entrainment (Zhao and Austin 2005). Stronger W can increase horizontal motions, which can further enhance droplet evaporation, which further enhances latent heat exchange and vertical motions, thus, positive feedback. This could also include latent heat released during condensation (Lee and Feingold 2010), which is more rapid for the greater surface areas of the smaller more numerous droplets. These theories imply a positive relationship between within-cloud W variations; i.e., standard deviation of W (σw) and CCN concentration (NCCN) rather than W and NCCN. This implies greater turbulence in polluted clouds, which could possibly counteract the reduction of cloudiness of anti-IAE. During two stratus cloud projects, 50 cloud penetrations in 9 MASE flights and 34 cloud penetrations in 13 POST flights, within-cloud σw-NCCN showed correlation coefficients (R) of 0.50 and 0.39. Panel a shows similar within-cloud σw-NCCN R in all altitude bands for 17 RICO flights in small cumulus clouds. R for W-NCCN showed similar values but only at low altitudes. Out-of-cloud σw-NCCN showed similar high values except at the highest altitudes. Within-cloud σw showed higher R than within-cloud W with droplet concentrations (Nc), especially at higher altitudes. Panel b for 13 ICE-T cumulus cloud flights in the same location as RICO but during the opposite season, however, showed σw and W uncorrelated with NCCN at all altitudes; and W and σw correlated with Nc only at the highest altitudes. On the other hand, out-of-cloud σw was correlated with NCCN at all altitudes with R similar to the corresponding R of the other projects

  17. CORRELATIONS IN CONFINED QUANTUM PLASMAS

    SciTech Connect

    DUFTY J W

    2012-01-11

    This is the final report for the project 'Correlations in Confined Quantum Plasmas', NSF-DOE Partnership Grant DE FG02 07ER54946, 8/1/2007 - 7/30/2010. The research was performed in collaboration with a group at Christian Albrechts University (CAU), Kiel, Germany. That collaboration, almost 15 years old, was formalized during the past four years under this NSF-DOE Partnership Grant to support graduate students at the two institutions and to facilitate frequent exchange visits. The research was focused on exploring the frontiers of charged particle physics evolving from new experimental access to unusual states associated with confinement. Particular attention was paid to combined effects of quantum mechanics and confinement. A suite of analytical and numerical tools tailored to the specific inquiry has been developed and employed

  18. Correlation effects in metallic cohesion

    NASA Astrophysics Data System (ADS)

    Haydock, Roger

    2014-03-01

    The electronic contribution to the cohesive energy of a correlated metal is the sum of the transition energies for adding successive electrons at successive Fermi levels until the system reaches its final electron density. This can be computed as the integral of energy over the projected density of transitions for adding single electrons to localized orbitals. In the case of independent electrons, this reduces to the usual integral over the projected density of states. As an example, cohesive energies for some simple transition metal structures are calculated using the recursion method* with a Hubbard repulsion between electrons. * Phys. Rev. B 61, 7953-64 Work supported by the Richmond F. Snyder gift to the University of Oregon.

  19. Correlative microscopy of detergent granules.

    PubMed

    van Dalen, G; Nootenboom, P; Heussen, P C M

    2011-03-01

    The microstructure of detergent products for textile cleaning determines to a large extent the physical properties of these products. Correlative microscopy was used to reveal the microstructure by reconciling images obtained by scanning electron microscopy with energy dispersive X-ray analysis, X-ray microtomography and Fourier transform infrared microscopy. These techniques were applied on the same location of a subsample of a spray-dried detergent base powder embedded in polyacrylate. In this way, the three-dimensional internal and external structure of detergent granules could be investigated from milli to nano scale with detailed spatial information about the components present. This will generate knowledge how to design optimal microstructures for laundry products to obtain product properties demanded by the market. This method is also very useful for other powder systems used in a large variety of industries (e.g. for pharmaceutical, food, ceramic and metal industries).

  20. Physiological correlates of mental workload

    NASA Technical Reports Server (NTRS)

    Zacharias, G. L.

    1980-01-01

    A literature review was conducted to assess the basis of and techniques for physiological assessment of mental workload. The study findings reviewed had shortcomings involving one or more of the following basic problems: (1) physiologic arousal can be easily driven by nonworkload factors, confounding any proposed metric; (2) the profound absence of underlying physiologic models has promulgated a multiplicity of seemingly arbitrary signal processing techniques; (3) the unspecified multidimensional nature of physiological "state" has given rise to a broad spectrum of competing noncommensurate metrics; and (4) the lack of an adequate definition of workload compels physiologic correlations to suffer either from the vagueness of implicit workload measures or from the variance of explicit subjective assessments. Using specific studies as examples, two basic signal processing/data reduction techniques in current use, time and ensemble averaging are discussed.

  1. Correlating thalamocortical connectivity and activity

    NASA Astrophysics Data System (ADS)

    da Fontoura Costa, Luciano; Sporns, Olaf

    2006-07-01

    The segregated regions of the mammalian cerebral cortex and thalamus form an extensive and complex network, whose structure and function are still only incompletely understood. The present letter describes an application of the concepts of complex networks and random walks that allows the identification of nonrandom, highly structured features of thalamocortical connections and their potential effects on dynamic interactions between cortical areas in the cat brain. Utilizing large-scale anatomical data sets of this thalamocortical system, we investigate uniform random walks in such a network by considering the steady state eigenvector of the respective stochastic matrix. It is shown that thalamocortical connections are organized in such a way as to guarantee strong correlation between the outdegree and occupancy rate (a stochastic measure potentially related to activation) of each cortical area. Possible organizational principles underlying this effect are identified and discussed.

  2. Fully resolved NMR correlation spectroscopy.

    PubMed

    Pitoux, Daisy; Plainchont, Bertrand; Merlet, Denis; Hu, Zhaoyu; Bonnaffé, David; Farjon, Jonathan; Giraud, Nicolas

    2015-06-15

    A new correlation experiment cited as "push-G-SERF" is reported. In the resulting phased 2D spectrum, the chemical shift information is selected along the direct dimension, whereas scalar couplings involving a selected proton nucleus are edited in the indirect domain. The robustness of this pulse sequence is demonstrated on compounds with increasing structural and spectral complexity, using state-of-the-art spectrometers. It allows for full resolution of both dimensions of the spectrum, yielding a straightforward assignment and measurement of the coupling network around a given proton in the molecule. This experiment is intended for chemists who want to address efficiently the structural analysis of molecules with an overcrowded spectrum.

  3. Vibration analysis using digital correlation

    NASA Technical Reports Server (NTRS)

    Gilbert, John A.; Lehner, David L.; Dudderar, T. Dixon; Matthys, Donald R.

    1988-01-01

    This paper demonstrates the use of a computer-based optical method for locating the positions of nodes and antinodes in vibrating members. Structured light patterns are projected at an angle onto the vibrating surface using a 35 mm slide projector. The vibrating surface and the projected images are captured in a time averaged photograph which is subsequently digitized. The inherent fringe patterns are filtered to determine amplitudes of vibration, and computer programs are used to compare the time averaged images to images recorded prior to excitation to locate nodes and antinodes. Some of the influences of pattern regularity on digital correlation are demonstrated, and a speckle-based method for determining the mode shapes and the amplitudes of vibration with variable sensitivity is suggested.

  4. Investigation of correlation classification techniques

    NASA Technical Reports Server (NTRS)

    Haskell, R. E.

    1975-01-01

    A two-step classification algorithm for processing multispectral scanner data was developed and tested. The first step is a single pass clustering algorithm that assigns each pixel, based on its spectral signature, to a particular cluster. The output of that step is a cluster tape in which a single integer is associated with each pixel. The cluster tape is used as the input to the second step, where ground truth information is used to classify each cluster using an iterative method of potentials. Once the clusters have been assigned to classes the cluster tape is read pixel-by-pixel and an output tape is produced in which each pixel is assigned to its proper class. In addition to the digital classification programs, a method of using correlation clustering to process multispectral scanner data in real time by means of an interactive color video display is also described.

  5. Correlation method of electrocardiogram analysis

    NASA Astrophysics Data System (ADS)

    Strinadko, Marina M.; Timochko, Katerina B.

    2002-02-01

    The electrocardiograph method is the informational source for functional heart state characteristics. The electrocardiogram parameters are the integrated map of many component characteristics of the heart system and depend on disturbance requirements of each device. In the research work the attempt of making the skeleton diagram of perturbation of the heart system is made by the characteristic description of its basic components and connections between them through transition functions, which are written down by the differential equations of the first and second order with the purpose to build-up and analyze electrocardiogram. Noting the vector character of perturbation and the various position of heart in each organism, we offer own coordinate system connected with heart. The comparative analysis of electrocardiogram was conducted with the usage of correlation method.

  6. Optimal measurements for nonlocal correlations

    NASA Astrophysics Data System (ADS)

    Schwarz, Sacha; Stefanov, André; Wolf, Stefan; Montina, Alberto

    2016-08-01

    A problem in quantum information theory is to find the experimental setup that maximizes the nonlocality of correlations with respect to some suitable measure such as the violation of Bell inequalities. There are however some complications with Bell inequalities. First and foremost it is unfeasible to determine the whole set of Bell inequalities already for a few measurements and thus unfeasible to find the experimental setup maximizing their violation. Second, the Bell violation suffers from an ambiguity stemming from the choice of the normalization of the Bell coefficients. An alternative measure of nonlocality with a direct information-theoretic interpretation is the minimal amount of classical communication required for simulating nonlocal correlations. In the case of many instances simulated in parallel, the minimal communication cost per instance is called nonlocal capacity, and its computation can be reduced to a convex-optimization problem. This quantity can be computed for a higher number of measurements and turns out to be useful for finding the optimal experimental setup. Focusing on the bipartite case, we present a simple method for maximizing the nonlocal capacity over a given configuration space and, in particular, over a set of possible measurements, yielding the corresponding optimal setup. Furthermore, we show that there is a functional relationship between Bell violation and nonlocal capacity. The method is illustrated with numerical tests and compared with the maximization of the violation of CGLMP-type Bell inequalities on the basis of entangled two-qubit as well as two-qutrit states. Remarkably, the anomaly of nonlocality displayed by qutrits turns out to be even stronger if the nonlocal capacity is employed as a measure of nonlocality.

  7. Correlated randomness and switching phenomena

    NASA Astrophysics Data System (ADS)

    Stanley, H. E.; Buldyrev, S. V.; Franzese, G.; Havlin, S.; Mallamace, F.; Kumar, P.; Plerou, V.; Preis, T.

    2010-08-01

    One challenge of biology, medicine, and economics is that the systems treated by these serious scientific disciplines have no perfect metronome in time and no perfect spatial architecture-crystalline or otherwise. Nonetheless, as if by magic, out of nothing but randomness one finds remarkably fine-tuned processes in time and remarkably fine-tuned structures in space. Further, many of these processes and structures have the remarkable feature of “switching” from one behavior to another as if by magic. The past century has, philosophically, been concerned with placing aside the human tendency to see the universe as a fine-tuned machine. Here we will address the challenge of uncovering how, through randomness (albeit, as we shall see, strongly correlated randomness), one can arrive at some of the many spatial and temporal patterns in biology, medicine, and economics and even begin to characterize the switching phenomena that enables a system to pass from one state to another. Inspired by principles developed by A. Nihat Berker and scores of other statistical physicists in recent years, we discuss some applications of correlated randomness to understand switching phenomena in various fields. Specifically, we present evidence from experiments and from computer simulations supporting the hypothesis that water’s anomalies are related to a switching point (which is not unlike the “tipping point” immortalized by Malcolm Gladwell), and that the bubbles in economic phenomena that occur on all scales are not “outliers” (another Gladwell immortalization). Though more speculative, we support the idea of disease as arising from some kind of yet-to-be-understood complex switching phenomenon, by discussing data on selected examples, including heart disease and Alzheimer disease.

  8. Astrochemical Correlations in Molecular Clouds

    NASA Astrophysics Data System (ADS)

    Gaches, Brandt A.L.; Offner, Stella

    2014-06-01

    We investigate the spectral correlations between different chemical tracers used to observe molecular clouds. We study a 600 Solar Mass molecular cloud with Mach number 6.6 modeled using the magnetohydrodynamic code ORION. The chemical abundances are calculated by 3D-PDR, a three-dimensional astrochemical code using a full network of 3300 reactions and 215 species. We take synthetic observations of 16 different species using the non-LTE radiative transfer code RADMC-3D. The effects of different lines of sight and spatial resolution on the emission maps of the 16 different species will be discussed in this talk.We use the Spectral Correlation Function to quantify the structure of the simulated cloud in position-position-velocity space, which measures the average rms velocity between spectra separated by a given length scale. This statistic has been shown to be sensitive to global hydrodynamic parameters, such as the sonic Mach number and velocity dispersion. The SCF is analytically fit by a power law, with the slope being the one free parameter. We verify that the SCF is generally insensitive to the sightline through the cloud. We discover that the beam size has a distinct effect on different chemical tracers. However, the change is not large enough to move the SCF slopes into different parts of the parameter space. This is the first quantitative 3D study of the spectral similarity of a variety of species. We predict the observed SCF for a broad range of observational tracers, and thus, identify complementary species. In particular, we show that the pairs C and CO, C+ and CN, NH3 and H2CS have very similar SCFs. The results from this study will also give observers a guide for selecting which chemical tracers would be best for observing different length scales.

  9. Electron correlations in copper oxides

    NASA Astrophysics Data System (ADS)

    Jefferson, J. H.

    A model which explicitly takes into account the hybridization of copper and oxygen orbitals and Coulomb correlations in copper-oxide chains and layers is considered. Degenerate perturbation theory is used to derive various effective Hamiltonians and shown to give rise to effective interactions which would be absent from a model that did not account for the oxygen states explicitly. In particular, there are hole-hole repulsion terms which mitigate against pairing. Exact solutions of the single hole problem and numerical solutions of the two-hole case for CuO chains confirm that the holes repel in the large correlation limit. Nous considérons un modèle dans lequel l'hybridation des orbitales de cuivre et d'oxygène et les corrélations de Coulomb en chaînes et en couches sont données explicitement. Les Hamiltoniens effectifs sont dérivés en utilisant la théorie de la perturbation dégénérée. On trouve les interactions effectives qui sont absentes d'un modèle dans lequel les états de l'oxygène ne sont pas considérés explicitement. Notamment, les forces répulsives entre les trous produisent une diminution de la probabilité d'association. Les solutions précises du problème pour un trou simple, et les solutions numériques du cas de deux trous dans les chaînes de CuO, confirment que dans la limite pour les corrélations fortes, les trous subissent une force répulsive.

  10. A Two Factor ANOVA-like Test for Correlated Correlations: CORANOVA

    ERIC Educational Resources Information Center

    Bilker, Warren B.; Brensinger, Colleen; Gur, Ruben C.

    2004-01-01

    Testing homogeneity of correlations with Fisher's Z is inappropriate when correlations are themselves correlated. Suppose measurements of brain activation and performance are taken before and during a verbal memory task. Of interest are changes in activity gradients in specific regions, R1, R2, R3, and performance, V. The "correlated correlations"…

  11. The Effect of Error Correlation on Interfactor Correlation in Psychometric Measurement

    ERIC Educational Resources Information Center

    Westfall, Peter H.; Henning, Kevin S. S.; Howell, Roy D.

    2012-01-01

    This article shows how interfactor correlation is affected by error correlations. Theoretical and practical justifications for error correlations are given, and a new equivalence class of models is presented to explain the relationship between interfactor correlation and error correlations. The class allows simple, parsimonious modeling of error…

  12. Inferring correlations: from exemplars to categories.

    PubMed

    Vogel, Tobias; Kutzner, Florian; Freytag, Peter; Fiedler, Klaus

    2014-10-01

    Research and theorizing suggest a processing advantage of category-level correlations over exemplar-level correlations. That research has also shown that category-level correlations serve as a proxy for inferring exemplar-level correlations. For example, an individual may learn that the demand for a product category, like cheese, in one store predicts the demand for this category in another. The individual could then draw the unwarranted conclusion that the demand for an exemplar, like cheddar, would also predict the demand for this exemplar in the other store. This notion is supported by previous experiments demonstrating that the subjective exemplar-level correlation follows the implication of the category-level correlation. However, in virtually all previous experiments suggesting a processing advantage for category-level over exemplar-level correlations, the stimulus correlation at the category level was substantial, whereas the correlation at the exemplar level was weak. Here, we tested the hypothesis that individuals process the level that is most informative, either the exemplar or the category level. We presented participants with a zero correlation at the category level, but varied the correlation at the exemplar level. Participants presented with a zero correlation across exemplar products correctly reproduced a zero correlation across product categories. When presented with a substantial correlation at the exemplar level, however, they erroneously reproduced a similar correlation at the category level. These findings therefore imply that there is no general processing advantage for correlations at higher aggregation levels. Instead, individuals seemingly attend to the level that holds the most regular information. Findings are discussed regarding the role of covariation strength in correlation detection and use. PMID:24493021

  13. 2004 Photon Correlation and Scattering Conference

    NASA Technical Reports Server (NTRS)

    Meyer, William (Editor); Smart, Anthony (Editor); Wegdam, Gerard (Editor); Dogariu, Aristide (Editor); Carpenter, Bradley (Editor)

    2004-01-01

    The Photon Correlation and Scattering (PCS) meeting welcomes all who are interested in the art and science of photon correlation and its application to optical scattering. The meeting is intended to enhance interactions between theory, applications, instrument design, and participants.

  14. Postulates for measures of genuine multipartite correlations

    SciTech Connect

    Bennett, Charles H.; Grudka, Andrzej; Horodecki, Michal; Horodecki, Ryszard; Horodecki, Pawel

    2011-01-15

    A lot of research has been done on multipartite correlations, but the problem of satisfactorily defining genuine multipartite correlations--those not trivially reducible to lower partite correlations--remains unsolved. In this paper we propose three reasonable postulates which each measure or indicator of genuine multipartite correlations (or genuine multipartite entanglement) should satisfy. We also introduce the concept of degree of correlations, which gives partial characterization of multipartite correlations. Then, we show that covariance does not satisfy two postulates and hence it cannot be used as an indicator of genuine multipartite correlations. Finally, we propose a candidate for a measure of genuine multipartite correlations based on the work that can be drawn from a local heat bath by means of a multipartite state.

