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Sample records for 1h-15n heteronuclear correlation

  1. MUSIC in Triple-Resonance Experiments: Amino Acid Type-Selective 1H- 15N Correlations

    NASA Astrophysics Data System (ADS)

    Schubert, Mario; Smalla, Maika; Schmieder, Peter; Oschkinat, Hartmut

    1999-11-01

    Amino acid type-selective triple-resonance experiments can be of great help for the assignment of protein spectra, since they help to remove ambiguities in either manual or automated assignment procedures. Here, modified triple-resonance experiments that yield amino acid type-selective 1H-15N correlations are presented. They are based on novel coherence transfer schemes, the MUSIC pulse sequence elements, that replace the initial INEPT transfer and are selective for XH2 or XH3 (X can be 15N or 13C). The desired amino acid type is thereby selected based on the topology of the side chain. Experiments for Gly (G-HSQC); Ala (A-HSQC); Thr, Val, Ile, and Ala (TAVI-HSQC); Thr and Ala (TA-HSQC), as well as Asn and Gln (N-HSQC and QN-HSQC), are described. The new experiments are recorded as two-dimensional experiments and therefore need only small amounts of spectrometer time. The performance of the experiments is demonstrated with the application to two protein domains.

  2. MUSIC in triple-resonance experiments: amino acid type-selective (1)H-(15)N correlations

    PubMed

    Schubert; Smalla; Schmieder; Oschkinat

    1999-11-01

    Amino acid type-selective triple-resonance experiments can be of great help for the assignment of protein spectra, since they help to remove ambiguities in either manual or automated assignment procedures. Here, modified triple-resonance experiments that yield amino acid type-selective (1)H-(15)N correlations are presented. They are based on novel coherence transfer schemes, the MUSIC pulse sequence elements, that replace the initial INEPT transfer and are selective for XH(2) or XH(3) (X can be (15)N or (13)C). The desired amino acid type is thereby selected based on the topology of the side chain. Experiments for Gly (G-HSQC); Ala (A-HSQC); Thr, Val, Ile, and Ala (TAVI-HSQC); Thr and Ala (TA-HSQC), as well as Asn and Gln (N-HSQC and QN-HSQC), are described. The new experiments are recorded as two-dimensional experiments and therefore need only small amounts of spectrometer time. The performance of the experiments is demonstrated with the application to two protein domains. Copyright 1999 Academic Press. PMID:10527741

  3. 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

  4. Mechanism of the bisphosphatase reaction of 6-phosphofructo-2-kinase/fructose-2,6-bisphosphatase probed by (1)H-(15)N NMR spectroscopy.

    PubMed

    Okar, D A; Live, D H; Devany, M H; Lange, A J

    2000-08-15

    The histidines in the bisphosphatase domain of rat liver 6-phosphofructo-2-kinase/fructose-2,6-bisphosphatase were labeled with (15)N, both specifically at N1' and globally, for use in heteronuclear single quantum correlation (HSQC) NMR spectroscopic analyses. The histidine-associated (15)N resonances were assigned by correlation to the C2' protons which had been assigned previously [Okar et al., Biochemistry 38, 1999, 4471-79]. Acquisition of the (1)H-(15)N HSQC from a phosphate-free sample demonstrated that the existence of His-258 in the rare N1' tautomeric state is dependent upon occupation of the phosphate binding site filled by the O2 phosphate of the substrate, fructose-2,6-bisphosphate, and subsequently, the phosphohistidine intermediate. The phosphohistidine intermediate is characterized by two hydrogen bonds involving the catalytic histidines, His-258 and His-392, which are directly observed at the N1' positions of the imidazole rings. The N1' of phospho-His-258 is protonated ((1)H chemical shift, 14.0 ppm) and hydrogen bonded to the backbone carbonyl of Gly-259. The N1' of cationic His-392 is hydrogen bonded ((1)H chemical shift, 13.5 ppm) to the phosphoryl moiety of the phosphohistidine. The existence of a protonated phospho-His-258 intermediate and the observation of a fairly strong hydrogen bond to the same phosphohistidine implies that hydrolysis of the covalent intermediate proceeds without any requirement for an "activated" water. Using the labeled histidines as probes of the catalytic site mutation of Glu-327 to alanine revealed that, in addition to its function as the proton donor to fructose-6-phosphate during formation of the transient phosphohistidine intermediate at the N3' of His-258, this residue has a significant role in maintaining the structural integrity of the catalytic site. The (1)H-(15)N HSQC data also provide clear evidence that despite being a surface residue, His-446 has a very acidic pK(a), much less than 6.0. On the basis of

  5. UV-visible and (1)H-(15)N NMR spectroscopic studies of colorimetric thiosemicarbazide anion sensors.

    PubMed

    Farrugia, Kristina N; Makuc, Damjan; Podborska, Agnieszka; Szaciłowski, Konrad; Plavec, Janez; Magri, David C

    2015-02-14

    Four model thiosemicarbazide anion chemosensors containing three N-H bonds, substituted with phenyl and/or 4-nitrophenyl units, were synthesised and studied for their anion binding abilities with hydroxide, fluoride, acetate, dihydrogen phosphate and chloride. The anion binding properties were studied in DMSO and 9 : 1 DMSO-H2O by UV-visible absorption and (1)H/(13)C/(15)N NMR spectroscopic techniques and corroborated with DFT studies. Significant changes were observed in the UV-visible absorption spectra with all anions, except for chloride, accompanied by dramatic colour changes visible to the naked eye. These changes were determined to be due to the deprotonation of the central N-H proton and not due to hydrogen bonding based on (1)H/(15)N NMR titration studies with acetate in DMSO-d6-0.5% water. Direct evidence for deprotonation was confirmed by the disappearance of the central thiourea proton and the formation of acetic acid. DFT and charge distribution calculations suggest that for all four compounds the central N-H proton is the most acidic. Hence, the anion chemosensors operate by a deprotonation mechanism of the central N-H proton rather than by hydrogen bonding as is often reported. PMID:25451865

  6. 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.

  7. A closer look at the nitrogen next door: 1H-15N NMR methods for glycosaminoglycan structural characterization

    NASA Astrophysics Data System (ADS)

    Langeslay, Derek J.; Beni, Szabolcs; Larive, Cynthia K.