  15. Wind-Tunnel/Flight Correlation, 1981

    NASA Technical Reports Server (NTRS)

    Mckinney, L. W. (Editor); Baals, D. D. (Editor)

    1982-01-01

    Wind-tunnel/flight correlation activities are reviewed to assure maximum effectiveness of the early experimental programs of the National Transonic Facility (NTF). Topics included a status report of the NTF, the role of tunnel-to-tunnel correlation, a review of past flight correlation research and the resulting data base, the correlation potential of future flight vehicles, and an assessment of the role of computational fluid dynamics.

  16. Prototype Optical Correlator For Robotic Vision System

    NASA Technical Reports Server (NTRS)

    Scholl, Marija S.

    1993-01-01

    Known and unknown images fed in electronically at high speed. Optical correlator and associated electronic circuitry developed for vision system of robotic vehicle. System recognizes features of landscape by optical correlation between input image of scene viewed by video camera on robot and stored reference image. Optical configuration is Vander Lugt correlator, in which Fourier transform of scene formed in coherent light and spatially modulated by hologram of reference image to obtain correlation.

  17. Surface Wear Measurement Using Optical Correlation Technique

    NASA Astrophysics Data System (ADS)

    Acinger, Kresimir

    1983-12-01

    The coherent optical correlation technique was applied for measuring the surface wear of a tappet (part of car engine), worn by friction with the camshaft. It was found that maximum correlation intensity decays exponentially with the number of wear cycles (i.e. camshaft revolutions). Tappets of the same make have an identical rate of correlation decay. Tappets of different makes have different rates of correlation decay which are in agreement with observed long term wear.

  18. Visual Perception in Correlated Noise

    NASA Astrophysics Data System (ADS)

    Myers, Kyle Jean

    This dissertation concerns the ability of human observers to perform detection tasks in medical images that contain structured noise. We shall show that physical measures of image quality, such as signal-to-noise ratio (SNR), resolution, modulation transfer function (MTF), and contrast, do not accurately predict how well an observer can detect lesions in an image. We have found that for images with equal pixel SNR, humans can detect a low contrast object more readily in images that have a low-pass noise structure, as opposed to a high-pass noise structure. This finding is important in the comparison of images generated by a classical pinhole imaging system with images generated by a computed tomography imager. We would like to have a figure of merit that accurately predicts a physician's ability to perform perceptual tasks. That is, we want a figure of merit for imaging systems that is more than an evaluation of the physician's performance, measured using human observers and an accepted method such as receiver operating characteristic (ROC) techniques. We want a figure of merit that we can calculate without requiring lengthy observer studies. To perform this calculation, we need a model of the imaging system hardware in cascade with a verified model of the human observer. We have chosen to approach this problem by modelling the human observer as an ideal observer. Our hypothesis is that the human observer acts approximately as an ideal -observer who does not have the ability to prewhiten the noise in an image. Without this ability, the ideal observer's detection performance for even a simple task is degraded substantially in correlated noise. This is just the effect that we have found for human observers. In search of a physiological explanation for a human observer's inability to do prewhitening, we shall investigate the detection capability of the ideal observer when a frequency-selective mechanism is invoked. This mechanism corresponds to the frequency channels

  19. Solvable Models of Correlated Particles

    NASA Astrophysics Data System (ADS)

    Ha, Zachary Nyong-Chol

    The Heisenberg spin chain with inverse-square exchange (ISE) has recently been introduced and has elevated general interest in the models with ISE. It has been known for a long time that the model is directly related to the random matrix theory. Recently, the matrix model in two -dimensional quantum gravity has also been shown to be related to the ISE model. In this thesis we show that the Bethe -ansatz-solvable, nearest-neighbor-exchange (NNE) models and the ISE model share a striking structure called the "string". Chapter 1 is a review of the Bethe ansatz, the "strings", and the ISE models. In Chapter 2 the "string" structure of one-dimensional Hubbard model eigenstates is studied numerically and is used to show the validity of thermodynamic Bethe ansatz equations (TBAE). We, furthermore, solve TBAE in a strong coupling expansion series form and obtain the thermodynamic potential which agrees with the known high temperature expansion series. We also calculate various thermodynamic quantities using our solution and provide some new features of the strongly correlated one -dimensional Hubbard model. In Chapter 3 a one-dimensional quantum N-body system of either fermions or bosons with SU(n) "spins" (or colors in particle physics language) interacting via inverse-square exchange is presented. A class of eigenstates of both the continuum and lattice version of the model Hamiltonians is constructed in terms of the Jastrow-product wave function. The class of states we construct corresponds to the ground state and the low-energy excitations of the model that can be described by the effective harmonic fluid Hamiltonian. By expanding the energy about the ground state, we find the harmonic fluid parameters (i.e., the charge, spin velocities, etc.) explicitly. The correlation exponent and the compressibility are also found. As expected, the general harmonic relation (i.e., v_ {S} = (v_{N}v_{J })^{1/2) is satisfied among the charge and the spin velocities. In Chapter 4, an

  20. Using of Correlating monomineral thermobarometry for mantle peridotites (correlating methods).

    NASA Astrophysics Data System (ADS)

    Ashchepkov, I. V.; Pokhilenko, N. P.; Sobolev, N. V.; Rotman, A. Y.; Afanasiev, V. P.; Logvinova, A. M.; Vladykin, N. V.; Kostrovitsky, S. I.; Karpenko, M. A.; Vishnyakova, E. V.

    2005-12-01

    Correlating monomineral thermobarometry using kimberlite mega- and xenocrysts and xenoliths allows to determine mantle layering with concentrate from kimberlites or placers. Orthopyroxene method (Brey, Kohler,1990)-(McGregor, 1974) was used for calibration of others. Clinopyroxene. Po =0.04*Kd *ToC/(1-2.4*Fe)-5.5 where KD = Na/Ca *Mg/(Al+Cr)and polynomial P = 0.00006*Po3 - 0.0156*Po2 + 1.6757*Po (R2 = 0.8245). The ToC (Nimis -Taylor, 2000) are corrected ToC= 000001*TooC**2 +0.9575*TooC+107.01 Garnet. Thermometers based on: 1) OPx's (Brey, Kohler,1990) estimates, ToC =5272.5*(Ln(KD)/P)3+10265* (Ln(KD)/P)2+ 6472* Ln(KD)/P +2113 where KD= MgO*TiO2/((CaO+MgO)2* FeO*Al2O3 2) CPx (Nimis, Taylor, 2000), : T0oC =362.05*(Ln(KD)/P)3+1880.4* (Ln(KD))/P2+2659.6* Ln(KD)/P +1695.5 where KD= Na2O*MnO*TiO2/(CaO+MgO)* FeO*Al2O3, 3) Gar-Cpx (Krogh, 1988) KD= Na2O*MnO*TiO2/(CaO+MgO)* FeO*Al2O3, 4)Ni in garnet thermometry (Griffin, 1989) with Ni(ppm) =88,877*E**(-5.021*Ni'), (R2=0.69) where Ni' =MnO*ln(FeO)/ln(MgO)*1.1-0.193*TiO2 +0.003*ln(Na2O)- 0.003*Cr2O3+0.0035*CaO+0.004*Al2O3 ToC =0.0004*Ni3-0.0304*Ni2 +7.6318*Ni+ 597.2 ( R2 = 0.69) Chromite P=0.86347*(Cr/(Cr+Al)* ToC/14+Ti*0.1) the second approximation P=0.0004*Po3-0.0342*Po2+1.5323*Po The temperatures are determined using monomineral version of the Ol-Sp thermometer (Taylor et al.,1998) Fo=0.06+0.0005*P for P >30 kbar and Fo=0.095+0.0001*Po for the lower pressures. The Sp-Ol oxybarometer (Taylor et al ., 1998) give the lineal correlation with monomineral version made in the same manner (R-0,96). Ilmenite. P= (TiO2-23.)*2.15-(ToC-700)/20*MgO*Cr2O3-1.5*MnO)*ToC/1273 and further P=10*(60-Po)/60+Po. Monomineral version Ol-Il thermometer (Taylor et al ., 1998) where Fo=0.11+0.00025*P for pressures lower then 30 kbar and Fo=0.10+0.00025*P for greater pressures. The monomineral fO2 oxybarometer same Fo content . Data for 7 kimberlite fields in Yakutia show large scale variations of the mantle different part of Siberian platform

  1. Functional Multiple-Set Canonical Correlation Analysis

    ERIC Educational Resources Information Center

    Hwang, Heungsun; Jung, Kwanghee; Takane, Yoshio; Woodward, Todd S.

    2012-01-01

    We propose functional multiple-set canonical correlation analysis for exploring associations among multiple sets of functions. The proposed method includes functional canonical correlation analysis as a special case when only two sets of functions are considered. As in classical multiple-set canonical correlation analysis, computationally, the…

  2. Problems with the Method of Correlated Vectors

    ERIC Educational Resources Information Center

    Ashton, M.C.; Lee, K.

    2005-01-01

    The method of correlated vectors has been used widely to identify variables that are associated with general intelligence (g). Briefly, this method involves finding the correlation between the vector of intelligence subtests' g-loadings and the vector of those subtests' correlations with the variable in question. We describe two major problems…

  3. An empirical estimate of the correlation energy

    NASA Astrophysics Data System (ADS)

    Spackman, M. A.; Maslen, E. N.

    1986-04-01

    The difference between experimental and accurate Hartree-Fock binding energies is strongly correlated with the classical electrostatic interaction between spherical atoms for a large number of diatomic and polyatomic molecules. The results lead to a useful estimate of the molecular extra correlation energy and indicate that one quarter of the electrostatic energy is an approximate lower bound to the molecular extra correlation energy.

  4. Quantum correlations which imply causation.

    PubMed

    Fitzsimons, Joseph F; Jones, Jonathan A; Vedral, Vlatko

    2015-01-01

    In ordinary, non-relativistic, quantum physics, time enters only as a parameter and not as an observable: a state of a physical system is specified at a given time and then evolved according to the prescribed dynamics. While the state can, and usually does, extend across all space, it is only defined at one instant of time. Here we ask what would happen if we defined the notion of the quantum density matrix for multiple spatial and temporal measurements. We introduce the concept of a pseudo-density matrix (PDM) which treats space and time indiscriminately. This matrix in general fails to be positive for measurement events which do not occur simultaneously, motivating us to define a measure of causality that discriminates between spatial and temporal correlations. Important properties of this measure, such as monotonicity under local operations, are proved. Two qubit NMR experiments are presented that illustrate how a temporal pseudo-density matrix approaches a genuinely allowed density matrix as the amount of decoherence is increased between two consecutive measurements.

  5. Neural correlates of mystical experience.

    PubMed

    Cristofori, Irene; Bulbulia, Joseph; Shaver, John H; Wilson, Marc; Krueger, Frank; Grafman, Jordan

    2016-01-01

    Mystical experiences, or subjectively believed encounters with a supernatural world, are widely reported across cultures and throughout human history. Previous theories speculate that executive brain functions underpin mystical experiences. To evaluate causal hypotheses, structural studies of brain lesion are required. Previous studies suffer from small samples or do not have valid measures of cognitive functioning prior to injury. We investigated mystical experience among participants from the Vietnam Head Injury Study and compared those who suffered penetrating traumatic brain injury (pTBI; n=116) with matched healthy controls (HC; n=32). Voxel-based lesion-symptom mapping analysis showed that lesions to frontal and temporal brain regions were linked with greater mystical experiences. Such regions included the dorsolateral prefrontal cortex (dlPFC) and middle/superior temporal cortex (TC). In a confirmatory analysis, we grouped pTBI patients by lesion location and compared mysticism experiences with the HC group. The dlPFC group presented markedly increased mysticism. Notably, longitudinal analysis of pre-injury data (correlating with general intelligence and executive performance) excludes explanations from individual differences. Our findings support previous speculation linking executive brain functions to mystical experiences, and reveal that executive functioning (dlPFC) causally contributes to the down-regulation of mystical experiences. PMID:26631541

  6. Hedging with a correlated asset

    NASA Astrophysics Data System (ADS)

    Windcliff, H.; Wang, J.; Forsyth, P. A.; Vetzal, K. R.

    2007-03-01

    Hedging a contingent claim with an asset which is not perfectly correlated with the underlying asset results in unhedgeable residual risk. Even if the residual risk is considered diversifiable, the option writer is faced with the problem of uncertainty in the estimation of the drift rates of the underlying and the hedging instrument. If the residual risk is not considered diversifiable, then this risk can be priced using an actuarial standard deviation principle in infinitesimal time. In both cases, these models result in the same nonlinear partial differential equation (PDE). A fully implicit, monotone discretization method is developed for solution of this pricing PDE. This method is shown to converge to the viscosity solution. Certain grid conditions are required to guarantee monotonicity. An algorithm is derived which, given an initial grid, inserts a finite number of nodes in the grid to ensure that the monotonicity condition is satisfied. At each timestep, the nonlinear discretized algebraic equations are solved using an iterative algorithm, which is shown to be globally convergent. Monte Carlo hedging examples are given to illustrate the profit and loss distribution at the expiry of the option.

  7. Loops in inflationary correlation functions

    NASA Astrophysics Data System (ADS)

    Tanaka, Takahiro; Urakawa, Yuko

    2013-12-01

    We review the recent progress regarding the loop corrections to the correlation functions in the inflationary universe. A naive perturbation theory predicts that the loop corrections generated during inflation suffer from various infrared (IR) pathologies. Introducing an IR cutoff by hand is neither satisfactory nor enough to fix the problem of a secular growth, which may ruin the predictive power of inflation models if the inflation lasts sufficiently long. We discuss the origin of the IR divergences and explore the regularity conditions of the loop corrections for the adiabatic perturbation, the iso-curvature perturbation, and the tensor perturbation, in turn. These three kinds of perturbations have qualitative differences, but in discussing the IR regularity there is a feature common to all cases, which is the importance of the proper identification of observable quantities. Genuinely, observable quantities should respect the gauge invariance from the view point of a local observer. Interestingly, we find that the requirement of the IR regularity restricts the allowed quantum states.

  8. Quantum correlations which imply causation

    PubMed Central

    Fitzsimons, Joseph F.; Jones, Jonathan A.; Vedral, Vlatko

    2015-01-01

    In ordinary, non-relativistic, quantum physics, time enters only as a parameter and not as an observable: a state of a physical system is specified at a given time and then evolved according to the prescribed dynamics. While the state can, and usually does, extend across all space, it is only defined at one instant of time. Here we ask what would happen if we defined the notion of the quantum density matrix for multiple spatial and temporal measurements. We introduce the concept of a pseudo-density matrix (PDM) which treats space and time indiscriminately. This matrix in general fails to be positive for measurement events which do not occur simultaneously, motivating us to define a measure of causality that discriminates between spatial and temporal correlations. Important properties of this measure, such as monotonicity under local operations, are proved. Two qubit NMR experiments are presented that illustrate how a temporal pseudo-density matrix approaches a genuinely allowed density matrix as the amount of decoherence is increased between two consecutive measurements. PMID:26675807

  9. Correlated measurement error hampers association network inference.

    PubMed

    Kaduk, Mateusz; Hoefsloot, Huub C J; Vis, Daniel J; Reijmers, Theo; van der Greef, Jan; Smilde, Age K; Hendriks, Margriet M W B

    2014-09-01

    Modern chromatography-based metabolomics measurements generate large amounts of data in the form of abundances of metabolites. An increasingly popular way of representing and analyzing such data is by means of association networks. Ideally, such a network can be interpreted in terms of the underlying biology. A property of chromatography-based metabolomics data is that the measurement error structure is complex: apart from the usual (random) instrumental error there is also correlated measurement error. This is intrinsic to the way the samples are prepared and the analyses are performed and cannot be avoided. The impact of correlated measurement errors on (partial) correlation networks can be large and is not always predictable. The interplay between relative amounts of uncorrelated measurement error, correlated measurement error and biological variation defines this impact. Using chromatography-based time-resolved lipidomics data obtained from a human intervention study we show how partial correlation based association networks are influenced by correlated measurement error. We show how the effect of correlated measurement error on partial correlations is different for direct and indirect associations. For direct associations the correlated measurement error usually has no negative effect on the results, while for indirect associations, depending on the relative size of the correlated measurement error, results can become unreliable. The aim of this paper is to generate awareness of the existence of correlated measurement errors and their influence on association networks. Time series lipidomics data is used for this purpose, as it makes it possible to visually distinguish the correlated measurement error from a biological response. Underestimating the phenomenon of correlated measurement error will result in the suggestion of biologically meaningful results that in reality rest solely on complicated error structures. Using proper experimental designs that allow

  10. Energetics of correlations in interacting systems.

    PubMed

    Friis, Nicolai; Huber, Marcus; Perarnau-Llobet, Martí

    2016-04-01

    A fundamental connection between thermodynamics and information theory arises from the fact that correlations exhibit an inherent work value. For noninteracting systems this translates to a work cost for establishing correlations. Here we investigate the relationship between work and correlations in the presence of interactions that cannot be controlled or removed. For such naturally coupled systems, which are correlated even in thermal equilibrium, we determine general strategies that can reduce the work cost of correlations, and illustrate these for a selection of exemplary physical systems.

  11. An easy measure of quantum correlation

    NASA Astrophysics Data System (ADS)

    Cao, Hui; Wu, Zhao-Qin; Hu, Li-Yun; Xu, Xue-Xiang; Huang, Jie-Hui

    2015-11-01

    To measure the quantum correlation of a bipartite state, a test matrix is constructed through the commutations among the blocks of its density matrix, which turns out to be a zero matrix for a classical state with zero quantum correlation, and a nonzero one for a quantum state with positive quantum correlation. The Frobenius norm of the test matrix is used to measure the quantum correlation, which satisfies the basic requirements for a good measure and coincides with Wootters concurrence for two-qubit pure states. Since no optimization is involved in the definition, this measure of quantum correlation is easy to compute and even can be calculated manually.

  12. Quantifying meta-correlations in financial markets

    NASA Astrophysics Data System (ADS)

    Kenett, Dror Y.; Preis, Tobias; Gur-Gershgoren, Gitit; Ben-Jacob, Eshel

    2012-08-01

    Financial markets are modular multi-level systems, in which the relationships between the individual components are not constant in time. Sudden changes in these relationships significantly affect the stability of the entire system, and vice versa. Our analysis is based on historical daily closing prices of the 30 components of the Dow Jones Industrial Average (DJIA) from March 15th, 1939 until December 31st, 2010. We quantify the correlation among these components by determining Pearson correlation coefficients, to investigate whether mean correlation of the entire portfolio can be used as a precursor for changes in the index return. To this end, we quantify the meta-correlation - the correlation of mean correlation and index return. We find that changes in index returns are significantly correlated with changes in mean correlation. Furthermore, we study the relationship between the index return and correlation volatility - the standard deviation of correlations for a given time interval. This parameter provides further evidence of the effect of the index on market correlations and their fluctuations. Our empirical findings provide new information and quantification of the index leverage effect, and have implications to risk management, portfolio optimization, and to the increased stability of financial markets.

  13. Topics in strongly correlated electrons

    NASA Astrophysics Data System (ADS)

    Berdnikov, Ilya

    The thesis is a collection of three topics connected together by the common themes of strong interactions, magnetism and quantum phases, such as the Aharonov-Bohm or Berry phase. The first part of the present dissertation discusses the possibility of examining microscopic origins of magnetism in strongly interacting systems by exploiting the setting of ultra-cold atomic gases in optical lattices. We discuss signatures of correlation in the trap, and propose an experiment to measure the phase diagram of itinerant magnetism directly. The second part focuses on the exotic phase of matter exhibiting the Fractional Quantum Hall Effect, which emerges when interacting particles are placed in a very strong magnetic field. We propose a trial ground state wave-function and prove that it is the unique highest density ground state of a well-motivated pseudo-potential Hamiltonian. The exchange statistics of quasiparticles are shown to be exotic, and overlaps with results of exact diagonalization are also discussed. The final part of the thesis studies frustrated magnetic systems, in which competing forces cannot not be satisfied simultaneously, doped with electrons. The interplay of frustration and itinerant behavior generates Berry phases associated with charge transport. We study the effects of these phases on electronic behavior, as well as the effect electrons have on the underlying magnetic textures. In the quasi-classical limit, we conjecture a field-driven metal-insulator transition, and discuss persistent currents arising in ground states selected by the presence of charge. In the quantum regime we derive the full Hamiltonian and discuss small fluctuations about the classical results.

  14. Separation of dynamic and nondynamic correlation.

    PubMed

    Ramos-Cordoba, Eloy; Salvador, Pedro; Matito, Eduard

    2016-08-24

    The account of electron correlation and its efficient separation into dynamic and nondynamic parts plays a key role in the development of computational methods. In this paper we suggest a physically-sound matrix formulation to split electron correlation into dynamic and nondynamic parts using the two-particle cumulant matrix and a measure of the deviation from idempotency of the first-order density matrix. These matrices are applied to a two-electron model, giving rise to a simplified electron correlation index that (i) depends only on natural orbitals and their occupancies, (ii) can be straightforwardly decomposed into orbital contributions and (iii) splits into dynamic and nondynamic correlation parts that (iv) admit a local version. These expressions are shown to account for dynamic and nondynamic correlation in a variety of systems containing different electron correlation regimes, thus providing the first separation of dynamic and nondynamic correlation using solely natural orbital occupancies. PMID:27523386

  15. Clustering stocks using partial correlation coefficients

    NASA Astrophysics Data System (ADS)

    Jung, Sean S.; Chang, Woojin

    2016-11-01

    A partial correlation analysis is performed on the Korean stock market (KOSPI). The difference between Pearson correlation and the partial correlation is analyzed and it is found that when conditioned on the market return, Pearson correlation coefficients are generally greater than those of the partial correlation, which implies that the market return tends to drive up the correlation between stock returns. A clustering analysis is then performed to study the market structure given by the partial correlation analysis and the members of the clusters are compared with the Global Industry Classification Standard (GICS). The initial hypothesis is that the firms in the same GICS sector are clustered together since they are in a similar business and environment. However, the result is inconsistent with the hypothesis and most clusters are a mix of multiple sectors suggesting that the traditional approach of using sectors to determine the proximity between stocks may not be sufficient enough to diversify a portfolio.

  16. An optical consensus correlator for cluttered targets

    NASA Astrophysics Data System (ADS)

    Putnam, Roger S.

    1992-08-01

    The phase-only Consensus Correlator improves the probability of detection of targets obscured by other objects such as a stand of trees. The technique involves masking out most of the input scene and using a standard correlator to search for small pieces of the expected target shape. The areas of the input scene that are found to contain pieces of the target are combined in a final correlation. The Consensus Correlator reduces the transfer of noise that is interspersed with pieces of the target in the input scene to the vicinity of the correlation spike in the correlation plane. A preliminary investigation of an appropriate figure of merit for comparing correlation spikes produced by different inputs and phase-only filters is also presented.

  17. Measuring and modeling correlations in multiplex networks.

    PubMed

    Nicosia, Vincenzo; Latora, Vito

    2015-09-01

    The interactions among the elementary components of many complex systems can be qualitatively different. Such systems are therefore naturally described in terms of multiplex or multilayer networks, i.e., networks where each layer stands for a different type of interaction between the same set of nodes. There is today a growing interest in understanding when and why a description in terms of a multiplex network is necessary and more informative than a single-layer projection. Here we contribute to this debate by presenting a comprehensive study of correlations in multiplex networks. Correlations in node properties, especially degree-degree correlations, have been thoroughly studied in single-layer networks. Here we extend this idea to investigate and characterize correlations between the different layers of a multiplex network. Such correlations are intrinsically multiplex, and we first study them empirically by constructing and analyzing several multiplex networks from the real world. In particular, we introduce various measures to characterize correlations in the activity of the nodes and in their degree at the different layers and between activities and degrees. We show that real-world networks exhibit indeed nontrivial multiplex correlations. For instance, we find cases where two layers of the same multiplex network are positively correlated in terms of node degrees, while other two layers are negatively correlated. We then focus on constructing synthetic multiplex networks, proposing a series of models to reproduce the correlations observed empirically and/or to assess their relevance. PMID:26465526

  18. An optical space domain volume holographic correlator

    NASA Astrophysics Data System (ADS)

    Birch, Philip; Gardezi, Akber; Mitra, Bhargav; Young, Rupert; Chatwin, Chris

    2009-04-01

    We propose a novel space domain volume holographic correlator system. One of the limitations of conventional correlators is the bandwidth limits imposed by updating the filter and the readout speed of the CCD. The volume holographic correlator overcomes these by storing a large number of filters that can be interrogated simultaneously. By using angle multiplexing, the match can be read out onto a high speed linear array of sensors. A scanning window can be used to implement shift invariance, thus, making the system operate like a space domain correlator. The space domain correlation method offers an advantage over the frequency domain correlator in that the correlation filter no longer has shift invariance imposed on it since the kernel can be modified depending on its position. This maybe used for normalising the kernel or imposing some non-linearity in an attempt to improve performance. However, one of the key advantages of the frequency domain method is lost using this technique, namely the speed of the computation. A large kernel space-domain correlation, performed on a computer, will be very slow compared to what is achievable using a 4f optical correlator. We propose a method of implementing this using the scanning holographic memory based correlator.

  19. Measuring and modeling correlations in multiplex networks

    NASA Astrophysics Data System (ADS)

    Nicosia, Vincenzo; Latora, Vito

    2015-09-01

    The interactions among the elementary components of many complex systems can be qualitatively different. Such systems are therefore naturally described in terms of multiplex or multilayer networks, i.e., networks where each layer stands for a different type of interaction between the same set of nodes. There is today a growing interest in understanding when and why a description in terms of a multiplex network is necessary and more informative than a single-layer projection. Here we contribute to this debate by presenting a comprehensive study of correlations in multiplex networks. Correlations in node properties, especially degree-degree correlations, have been thoroughly studied in single-layer networks. Here we extend this idea to investigate and characterize correlations between the different layers of a multiplex network. Such correlations are intrinsically multiplex, and we first study them empirically by constructing and analyzing several multiplex networks from the real world. In particular, we introduce various measures to characterize correlations in the activity of the nodes and in their degree at the different layers and between activities and degrees. We show that real-world networks exhibit indeed nontrivial multiplex correlations. For instance, we find cases where two layers of the same multiplex network are positively correlated in terms of node degrees, while other two layers are negatively correlated. We then focus on constructing synthetic multiplex networks, proposing a series of models to reproduce the correlations observed empirically and/or to assess their relevance.

  20. Active motion assisted by correlated stochastic torques.

    PubMed

    Weber, Christian; Radtke, Paul K; Schimansky-Geier, Lutz; Hänggi, Peter

    2011-07-01

    The stochastic dynamics of an active particle undergoing a constant speed and additionally driven by an overall fluctuating torque is investigated. The random torque forces are expressed by a stochastic differential equation for the angular dynamics of the particle determining the orientation of motion. In addition to a constant torque, the particle is supplemented by random torques, which are modeled as an Ornstein-Uhlenbeck process with given correlation time τ(c). These nonvanishing correlations cause a persistence of the particles' trajectories and a change of the effective spatial diffusion coefficient. We discuss the mean square displacement as a function of the correlation time and the noise intensity and detect a nonmonotonic dependence of the effective diffusion coefficient with respect to both correlation time and noise strength. A maximal diffusion behavior is obtained if the correlated angular noise straightens the curved trajectories, interrupted by small pirouettes, whereby the correlated noise amplifies a straightening of the curved trajectories caused by the constant torque.

  1. Angular correlations and high energy evolution

    SciTech Connect

    Kovner, Alex; Lublinsky, Michael

    2011-11-01

    We address the question of to what extent JIMWLK evolution is capable of taking into account angular correlations in a high energy hadronic wave function. Our conclusion is that angular (and indeed other) correlations in the wave function cannot be reliably calculated without taking into account Pomeron loops in the evolution. As an example we study numerically the energy evolution of angular correlations between dipole scattering amplitudes in the framework of the large N{sub c} approximation to JIMWLK evolution (the 'projectile dipole model'). Target correlations are introduced via averaging over an (isotropic) ensemble of anisotropic initial conditions. We find that correlations disappear very quickly with rapidity even inside the saturation radius. This is in accordance with our physical picture of JIMWLK evolution. The actual correlations inside the saturation radius in the target QCD wave function, on the other hand, should remain sizable at any rapidity.

  2. Maximally Nonlocal and Monogamous Quantum Correlations

    NASA Astrophysics Data System (ADS)

    Barrett, Jonathan; Kent, Adrian; Pironio, Stefano

    2006-10-01

    We introduce a version of the chained Bell inequality for an arbitrary number of measurement outcomes and use it to give a simple proof that the maximally entangled state of two d-dimensional quantum systems has no local component. That is, if we write its quantum correlations as a mixture of local correlations and general (not necessarily quantum) correlations, the coefficient of the local correlations must be zero. This suggests an experimental program to obtain as good an upper bound as possible on the fraction of local states and provides a lower bound on the amount of classical communication needed to simulate a maximally entangled state in d×d dimensions. We also prove that the quantum correlations violating the inequality are monogamous among nonsignaling correlations and, hence, can be used for quantum key distribution secure against postquantum (but nonsignaling) eavesdroppers.

  3. Visualisation of enantiomers via insertion of a BIRD module in X H correlation experiments in chiral liquid crystal solvent

    NASA Astrophysics Data System (ADS)

    Ziani, L.; Courtieu, J.; Merlet, D.

    2006-11-01

    Several 13C- 1H NMR techniques are derived simplifying the visualisation of enantiomers in chiral ordering solvents. They proceed through various heteronuclear 2D experiments where a bilinear rotation decoupling sequence (BIRD) is inserted in the middle of the t1 evolution period. In this way, the small couplings are refocused while the large couplings are preserved. The methods allow extracting precise values of one-bond carbon-proton residual dipolar couplings for each enantiomer out of unresolved proton-coupled 13C or carbon-coupled 1H spectra. Illustrative examples are analysed and discussed using various pulse sequences.

  4. Disordered strongly correlated electronic systems

    NASA Astrophysics Data System (ADS)

    Javan Mard, Hossein

    Disorder can have a vast variety of consequences for the physics of phase transitions. Some transitions remain unchanged in the presence of disorder while others are completely destroyed. In this dissertation we study the effects of quenched disorder on electronic systmens at zero temperature. First, we perform variational studies of the interaction-localization problem to describe the interaction-induced renormalizations of the effective (screened) random potential seen by quasiparticles. Here we present results of careful finite-size scaling studies for the conductance of disordered Hubbard chains at half-filling and zero temperature. While our results indicate that quasiparticle wave functions remain exponentially localized even in the presence of moderate to strong repulsive interactions, we show that interactions produce a strong decrease of the characteristic conductance scale g* signaling the crossover to strong localization. This effect, which cannot be captured by a simple renormalization of the disorder strength, instead reflects a peculiar non-Gaussian form of the spatial correlations of the screened disordered potential, a hitherto neglected mechanism to dramatically reduce the impact of Anderson localization (interference) effects. Second, we formulate a strong-disorder renormalization-group (SDRG) approach to study the beta function of the tight-binding model in one dimension with both diagonal and off-diagonal disorder for states at the band center. We show that the SDRG method, when used to compute transport properties, yields exact results since it is identical to the transfer matrix method. The beta function is shown to be universal when only off-diagonal disorder is present even though single-parameter scaling is known to be violated. A different single-parameter scaling theory is formulated for this particular (particle-hole symmetric) case. Upon breaking particle-hole symmetry (by adding diagonal disorder), the beta function is shown to

  5. Correlation of Helium Solubility in Liquid Nitrogen

    NASA Technical Reports Server (NTRS)

    VanDresar, Neil T.; Zimmerli, Gregory A.

    2012-01-01

    A correlation has been developed for the equilibrium mole fraction of soluble gaseous helium in liquid nitrogen as a function of temperature and pressure. Experimental solubility data was compiled and provided by National Institute of Standards and Technology (NIST). Data from six sources was used to develop a correlation within the range of 0.5 to 9.9 MPa and 72.0 to 119.6 K. The relative standard deviation of the correlation is 6.9 percent.

  6. Stress tensor correlators in three dimensional gravity

    NASA Astrophysics Data System (ADS)

    Bagchi, Arjun; Grumiller, Daniel; Merbis, Wout

    2016-03-01

    We calculate holographically arbitrary n -point correlators of the boundary stress tensor in three-dimensional Einstein gravity with negative or vanishing cosmological constant. We provide explicit expressions up to 5-point (connected) correlators and show consistency with the Galilean conformal field theory Ward identities and recursion relations of correlators, which we derive. This provides a novel check of flat space holography in three dimensions.

  7. Structure of quantum and broadcasting nonlocal correlations

    NASA Astrophysics Data System (ADS)

    Saha, Debashis; Pawłowski, Marcin

    2015-12-01

    The multipartite setting offers much more complexity of nonlocality than the bipartite one. We analyze the structure of tripartite nonlocal correlations by proposing inequalities satisfied by each of type bilocal, broadcasting, and quantum but violated by the other two. One of the inequalities satisfied by broadcasting correlations is generalized for multipartite systems. The study of its quantum mechanical violation reveals that Greenberger-Horne-Zeilinger-like states exhibit new, powerful correlations.

  8. An FX software correlator for VLBI

    NASA Astrophysics Data System (ADS)

    Deller, Adam

    This talk will present recent work undertaken at Swinburne developing an FX software correlator, which will initially be used with the Australian Long Baseline Array (LBA). In conjunction with existing disk-based recorders, the software correlator will allow gigabit per second science operations to be undertaken with the LBA. Platform options for the software correlator will be discussed, as will current performance and future developments and applications.

  9. Correlation and prediction of gaseous diffusion coefficients.

    NASA Technical Reports Server (NTRS)

    Marrero, T. R.; Mason, E. A.

    1973-01-01

    A new correlation method for binary gaseous diffusion coefficients from very low temperatures to 10,000 K is proposed based on an extended principle of corresponding states, and having greater range and accuracy than previous correlations. There are two correlation parameters that are related to other physical quantities and that are predictable in the absence of diffusion measurements. Quantum effects and composition dependence are included, but high-pressure effects are not. The results are directly applicable to multicomponent mixtures.

  10. SAGE II aerosol correlative observations - Profile measurements

    NASA Technical Reports Server (NTRS)

    Osborn, M. T.; Rosen, J. M.; Mccormick, M. P.; Wang, Pi-Huan; Livinfston, J. M.

    1989-01-01

    Profiles of the aerosol extinction measurements from the Stratospheric Aerosol and Gas Experiment (SAGE) II are compared with profiles from five correlative experiments between November 1984 and July 1986. The correlative profiles were derived from six-channel dustsonde measurements and two-wavelength lidar backscatter data. The correlation between the dustsonde- and lidar-derived measurements and the SAGE II data is good, validating the SAGE II lower stratospheric aerosol extinction measurements.

  11. Correlated edge overlaps in multiplex networks

    NASA Astrophysics Data System (ADS)

    Baxter, Gareth J.; Bianconi, Ginestra; da Costa, Rui A.; Dorogovtsev, Sergey N.; Mendes, José F. F.

    2016-07-01

    We develop the theory of sparse multiplex networks with partially overlapping links based on their local treelikeness. This theory enables us to find the giant mutually connected component in a two-layer multiplex network with arbitrary correlations between connections of different types. We find that correlations between the overlapping and nonoverlapping links markedly change the phase diagram of the system, leading to multiple hybrid phase transitions. For assortative correlations we observe recurrent hybrid phase transitions.