    2012-03-01

    Recently, experimental conditions were presented for the detection of the N-sulfoglucosamine (GlcNS) NHSO3- or sulfamate 1H and 15N NMR resonances of the pharmaceutically and biologically important glycosaminoglycan (GAG) heparin in aqueous solution. In the present work, we explore further the applicability of nitrogen-bound proton detection to provide structural information for GAGs. Compared to the detection of 15N chemical shifts of aminosugars through long-range couplings using the IMPACT-HNMBC pulse sequence, the more sensitive two-dimensional 1H-15N HSQC-TOCSY experiments provided additional structural data. The IMPACT-HNMBC experiment remains a powerful tool as demonstrated by the spectrum measured for the unsubstituted amine of 3-O-sulfoglucosamine (GlcN(3S)), which cannot be observed with the 1H-15N HSQC-TOCSY experiment due to the fast exchange of the amino group protons with solvent. The 1H-15N HSQC-TOCSY NMR spectrum reported for the mixture of model compounds GlcNS and N-acetylglucosamine (GlcNAc) demonstrate the broad utility of this approach. Measurements for the synthetic pentasaccharide drug Arixtra® (Fondaparinux sodium) in aqueous solution illustrate the power of this NMR pulse sequence for structural characterization of highly similar N-sulfoglucosamine residues in GAG-derived oligosaccharides.

  8. 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

  9. 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.…

  10. Absolute hydrogen depth profiling using the resonant 1H(15N, αγ)12C nuclear reaction

    NASA Astrophysics Data System (ADS)

    Reinhardt, Tobias P.; Akhmadaliev, Shavkat; Bemmerer, Daniel; Stöckel, Klaus; Wagner, Louis

    2016-08-01

    Resonant nuclear reactions are a powerful tool for the determination of the amount and profile of hydrogen in thin layers of material. Usually, this tool requires the use of a standard of well-known composition. The present work, by contrast, deals with standard-less hydrogen depth profiling. This approach requires precise nuclear data, e.g. on the widely used 1 H(15 N, αγ)12 C reaction, resonant at 6.4 MeV 15 N beam energy. Here, the strongly anisotropic angular distribution of the emitted γ -rays from this resonance has been re-measured, resolving a previous discrepancy. Coefficients of (0.38 ± 0.04) and (0.80 ± 0.04) have been deduced for the second and fourth order Legendre polynomials, respectively. In addition, the resonance strength has been re-evaluated to (25.0 ± 1.5) eV, 10% higher than previously reported. A simple working formula for the hydrogen concentration is given for cases with known γ -ray detection efficiency. Finally, the absolute approach is illustrated using two examples.

  11. 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.

  12. 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

  13. 2D 1H and 3D 1H-15N NMR of zinc-rubredoxins: contributions of the beta-sheet to thermostability.

    PubMed Central

    Richie, K. A.; Teng, Q.; Elkin, C. J.; Kurtz, D. M.

    1996-01-01

    Based on 2D 1H-1H and 2D and 3D 1H-15N NMR spectroscopies, complete 1H NMR assignments are reported for zinc-containing Clostridium pasteurianum rubredoxin (Cp ZnRd). Complete 1H NMR assignments are also reported for a mutated Cp ZnRd, in which residues near the N-terminus, namely, Met 1, Lys 2, and Pro 15, have been changed to their counterparts, (-), Ala and Glu, respectively, in rubredoxin from the hyperthermophilic archaeon, Pyrococcus furiosus (Pf Rd). The secondary structure of both wild-type and mutated Cp ZnRds, as determined by NMR methods, is essentially the same. However, the NMR data indicate an extension of the three-stranded beta-sheet in the mutated Cp ZnRd to include the N-terminal Ala residue and Glu 15, as occurs in Pf Rd. The mutated Cp Rd also shows more intense NOE cross peaks, indicating stronger interactions between the strands of the beta-sheet and, in fact, throughout the mutated Rd. However, these stronger interactions do not lead to any significant increase in thermostability, and both the mutated and wild-type Cp Rds are much less thermostable than Pf Rd. These correlations strongly suggest that, contrary to a previous proposal [Blake PR et al., 1992, Protein Sci 1:1508-1521], the thermostabilization mechanism of Pf Rd is not dominated by a unique set of hydrogen bonds or electrostatic interactions involving the N-terminal strand of the beta-sheet. The NMR results also suggest that an overall tighter protein structure does not necessarily lead to increased thermostability. PMID:8732760

  14. 1H, 15N and 13C assignment of the amyloidogenic protein medin using fast-pulsing NMR techniques.

    PubMed

    Davies, H A; Phelan, M M; Madine, J

    2016-04-01

    Thirty-one proteins are known to form extracellular fibrillar amyloid in humans. Molecular information about many of these proteins in their monomeric, intermediate or fibrillar form and how they aggregate and interact to form the insoluble fibrils is sparse. This is because amyloid proteins are notoriously difficult to study in their soluble forms, due to their inherent propensity to aggregate. Using recent developments in fast NMR techniques, band-selective excitation short transient and band-selective optimized flip-angle short-transient heteronuclear multiple quantum coherence we have been able to assign a 5 kDa full-length amyloidogenic protein called medin. Medin is the key protein component of the most common form of localised amyloid with a proposed role in aortic aneurysm and dissection. This assignment will now enable the study of the early interactions that could influence initiation and progression of medin aggregation. The chemical shifts have been deposited in the BioMagRes-Bank accession Nos. 25399 and 26576. PMID:26377205

  15. Sequence-specific 1H, 15N and 13C resonance assignments of the 23.7-kDa homodimeric toxin CcdB from Vibrio fischeri.

    PubMed

    Respondek, Michal; Buts, Lieven; De Jonge, Natalie; Haesaerts, Sarah; Loris, Remy; Van Melderen, Laurence; Wyns, Lode; Zangger, Klaus

    2009-06-01

    CcdB is the toxic component of a bacterial toxin-antitoxin system. It inhibits DNA gyrase (a type II topoisomerase), and its toxicity can be neutralized by binding of its antitoxin CcdA. Here we report the sequential backbone and sidechain (1)H, (15)N and (13)C resonance assignments of CcdB(Vfi) from the marine bacterium Vibrio fischeri. The BMRB accession number is 16135. PMID:19636967

  16. Application of unsymmetrical indirect covariance NMR methods to the computation of the (13)C <--> (15)N HSQC-IMPEACH and (13)C <--> (15)N HMBC-IMPEACH correlation spectra.