  12. Parallel auto-correlative statistics with VTK.

    SciTech Connect

    Pebay, Philippe Pierre; Bennett, Janine Camille

    2013-08-01

    This report summarizes existing statistical engines in VTK and presents both the serial and parallel auto-correlative statistics engines. It is a sequel to [PT08, BPRT09b, PT09, BPT09, PT10] which studied the parallel descriptive, correlative, multi-correlative, principal component analysis, contingency, k-means, and order statistics engines. The ease of use of the new parallel auto-correlative statistics engine is illustrated by the means of C++ code snippets and algorithm verification is provided. This report justifies the design of the statistics engines with parallel scalability in mind, and provides scalability and speed-up analysis results for the autocorrelative statistics engine.

  13. Response time correlations for platinum resistance thermometers

    NASA Technical Reports Server (NTRS)

    Pandey, D. K.; Ash, R. L.; Dillon-Townes, L. A.

    1985-01-01

    The 'plunge method' recommended by ASTM has been used to determine the time constant of 100-ohm platinum resistance thermometers (PRT) considered for use in the National Transonic Facility. It is shown that the response time of ventilated PRT can be correlated with the reciprocal of the heat transfer coefficient in a given field. Universal correlations are established for the 100- and 1000-ohm PRT with uncertainties of 20 and 30 percent, respectively. The correlations are found to be consistent with the uncertainty involved in heat transfer correlations available in the literature and are recommended for use in flowing liquids and gases.

  14. Phase space correlation to improve detection accuracy.

    PubMed

    Carroll, T L; Rachford, F J

    2009-09-01

    The standard method used for detecting signals in radar or sonar is cross correlation. The accuracy of the detection with cross correlation is limited by the bandwidth of the signals. We show that by calculating the cross correlation based on points that are nearby in phase space rather than points that are simultaneous in time, the detection accuracy is improved. The phase space correlation technique works for some standard radar signals, but it is especially well suited to chaotic signals because trajectories that are adjacent in phase space move apart from each other at an exponential rate.

  15. The genetic correlation between procrastination and impulsivity.

    PubMed

    Loehlin, John C; Martin, Nicholas G

    2014-12-01

    The reported genetic correlation of 1.0 between the traits of procrastination and impulsivity (Gustavson, D. E., Miyake, A., Hewitt, J. K., & Friedman, N. P. (2014). Psychological Science), which was held to support an evolutionary origin of the relationship between the two traits, was tested in data from two large samples of twins from Australia. A genetic correlation of 0.299 was obtained. It was concluded that, although the presence of a genetic correlation between the two traits was supported, the modest magnitude of the correlation was such as to be consistent with many possible hypotheses, evolutionary and otherwise, about causal relationships between the traits in question. PMID:25431285

  16. The genetic correlation between procrastination and impulsivity.

    PubMed

    Loehlin, John C; Martin, Nicholas G

    2014-12-01

    The reported genetic correlation of 1.0 between the traits of procrastination and impulsivity (Gustavson, D. E., Miyake, A., Hewitt, J. K., & Friedman, N. P. (2014). Psychological Science), which was held to support an evolutionary origin of the relationship between the two traits, was tested in data from two large samples of twins from Australia. A genetic correlation of 0.299 was obtained. It was concluded that, although the presence of a genetic correlation between the two traits was supported, the modest magnitude of the correlation was such as to be consistent with many possible hypotheses, evolutionary and otherwise, about causal relationships between the traits in question.

  17. RECONSTRUCTING THE SHAPE OF THE CORRELATION FUNCTION

    SciTech Connect

    Huffenberger, K. M.; Galeazzi, M.; Ursino, E.

    2013-06-01

    We develop an estimator for the correlation function which, in the ensemble average, returns the shape of the correlation function, even for signals that have significant correlations on the scale of the survey region. Our estimator is general and works in any number of dimensions. We develop versions of the estimator for both diffuse and discrete signals. As an application, we apply them to Monte Carlo simulations of X-ray background measurements. These include a realistic, spatially inhomogeneous population of spurious detector events. We discuss applying the estimator to the averaging of correlation functions evaluated on several small fields, and to other cosmological applications.

  18. Burst Firing Enhances Neural Output Correlation

    PubMed Central

    Chan, Ho Ka; Yang, Dong-Ping; Zhou, Changsong; Nowotny, Thomas

    2016-01-01

    Neurons communicate and transmit information predominantly through spikes. Given that experimentally observed neural spike trains in a variety of brain areas can be highly correlated, it is important to investigate how neurons process correlated inputs. Most previous work in this area studied the problem of correlation transfer analytically by making significant simplifications on neural dynamics. Temporal correlation between inputs that arises from synaptic filtering, for instance, is often ignored when assuming that an input spike can at most generate one output spike. Through numerical simulations of a pair of leaky integrate-and-fire (LIF) neurons receiving correlated inputs, we demonstrate that neurons in the presence of synaptic filtering by slow synapses exhibit strong output correlations. We then show that burst firing plays a central role in enhancing output correlations, which can explain the above-mentioned observation because synaptic filtering induces bursting. The observed changes of correlations are mostly on a long time scale. Our results suggest that other features affecting the prevalence of neural burst firing in biological neurons, e.g., adaptive spiking mechanisms, may play an important role in modulating the overall level of correlations in neural networks. PMID:27242499

  19. Indirectly detected chemical shift correlation NMR spectroscopy in solids under fast magic angle spinning

    SciTech Connect

    Mao, Kanmi

    2011-01-01

    The development of fast magic angle spinning (MAS) opened up an opportunity for the indirect detection of insensitive low-γ nuclei (e.g., 13C and 15N) via the sensitive high-{gamma} nuclei (e.g., 1H and 19F) in solid-state NMR, with advanced sensitivity and resolution. In this thesis, new methodology utilizing fast MAS is presented, including through-bond indirectly detected heteronuclear correlation (HETCOR) spectroscopy, which is assisted by multiple RF pulse sequences for 1H-1H homonuclear decoupling. Also presented is a simple new strategy for optimization of 1H-1H homonuclear decoupling. As applications, various classes of materials, such as catalytic nanoscale materials, biomolecules, and organic complexes, are studied by combining indirect detection and other one-dimensional (1D) and two-dimensional (2D) NMR techniques. Indirectly detected through-bond HETCOR spectroscopy utilizing refocused INEPT (INEPTR) mixing was developed under fast MAS (Chapter 2). The time performance of this approach in 1H detected 2D 1H{l_brace}13C{r_brace} spectra was significantly improved, by a factor of almost 10, compared to the traditional 13C detected experiments, as demonstrated by measuring naturally abundant organic-inorganic mesoporous hybrid materials. The through-bond scheme was demonstrated as a new analytical tool, which provides complementary structural information in solid-state systems in addition to through-space correlation. To further benefit the sensitivity of the INEPT transfer in rigid solids, the combined rotation and multiple-pulse spectroscopy (CRAMPS) was implemented for homonuclear 1H decoupling under fast MAS (Chapter 3). Several decoupling schemes (PMLG5m$\\bar{x}$, PMLG5mm$\\bar{x}$x and SAM3) were analyzed to maximize the performance of through-bond transfer based

  20. A fast, flexible algorithm for calculating correlations in Fluorescence Correlation Spectroscopy

    SciTech Connect

    Laurence, T; Fore, S; Huser, T

    2005-10-13

    A new algorithm is introduced for computing correlations of photon arrival time data acquired in single-molecule fluorescence spectroscopy and fluorescence correlation spectroscopy (FCS). The correlation is first rewritten as a counting operation on photon pairs. For each photon, the contribution to the correlation function for each subsequent photon is calculated for arbitrary bin spacings of the correlation time lag. By retaining the bin positions in the photon sequence after each photon, the correlation can be performed efficiently. Example correlations for simulations of FCS experiments are shown, with comparable execution speed to the commonly used multiple-tau correlation technique. Also, wide bin spacings are possible that allow for real-time software calculation of correlations even for high count rates ({approx}350 kHz). The flexibility and broad applicability of the algorithm is demonstrated using results from single molecule photon antibunching experiments.

  1. Personality Correlates of Pain Perception and Tolerance.

    ERIC Educational Resources Information Center

    Lukin, Penny R.; Ray, A. Bartow

    1982-01-01

    Explored personality correlates of pain perception and tolerance in a nonmedical sample and setting. Results showed no significant correlations with personality measures and cold-pressor scores, but a significant relationship between pain tolerance and cognitive focus; those who focused on the experimental situation had much shorter tolerance…

  2. Optical correlation recognition based on LCOS

    NASA Astrophysics Data System (ADS)

    Tang, Mingchuan; Wu, Jianhong

    2013-08-01

    Vander-Lugt correlator[1] plays an important role in optical pattern recognition due to the characteristics of accurate positioning and high signal-to-noise ratio. The ideal Vander-Lugt correlator should have the ability of outputting strong and sharp correlation peak in allusion to the true target, in the existing Spatial Light Modulators[2], Liquid Crystal On Silicon(LCOS) has been the most competitive candidate for the matched filter owing to the continuous phase modulation peculiarity. Allowing for the distortions of the target to be identified including rotations, scaling changes, perspective changes, which can severely impact the correlation recognition results, herein, we present a modified Vander-Lugt correlator based on the LCOS by means of applying an iterative algorithm to the design of the filter so that the correlator can invariant to the distortions while maintaining good performance. The results of numerical simulation demonstrate that the filter could get the similar recognition results for all the training images. And the experiment shows that the modified correlator achieves the 180° rotating tolerance significantly improving the recognition efficiency of the correlator.

  3. Correlation as Probability of Common Descent.

    ERIC Educational Resources Information Center

    Falk, Ruma; Well, Arnold D.

    1996-01-01

    One interpretation of the Pearson product-moment correlation ("r"), correlation as the probability of originating from common descent, important to the genetic measurement of inbreeding, is examined. The conditions under which "r" can be interpreted as the probability of "identity by descent" are specified, and the possibility of generalizing this…

  4. The Bonn Astro/Geo Correlator

    NASA Technical Reports Server (NTRS)

    Bernhart, Simone; Alef, Walter; Bertarini, Alessandra; La Porta, Laura; Muskens, Arno; Rottmann, Helge; Roy, Alan

    2013-01-01

    The Bonn Distributed FX (DiFX) correlator is a software correlator operated jointly by the Max- Planck-Institut fur Radioastronomie (MPIfR), the Institut fur Geodasie und Geoinformation der Universitat Bonn (IGG), and the Bundesamt fur Kartographie und Geodasie (BKG) in Frankfurt.

  5. Transformation of stimulus correlations by the retina.

    PubMed

    Simmons, Kristina D; Prentice, Jason S; Tkačik, Gašper; Homann, Jan; Yee, Heather K; Palmer, Stephanie E; Nelson, Philip C; Balasubramanian, Vijay

    2013-01-01

    Redundancies and correlations in the responses of sensory neurons may seem to waste neural resources, but they can also carry cues about structured stimuli and may help the brain to correct for response errors. To investigate the effect of stimulus structure on redundancy in retina, we measured simultaneous responses from populations of retinal ganglion cells presented with natural and artificial stimuli that varied greatly in correlation structure; these stimuli and recordings are publicly available online. Responding to spatio-temporally structured stimuli such as natural movies, pairs of ganglion cells were modestly more correlated than in response to white noise checkerboards, but they were much less correlated than predicted by a non-adapting functional model of retinal response. Meanwhile, responding to stimuli with purely spatial correlations, pairs of ganglion cells showed increased correlations consistent with a static, non-adapting receptive field and nonlinearity. We found that in response to spatio-temporally correlated stimuli, ganglion cells had faster temporal kernels and tended to have stronger surrounds. These properties of individual cells, along with gain changes that opposed changes in effective contrast at the ganglion cell input, largely explained the pattern of pairwise correlations across stimuli where receptive field measurements were possible.

  6. The Correlates and Dimensions of Age Identification.

    ERIC Educational Resources Information Center

    Daum, Menachem

    A review of the age identification literature suggests older identifiers to be chronologically older and to perceive their health and morale less positively. Most studies examining other correlates fail to control for age or health. The correlates of age identification are examined in a group of 200 workers, aged 55 and over, who predominantly…

  7. Periodically correlated processes and their stationary dilations

    NASA Technical Reports Server (NTRS)

    Miamee, A. G.

    1988-01-01

    An explicit form for a stationary dilation for periodically correlated random processes is obtained. This is then used to give spectral conditions for a periodically correlated process to be non-deterministic, purely deterministic, minimal, and to have a positive angle between its past and future.

  8. Part and Bipartial Canonical Correlation Analysis.

    ERIC Educational Resources Information Center

    Timm, Neil H.; Carlson, James E.

    Part and bi-partial canonical correlations were developed by extending the definitions of part and bi-partial correlation to sets of variates. These coefficients may be used to help researchers explore relationships which exist among several sets of normally distributed variates. (Author)

  9. Is the G Index a Correlation Coefficient?

    ERIC Educational Resources Information Center

    Vegelius, Jan

    1980-01-01

    One argument against the G index is that, unlike phi, it is not a correlation coefficient; yet, G conforms to the Kendall and E-coefficient definitions. The G index is also equal to the Pearson product moment correlation coefficient obtained from double scoring. (Author/CP)

  10. Intelligence and Semen Quality Are Positively Correlated

    ERIC Educational Resources Information Center

    Arden, Rosalind; Gottfredson, Linda S.; Miller, Geoffrey; Pierce, Arand

    2009-01-01

    Human cognitive abilities inter-correlate to form a positive matrix, from which a large first factor, called "Spearman's g" or general intelligence, can be extracted. General intelligence itself is correlated with many important health outcomes including cardio-vascular function and longevity. However, the important evolutionary question of…

  11. On the insignificance of Herschel's sunspot correlation

    USGS Publications Warehouse

    Love, Jeffrey J.

    2013-01-01

    We examine William Herschel's hypothesis that solar-cycle variation of the Sun's irradiance has a modulating effect on the Earth's climate and that this is, specifically, manifested as an anticorrelation between sunspot number and the market price of wheat. Since Herschel first proposed his hypothesis in 1801, it has been regarded with both interest and skepticism. Recently, reports have been published that either support Herschel's hypothesis or rely on its validity. As a test of Herschel's hypothesis, we seek to reject a null hypothesis of a statistically random correlation between historical sunspot numbers, wheat prices in London and the United States, and wheat farm yields in the United States. We employ binary-correlation, Pearson-correlation, and frequency-domain methods. We test our methods using a historical geomagnetic activity index, well known to be causally correlated with sunspot number. As expected, the measured correlation between sunspot number and geomagnetic activity would be an unlikely realization of random data; the correlation is “statistically significant.” On the other hand, measured correlations between sunspot number and wheat price and wheat yield data would be very likely realizations of random data; these correlations are “insignificant.” Therefore, Herschel's hypothesis must be regarded with skepticism. We compare and contrast our results with those of other researchers. We discuss procedures for evaluating hypotheses that are formulated from historical data.

  12. Mark 3 correlator hardware and software

    NASA Technical Reports Server (NTRS)

    Whitney, A. R.

    1980-01-01

    The Mark 3 correlator system is described in some detail. The correlator system is based on a modular philosophy. Each correlator module independently processes the data from one track pair. Therefore, 28 modules are necessary to complete a full one baseline processor and 84 modules for a full 3 baseline processor. Each correlator module has two interfaces: (1) data and clock from each of the two tracks to be correlated and (2) Computer Automated Measurement and Control (CAMAC) dataway interface to the computer. The processor is organized around the IEEE CAMAC standard architecture, housing 15 correlator modules in each of 6 crates. This allows one pass processing of a full 3 baseline 28 track observation or a 6 baseline (4 station) 14 track observation. The correlator architecture allows easy expansion for up to 8 stations. The computer system is an HP 1000 system utilizing a 16 bit minicomputer with disc and tape peripherals. The processing software is also organized in a modular fashion with many independent but cooperative programs controlling the operation of the Mark 3 processor. Processing time through the correlator is normally real time or faster, with graphics displays providing real time monitor and control of the processing operation.

  13. ANALYZING CORRELATIONS BETWEEN STREAM AND WATERSHED ATTRIBUTES

    EPA Science Inventory

    Bivariate correlation analysis has been widely used to explore relationships between stream and watershed attributes that have all been measured on the same set of watersheds or sampling locations. Researchers routinely test H0: =0 for each correlation in a large table and then ...

  14. Transport of correlations in a harmonic chain

    NASA Astrophysics Data System (ADS)

    Nicacio, F.; Semião, F. L.

    2016-07-01

    We study the propagation of different types of correlations through a quantum bus formed by a chain of coupled harmonic oscillators. This includes steering, entanglement, mutual information, quantum discord, and Bell-like nonlocality. The whole system consists of the quantum bus (propagation medium) and other quantum harmonic oscillators (sources and receivers of quantum correlations) weakly coupled to the chain. We are particularly interested in using the point of view of transport to spot distinctive features displayed by different kinds of correlations. We found, for instance, that there are fundamental differences in the way steering and discord propagate, depending on the way they are defined with respect to the parties involved in the initial correlated state. We analyzed both the closed- and open-system dynamics as well as the role played by thermal excitations in the propagation of the correlations.

  15. Seeking positive experiences can produce illusory correlations.

    PubMed

    Denrell, Jerker; Le Mens, Gaël

    2011-06-01

    Individuals tend to select again alternatives about which they have positive impressions and to avoid alternatives about which they have negative impressions. Here we show how this sequential sampling feature of the information acquisition process leads to the emergence of an illusory correlation between estimates of the attributes of multi-attribute alternatives. The sign of the illusory correlation depends on how the decision maker combines estimates in making her sampling decisions. A positive illusory correlation emerges when evaluations are compensatory or disjunctive and a negative illusory correlation can emerge when evaluations are conjunctive. Our theory provides an alternative explanation for illusory correlations that does not rely on biased information processing nor selective attention to different pieces of information. It provides a new perspective on several well-established empirical phenomena such as the 'Halo' effect in personality perception, the relation between proximity and attitudes, and the in-group out-group bias in stereotype formation. PMID:21397900

  16. Field and intensity correlation in random media

    PubMed

    Sebbah; Pnini; Genack

    2000-11-01

    We have obtained the spectral and spatial field correlation functions, C(E)(Deltaomega) and C(E)(Deltax), respectively, from measurement of the microwave field spectrum at a series of points along a line on the output of a random dielectric medium. C(E)(Deltaomega) and C(E)(Deltax) are shown to be the Fourier transforms, respectively, of the time of flight distribution, obtained from pulsed measurements, and of the specific intensity. Unlike C(E)(Deltaomega), the imaginary part of C(E)(Deltax) is shown to vanish as a result of the isotropy of the correlation function in the output plane. The complex square of the field correlation function gives the short-range or C1 contribution to the intensity correlation function C. Longer-range contributions to the intensity correlation function are obtained directly by subtracting C1 from C and are in good agreement with theory.

  17. Holographic thermalization with initial long range correlation

    DOE PAGES

    Lin, Shu

    2016-01-19

    Here, we studied the evolution of the Wightman correlator in a thermalizing state modeled by AdS3-Vaidya background. A prescription was given for calculating the Wightman correlator in coordinate space without using any approximation. For equal-time correlator , we obtained an enhancement factor v2 due to long range correlation present in the initial state. This was missed by previous studies based on geodesic approximation. Moreover, we found that the long range correlation in initial state does not lead to significant modification to thermalization time as compared to known results with generic initial state. We also studied the spatially integrated Wightman correlatormore » and showed evidence on the distinction between long distance and small momentum physics for an out-of-equilibrium state. We also calculated the radiation spectrum of particles weakly coupled to O and found that lower frequency mode approaches thermal spectrum faster than high frequency mode.« less

  18. Does "cooling by heating" protect quantum correlations?

    NASA Astrophysics Data System (ADS)

    Villas-Boas, C. J.; Cardoso, W. B.; Avelar, A. T.; Xuereb, A.; de Almeida, N. G.

    2016-05-01

    The connection between nonequilibrium quantum correlations, such as entanglement and quantum discord, and cooling by heating is investigated for a system composed by two atoms interacting with a single electromagnetic mode of a lossy cavity. This Hamiltonian model is experimentally feasible in the quantum optics domain and presents the occurrence of both nonequilibrium quantum correlations and cooling by heating for a range of parameters. Since in the cooling by heating phenomenon the effective temperature of the system decreases even increasing the environments temperature, it could be expected that quantum correlations could be enhanced. Interestingly, for some parameters we show that, contrary to this expectation, in the case studied here the lowering of the system effective temperature leads to no enhancement in the quantum correlations. In addition, we found that at both zero and finite temperature, depending on the parameters used, quantum correlations can be enhanced even when increasing the damping rates, a somewhat counterintuitive result.

  19. Correlators at large c without information loss

    NASA Astrophysics Data System (ADS)

    Galliani, Andrea; Giusto, Stefano; Moscato, Emanuele; Russo, Rodolfo

    2016-09-01

    We study a simple class of correlators with two heavy and two light operators both in the D1D5 CFT and in the dual AdS3 × S 3 × T 4 description. On the CFT side we focus on the free orbifold point and discuss how these correlators decompose in terms of conformal blocks, showing that they are determined by protected quantities. On the gravity side, the heavy states are described by regular, asymptotically AdS3 × S 3 × T 4 solutions and the correlators are obtained by studying the wave equation in these backgrounds. We find that the CFT and the gravity results agree and that, even in the large central charge limit, these correlators do not have (Euclidean) spurious singularities. We suggest that this is indeed a general feature of the heavy-light correlators in unitary CFTs, which can be relevant for understanding how information is encoded in black hole microstates.

  20. Correlated activity supports efficient cortical processing

    PubMed Central

    Hung, Chou P.; Cui, Ding; Chen, Yueh-peng; Lin, Chia-pei; Levine, Matthew R.

    2015-01-01

    Visual recognition is a computational challenge that is thought to occur via efficient coding. An important concept is sparseness, a measure of coding efficiency. The prevailing view is that sparseness supports efficiency by minimizing redundancy and correlations in spiking populations. Yet, we recently reported that “choristers”, neurons that behave more similarly (have correlated stimulus preferences and spontaneous coincident spiking), carry more generalizable object information than uncorrelated neurons (“soloists”) in macaque inferior temporal (IT) cortex. The rarity of choristers (as low as 6% of IT neurons) indicates that they were likely missed in previous studies. Here, we report that correlation strength is distinct from sparseness (choristers are not simply broadly tuned neurons), that choristers are located in non-granular output layers, and that correlated activity predicts human visual search efficiency. These counterintuitive results suggest that a redundant correlational structure supports efficient processing and behavior. PMID:25610392

  1. Spectral correlations of fractional Brownian motion

    SciTech Connect

    Oigaard, Tor Arne; Hanssen, Alfred; Scharf, Louis L.

    2006-09-15

    Fractional Brownian motion (fBm) is a ubiquitous nonstationary model for many physical processes with power-law time-averaged spectra. In this paper, we exploit the nonstationarity to derive the full spectral correlation structure of fBm. Starting from the time-varying correlation function, we derive two different time-frequency spectral correlation functions (the ambiguity function and the Kirkwood-Rihaczek spectrum), and one dual-frequency spectral correlation function. The dual-frequency spectral correlation has a surprisingly simple structure, with spectral support on three discrete lines. The theoretical predictions are verified by spectrum estimates of Monte Carlo simulations and of a time series of earthquakes with a magnitude of 7 and higher.

  2. Bell Inequalities as Constraints on Unmeasurable Correlations

    NASA Astrophysics Data System (ADS)

    Budroni, Costantino; Morchio, Giovanni

    2012-04-01

    The interpretation of the violation of Bell-Clauser-Horne inequalities is revisited, in relation with the notion of extension of QM predictions to unmeasurable correlations. Such extensions are compatible with QM predictions in many cases, in particular for observables with compatibility relations described by tree graphs. This implies classical representability of any set of correlations < A i >, < B>, < A i B>, and the equivalence of the Bell-Clauser-Horne inequalities to a non void intersection between the ranges of values for the unmeasurable correlation < A 1 A 2> associated to different choices for B. The same analysis applies to the Hardy model and to the "perfect correlations" discussed by Greenberger, Horne, Shimony and Zeilinger. In all the cases, the dependence of an unmeasurable correlation on a set of variables allowing for a classical representation is the only basis for arguments about violations of locality and causality.

  3. Phase coherence induced by correlated disorder

    NASA Astrophysics Data System (ADS)

    Hong, Hyunsuk; O'Keeffe, Kevin P.; Strogatz, Steven H.

    2016-02-01

    We consider a mean-field model of coupled phase oscillators with quenched disorder in the coupling strengths and natural frequencies. When these two kinds of disorder are uncorrelated (and when the positive and negative couplings are equal in number and strength), it is known that phase coherence cannot occur and synchronization is absent. Here we explore the effects of correlating the disorder. Specifically, we assume that any given oscillator either attracts or repels all the others, and that the sign of the interaction is deterministically correlated with the given oscillator's natural frequency. For symmetrically correlated disorder with zero mean, we find that the system spontaneously synchronizes, once the width of the frequency distribution falls below a critical value. For asymmetrically correlated disorder, the model displays coherent traveling waves: the complex order parameter becomes nonzero and rotates with constant frequency different from the system's mean natural frequency. Thus, in both cases, correlated disorder can trigger phase coherence.

  4. Short-Range Nucleon-Nucleon Correlations

    SciTech Connect

    Douglas Higinbotham

    2011-10-01

    Valence-shell nucleon knock-out experiments, such as 12C(e,e'p)11B, measure less strength then is predicted by independent particle shell model calculations. The theoretical solution to this problem is to include the correlations between the nucleons in the nucleus in the calculations. Motivated by these results, many electron scattering experiments have tried to directly observe these correlations in order to gain new insight into the short-range part of the nucleon-nucleon potential. Unfortunately, many competing mechanisms can cause the same observable final-state as an initial-state correlation, making truly isolating the signal extremely challenging. This paper reviews the recent experimental evidence for short-range correlations, as well as explores the possibility that such correlations are responsible for the EMC effect in the 0.3 < xB < 0.7 deep inelastic scattering ratios.

  5. Statistical correlations in the Moshinsky atom

    SciTech Connect

    Laguna, H. G.; Sagar, R. P.

    2011-07-15

    We study the influence of the interparticle and confining potentials on statistical correlation via the correlation coefficient and mutual information in ground and some excited states of the Moshinsky atom in position and momentum space. The magnitude of the correlation between positions and between momenta is equal in the ground state. In excited states, the correlation between the momenta of the particles is greater than between their positions when they interact through an attractive potential whereas for repulsive interparticle potentials the opposite is true. Shannon entropies, and their sums (entropic formulations of the uncertainty principle), are also analyzed, showing that the one-particle entropy sum is dependent on the interparticle potential and thus able to detect the correlation between particles.

  6. Motion-sensitive optical correlator using a VanderLugt correlator

    NASA Technical Reports Server (NTRS)

    Liu, Tsuen-Hsi (Inventor)

    1994-01-01

    A new type of optical correlator is presented. The correlator performs motion detection or background clutter suppression and correlation simultaneously in a single photorefractive crystal. Additionally, the device is useful for moving target identification and tracking and for stationary clutter rejection. The correlation is of the VanderLugt type, and the motion detection or background clutter suppression is based on the erasing property of photorefractive crystals.

  7. Energy Correlation of Prompt Fission Neutrons

    NASA Astrophysics Data System (ADS)

    Elter, Zs.; Pázsit, I.

    2016-03-01

    In all cases where neutron fluctuations in a branching process (such as in multiplicity measurements) are treated in an energy dependent description, the energy correlations of the branching itself (energy correlations of the fission neutrons) need to be known. To date, these are not known from experiments. Such correlations can be theoretically and numerically derived by modelling the details of the fission process. It was suggested earlier that the fact that the prompt neutrons are emitted from the moving fission targets, will influence their energy and angular distributions in the lab system, which possibly induces correlations. In this paper the influence of the neutron emission process from the moving targets on the energy correlations is investigated analytically and via numerical simulations. It is shown that the correlations are generated by the random energy and direction distributions of the fission fragments. Analytical formulas are derived for the two-point energy distributions, and quantitative results are obtained by Monte-Carlo simulations. The results lend insight into the character of the two-point distributions, and give quantitative estimates of the energy correlations, which are generally small.

  8. Using neural networks to describe tracer correlations

    NASA Astrophysics Data System (ADS)

    Lary, D. J.; Müller, M. D.; Mussa, H. Y.

    2003-11-01

    Neural networks are ideally suited to describe the spatial and temporal dependence of tracer-tracer correlations. The neural network performs well even in regions where the correlations are less compact and normally a family of correlation curves would be required. For example, the CH4-N2O correlation can be well described using a neural 5 network trained with the latitude, pressure, time of year, and CH4 volume mixing ratio (v.m.r.). In this study a neural network using Quickprop learning and one hidden layer with eight nodes was able to reproduce the CH4-N2O correlation with a correlation co-efficient of 0.9995. Such an accurate representation of tracer-tracer correlations allows more use to be made of long-term datasets to constrain chemical models. Such as the 10 dataset from the Halogen Occultation Experiment (HALOE) which has continuously observed CH4 (but not N2O) from 1991 till the present. The neural network Fortran code used is available for download

  9. Using neural networks to describe tracer correlations

    NASA Astrophysics Data System (ADS)

    Lary, D. J.; Müller, M. D.; Mussa, H. Y.

    2004-01-01

    Neural networks are ideally suited to describe the spatial and temporal dependence of tracer-tracer correlations. The neural network performs well even in regions where the correlations are less compact and normally a family of correlation curves would be required. For example, the CH4-N2O correlation can be well described using a neural network trained with the latitude, pressure, time of year, and methane volume mixing ratio (v.m.r.). In this study a neural network using Quickprop learning and one hidden layer with eight nodes was able to reproduce the CH4-N2O correlation with a correlation coefficient between simulated and training values of 0.9995. Such an accurate representation of tracer-tracer correlations allows more use to be made of long-term datasets to constrain chemical models. Such as the dataset from the Halogen Occultation Experiment (HALOE) which has continuously observed CH4 (but not N2O) from 1991 till the present. The neural network Fortran code used is available for download.

  10. Using Neural Networks to Describe Tracer Correlations

    NASA Technical Reports Server (NTRS)

    Lary, D. J.; Mueller, M. D.; Mussa, H. Y.

    2003-01-01

    Neural networks are ideally suited to describe the spatial and temporal dependence of tracer-tracer correlations. The neural network performs well even in regions where the correlations are less compact and normally a family of correlation curves would be required. For example, the CH4-N2O correlation can be well described using a neural network trained with the latitude, pressure, time of year, and CH4 volume mixing ratio (v.m.r.). In this study a neural network using Quickprop learning and one hidden layer with eight nodes was able to reproduce the CH4-N2O correlation with a correlation co- efficient of 0.9995. Such an accurate representation of tracer-tracer correlations allows more use to be made of long-term datasets to constrain chemical models. Such as the dataset from the Halogen Occultation Experiment (HALOE) which has continuously observed CH4, (but not N2O) from 1991 till the present. The neural network Fortran code used is available for download.

  11. Management of ambiguities in magnetostratigraphic correlation

    NASA Astrophysics Data System (ADS)

    Lallier, Florent; Antoine, Christophe; Charreau, Julien; Caumon, Guillaume; Ruiu, Jeremy

    2013-06-01

    Magnetostratigraphy is a powerful tool to provide absolute dating of sediments enabling robust and detailed chronostratigraphic correlations. It is based on the correlation of a magnetic polarity column, observed and measured in a given sediment section, to a magnetic polarity reference scale where polarity changes are well dated via other independent methods. However, magnetostratigraphic correlations are loose as they are only constrained by binary magnetic chrons (i.e. normal or reversal) and their thickness, which are both defined from depth variations of the magnetic remanent directions. The thickness of a given magnetic polarity zone is a function of time and sediment accumulation rate, which may not be stationary, leading to ambiguities when performing the correlations. To address these ambiguities, a numerical method based on the Dynamic Time Warping algorithm is proposed. Magnetostratigraphic correlations are computed in order to minimise the local variation of the accumulation rate. The main advantage of the proposed method is to automatically provide a set of reasonably likely correlations. This set can then be scrutinised for further analysis and interpretation. However, the likelihood of a correlation should be handled carefully as it depends on the information content of the magnetostratigraphic section itself and remain ultimately valid by ancillary constraint. Nevertheless, the method gives consistent results on difficult synthetic cases that simulate abrupt variations of the sedimentation rate. Insights on true sections debated by previous authors are also given.

  12. Management of ambiguities in magnetostratigraphic correlation

    NASA Astrophysics Data System (ADS)

    Charreau, J.; Lallier, F.; Antoine, C.; Caumon, G.; Ruiu, J.

    2012-12-01

    Magnetostratigraphy is a powerful tool to provide absolute dating of sediments enabling good and detailed chronostratigraphic correlations. It is based on the correlation of a magnetic polarity column, observed and measured in a given sediment section, to a magnetic polarity reference scale where polarity changes are well dated via other independent methods. However, magnetostratigraphic correlations are loose because only constrained by binary magnetic chrons (i.e normal or reversal) and their thickness, which are both defined from depth variations of the magnetic remanent directions. The thickness of a given magnetic chron is a function of time and sediment accumulation rate, which may not be stationary, leading to ambiguities when performing the correlations. To address these ambiguities, a numerical method based on the Dynamic Time Warping algorithm is proposed. Magnetostratigraphics correlation are computed in order to minimize the local variation of accumulation rate. The main advantage of the proposed method is to automatically provide a set of reasonably likely correlations. This set can then be scrutinized for further analysis and interpretation. However, the likelihood of a correlation should be handled carefully. It depends on the information content of the magnetotratigraphic section itself and remain ultimately valid by ancillary constraint. Nevertheless, the method is shown to present consistent results on difficult synthetic cases simulating abrupt variations of the sedimentation rate, and provides interesting insights on true sections debated by previous authors.

  13. A fast SEQUEST cross correlation algorithm.

    PubMed

    Eng, Jimmy K; Fischer, Bernd; Grossmann, Jonas; Maccoss, Michael J

    2008-10-01

    The SEQUEST program was the first and remains one of the most widely used tools for assigning a peptide sequence within a database to a tandem mass spectrum. The cross correlation score is the primary score function implemented within SEQUEST and it is this score that makes the tool particularly sensitive. Unfortunately, this score is computationally expensive to calculate, and thus, to make the score manageable, SEQUEST uses a less sensitive but fast preliminary score and restricts the cross correlation to just the top 500 peptides returned by the preliminary score. Classically, the cross correlation score has been calculated using Fast Fourier Transforms (FFT) to generate the full correlation function. We describe an alternate method of calculating the cross correlation score that does not require FFTs and can be computed efficiently in a fraction of the time. The fast calculation allows all candidate peptides to be scored by the cross correlation function, potentially mitigating the need for the preliminary score, and enables an E-value significance calculation based on the cross correlation score distribution calculated on all candidate peptide sequences obtained from a sequence database. PMID:18774840

  14. Inverse Ising inference with correlated samples

    NASA Astrophysics Data System (ADS)

    Obermayer, Benedikt; Levine, Erel

    2014-12-01

    Correlations between two variables of a high-dimensional system can be indicative of an underlying interaction, but can also result from indirect effects. Inverse Ising inference is a method to distinguish one from the other. Essentially, the parameters of the least constrained statistical model are learned from the observed correlations such that direct interactions can be separated from indirect correlations. Among many other applications, this approach has been helpful for protein structure prediction, because residues which interact in the 3D structure often show correlated substitutions in a multiple sequence alignment. In this context, samples used for inference are not independent but share an evolutionary history on a phylogenetic tree. Here, we discuss the effects of correlations between samples on global inference. Such correlations could arise due to phylogeny but also via other slow dynamical processes. We present a simple analytical model to address the resulting inference biases, and develop an exact method accounting for background correlations in alignment data by combining phylogenetic modeling with an adaptive cluster expansion algorithm. We find that popular reweighting schemes are only marginally effective at removing phylogenetic bias, suggest a rescaling strategy that yields better results, and provide evidence that our conclusions carry over to the frequently used mean-field approach to the inverse Ising problem.