    PubMed

    Martin, Gary E; Hilton, Bruce D; Irish, Patrick A; Blinov, Kirill A; Williams, Antony J

    2007-10-01

    Utilization of long-range (1)H--(15)N heteronuclear chemical shift correlation has continually grown in importance since the first applications were reported in 1995. More recently, indirect covariance NMR methods have been introduced followed by the development of unsymmetrical indirect covariance processing methods. The latter technique has been shown to allow the calculation of hyphenated 2D NMR data matrices from more readily acquired nonhyphenated 2D NMR spectra. We recently reported the use of unsymmetrical indirect covariance processing to combine (1)H--(13)C GHSQC and (1)H--(15)N GHMBC long-range spectra to yield a (13)C--(15)N HSQC-HMBC chemical shift correlation spectrum that could not be acquired in a reasonable period of time without resorting to (15)N-labeled molecules. We now report the unsymmetrical indirect covariance processing of (1)H--(13)C GHMBC and (1)H--(15)N IMPEACH spectra to afford a (13)C--(15)N HMBC-IMPEACH spectrum that has the potential to span as many as six to eight bonds. Correlations for carbon resonances long-range coupled to a protonated carbon in the (1)H--(13)C HMBC spectrum are transferred via the long-range (1)H--(15)N coupling pathway in the (1)H--(15)N IMPEACH spectrum to afford a much broader range of correlation possibilities in the (13)C--(15)N HMBC-IMPEACH correlation spectrum. The indole alkaloid vincamine is used as a model compound to illustrate the application of the method. PMID:17729230

  17. Generation of heteronuclear 13C 1H chemical-shift correlations using soft pulses

    NASA Astrophysics Data System (ADS)

    Doddrell, David M.; Brooks, William; Field, James; Lynden-Bell, R. M.

    Two multipulse sequences are analyzed which can be used to generate heteronuclear 13C, 1H chemical-shift correlations without 2D NMR techniques. Both sequences utilize polarization-transfer techniques and generate the required chemical-shift correlation using a single soft proton pulse. The most useful technique is an extension of the DEPT method of polarization transfer since not only are the chemical-shift correlations generated in an easy to interpret form, but depending on the specific form of the pulse train used, the method can be employed to obtain information on the CH n group multiplicity. The methods are illustrated by applying them to generate 13C, 1H chemical-shift correlation spectra for menthol and cholesterol.

  18. Sequential acquisition of multi-dimensional heteronuclear chemical shift correlation spectra with 1H detection

    PubMed Central

    Bellstedt, Peter; Ihle, Yvonne; Wiedemann, Christoph; Kirschstein, Anika; Herbst, Christian; Görlach, Matthias; Ramachandran, Ramadurai

    2014-01-01

    RF pulse schemes for the simultaneous acquisition of heteronuclear multi-dimensional chemical shift correlation spectra, such as {HA(CA)NH & HA(CACO)NH}, {HA(CA)NH & H(N)CAHA} and {H(N)CAHA & H(CC)NH}, that are commonly employed in the study of moderately-sized protein molecules, have been implemented using dual sequential 1H acquisitions in the direct dimension. Such an approach is not only beneficial in terms of the reduction of experimental time as compared to data collection via two separate experiments but also facilitates the unambiguous sequential linking of the backbone amino acid residues. The potential of sequential 1H data acquisition procedure in the study of RNA is also demonstrated here. PMID:24671105

  19. Spectroscopic labeling of A, S/T in the 1H- 15N HSQC spectrum of uniformly ( 15N- 13C) labeled proteins

    NASA Astrophysics Data System (ADS)

    Chugh, Jeetender; Hosur, Ramakrishna V.

    2008-10-01

    A new triple resonance two-dimensional experiment, termed (HC)NH, has been described to generate specific labels on the peaks of alanines and serines/threonines, separately, in the 1H- 15N HSQC spectrum of a protein. The performance of the pulse sequence has been demonstrated with a 151 residue protein. The method permits the investigation of local environments around those specific residues without actually having to obtain complete resonance assignments for the entire protein. With this one can envisage use of the technique for studying large protein systems from different points of view.

  20. Extending long-range heteronuclear NMR connectivities by HSQMBC-COSY and HSQMBC-TOCSY experiments

    NASA Astrophysics Data System (ADS)

    Saurí, Josep; Marcó, Núria; Williamson, R. Thomas; Martin, Gary E.; Parella, Teodor

    2015-09-01

    The detection of long-range heteronuclear correlations presenting J(CH) coupling values smaller than 1-2 Hz is a challenge in the structural analysis of small molecules and natural products. HSQMBC-COSY and HSQMBC-TOCSY pulse schemes are evaluated as complementary NMR methods to standard HMBC/HSQMBC experiments. Incorporation of an additional J(HH) transfer step in the basic HSQMBC pulse scheme can favor the sensitive observation of traditionally missing or very weak correlations and, in addition, facilitates the detection of a significant number of still longer-range connectivities to both protonated and non-protonated carbons under optimum sensitivity conditions. A comparative 1H-13C study is performed using strychnine as a model compound and several examples are also provided including 1H-15N applications.

  1. Site-specific analysis of heteronuclear Overhauser effects in microcrystalline proteins.

    PubMed

    del Amo, Juan Miguel Lopez; Agarwal, Vipin; Sarkar, Riddhiman; Porter, Justin; Asami, Sam; Rübbelke, Martin; Fink, Uwe; Xue, Yi; Lange, Oliver F; Reif, Bernd

    2014-08-01

    Relaxation parameters such as longitudinal relaxation are susceptible to artifacts such as spin diffusion, and can be affected by paramagnetic impurities as e.g. oxygen, which make a quantitative interpretation difficult. We present here the site-specific measurement of [(1)H](13)C and [(1)H](15)N heteronuclear rates in an immobilized protein. For methyls, a strong effect is expected due to the three-fold rotation of the methyl group. Quantification of the [(1)H](13)C heteronuclear NOE in combination with (13)C-R 1 can yield a more accurate analysis of side chain motional parameters. The observation of significant [(1)H](15)N heteronuclear NOEs for certain backbone amides, as well as for specific asparagine/glutamine sidechain amides is consistent with MD simulations. The measurement of site-specific heteronuclear NOEs is enabled by the use of highly deuterated microcrystalline protein samples in which spin diffusion is reduced in comparison to protonated samples. PMID:24989039

  2. Complete 1H, 15N and 13C assignment of trappin-2 and 1H assignment of its two domains, elafin and cementoin.

    PubMed

    Loth, Karine; Alami, Soha Abou Ibrahim; Habès, Chahrazed; Garrido, Solène; Aucagne, Vincent; Delmas, Agnès F; Moreau, Thierry; Zani, Marie-Louise; Landon, Céline

    2016-04-01

    Trappin-2 is a serine protease inhibitor with a very narrow inhibitory spectrum and has significant anti-microbial activities. It is a 10 kDa cationic protein composed of two distinct domains. The N-terminal domain (38 residues) named cementoin is known to be intrinsically disordered when it is not linked to the elafin. The C-terminal domain (57 residues), corresponding to elafin, is a cysteine-rich domain stabilized by four disulfide bridges and is characterized by a flat core and a flexible N-terminal part. To our knowledge, there is no structural data available on trappin-2. We report here the complete (1)H, (15)N and (13)C resonance assignment of the recombinant trappin-2 and the (1)H assignments of cementoin and elafin, under the same experimental conditions. This is the first step towards the 3D structure determination of the trappin-2. PMID:26878852

  3. Solution 1H, 15N NMR spectroscopic characterization of substrate-bound, cyanide-inhibited human heme oxygenase: water occupation of the distal cavity.