  15. Neural population densities shape network correlations

    NASA Astrophysics Data System (ADS)

    Lefebvre, Jérémie; Perkins, Theodore J.

    2012-02-01

    The way sensory microcircuits manage cellular response correlations is a crucial question in understanding how such systems integrate external stimuli and encode information. Most sensory systems exhibit heterogeneities in terms of population sizes and features, which all impact their dynamics. This work addresses how correlations between the dynamics of neural ensembles depend on the relative size or density of excitatory and inhibitory populations. To do so, we study an apparently symmetric system of coupled stochastic differential equations that model the evolution of the populations’ activities. Excitatory and inhibitory populations are connected by reciprocal recurrent connections, and both receive different stimuli exhibiting a certain level of correlation with each other. A stability analysis is performed, which reveals an intrinsic asymmetry in the distribution of the fixed points with respect to the threshold of the nonlinearities. Based on this, we show how the cross correlation between the population responses depends on the density of the inhibitory population, and that a specific ratio between both population sizes leads to a state of zero correlation. We show that this so-called asynchronous state subsists, despite the presence of stimulus correlation, and most importantly, that it occurs only in asymmetrical systems where one population outnumbers the other. Using linear approximations, we derive analytical expressions for the root of the cross-correlation function and study how the asynchronous state is impacted by the model's parameters. This work suggests a possible explanation for why inhibitory cells outnumber excitatory cells in the visual system.

  16. Product Correlation When Original Variables Are Jointly Distributed Multivariate Normal: A Comparison with Sum Correlation

    ERIC Educational Resources Information Center

    Sockloff, Alan L.

    1977-01-01

    Product correlation was studied under the condition that the original variables are jointly distributed multivariate normal with equal coefficients of variation. Product correlation was shown to range between the two extremes of sum correlation and either the value zero or an unfamiliar function of the intercorrelations of the original variables.…

  17. BOLD fMRI Correlation Reflects Frequency-Specific Neuronal Correlation.

    PubMed

    Hipp, Joerg F; Siegel, Markus

    2015-05-18

    The brain-wide correlation of hemodynamic signals as measured with BOLD fMRI is widely studied as a proxy for integrative brain processes. However, the relationship between hemodynamic correlation structure and neuronal correlation structure remains elusive. We investigated this relation using BOLD fMRI and spatially co-registered, source-localized MEG in resting humans. We found that across the entire cortex BOLD correlation reflected the co-variation of frequency-specific neuronal activity. Resolving the relation between electrophysiological and hemodynamic correlation structures locally in cortico-cortical connection space, we found that this relation was subject specific and even persisted on the centimeter scale. At first sight, this relation was strongest in the alpha to beta frequency range (8-32 Hz). However, correcting for differences in signal-to-noise ratios across electrophysiological frequencies, we found that the relation extended over a broad frequency range from 2 to 128 Hz. Moreover, we found that the frequency with the tightest link to BOLD correlation varied across cortico-cortical space. For every cortico-cortical connection, we show which specific correlated oscillations were most related to BOLD correlations. Our work provides direct evidence for the neuronal origin of BOLD correlation structure. Moreover, our work suggests that, across the brain, BOLD correlation reflects correlation of different types of neuronal network processes and that frequency-specific electrophysiological correlation provides information about large-scale neuronal interactions complementary to BOLD fMRI.

  18. Bayesian Correlation Analysis for Sequence Count Data

    PubMed Central

    Lau, Nelson; Perkins, Theodore J.

    2016-01-01

    Evaluating the similarity of different measured variables is a fundamental task of statistics, and a key part of many bioinformatics algorithms. Here we propose a Bayesian scheme for estimating the correlation between different entities’ measurements based on high-throughput sequencing data. These entities could be different genes or miRNAs whose expression is measured by RNA-seq, different transcription factors or histone marks whose expression is measured by ChIP-seq, or even combinations of different types of entities. Our Bayesian formulation accounts for both measured signal levels and uncertainty in those levels, due to varying sequencing depth in different experiments and to varying absolute levels of individual entities, both of which affect the precision of the measurements. In comparison with a traditional Pearson correlation analysis, we show that our Bayesian correlation analysis retains high correlations when measurement confidence is high, but suppresses correlations when measurement confidence is low—especially for entities with low signal levels. In addition, we consider the influence of priors on the Bayesian correlation estimate. Perhaps surprisingly, we show that naive, uniform priors on entities’ signal levels can lead to highly biased correlation estimates, particularly when different experiments have widely varying sequencing depths. However, we propose two alternative priors that provably mitigate this problem. We also prove that, like traditional Pearson correlation, our Bayesian correlation calculation constitutes a kernel in the machine learning sense, and thus can be used as a similarity measure in any kernel-based machine learning algorithm. We demonstrate our approach on two RNA-seq datasets and one miRNA-seq dataset. PMID:27701449

  19. Discovering correlated fermions using quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Wagner, Lucas K.; Ceperley, David M.

    2016-09-01

    It has become increasingly feasible to use quantum Monte Carlo (QMC) methods to study correlated fermion systems for realistic Hamiltonians. We give a summary of these techniques targeted at researchers in the field of correlated electrons, focusing on the fundamentals, capabilities, and current status of this technique. The QMC methods often offer the highest accuracy solutions available for systems in the continuum, and, since they address the many-body problem directly, the simulations can be analyzed to obtain insight into the nature of correlated quantum behavior.

  20. Quantum correlations among optical and vibrational quanta

    NASA Astrophysics Data System (ADS)

    Carlig, Sergiu; Macovei, Mihai A.

    2014-05-01

    We investigate the feasibility of correlating an optical cavity field and a vibrational phonon mode. A laser pumped quantum dot fixed on a nanomechanical resonator beam interacts as a whole with the optical resonator mode. When the quantum dot variables are faster than the optical and phonon ones, we obtain a final master equation describing the involved modes only. Increasing the temperature, which directly affects the vibrational degrees of freedom, one can as well influence the cavity photon intensity, i.e., the optical and phonon modes are correlated. Furthermore, the corresponding Cauchy-Schwarz inequality is violated demonstrating the quantum nature of those correlations.

  1. The IAA RAS Correlator First Results

    NASA Technical Reports Server (NTRS)

    Surkis, Igor; Melnikov, Alexey; Shantyr, Violet; Zimovsky, Vladimir

    2010-01-01

    In 2009 the national Russian VLBI observations were processed by the new correlator ARC (Astrometric Radiointerferometric Correlator). The ARC is a VSI-H correlator and equipped with Mark 5B playback terminals. During 2009 ARC was used to process a series of VLBI sessions, observed on stations Svetloe, Zelenchukskaya, and Badary. NGS files were formed, and EOP parameters were obtained by IAA RAS Analysis Center. The accuracies of the pole coordinates and UT1-UTC were 1-2 mas and 0.07-0.1 ms, respectively.

  2. Dynamical correlations in Coulomb drag effect

    NASA Astrophysics Data System (ADS)

    Tanatar, B.; Davoudi, B.; Hu, B. Y.-K.

    2003-05-01

    Motivated by recent Coulomb drag experiments in pairs of low-density two-dimensional (2D) electron gases, we investigate the influence of correlation effects on the interlayer drag rate as a function of temperature. We use the self-consistent field method to calculate the intra and interlayer local-field factors Gij( q, T) which embody the short-range correlation effects. We calculate the transresistivity using the screened effective interlayer interactions that result from incorporating these local-field factors within various approximation schemes. Our results suggest that dynamic (frequency dependent) correlations play an important role in enhancing the Coulomb drag rate.

  3. Strong correlation in Kohn-Sham DFT

    NASA Astrophysics Data System (ADS)

    Malet Giralt, Francesc; Mirtschink, André; Cremon, Jonas; Mendl, Christian; Giesbertz, Klaas; Reimann, Stephanie; Gori-Giorgi, Paola; Mathematical Physics, Lund University Collaboration; Mathematics Department, Technische Universität München Collaboration

    2014-03-01

    The knowledge on the strong-interacting limit of density functional theory can be used to construct exchange- correlation functionals able to address strongly-correlated systems without introducing any symmetry breaking. We report calculations on semiconductor nanostructures and one-dimensional models for chemical systems, showing that this approach yields quantitatively good results in both the weakly- and the strongly-correlated regimes, with a numerical cost much lower than the traditional wavefunction methods. This work has been supported by a VIDI grant of the NWO and a Marie Curie grant within the FP7 programme.

  4. Entanglement swapping for generalized nonlocal correlations

    SciTech Connect

    Short, A. J.; Popescu, S.; Gisin, N.

    2006-01-15

    We consider an analog of entanglement-swapping for a set of black boxes with the most general nonlocal correlations consistent with relativity (including correlations which are stronger than any attainable in quantum theory). In an attempt to incorporate this phenomenon, we consider expanding the space of objects to include not only correlated boxes, but 'couplers', which are an analog for boxes of measurements with entangled eigenstates in quantum theory. Surprisingly, we find that no couplers exist for two binary-input-binary-output boxes, and hence that there is no analog of entanglement swapping for such boxes.

  5. Current Correlations from a Mesoscopic Anyon Collider.

    PubMed

    Rosenow, Bernd; Levkivskyi, Ivan P; Halperin, Bertrand I

    2016-04-15

    Fermions and bosons are fundamental realizations of exchange statistics, which governs the probability for two particles being close to each other spatially. Anyons in the fractional quantum Hall effect are an example for exchange statistics intermediate between bosons and fermions. We analyze a mesoscopic setup in which two dilute beams of anyons collide with each other, and relate the correlations of current fluctuations to the probability of particles excluding each other spatially. While current correlations for fermions vanish, negative correlations for anyons are a clear signature of a reduced spatial exclusion as compared to fermions.

  6. Magnitude and sign correlations in heartbeat fluctuations

    NASA Technical Reports Server (NTRS)

    Ashkenazy, Y.; Ivanov, P. C.; Havlin, S.; Peng, C. K.; Goldberger, A. L.; Stanley, H. E.

    2001-01-01

    We propose an approach for analyzing signals with long-range correlations by decomposing the signal increment series into magnitude and sign series and analyzing their scaling properties. We show that signals with identical long-range correlations can exhibit different time organization for the magnitude and sign. We find that the magnitude series relates to the nonlinear properties of the original time series, while the sign series relates to the linear properties. We apply our approach to the heartbeat interval series and find that the magnitude series is long-range correlated, while the sign series is anticorrelated and that both magnitude and sign series may have clinical applications.

  7. Teleportation-induced correlated quantum channels.

    PubMed

    Caruso, F; Giovannetti, V; Palma, G M

    2010-01-15

    Quantum teleportation of an n-qubit state performed using as an entangled resource a general bipartite state of 2n qubits instead of n Bell states is equivalent to a correlated Pauli channel. This yields a new characterization of such channels in terms of many-body correlation functions of the teleporting media. It provides a relatively simple method for determining whether a correlated quantum channel is able to reliably convey quantum messages by studying the entanglement properties of the teleportation mediating system. Our model is then generalized to the continuous-variable case.

  8. Top Quark Spin Correlations at the Tevatron

    SciTech Connect

    Head, Tim; /Manchester U.

    2010-07-01

    Recent measurements of the correlation between the spin of the top and the spin of the anti-top quark produced in proton anti-proton scattering at a center of mass energy of {radical}s = 1.96 Tev by the CDF and D0 collaborations are discussed. using up to 4.3 fb{sup -1} of data taken with the CDF and D0 detectors the spin correlation parameter C, the degree to which the spins are correlated, is measured in dileptonic and semileptonic final states. The measurements are found to be in agreement with Standard Model predictions.

  9. Correlation of signals of thermal acoustic radiation

    NASA Astrophysics Data System (ADS)

    Anosov, A. A.; Passechnik, V. I.

    2003-03-01

    The spatial correlation function is measured for the pressure of thermal acoustic radiation from a source (a narrow plasticine plate) whose temperature is made both higher and lower than the temperature of the receiver. The spatial correlation function of the pressure of thermal acoustic radiation is found to be oscillatory in character. The oscillation amplitude is determined not by the absolute temperature of the source but by the temperature difference between the source and the receiver. The correlation function changes its sign when a source heated with respect to the receiver is replaced by a cooled one.

  10. Correlations between outcomes of random measurements

    NASA Astrophysics Data System (ADS)

    Tran, Minh Cong; Dakić, Borivoje; Laskowski, Wiesław; Paterek, Tomasz

    2016-10-01

    We recently showed that multipartite correlations between outcomes of random observables detect quantum entanglement in all pure and some mixed states. In this followup article we further develop this approach, derive a maximal amount of such correlations, and show that they are not monotonous under local operations and classical communication. Nevertheless, we demonstrate their usefulness in entanglement detection with a single random observable per party. Finally we study convex-roof extension of the correlations and provide a closed-form necessary and sufficient condition for entanglement in rank-2 mixed states and a witness in general.

  11. Redundant correlation effect on personalized recommendation

    NASA Astrophysics Data System (ADS)

    Qiu, Tian; Han, Teng-Yue; Zhong, Li-Xin; Zhang, Zi-Ke; Chen, Guang

    2014-02-01

    The high-order redundant correlation effect is investigated for a hybrid algorithm of heat conduction and mass diffusion (HHM), through both heat conduction biased (HCB) and mass diffusion biased (MDB) correlation redundancy elimination processes. The HCB and MDB algorithms do not introduce any additional tunable parameters, but keep the simple character of the original HHM. Based on two empirical datasets, the Netflix and MovieLens, the HCB and MDB are found to show better recommendation accuracy for both the overall objects and the cold objects than the HHM algorithm. Our work suggests that properly eliminating the high-order redundant correlations can provide a simple and effective approach to accurate recommendation.

  12. Discovering correlated fermions using quantum Monte Carlo.

    PubMed

    Wagner, Lucas K; Ceperley, David M

    2016-09-01

    It has become increasingly feasible to use quantum Monte Carlo (QMC) methods to study correlated fermion systems for realistic Hamiltonians. We give a summary of these techniques targeted at researchers in the field of correlated electrons, focusing on the fundamentals, capabilities, and current status of this technique. The QMC methods often offer the highest accuracy solutions available for systems in the continuum, and, since they address the many-body problem directly, the simulations can be analyzed to obtain insight into the nature of correlated quantum behavior. PMID:27518859

  13. Long-range correlations in nucleotide sequences

    NASA Astrophysics Data System (ADS)

    Peng, C.-K.; Buldyrev, S. V.; Goldberger, A. L.; Havlin, S.; Sciortino, F.; Simons, M.; Stanley, H. E.

    1992-03-01

    DNA SEQUENCES have been analysed using models, such as an it-step Markov chain, that incorporate the possibility of short-range nucleotide correlations1. We propose here a method for studying the stochastic properties of nucleotide sequences by constructing a 1:1 map of the nucleotide sequence onto a walk, which we term a 'DNA walk'. We then use the mapping to provide a quantitative measure of the correlation between nucleotides over long distances along the DNA chain. Thus we uncover in the nucleotide sequence a remarkably long-range power law correlation that implies a new scale-invariant property of DNA. We find such long-range correlations in intron-containing genes and in nontranscribed regulatory DNA sequences, but not in complementary DNA sequences or intron-less genes.

  14. Long-range correlations in nucleotide sequences

    NASA Technical Reports Server (NTRS)

    Peng, C. K.; Buldyrev, S. V.; Goldberger, A. L.; Havlin, S.; Sciortino, F.; Simons, M.; Stanley, H. E.

    1992-01-01

    DNA sequences have been analysed using models, such as an n-step Markov chain, that incorporate the possibility of short-range nucleotide correlations. We propose here a method for studying the stochastic properties of nucleotide sequences by constructing a 1:1 map of the nucleotide sequence onto a walk, which we term a 'DNA walk'. We then use the mapping to provide a quantitative measure of the correlation between nucleotides over long distances along the DNA chain. Thus we uncover in the nucleotide sequence a remarkably long-range power law correlation that implies a new scale-invariant property of DNA. We find such long-range correlations in intron-containing genes and in nontranscribed regulatory DNA sequences, but not in complementary DNA sequences or intron-less genes.

  15. Serial-data correlator/code translator

    NASA Technical Reports Server (NTRS)

    Morgan, L. E.

    1977-01-01

    System, consisting of sampling flip flop, memory (either RAM or ROM), and memory buffer, correlates sampled data with predetermined acceptance code patterns, translates acceptable code patterns to nonreturn-to-zero code, and identifies data dropouts.

  16. Strongly correlated quantum spin liquid in herbertsmithite

    SciTech Connect

    Shaginyan, V. R.; Popov, K. G.; Khodel, V. A.

    2013-05-15

    Strongly correlated Fermi systems are among the most intriguing and fundamental systems in physics. We show that the herbertsmithite ZnCu{sub 3}(OH){sub 6}Cl{sub 2} can be regarded as a new type of strongly correlated electrical insulator that possesses properties of heavy-fermion metals with one exception: it resists the flow of electric charge. We demonstrate that herbertsmithite's low-temperature properties are defined by a strongly correlated quantum spin liquid made with hypothetic particles such as fermionic spinons that carry spin 1/2 and no charge. Our calculations of its thermodynamic and relaxation properties are in good agreement with recent experimental facts and allow us to reveal their scaling behavior, which strongly resembles that observed in heavy-fermion metals. Analysis of the dynamic magnetic susceptibility of strongly correlated Fermi systems suggests that there exist at least two types of its scaling.