    PubMed

    Li, Yiming; Syvitski, Ray T; Auclair, Karine; Ortiz de Montellano, Paul; La Mar, Gerd N

    2003-11-01

    A solution NMR spectroscopic study of the cyanide-inhibited, substrate-bound complex of uniformly (15)N-labeled human heme oxygenase, hHO, has led to characterization of the active site with respect to the nature and identity of strong hydrogen bonds and the occupation of ordered water molecules within both the hydrogen bonding network and an aromatic cluster on the distal side. [(1)H-(15)N]-HSQC spectra confirm the functionalities of several key donors in particularly robust H-bonds, and [(1)H-(15)N]HSQC-NOESY spectra lead to the identification of three additional robust H-bonds, as well as the detection of two more relatively strong H-bonds whose identities could not be established. The 3D NMR experiments provided only a modest, but important, extension of assignments because of the loss of key TOCSY cross-peaks due to the line broadening from a dynamic heterogeneity in the active site. Steady-state NOEs upon saturating the water signal locate nine ordered water molecules in the immediate vicinity of the H-bond donors, six of which are readily identified in the crystal structure. The additional three are positioned in available spaces to account for the observed NOEs. (15)N-filtered steady-state NOEs upon saturating the water resonances and (15)N-filtered NOESY spectra demonstrate significant negative NOEs between water molecules and the protons of five aromatic rings. Many of the NOEs can be rationalized by water molecules located in the crystal structure, but strong water NOEs, particularly to the rings of Phe47 and Trp96, demand the presence of at least an additional two immobilized water molecules near these rings. The H-bond network appears to function to order water molecules to provide stabilization for the hydroperoxy intermediate and to serve as a conduit to the active site for the nine protons required per HO turnover. PMID:14583035

  4. 1H/15N HSQC NMR studies of ligand carboxylate group interactions with arginine residues in complexes of brodimoprim analogues and Lactobacillus casei dihydrofolate reductase.

    PubMed

    Morgan, W D; Birdsall, B; Nieto, P M; Gargaro, A R; Feeney, J

    1999-02-16

    1H and 15N NMR studies have been undertaken on complexes of Lactobacillus casei dihydrofolate reductase (DHFR) formed with analogues of the antibacterial drug brodimoprim (2,4-diamino-5-(3', 5'-dimethoxy-4'-bromobenzyl)pyrimidine) in order to monitor interactions between carboxylate groups on the ligands and basic residues in the protein. These analogues had been designed by computer modeling with carboxylated alkyl chains introduced at the 3'-O position in order to improve their binding properties by making additional interactions with basic groups in the protein. Specific interactions between ligand carboxylate groups and the conserved Arg57 residue have been detected in studies of 1H/15N HSQC spectra of complexes of DHFR with both the 4-carboxylate and the 4, 6-dicarboxylate brodimoprim analogues. The spectra from both complexes showed four resolved signals for the four NHeta protons of the guanidino group of Arg57, and this is consistent with hindered rotation in the guanidino group resulting from interactions with the 4-carboxylate group in each analogue. In the spectra of each complex, one of the protons from each of the two NH2 groups and both nitrogens are considerably deshielded compared to the shielding values normally observed for such nuclei. This pattern of deshielding is that expected for a symmetrical end-on interaction of the carboxylate oxygens with the NHeta12 and NHeta22 guanidino protons. The differences in the degree of deshielding between the complexes of the two structurally similar brodimoprim analogues and the methotrexate indicates that the shielding is very sensitive to geometry, most probably to hydrogen bond lengths. The 1H/15N HSQC spectrum of the DHFR complex with the brodimoprim-6-carboxylate analogue does not feature any deshielded Arg NHeta protons and this argues against a similar interaction with the Arg57 in this case. It has not proved possible to determine whether the 6-carboxylate in this analogue is interacting directly with

  5. 1H, 15N and 13C resonance assignments of light organ-associated fatty acid-binding protein of Taiwanese fireflies.

    PubMed

    Tseng, Kai-Li; Lee, Yi-Zong; Chen, Yun-Ru; Lyu, Ping-Chiang

    2016-04-01

    Fatty acid-binding proteins (FABPs) are a family of proteins that modulate the transfer of various fatty acids in the cytosol and constitute a significant portion in many energy-consuming cells. The ligand binding properties and specific functions of a particular type of FABP seem to be diverse and depend on the respective binding cavity as well as the cell type from which this protein is derived. Previously, a novel FABP (lcFABP; lc: Luciola cerata) was identified in the light organ of Taiwanese fireflies. The lcFABP was proved to possess fatty acids binding capabilities, especially for fatty acids of length C14-C18. However, the structural details are unknown, and the structure-function relationship has remained to be further investigated. In this study, we finished the (1)H, (15)N and (13)C chemical shift assignments of (15)N/(13)C-enriched lcFABP by solution NMR spectroscopy. In addition, the secondary structure distribution was revealed based on the backbone N, H, Cα, Hα, C and side chain Cβ assignments. These results can provide the basis for further structural exploration of lcFABP. PMID:26373428

  6. Sequence-specific (1)H, (15)N, and (13)C resonance assignments of the autophagy-related protein LC3C.

    PubMed

    Krichel, Carsten; Weiergräber, Oliver H; Pavlidou, Marina; Mohrlüder, Jeannine; Schwarten, Melanie; Willbold, Dieter; Neudecker, Philipp

    2016-04-01

    Autophagy is a versatile catabolic pathway for lysosomal degradation of cytoplasmic material. While the phenomenological and molecular characteristics of autophagic non-selective (bulk) decomposition have been investigated for decades, the focus of interest is increasingly shifting towards the selective mechanisms of autophagy. Both, selective as well as bulk autophagy critically depend on ubiquitin-like modifiers belonging to the Atg8 (autophagy-related 8) protein family. During evolution, Atg8 has diversified into eight different human genes. While all human homologues participate in the formation of autophagosomal membrane compartments, microtubule-associated protein light chain 3C (LC3C) additionally plays a unique role in selective autophagic clearance of intracellular pathogens (xenophagy), which relies on specific protein-protein recognition events mediated by conserved motifs. The sequence-specific (1)H, (15)N, and (13)C resonance assignments presented here form the stepping stone to investigate the high-resolution structure and dynamics of LC3C and to delineate LC3C's complex network of molecular interactions with the autophagic machinery by NMR spectroscopy. PMID:26280529

  7. Heteronuclear proton assisted recoupling

    NASA Astrophysics Data System (ADS)

    De Paëpe, Gaël; Lewandowski, Józef R.; Loquet, Antoine; Eddy, Matt; Megy, Simon; Böckmann, Anja; Griffin, Robert G.