  17. Temporal evolution of financial-market correlations.

    PubMed

    Fenn, Daniel J; Porter, Mason A; Williams, Stacy; McDonald, Mark; Johnson, Neil F; Jones, Nick S

    2011-08-01

    We investigate financial market correlations using random matrix theory and principal component analysis. We use random matrix theory to demonstrate that correlation matrices of asset price changes contain structure that is incompatible with uncorrelated random price changes. We then identify the principal components of these correlation matrices and demonstrate that a small number of components accounts for a large proportion of the variability of the markets that we consider. We characterize the time-evolving relationships between the different assets by investigating the correlations between the asset price time series and principal components. Using this approach, we uncover notable changes that occurred in financial markets and identify the assets that were significantly affected by these changes. We show in particular that there was an increase in the strength of the relationships between several different markets following the 2007-2008 credit and liquidity crisis. PMID:21929066

  18. Quantum correlations require multipartite information principles.

    PubMed

    Gallego, Rodrigo; Würflinger, Lars Erik; Acín, Antonio; Navascués, Miguel

    2011-11-18

    Identifying which correlations among distant observers are possible within our current description of nature, based on quantum mechanics, is a fundamental problem in physics. Recently, information concepts have been proposed as the key ingredient to characterize the set of quantum correlations. Novel information principles, such as information causality or nontrivial communication complexity, have been introduced in this context and successfully applied to some concrete scenarios. We show in this work a fundamental limitation of this approach: no principle based on bipartite information concepts is able to singleout the set of quantum correlations for an arbitrary number of parties. Our results reflect the intricate structure of quantum correlations and imply that new and intrinsically multipartite information concepts are needed for their full understanding.

  19. Some Correlates of the Arab Character.

    ERIC Educational Resources Information Center

    Moracco, John

    1983-01-01

    Describes cultural correlates of the Arab character in terms of family patterns, international relations, and implications for therapists and other human service personnel. Discusses the Bedouin influence and religious values and suggests that cultural stereotypes may restrict true understanding. (JAC)

  20. Exchange fluctuation theorem for correlated quantum systems.

    PubMed

    Jevtic, Sania; Rudolph, Terry; Jennings, David; Hirono, Yuji; Nakayama, Shojun; Murao, Mio

    2015-10-01

    We extend the exchange fluctuation theorem for energy exchange between thermal quantum systems beyond the assumption of molecular chaos, and describe the nonequilibrium exchange dynamics of correlated quantum states. The relation quantifies how the tendency for systems to equilibrate is modified in high-correlation environments. In addition, a more abstract approach leads us to a "correlation fluctuation theorem". Our results elucidate the role of measurement disturbance for such scenarios. We show a simple application by finding a semiclassical maximum work theorem in the presence of correlations. We also present a toy example of qubit-qudit heat exchange, and find that non-classical behaviour such as deterministic energy transfer and anomalous heat flow are reflected in our exchange fluctuation theorem. PMID:26565174

  1. Implant-isolated SAW storage correlator

    NASA Astrophysics Data System (ADS)

    Schwartz, S. S.; Gunshor, R. L.; Pierret, R. F.

    1985-09-01

    The development of surface acoustic wave (SAW) convolvers and correlators is reviewed. This is followed by the introduction of a new type of monolithic metal-zinc oxide-silicon dioxide-silicon storage correlator. Fabrication and operation of the implant isolated storage correlator, which relies on ion implantation for confinement of storage regions, is detailed. A capacitance-time measurement procedure for evaluation of the charge storage capability of the device is described, and correlation output information is used to estimate the effective recombination rate of the inversion layer charges. Finally, operational characteristics are examined and the new bias stable device is shown to exhibit a 3-dB storage time in excess of 0.5 s. The cited storage time exceeds reported storage times of other structures fabricated in the ZnO-SiO2-Si layered medium configuration.

  2. Visualization of a stock market correlation matrix

    NASA Astrophysics Data System (ADS)

    Rea, Alethea; Rea, William

    2014-04-01

    This paper presents a novel application of Neighbor-Net, a clustering algorithm developed for constructing a phylogenetic network in the field of evolutionary biology, to visualizing a correlation matrix. We apply Neighbor-Net as implemented in the SplitsTree software package to 48 stocks listed on the New Zealand Stock Exchange. We show that by visualizing the correlation matrix using a Neighbor-Net splits graph and its associated circular ordering of the stocks that some of the problems associated with understanding the large number of correlations between the individual stocks can be overcome. We compare the visualization of Neighbor-Net with that provided by hierarchical clustering trees and minimum spanning trees. The use of Neighbor-Net networks, or splits graphs, yields greater insight into how closely individual stocks are related to each other in terms of their correlations and suggests new avenues of research into how to construct small diversified stock portfolios.

  3. Velocity correlations in laboratory insect swarms

    NASA Astrophysics Data System (ADS)

    Ni, R.; Ouellette, N. T.

    2015-12-01

    In contrast to animal groups such as bird flocks or migratory herds that display net, directed motion, insect swarms do not possess global order. Without such order, it is difficult to define and characterize the transition to collective behavior in swarms; nevertheless, visual observation of swarms strongly suggests that swarming insects do behave collectively. It has recently been suggested that correlation rather than order is the hallmark of emergent collective behavior. Here, we report measurements of spatial velocity correlation functions in laboratory mating swarms of the non-biting midge Chironomus riparius. Although we find some correlation at short distances, our swarms are in general only weakly correlated, in contrast to what has been observed in field studies. Our results hint at the potentially important role of environmental conditions on collective behavior, and suggest that general indicators of the collective nature of swarming are still needed.

  4. Learning Bayesian Networks from Correlated Data

    NASA Astrophysics Data System (ADS)

    Bae, Harold; Monti, Stefano; Montano, Monty; Steinberg, Martin H.; Perls, Thomas T.; Sebastiani, Paola

    2016-05-01

    Bayesian networks are probabilistic models that represent complex distributions in a modular way and have become very popular in many fields. There are many methods to build Bayesian networks from a random sample of independent and identically distributed observations. However, many observational studies are designed using some form of clustered sampling that introduces correlations between observations within the same cluster and ignoring this correlation typically inflates the rate of false positive associations. We describe a novel parameterization of Bayesian networks that uses random effects to model the correlation within sample units and can be used for structure and parameter learning from correlated data without inflating the Type I error rate. We compare different learning metrics using simulations and illustrate the method in two real examples: an analysis of genetic and non-genetic factors associated with human longevity from a family-based study, and an example of risk factors for complications of sickle cell anemia from a longitudinal study with repeated measures.

  5. Correlation dynamics after short-pulse photoassociation

    SciTech Connect

    Koch, Christiane P.; Kosloff, Ronnie

    2010-06-15

    Two atoms in an ultracold gas are correlated at short interatomic distances due to threshold effects in which the potential energy of their interaction dominates the kinetic energy. The correlations manifest themselves in a distinct nodal structure of the density matrix at short interatomic distances. Pump-probe spectroscopy has recently been suggested [Phys. Rev. Lett. 103, 260401 (2009)] to probe these pair correlations: A suitably chosen, short photoassociation laser pulse depletes the ground-state pair density within the photoassociation window, creating a nonstationary wave packet in the electronic ground state. The dynamics of this nonstationary wave packet is monitored by time-delayed probe and ionization pulses. Here we discuss how the choice of the pulse parameters affects the experimental feasibility of this pump-probe spectroscopy of two-body correlations.

  6. Correlation functions along a massless flow

    SciTech Connect

    Delfino, G.; Mussardo, G.; Simonetti, P.

    1995-06-15

    A nonperturbative method based on the form factor bootstrap approach is proposed for the analysis of correlation functions of two-dimensional massless integrable theories and applied to the massless flow between the tricritical Ising and the critical Ising models.

  7. Synchronous correlation matrices and Connes' embedding conjecture

    NASA Astrophysics Data System (ADS)

    Dykema, Kenneth J.; Paulsen, Vern

    2016-01-01

    In the work of Paulsen et al. [J. Funct. Anal. (in press); preprint arXiv:1407.6918], the concept of synchronous quantum correlation matrices was introduced and these were shown to correspond to traces on certain C*-algebras. In particular, synchronous correlation matrices arose in their study of various versions of quantum chromatic numbers of graphs and other quantum versions of graph theoretic parameters. In this paper, we develop these ideas further, focusing on the relations between synchronous correlation matrices and microstates. We prove that Connes' embedding conjecture is equivalent to the equality of two families of synchronous quantum correlation matrices. We prove that if Connes' embedding conjecture has a positive answer, then the tracial rank and projective rank are equal for every graph. We then apply these results to more general non-local games.

  8. On the measurability of quantum correlation functions

    SciTech Connect

    Lima Bernardo, Bertúlio de Azevedo, Sérgio; Rosas, Alexandre

    2015-05-15

    The concept of correlation function is widely used in classical statistical mechanics to characterize how two or more variables depend on each other. In quantum mechanics, on the other hand, there are observables that cannot be measured at the same time; the so-called incompatible observables. This prospect imposes a limitation on the definition of a quantum analog for the correlation function in terms of a sequence of measurements. Here, based on the notion of sequential weak measurements, we circumvent this limitation by introducing a framework to measure general quantum correlation functions, in principle, independently of the state of the system and the operators involved. To illustrate, we propose an experimental configuration to obtain explicitly the quantum correlation function between two Pauli operators, in which the input state is an arbitrary mixed qubit state encoded on the polarization of photons.

  9. Correlation cross sections along the international border

    SciTech Connect

    Martiniuk, C.D. ); Le Fever, J.A.; Anderson, S.B. )

    1991-06-01

    The Manitoba-North Dakota (Canada-US) stratigraphic correlation project is a joint study between the Petroleum Branch of Manitoba Energy and Mines and the North Dakota Geological Survey. It is an attempt to correlate the differing stratigraphic terminologies established in the two jurisdictions by providing a reference cross section across the international boundary. The study involves the subsurface correlation of logs of the Paleozoic and Mesozoic sequences in the Manitoba and North Dakota portions of the Williston basin. The Paleozoic and Mesozoic sequences are subdivided for presentation into the following stratigraphic intervals: (a) Cambrian-Ordovician-Silurian, (b) Devonian, (c) Mississippian, (d) Jurassic, and (e) Cretaceous. Wireline logs show the actual stratigraphic correlations. A nomenclature chart is also presented from each sequence. In addition, the sections include a generalized description of lithologies, thicknesses, environments of deposition, and petroleum potential for each geographic area.

  10. On the measurability of quantum correlation functions

    NASA Astrophysics Data System (ADS)

    de Lima Bernardo, Bertúlio; Azevedo, Sérgio; Rosas, Alexandre

    2015-05-01

    The concept of correlation function is widely used in classical statistical mechanics to characterize how two or more variables depend on each other. In quantum mechanics, on the other hand, there are observables that cannot be measured at the same time; the so-called incompatible observables. This prospect imposes a limitation on the definition of a quantum analog for the correlation function in terms of a sequence of measurements. Here, based on the notion of sequential weak measurements, we circumvent this limitation by introducing a framework to measure general quantum correlation functions, in principle, independently of the state of the system and the operators involved. To illustrate, we propose an experimental configuration to obtain explicitly the quantum correlation function between two Pauli operators, in which the input state is an arbitrary mixed qubit state encoded on the polarization of photons.

  11. Electron correlation dynamics in atoms and molecules.

    PubMed

    Nest, M; Ludwig, M; Ulusoy, I; Klamroth, T; Saalfrank, P

    2013-04-28

    In this paper, we present quantum dynamical calculations on electron correlation dynamics in atoms and molecules using explicitly time-dependent ab initio configuration interaction theory. The goals are (i) to show that in which cases it is possible to switch off the electronic correlation by ultrashort laser pulses, and (ii) to understand the temporal evolution and the time scale on which it reappears. We characterize the appearance of correlation through electron-electron scattering when starting from an uncorrelated state, and we identify pathways for the preparation of a Hartree-Fock state from the correlated, true ground state. Exemplary results for noble gases, alkaline earth elements, and selected molecules are provided. For Mg we show that the uncorrelated state can be prepared using a shaped ultrashort laser pulse.

  12. Temporal evolution of financial-market correlations

    NASA Astrophysics Data System (ADS)

    Fenn, Daniel J.; Porter, Mason A.; Williams, Stacy; McDonald, Mark; Johnson, Neil F.; Jones, Nick S.

    2011-08-01

    We investigate financial market correlations using random matrix theory and principal component analysis. We use random matrix theory to demonstrate that correlation matrices of asset price changes contain structure that is incompatible with uncorrelated random price changes. We then identify the principal components of these correlation matrices and demonstrate that a small number of components accounts for a large proportion of the variability of the markets that we consider. We characterize the time-evolving relationships between the different assets by investigating the correlations between the asset price time series and principal components. Using this approach, we uncover notable changes that occurred in financial markets and identify the assets that were significantly affected by these changes. We show in particular that there was an increase in the strength of the relationships between several different markets following the 2007-2008 credit and liquidity crisis.

  13. DNA pattern recognition using canonical correlation algorithm.

    PubMed

    Sarkar, B K; Chakraborty, Chiranjib

    2015-10-01

    We performed canonical correlation analysis as an unsupervised statistical tool to describe related views of the same semantic object for identifying patterns. A pattern recognition technique based on canonical correlation analysis (CCA) was proposed for finding required genetic code in the DNA sequence. Two related but different objects were considered: one was a particular pattern, and other was test DNA sequence. CCA found correlations between two observations of the same semantic pattern and test sequence. It is concluded that the relationship possesses maximum value in the position where the pattern exists. As a case study, the potential of CCA was demonstrated on the sequence found from HIV-1 preferred integration sites. The subsequences on the left and right flanking from the integration site were considered as the two views, and statistically significant relationships were established between these two views to elucidate the viral preference as an important factor for the correlation. PMID:26564973

  14. Hardness/intensity correlations among BATSE bursts

    NASA Technical Reports Server (NTRS)

    Paciesas, William S.; Pendleton, Geoffrey N.; Kouveliotou, Chryssa; Fishman, Gerald J.; Meegan, Charles A.; Wilson, Robert B.

    1992-01-01

    Conclusions about the nature of gamma-ray bursts derived from the size-frequency distribution may be altered if a significant correlation exists between burst intensity and spectral shape. Moreover, if gamma-ray bursts have a cosmological origin, such a correlation may be expected to result from the expansion of the universe. We have performed a rudimentary search of the BATSE bursts for hardness/intensity correlations. The range of spectral shapes was determined for each burst by computing the ratio of the intensity in the range 100-300 keV to that in 55-300 keV. We find weak evidence for the existence of a correlation, the strongest effect being present when comparing the maximum hardness ratio for each burst with its maximum rate.

  15. Lattice model of spatial correlations in catalysis

    NASA Astrophysics Data System (ADS)

    Loring, Roger F.

    2016-10-01

    Optically detected single-turnover measurements of biological and inorganic catalysts provide a detailed picture of structural and dynamical influences on catalytic activity. Measurement at the single-molecule level of catalysis of a fluorogenic reaction (or its reverse) yields a stochastic fluorescence trajectory reflecting the statistics of individual reaction and product dissociation events. Analysis of time correlations displayed by this trajectory reveals reaction details inaccessible in a bulk measurement of averaged dynamics. Superresolution optical detection techniques can provide a spatial resolution over which correlations could be observed in space as well as time. A model is constructed here for spatial correlations in catalytic activity produced by an entity transported among multiple active sites. An approximation strategy based on perturbation theory in the coupling between transport and reaction dynamics is applied to calculate the mean dwell time of a reactant on an active site and the correlation between dwell times of reactants at different locations.

  16. Plasma arginine correlations in trauma and sepsis.

    PubMed

    Chiarla, C; Giovannini, I; Siegel, J H

    2006-02-01

    Arginine (ARG) is an amino acid (AA) with unique properties and with a key-role in the metabolic, immune and reparative response to trauma and sepsis. This study has been performed to characterize the correlations between plasma levels of ARG, of other AA and of multiple metabolic variables in trauma and sepsis. Two-hundred and sixty-three plasma amino-acidograms with a large series of additional biochemical and blood variables were obtained consecutively in 9 trauma patients who developed sepsis, undergoing total parenteral nutrition with dextrose, fat and a mixed AA solution containing 10.4% arginine. ARG was low soon after trauma, then it increased with increasing distance from trauma and with the development of sepsis. ARG was also directly related to the AA infusion rate (AAIR) and for any given AAIR, was lower after trauma than after the development of sepsis. ARG was also related directly to the plasma levels of most of the other AA, the best correlation being that with lysine (r(2) = 0.81, p < 0.001). These correlations were often shifted downwards (showing lower ARG for any given level of the other AA) in measurements performed after trauma, compared to those performed after development of sepsis; this effect was more pronounced for the correlations with branched chain AA. Correlations between ARG and non-AA variables were not particularly relevant. The best simultaneous correlates of ARG, among variables involved in plasma ARG availability, were citrulline level, AAIR and urinary 3-methylhistidine excretion (accounting for the effect of endogenous proteolysis) (multiple r(2) = 0.70, p < 0.001). Plasma ornithine (ORN), the AA more specifically linked to ARG metabolism, correlated with AAIR better than ARG and, for any given AAIR, was lower after trauma than after the development of sepsis. Correlations of ORN with other AA levels were poorer than those found for ARG, however ORN was directly related to white blood cell and platelet count, fibrinogen

  17. Design of exchange-correlation functionals through the correlation factor approach

    SciTech Connect

    Pavlíková Přecechtělová, Jana E-mail: Matthias.Ernzerhof@UMontreal.ca

    2015-10-14

    The correlation factor model is developed in which the spherically averaged exchange-correlation hole of Kohn-Sham theory is factorized into an exchange hole model and a correlation factor. The exchange hole model reproduces the exact exchange energy per particle. The correlation factor is constructed in such a manner that the exchange-correlation energy correctly reduces to exact exchange in the high density and rapidly varying limits. Four different correlation factor models are presented which satisfy varying sets of physical constraints. Three models are free from empirical adjustments to experimental data, while one correlation factor model draws on one empirical parameter. The correlation factor models are derived in detail and the resulting exchange-correlation holes are analyzed. Furthermore, the exchange-correlation energies obtained from the correlation factor models are employed to calculate total energies, atomization energies, and barrier heights. It is shown that accurate, non-empirical functionals can be constructed building on exact exchange. Avenues for further improvements are outlined as well.

  18. Rapidity correlation structure in nuclear collisions

    NASA Astrophysics Data System (ADS)

    Gavin, Sean; Moschelli, George; Zin, Christopher

    2016-08-01

    We show that measurements of the rapidity dependence of transverse momentum correlations can be used to determine the characteristic time τπ that dictates the rate of isotropization of the stress energy tensor, as well as the shear viscosity ν =η /s T . We formulate methods for computing these correlations using second-order dissipative hydrodynamics with noise. Current data are consistent with τπ/ν ˜10 , but targeted measurements can improve this precision.