    2011-03-01

    We describe a theoretical framework for understanding the heteronuclear version of the third spin assisted recoupling polarization transfer mechanism and demonstrate its potential for detecting long-distance intramolecular and intermolecular 15N-13C contacts in biomolecular systems. The pulse sequence, proton assisted insensitive nuclei cross polarization (PAIN-CP) relies on a cross term between 1H-15N and 1H-13C dipolar couplings to mediate zero- and/or double-quantum 15N-13C recoupling. In particular, using average Hamiltonian theory we derive effective Hamiltonians for PAIN-CP and show that the transfer is mediated by trilinear terms of the form N±C∓Hz (ZQ) or N±C±Hz (DQ) depending on the rf field strengths employed. We use analytical and numerical simulations to explain the structure of the PAIN-CP optimization maps and to delineate the appropriate matching conditions. We also detail the dependence of the PAIN-CP polarization transfer with respect to local molecular geometry and explain the observed reduction in dipolar truncation. In addition, we demonstrate the utility of PAIN-CP in structural studies with 15N-13C spectra of two uniformly 13C,15N labeled model microcrystalline proteins—GB1, a 56 amino acid peptide, and Crh, a 85 amino acid domain swapped dimer (MW = 2 × 10.4 kDa). The spectra acquired at high magic angle spinning frequencies (ωr/2π > 20 kHz) and magnetic fields (ω0H/2π = 700-900 MHz) using moderate rf fields, yield multiple long-distance intramonomer and intermonomer 15N-13C contacts. We use these distance restraints, in combination with the available x-ray structure as a homology model, to perform a calculation of the monomer subunit of the Crh protein.

  8. 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

  9. Heteronuclear correlations by multiple-quantum evolution. II. Proton-proton "decoupling" and multiplicity labeling in a constant-time experiment using carbon detection

    NASA Astrophysics Data System (ADS)

    Batta, Gyula; Kövér, Katalin E.

    Modified Müller-Bolton type heteronuclear multiple-quantum correlation experiments are analyzed theoretically and experimentally. It is shown that the constant-time version offers homonuclear decoupling, multiplicity labeling, and a very efficient suppression of strong coupling artifacts. Such sequences may have advantages for studying macromolecules.

  10. 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.

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

    PubMed

    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 (13)C 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 (1)JHC 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. PMID:26298081

  12. 15N-labeled tRNA. Identification of 4-thiouridine in Escherichia coli tRNASer1 and tRNATyr2 by 1H-15N two-dimensional NMR spectroscopy.

    PubMed

    Griffey, R H; Davis, D R; Yamaizumi, Z; Nishimura, S; Hawkins, B L; Poulter, C D

    1986-09-15

    Uridine is uniquely conserved at position 8 in elongator tRNAs and binds to A14 to form a reversed Hoogsteen base pair which folds the dihydrouridine loop back into the core of the L-shaped molecule. On the basis of 1H NMR studies, Hurd and co-workers (Hurd, R. E., Robillard, G. T., and Reid, B. R. (1977) Biochemistry 16, 2095-2100) concluded that the interaction between positions 8 and 14 is absent in Escherichia coli tRNAs with only 3 base pairs in the dihydrouridine stem. We have taken advantage of the unique 15N chemical shift of N3 in thiouridine to identify 1H and 15N resonances for the imino units of S4U8 and s4U9 in E. coli tRNASer1 and tRNATyr2. Model studies with chloroform-soluble derivatives of uridine and 4-thiouridine show that the chemical shifts of the protons in the imino moieties move downfield from 7.9 to 14.4 ppm and from 9.1 to 15.7 ppm, respectively; whereas, the corresponding 15N chemical shifts move downfield from 157.5 to 162.5 ppm and from 175.5 to 180.1 ppm upon hydrogen bonding to 5'-O-acetyl-2',3'-isopropylidene adenosine. The large difference in 15N chemical shifts for U and s4U allows one to unambiguously identify s4U imino resonances by 15N NMR spectroscopy. E. coli tRNASer1 and tRNATyr2 were selectively enriched with 15N at N3 of all uridines and modified uridines. Two-dimensional 1H-15N chemical shift correlation NMR spectroscopy revealed that both tRNAs have resonances with 1H and 15N chemical shifts characteristic of s4UA pairs. The 1H shift is approximately 1 ppm upfield from the typical s4U8 resonance at 14.8 ppm, presumably as a result of local diamagnetic anisotropies. An additional s4U resonance with 1H and 15N shifts typical of interaction of a bound water or a sugar hydroxyl group with s4U9 was discovered in the spectrum of tRNATyr2. Our NMR results for tRNAs with 3-base pair dihydrouridine stems suggest that these molecules have an U8A14 tertiary interaction similar to that found in tRNAs with 4-base pair dihydrouridine

  13. 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.

  14. Heteronuclear 19F-1H statistical total correlation spectroscopy as a tool in drug metabolism: study of flucloxacillin biotransformation.

    PubMed

    Keun, Hector C; Athersuch, Toby J; Beckonert, Olaf; Wang, Yulan; Saric, Jasmina; Shockcor, John P; Lindon, John C; Wilson, Ian D; Holmes, Elaine; Nicholson, Jeremy K

    2008-02-15

    We present a novel application of the heteronuclear statistical total correlation spectroscopy (HET-STOCSY) approach utilizing statistical correlation between one-dimensional 19F/1H NMR spectroscopic data sets collected in parallel to study drug metabolism. Parallel one-dimensional (1D) 800 MHz 1H and 753 MHz 19F{1H} spectra (n = 21) were obtained on urine samples collected from volunteers (n = 6) at various intervals up to 24 h after oral dosing with 500 mg of flucloxacillin. A variety of statistical relationships between and within the spectroscopic datasets were explored without significant loss of the typically high 1D spectral resolution, generating 1H-1H STOCSY plots, and novel 19F-1H HET-STOCSY, 19F-19F STOCSY, and 19F-edited 1H-1H STOCSY (X-STOCSY) spectroscopic maps, with a resolution of approximately 0.8 Hz/pt for both nuclei. The efficient statistical editing provided by these methods readily allowed the collection of drug metabolic data and assisted structure elucidation. This approach is of general applicability for studying the metabolism of other fluorine-containing drugs, including important anticancer agents such as 5-fluorouracil and flutamide, and is extendable to any drug metabolism study where there is a spin-active X-nucleus (e.g., 13C, 15N, 31P) label present. PMID:18211034

  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 PAGESBeta

    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. Synthesis of 7-15N-Oroidin and Evaluation of Utility for Biosynthetic Studies of Pyrrole-Imidazole Alkaloids by Microscale1H-15N HSQC and FTMS†

    PubMed Central

    Wang, Yong-Gang; Morinaka, Brandon I.; Reyes, Jeremy Chris P.; Wolff, Jeremy H.; Romo, Daniel; Molinski, Tadeusz F.

    2010-01-01

    Numerous marine-derived pyrrole-imidazole alkaloids (PIAs), ostensibly derived from the simple precursor oroidin, 1a, have been reported and have garnered intense synthetic interest due to their complex structures and in some cases biological activity; however very little is known regarding their biosynthesis. We describe a concise synthesis of 7-15N-oroidin (1d) from urocanic acid and a direct method for measurement of 15N incorporation by pulse labeling and analysis by 1D 1H-15N HSQC NMR and FTMS. Using a mock pulse labeling experiment, we estimate the limit of detection (LOD) for incorporation of newly biosynthesized PIA by 1D 1H-15N HSQC to be 0.96 μg equivalent of 15N oroidin (2.4 nmole) in a background of 1500 μg unlabeled oroidin (about 1 part per 1600). 7-15N-Oroidin will find utility in biosynthetic feeding experiments with live sponges to provide direct information to clarify the pathways leading to more complex pyrrole-imidazole alkaloids. PMID:20095632

  18. Backbone 1H, 15N, and 13C resonance assignments and secondary structure of a novel protein OGL-20P(T)-358 from hyperthermophile Thermococcus thioreducens sp. nov.

    PubMed

    Wilson, Randall; Hughes, Ronny; Curto, Ernest; Ng, Joseph; Twigg, Pamela

    2007-12-31

    OGL-20P(T)-358 is a novel 66 amino acid residue protein from the hyperthermophile Thermococcus thioreducens sp. nov., strain OGL-20PT, which was collected from the wall of the hydrothermal black smoker in the Rainbow Vent along the mid-Atlantic ridge. This protein, which has no detectable sequence homology with proteins or domains of known function, has a calculated pI of 4.76 and a molecular mass of 8.2 kDa. We report here the backbone 1H, 15N, and 13C resonance assignments of OGL-20PT-358. Assignments are 97.5% (316/324) complete. Chemical shift index was used to determine the secondary structure of the protein, which appears to consist of primarily alpha-helical regions. This work is the foundation for future studies to determine the three-dimensional solution structure of the protein. PMID:18182861

  19. HN-NCA heteronuclear TOCSY-NH experiment for (1)H(N) and (15)N sequential correlations in ((13)C, (15)N) labelled intrinsically disordered proteins.

    PubMed

    Wiedemann, Christoph; Goradia, Nishit; Häfner, Sabine; Herbst, Christian; Görlach, Matthias; Ohlenschläger, Oliver; Ramachandran, Ramadurai

    2015-10-01

    A simple triple resonance NMR experiment that leads to the correlation of the backbone amide resonances of each amino acid residue 'i' with that of residues 'i-1' and 'i+1' in ((13)C, (15)N) labelled intrinsically disordered proteins (IDPs) is presented. The experimental scheme, {HN-NCA heteronuclear TOCSY-NH}, exploits the favourable relaxation properties of IDPs and the presence of (1) J CαN and (2) J CαN couplings to transfer the (15)N x magnetisation from amino acid residue 'i' to adjacent residues via the application of a band-selective (15)N-(13)C(α) heteronuclear cross-polarisation sequence of ~100 ms duration. Employing non-uniform sampling in the indirect dimensions, the efficacy of the approach has been demonstrated by the acquisition of 3D HNN chemical shift correlation spectra of α-synuclein. The experimental performance of the RF pulse sequence has been compared with that of the conventional INEPT-based HN(CA)NH pulse scheme. As the availability of data from both the HCCNH and HNN experiments will make it possible to use the information extracted from one experiment to simplify the analysis of the data of the other and lead to a robust approach for unambiguous backbone and side-chain resonance assignments, a time-saving strategy for the simultaneous collection of HCCNH and HNN data is also described. PMID:26282620

  20. Electron correlation and relativistic effects in the coinage metal compounds. II. Heteronuclear dimers: CuAg, CuAu, and AgAu

    NASA Astrophysics Data System (ADS)

    Kellö, Vladimir; Sadlej, Andrzej J.

    1995-08-01

    Electric properties of heteronuclear dimers of the coinage metals are calculated at the level of the CCSD(T) approximation applied to 38 electrons of the valence and next-to-valence atomic shells. The relativistic effects are accounted for by using the scalar approximation to the Pauli hamiltonian. Both the pure relativistic and mixed relativistic-correlation contributions to energies and electric properties are computed. All calculations have been carried out by using the recently developed first-order polarized basis sets of the coinage metal atoms. In the non-relativistic approximation all studied dimers show only a moderate degree of polarity; the non-relativistic CuAg turns out to be the most polar dimer with the Cu(-)Ag(+) polarity. The relativistic effects considerably reduce the negative value of the CuAg dipole moment, change the sign of the CuAu dipole moment, and make the AgAu molecule the most polar species in the series. Simultaneously, the parallel component of the dipole polarizability shows only a small relativistic contraction. The calculated quasirelativistic interaction potentials have a correct behavior in the vicinity of their minima and give the Re and ωe values in complete agreement with experiment. Much less satisfactory are the dissociation energy data which seem to suffer from the single reference configuration approximation.

  1. Multiplet-separated heteronuclear two-dimensional NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Levitt, Malcolm H.; Sørensen, O. W.; Ernst, R. R.

    1983-02-01

    Techniques are described for the identification and separation of peaks of different multiplicity in heteronuclear two-dimensional NMR spectroscopy. The methods are applied to the two-dimensional 13C- 1H shift correlation spectrum of menthol.

  2. 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

  3. Heteronuclear decoupling by optimal tracking.

    PubMed

    Neves, Jorge L; Heitmann, Björn; Khaneja, Navin; Glaser, Steffen J

    2009-11-01

    The problem to design efficient heteronuclear decoupling sequences is studied using optimal control methods. A generalized version of the gradient ascent engineering (GRAPE) algorithm is presented that makes it possible to design complex non-periodic decoupling sequences which are characterized by tens of thousands of pulse sequence parameters. In contrast to conventional approaches based on average Hamiltonian theory, the concept of optimal tracking is used: a pulse sequence is designed that steers the evolution of an ensemble of spin systems such that at a series of time points, a specified trajectory of the density operator is tracked as closely as possible. The approach is demonstrated for the case of low-power heteronuclear decoupling in the liquid state for in vivo applications. Compared to conventional sequences, significant gains in decoupling efficiency and robustness with respect to offset and inhomogeneity of the radio-frequency field were found in simulations and experiments. PMID:19695913

  4. A General Assignment Method for Oriented Sample (OS) Solid-state NMR of Proteins Based on The Correlation of Resonances through Heteronuclear Dipolar Couplings in Samples Aligned Parallel and Perpendicular to the Magnetic Field

    PubMed Central

    Lu, George J.; Son, Woo Sung; Opella, Stanley J.