  19. Photonic Bloch oscillations of correlated particles.

    PubMed

    Longhi, Stefano

    2011-08-15

    A photonic realization of Bloch oscillations (BOs) of two correlated electrons that move on a one-dimensional periodic lattice, based on spatial light transport in a square waveguide array with a defect line, is theoretically proposed. The signature of correlated BOs, such as frequency doubling of the oscillation frequency induced by particle interaction, can be simply visualized by monitoring the spatial path followed by an optical beam that excites the array near the defect line.

  20. Magnitude correlations and dynamical scaling for seismicity

    SciTech Connect

    Godano, Cataldo; Lippiello, Eugenio; De Arcangelis, Lucilla

    2007-12-06

    We analyze the experimental seismic catalog of Southern California and we show the existence of correlations between earthquake magnitudes. We propose a dynamical scaling hypothesis relating time and magnitude as the physical mechanism responsible of the observed magnitude correlations. We show that experimental distributions in size and time naturally originate solely from this scaling hypothesis. Furthermore we generate a synthetic catalog reproducing the organization in time and magnitude of experimental data.

  1. AMiBA WIDEBAND ANALOG CORRELATOR

    SciTech Connect

    Li, Chao-Te; Kubo, Derek Y.; Lin, Kai-Yang; Chen, Ming-Tang; Ho, P. T. P.; Chen, Chung-Cheng; Han, Chih-Chiang; Oshiro, Peter; Martin-Cocher, Pierre; Chang, Chia-Hao; Chang, Shu-Hao; Altamirano, Pablo; Jiang, Homin; Wilson, Warwick; Chiueh, Tzi-Dar; Lien, Chun-Hsien; Wang, Huei; Wei, Ray-Ming; Yang, Chia-Hsiang; Peterson, Jeffrey B.

    2010-06-10

    A wideband analog correlator has been constructed for the Yuan-Tseh Lee Array for Microwave Background Anisotropy. Lag correlators using analog multipliers provide large bandwidth and moderate frequency resolution. Broadband intermediate frequency distribution, back-end signal processing, and control are described. Operating conditions for optimum sensitivity and linearity are discussed. From observations, a large effective bandwidth of around 10 GHz has been shown to provide sufficient sensitivity for detecting cosmic microwave background variations.

  2. Thermally correlated states in loop quantum gravity

    NASA Astrophysics Data System (ADS)

    Chirco, Goffredo; Rovelli, Carlo; Ruggiero, Paola

    2015-02-01

    We study a class of loop-quantum-gravity states characterized by (ultra-local) thermal correlations that reproduce some features of the ultraviolet structure of the perturbative quantum field theory vacuum. In particular, they satisfy an analog of the Bisognano-Wichmann theorem. These states are peaked on the intrinsic geometry and admit a semiclassical interpretation. We study how the correlations extend on the spin network beyond the ultra local limit.

  3. Optimizing correlation techniques for improved earthquake location

    USGS Publications Warehouse

    Schaff, D.P.; Bokelmann, G.H.R.; Ellsworth, W.L.; Zanzerkia, E.; Waldhauser, F.; Beroza, G.C.

    2004-01-01

    Earthquake location using relative arrival time measurements can lead to dramatically reduced location errors and a view of fault-zone processes with unprecedented detail. There are two principal reasons why this approach reduces location errors. The first is that the use of differenced arrival times to solve for the vector separation of earthquakes removes from the earthquake location problem much of the error due to unmodeled velocity structure. The second reason, on which we focus in this article, is that waveform cross correlation can substantially reduce measurement error. While cross correlation has long been used to determine relative arrival times with subsample precision, we extend correlation measurements to less similar waveforms, and we introduce a general quantitative means to assess when correlation data provide an improvement over catalog phase picks. We apply the technique to local earthquake data from the Calaveras Fault in northern California. Tests for an example streak of 243 earthquakes demonstrate that relative arrival times with normalized cross correlation coefficients as low as ???70%, interevent separation distances as large as to 2 km, and magnitudes up to 3.5 as recorded on the Northern California Seismic Network are more precise than relative arrival times determined from catalog phase data. Also discussed are improvements made to the correlation technique itself. We find that for large time offsets, our implementation of time-domain cross correlation is often more robust and that it recovers more observations than the cross spectral approach. Longer time windows give better results than shorter ones. Finally, we explain how thresholds and empirical weighting functions may be derived to optimize the location procedure for any given region of interest, taking advantage of the respective strengths of diverse correlation and catalog phase data on different length scales.

  4. Joint transform correlator employing electron trapping materials

    NASA Astrophysics Data System (ADS)

    Yu, Dong X.; Storti, George M.; Gregory, Don A.

    1992-07-01

    Quantex's electron trapping (ET) materials are investigated as an integrated spatial light modulator (SLM) at the filter plane in a joint transform correlator (JTC). The ET based spatial light modulator can detect visible incoherent light, store an image pattern, and modulate the incoming coherent infrared light. Such a JTC architecture eliminates the electronic-to-optical and optical-to-electronic conversion between the square law detector and the next SLM in a joint transform correlator.

  5. Biochemical correlates of neurosensory changes in weightlessness

    NASA Technical Reports Server (NTRS)

    Leach, Carolyn S.; Reschke, Millard F.

    1989-01-01

    The possible existence of a relationship between space motion sickness and chemical and biochemical variables measured in body fluids is studied. Clinical chemistry and endocrine measurements from blood and urine samples taken before and after Space Shuttle flights were analyzed along with the occurrence of SMS during flight and provocative testing before flight. Significant positive correlations were observed with serum chloride and significant negative correlations with serum phosphate, serum uric acid, and plasma thyroid stimulating hormone.

  6. Temperature-polarization correlations from tensor fluctuations

    SciTech Connect

    Crittenden, R.G.; Coulson, D.; Turok, N.G. |

    1995-11-15

    We study the polarization-temperature correlations on the cosmic microwave sky resulting from an initial scale-invariant spectrum of tensor (gravity wave) fluctuations, such as those which might arise during inflation. The correlation function has the opposite sign to that for scalar fluctuations on large scales, raising the possibility of a direct determination of whether the microwave anisotropies have a significant tensor component. We briefly discuss the important problem of estimating the expected foreground contamination.

  7. Dissipation, correlation and lags in heat engines

    NASA Astrophysics Data System (ADS)

    Campisi, Michele; Fazio, Rosario

    2016-08-01

    By modelling heat engines as driven multi-partite system we show that their dissipation can be expressed in terms of the lag (relative entropy) between the perturbed state of each partition and their equilibrium state, and the correlations that build up among the partitions. We show that the non-negativity of the overall dissipation implies Carnot formulation of the second law. We illustrate the rich interplay between correlations and lags with a two-qubit device driven by a quantum gate.

  8. Coulomb correlations and optical gap in polyacetylene

    SciTech Connect

    Baeriswyl, D.; Maki, K.

    1986-01-01

    A model including both electron-phonon coupling (as in the SSH Hamiltonian) and electron-electron interactions (on-site term U, nearest-neighbor term V) is treated within the variational scheme of Gutswiller. It is shown that for weak electron-phonon coupling the primary effect is a bond-order wave induced by electronic correlation, whereas the lattice dimerization is a secondary effect. Correspondingly the optical gap is mainly due to electronic correlation.

  9. Exponential Decay of Correlations Implies Area Law

    NASA Astrophysics Data System (ADS)

    Brandão, Fernando G. S. L.; Horodecki, Michał

    2015-01-01

    We prove that a finite correlation length, i.e., exponential decay of correlations, implies an area law for the entanglement entropy of quantum states defined on a line. The entropy bound is exponential in the correlation length of the state, thus reproducing as a particular case Hastings's proof of an area law for groundstates of 1D gapped Hamiltonians. As a consequence, we show that 1D quantum states with exponential decay of correlations have an efficient classical approximate description as a matrix product state of polynomial bond dimension, thus giving an equivalence between injective matrix product states and states with a finite correlation length. The result can be seen as a rigorous justification, in one dimension, of the intuition that states with exponential decay of correlations, usually associated with non-critical phases of matter, are simple to describe. It also has implications for quantum computing: it shows that unless a pure state quantum computation involves states with long-range correlations, decaying at most algebraically with the distance, it can be efficiently simulated classically. The proof relies on several previous tools from quantum information theory—including entanglement distillation protocols achieving the hashing bound, properties of single-shot smooth entropies, and the quantum substate theorem—and also on some newly developed ones. In particular we derive a new bound on correlations established by local random measurements, and we give a generalization to the max-entropy of a result of Hastings concerning the saturation of mutual information in multiparticle systems. The proof can also be interpreted as providing a limitation on the phenomenon of data hiding in quantum states.

  10. Another look at abundance correlations among comets

    NASA Technical Reports Server (NTRS)

    Cochran, Anita L.

    1987-01-01

    Abundance correlations among comets are examined using three different data sets. The C2 and C3 production rates prove to be well correlated with CN production rates, but large scatter exists. It is concluded that a 'normal' comet is one for which Q(C3)/Q(CN) = 0.19 + or - 0.13 and Q(C2)/Q(CN) = 1.46 + or 0.68.

  11. AMiBA Wideband Analog Correlator

    NASA Astrophysics Data System (ADS)

    Li, Chao-Te; Kubo, Derek Y.; Wilson, Warwick; Lin, Kai-Yang; Chen, Ming-Tang; Ho, P. T. P.; Chen, Chung-Cheng; Han, Chih-Chiang; Oshiro, Peter; Martin-Cocher, Pierre; Chang, Chia-Hao; Chang, Shu-Hao; Altamirano, Pablo; Jiang, Homin; Chiueh, Tzi-Dar; Lien, Chun-Hsien; Wang, Huei; Wei, Ray-Ming; Yang, Chia-Hsiang; Peterson, Jeffrey B.; Chang, Su-Wei; Huang, Yau-De; Hwang, Yuh-Jing; Kesteven, Michael; Koch, Patrick; Liu, Guo-Chin; Nishioka, Hiroaki; Umetsu, Keiichi; Wei, Tashun; Proty Wu, Jiun-Huei

    2010-06-01

    A wideband analog correlator has been constructed for the Yuan-Tseh Lee Array for Microwave Background Anisotropy. Lag correlators using analog multipliers provide large bandwidth and moderate frequency resolution. Broadband intermediate frequency distribution, back-end signal processing, and control are described. Operating conditions for optimum sensitivity and linearity are discussed. From observations, a large effective bandwidth of around 10 GHz has been shown to provide sufficient sensitivity for detecting cosmic microwave background variations.

  12. Correlation of Spacecraft Mission and Project Costs

    NASA Technical Reports Server (NTRS)

    Swan, Christopher; Jarrett, Shawn

    2007-01-01

    A key component of any cost risk analysis is the level of correlation between individual elements of cost. This analysis supplements the available historical records with the cost estimates from the JPL Advanced Design Team. The costs from actual JPL flight projects are then used to validate the results, clearly indicating that, on average, the correlation between elements of cost is between 0.4 and 0.7.

  13. Pentagon-pentagon correlations in water

    SciTech Connect

    Speedy, R.J.; Mezei, M.

    1985-01-03

    Computer simulation studies on the concentration of pentagonal rings of hydrogen-bonded water molecules (pentagons) and the spatial correlation of pentagons in liquid water are detailed. The pentagon-pentagon correlation function g/sub 55/(r) has a peak at r similarly ordered 3.2 A. The results support the idea that the anomalies of water may be related to the self-replicating propensity of pentagons in the random network. 24 references, 8 figures, 1 table.

  14. Percolation of secret correlations in a network

    SciTech Connect

    Leverrier, Anthony; Garcia-Patron, Raul

    2011-09-15

    In this work, we explore the analogy between entanglement and secret classical correlations in the context of large networks--more precisely, the question of percolation of secret correlations in a network. It is known that entanglement percolation in quantum networks can display a highly nontrivial behavior depending on the topology of the network and on the presence of entanglement between the nodes. Here we show that this behavior, thought to be of a genuine quantum nature, also occurs in a classical context.

  15. Correlation reception of thermal acoustic radiation

    NASA Astrophysics Data System (ADS)

    Anosov, A. A.; Barabanenkov, Yu. N.; Sel'Skii, A. G.

    2003-11-01

    Correlated signals of thermal acoustic radiation from heated sources extending in the transverse direction (a pair of narrow plasticine plates and a wide plasticine strip) are measured. The measurements are performed by multiplying together the signals that are shifted in time with respect to each other and detected by two piezoelectric transducers. The values of the correlated signals of thermal acoustic radiation are determined by the spatial variation of temperature in the medium under study.

  16. Periodic-Orbit Theory of Level Correlations

    NASA Astrophysics Data System (ADS)

    Heusler, Stefan; Müller, Sebastian; Altland, Alexander; Braun, Petr; Haake, Fritz

    2007-01-01

    We present a semiclassical explanation of the so-called Bohigas-Giannoni-Schmit conjecture which asserts universality of spectral fluctuations in chaotic dynamics. We work with a generating function whose semiclassical limit is determined by quadruplets of sets of periodic orbits. The asymptotic expansions of both the nonoscillatory and the oscillatory part of the universal spectral correlator are obtained. Borel summation of the series reproduces the exact correlator of random-matrix theory.

  17. Effect of noise correlations on randomized benchmarking

    NASA Astrophysics Data System (ADS)

    Ball, Harrison; Stace, Thomas M.; Flammia, Steven T.; Biercuk, Michael J.

    2016-02-01

    Among the most popular and well-studied quantum characterization, verification, and validation techniques is randomized benchmarking (RB), an important statistical tool used to characterize the performance of physical logic operations useful in quantum information processing. In this work we provide a detailed mathematical treatment of the effect of temporal noise correlations on the outcomes of RB protocols. We provide a fully analytic framework capturing the accumulation of error in RB expressed in terms of a three-dimensional random walk in "Pauli space." Using this framework we derive the probability density function describing RB outcomes (averaged over noise) for both Markovian and correlated errors, which we show is generally described by a Γ distribution with shape and scale parameters depending on the correlation structure. Long temporal correlations impart large nonvanishing variance and skew in the distribution towards high-fidelity outcomes—consistent with existing experimental data—highlighting potential finite-sampling pitfalls and the divergence of the mean RB outcome from worst-case errors in the presence of noise correlations. We use the filter-transfer function formalism to reveal the underlying reason for these differences in terms of effective coherent averaging of correlated errors in certain random sequences. We conclude by commenting on the impact of these calculations on the utility of single-metric approaches to quantum characterization, verification, and validation.

  18. Origin of information-limiting noise correlations

    PubMed Central

    Kanitscheider, Ingmar; Coen-Cagli, Ruben; Pouget, Alexandre

    2015-01-01

    The ability to discriminate between similar sensory stimuli relies on the amount of information encoded in sensory neuronal populations. Such information can be substantially reduced by correlated trial-to-trial variability. Noise correlations have been measured across a wide range of areas in the brain, but their origin is still far from clear. Here we show analytically and with simulations that optimal computation on inputs with limited information creates patterns of noise correlations that account for a broad range of experimental observations while at same time causing information to saturate in large neural populations. With the example of a network of V1 neurons extracting orientation from a noisy image, we illustrate to our knowledge the first generative model of noise correlations that is consistent both with neurophysiology and with behavioral thresholds, without invoking suboptimal encoding or decoding or internal sources of variability such as stochastic network dynamics or cortical state fluctuations. We further show that when information is limited at the input, both suboptimal connectivity and internal fluctuations could similarly reduce the asymptotic information, but they have qualitatively different effects on correlations leading to specific experimental predictions. Our study indicates that noise at the sensory periphery could have a major effect on cortical representations in widely studied discrimination tasks. It also provides an analytical framework to understand the functional relevance of different sources of experimentally measured correlations. PMID:26621747

  19. Correlation resonance generated by coupled enzymatic processing.

    PubMed

    Mather, William H; Cookson, Natalie A; Hasty, Jeff; Tsimring, Lev S; Williams, Ruth J

    2010-11-17

    A major challenge for systems biology is to deduce the molecular interactions that underlie correlations observed between concentrations of different intracellular molecules. Although direct explanations such as coupled transcription or direct protein-protein interactions are often considered, potential indirect sources of coupling have received much less attention. Here we show how correlations can arise generically from a posttranslational coupling mechanism involving the processing of multiple protein species by a common enzyme. By observing a connection between a stochastic model and a multiclass queue, we obtain a closed form expression for the steady-state distribution of the numbers of molecules of each protein species. Upon deriving explicit analytic expressions for moments and correlations associated with this distribution, we discover a striking phenomenon that we call correlation resonance: for small dilution rate, correlations peak near the balance-point where the total rate of influx of proteins into the system is equal to the maximum processing capacity of the enzyme. Given the limited number of many important catalytic molecules, our results may lead to new insights into the origin of correlated behavior on a global scale.

  20. High-Fidelity Coding with Correlated Neurons

    PubMed Central

    da Silveira, Rava Azeredo; Berry, Michael J.

    2014-01-01

    Positive correlations in the activity of neurons are widely observed in the brain. Previous studies have shown these correlations to be detrimental to the fidelity of population codes, or at best marginally favorable compared to independent codes. Here, we show that positive correlations can enhance coding performance by astronomical factors. Specifically, the probability of discrimination error can be suppressed by many orders of magnitude. Likewise, the number of stimuli encoded—the capacity—can be enhanced more than tenfold. These effects do not necessitate unrealistic correlation values, and can occur for populations with a few tens of neurons. We further show that both effects benefit from heterogeneity commonly seen in population activity. Error suppression and capacity enhancement rest upon a pattern of correlation. Tuning of one or several effective parameters can yield a limit of perfect coding: the corresponding pattern of positive correlation leads to a ‘lock-in’ of response probabilities that eliminates variability in the subspace relevant for stimulus discrimination. We discuss the nature of this pattern and we suggest experimental tests to identify it. PMID:25412463