    2011-01-01

    A general method for assigning oriented sample (OS) solid-state NMR spectra of proteins is demonstrated. In principle, this method requires only a single sample of a uniformly 15N-labeled membrane protein in magnetically aligned bilayers, and a previously assigned isotropic chemical shift spectrum obtained either from solution NMR on micelle or isotropic bicelle samples or from magic angle spinning (MAS) solid-state NMR on unoriented proteoliposomes. The sequential isotropic resonance assignments are transferred to the OS solid-state NMR spectra of aligned samples by correlating signals from the same residue observed in protein-containing bilayers aligned with their normals parallel and perpendicular to the magnetic field. The underlying principle is that the resonances from the same residue have heteronuclear dipolar couplings that differ by exactly a factor of two between parallel and perpendicular alignments. The method is demonstrated on the membrane-bound form of Pf1 coat protein in phospholipid bilayers, whose assignments have been previously made using an earlier generation of methods that relied on the preparation of many selectively labeled (by residue type) samples. The new method provides the correct resonance assignments using only a single uniformly 15N-labeled sample, two solid-state NMR spectra, and a previously assigned isotropic spectrum. Significantly, this approach is equally applicable to residues in alpha helices, beta sheets, loops, and any other elements of tertiary structure. Moreover, the strategy bridges between OS solid-state NMR of aligned samples and solution NMR or MAS solid-state NMR of unoriented samples. In combination with the development of complementary experimental methods, it provides a step towards unifying these apparently different NMR approaches. PMID:21316275

  5. 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.

  6. 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

  7. Flexible Stoichiometry and Asymmetry of the PIDDosome Core Complex by Heteronuclear NMR Spectroscopy and Mass Spectrometry

    PubMed Central

    Nematollahi, Lily A.; Garza-Garcia, Acely; Bechara, Chérine; Esposito, Diego; Morgner, Nina; Robinson, Carol V.; Driscoll, Paul C.

    2015-01-01

    Homotypic death domain (DD)–DD interactions are important in the assembly of oligomeric signaling complexes such as the PIDDosome that acts as a platform for activation of caspase-2-dependent apoptotic signaling. The structure of the PIDDosome core complex exhibits an asymmetric three-layered arrangement containing five PIDD-DDs in one layer, five RAIDD-DDs in a second layer and an additional two RAIDD-DDs. We addressed complex formation between PIDD-DD and RAIDD-DD in solution using heteronuclear nuclear magnetic resonance (NMR) spectroscopy, nanoflow electrospray ionization mass spectrometry and size-exclusion chromatography with multi-angle light scattering. The DDs assemble into complexes displaying molecular masses in the range 130–158 kDa and RAIDD-DD:PIDD-DD stoichiometries of 5:5, 6:5 and 7:5. These data suggest that the crystal structure is representative of only the heaviest species in solution and that two RAIDD-DDs are loosely attached to the 5:5 core. Two-dimensional 1H,15N-NMR experiments exhibited signal loss upon complexation consistent with the formation of high-molecular-weight species. 13C-Methyl-transverse relaxation optimized spectroscopy measurements of the PIDDosome core exhibit signs of differential line broadening, cross-peak splitting and chemical shift heterogeneity that reflect the presence of non-equivalent sites at interfaces within an asymmetric complex. Experiments using a mutant RAIDD-DD that forms a monodisperse 5:5 complex with PIDD-DD show that the spectroscopic signature derives from the quasi- but non-exact equivalent environments of each DD. Since this characteristic was previously demonstrated for the complex between the DDs of CD95 and FADD, the NMR data for this system are consistent with the formation of a structure homologous to the PIDDosome core. PMID:25528640

  8. Flexible stoichiometry and asymmetry of the PIDDosome core complex by heteronuclear NMR spectroscopy and mass spectrometry.

    PubMed

    Nematollahi, Lily A; Garza-Garcia, Acely; Bechara, Chérine; Esposito, Diego; Morgner, Nina; Robinson, Carol V; Driscoll, Paul C

    2015-02-27

    Homotypic death domain (DD)-DD interactions are important in the assembly of oligomeric signaling complexes such as the PIDDosome that acts as a platform for activation of caspase-2-dependent apoptotic signaling. The structure of the PIDDosome core complex exhibits an asymmetric three-layered arrangement containing five PIDD-DDs in one layer, five RAIDD-DDs in a second layer and an additional two RAIDD-DDs. We addressed complex formation between PIDD-DD and RAIDD-DD in solution using heteronuclear nuclear magnetic resonance (NMR) spectroscopy, nanoflow electrospray ionization mass spectrometry and size-exclusion chromatography with multi-angle light scattering. The DDs assemble into complexes displaying molecular masses in the range 130-158kDa and RAIDD-DD:PIDD-DD stoichiometries of 5:5, 6:5 and 7:5. These data suggest that the crystal structure is representative of only the heaviest species in solution and that two RAIDD-DDs are loosely attached to the 5:5 core. Two-dimensional (1)H,(15)N-NMR experiments exhibited signal loss upon complexation consistent with the formation of high-molecular-weight species. (13)C-Methyl-transverse relaxation optimized spectroscopy measurements of the PIDDosome core exhibit signs of differential line broadening, cross-peak splitting and chemical shift heterogeneity that reflect the presence of non-equivalent sites at interfaces within an asymmetric complex. Experiments using a mutant RAIDD-DD that forms a monodisperse 5:5 complex with PIDD-DD show that the spectroscopic signature derives from the quasi- but non-exact equivalent environments of each DD. Since this characteristic was previously demonstrated for the complex between the DDs of CD95 and FADD, the NMR data for this system are consistent with the formation of a structure homologous to the PIDDosome core. PMID:25528640

  9. Conditional rotations of heteronuclear coupled spins.

    PubMed

    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 InS spin systems. Experimental demonstrations are shown in (13)C labeled chloroform, dichloromethane, and toluene samples and in unlabeled 2,3-dibromopropionic acid and brucine samples. PMID:25506815

  10. 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.

  11. Synthesis of 2,4,5,8-tetrabromotricyclo(4. 2. 2. 0/sup 1,5/)decane and determination of its structure by two-dimensional homonuclear and heteronuclear correlation /sup 1/H and /sup 13/C NMR spectroscopy and x-ray crystallographic analysis

    SciTech Connect

    Sekatsis, I.P.; Kemme, A.A.; Liepin'sh, E.E.; Bleidelis, Ya.Ya.; Gavars, M.P.; Raguel, B.P.; Polis, Ya.Yu.

    1988-08-10

    It is known that the bromination of endotricyclo(5.2.1.0/sup 2,6/)decane (I) with bromine in the presence of aluminum bromide leads to the formation of 1,3,5- and 1,3,6-tribromoadamantanes and 1,2,3,5,6,7-hexabromonaphthalene. In view of the complexity of the isomerization of the endo-decane (I) to adamantane the authors studied the bromination of (I) with bromine in order to detect the intermediate products of this isomerization. 2,4,5,8-Tetrabromotricyclo(4.2.2.0/sup 1,5/)decane was synthesized by the bromination of endo-tricyclo(5.2.1.0/sup 2,6/)decane, and its structure was determined by two-dimensional homonuclear and heteronuclear correlation NMR spectroscopy with full assignment of the signals and was confirmed by x-ray crystallographic analysis.

  12. 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.

  13. 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…

  14. 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.

  15. 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

  16. Heteronuclear decoupling by multiple rotating frame technique

    PubMed Central

    Arthanari, Haribabu; Wagner, Gerhard; Khaneja, Navin

    2011-01-01

    The paper describes the multiple rotating frame technique for designing modulated rf fields, that perform broadband heteronuclear decoupling in solution NMR spectroscopy. The decoupling method presented here is understood by performing a sequence of coordinate transformations, each of which demodulates a component of the rf field to a static component, that progressively averages the chemical shift and the dipolar interaction. We show that by increasing the number of modulations in the decoupling field, the ratio of dispersion in the chemical shift to the strength of the static component of the rf field is successively reduced in the progressive frames. The known decoupling methods like continuous wave decoupling, TPPM, etc., can be viewed as special cases of this method and their performance improves by adding additional modulations in the decoupling field. The technique is also expected to find use in design of broadband excitation, inversion and mixing sequences and broadband experiments in solid state NMR. PMID:21227724

  17. High-resolution heteronuclear multi-dimensional NMR spectroscopy in magnetic fields with unknown spatial variations

    NASA Astrophysics Data System (ADS)

    Zhang, Zhiyong; Huang, Yuqing; Smith, Pieter E. S.; Wang, Kaiyu; Cai, Shuhui; Chen, Zhong

    2014-05-01

    Heteronuclear NMR spectroscopy is an extremely powerful tool for determining the structures of organic molecules and is of particular significance in the structural analysis of proteins. In order to leverage the method’s potential for structural investigations, obtaining high-resolution NMR spectra is essential and this is generally accomplished by using very homogeneous magnetic fields. However, there are several situations where magnetic field distortions and thus line broadening is unavoidable, for example, the samples under investigation may be inherently heterogeneous, and the magnet’s homogeneity may be poor. This line broadening can hinder resonance assignment or even render it impossible. We put forth a new class of pulse sequences for obtaining high-resolution heteronuclear spectra in magnetic fields with unknown spatial variations based on distant dipolar field modulations. This strategy’s capabilities are demonstrated with the acquisition of high-resolution 2D gHSQC and gHMBC spectra. These sequences’ performances are evaluated on the basis of their sensitivities and acquisition efficiencies. Moreover, we show that by encoding and decoding NMR observables spatially, as is done in ultrafast NMR, an extra dimension containing J-coupling information can be obtained without increasing the time necessary to acquire a heteronuclear correlation spectrum. Since the new sequences relax magnetic field homogeneity constraints imposed upon high-resolution NMR, they may be applied in portable NMR sensors and studies of heterogeneous chemical and biological materials.

  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. Accurate potential energy, dipole moment curves, and lifetimes of vibrational states of heteronuclear alkali dimers

    SciTech Connect

    Fedorov, Dmitry A.; Varganov, Sergey A.; Derevianko, Andrei

    2014-05-14

    We calculate the potential energy curves, the permanent dipole moment curves, and the lifetimes of the ground and excited vibrational states of the heteronuclear alkali dimers XY (X, Y = Li, Na, K, Rb, Cs) in the X{sup 1}Σ{sup +} electronic state using the coupled cluster with singles doubles and triples method. All-electron quadruple-ζ basis sets with additional core functions are used for Li and Na, and small-core relativistic effective core potentials with quadruple-ζ quality basis sets are used for K, Rb, and Cs. The inclusion of the coupled cluster non-perturbative triple excitations is shown to be crucial for obtaining the accurate potential energy curves. A large one-electron basis set with additional core functions is needed for the accurate prediction of permanent dipole moments. The dissociation energies are overestimated by only 14 cm{sup −1} for LiNa and by no more than 114 cm{sup −1} for the other molecules. The discrepancies between the experimental and calculated harmonic vibrational frequencies are less than 1.7 cm{sup −1}, and the discrepancies for the anharmonic correction are less than 0.1 cm{sup −1}. We show that correlation between atomic electronegativity differences and permanent dipole moment of heteronuclear alkali dimers is not perfect. To obtain the vibrational energies and wave functions the vibrational Schrödinger equation is solved with the B-spline basis set method. The transition dipole moments between all vibrational states, the Einstein coefficients, and the lifetimes of the vibrational states are calculated. We analyze the decay rates of the vibrational states in terms of spontaneous emission, and stimulated emission and absorption induced by black body radiation. In all studied heteronuclear alkali dimers the ground vibrational states have much longer lifetimes than any excited states.

  20. Accurate potential energy, dipole moment curves, and lifetimes of vibrational states of heteronuclear alkali dimers

    NASA Astrophysics Data System (ADS)

    Fedorov, Dmitry A.; Derevianko, Andrei; Varganov, Sergey A.

    2014-05-01

    We calculate the potential energy curves, the permanent dipole moment curves, and the lifetimes of the ground and excited vibrational states of the heteronuclear alkali dimers XY (X, Y = Li, Na, K, Rb, Cs) in the X1Σ+ electronic state using the coupled cluster with singles doubles and triples method. All-electron quadruple-ζ basis sets with additional core functions are used for Li and Na, and small-core relativistic effective core potentials with quadruple-ζ quality basis sets are used for K, Rb, and Cs. The inclusion of the coupled cluster non-perturbative triple excitations is shown to be crucial for obtaining the accurate potential energy curves. A large one-electron basis set with additional core functions is needed for the accurate prediction of permanent dipole moments. The dissociation energies are overestimated by only 14 cm-1 for LiNa and by no more than 114 cm-1 for the other molecules. The discrepancies between the experimental and calculated harmonic vibrational frequencies are less than 1.7 cm-1, and the discrepancies for the anharmonic correction are less than 0.1 cm-1. We show that correlation between atomic electronegativity differences and permanent dipole moment of heteronuclear alkali dimers is not perfect. To obtain the vibrational energies and wave functions the vibrational Schrödinger equation is solved with the B-spline basis set method. The transition dipole moments between all vibrational states, the Einstein coefficients, and the lifetimes of the vibrational states are calculated. We analyze the decay rates of the vibrational states in terms of spontaneous emission, and stimulated emission and absorption induced by black body radiation. In all studied heteronuclear alkali dimers the ground vibrational states have much longer lifetimes than any excited states.

  1. Symbiotic solitons in heteronuclear multicomponent Bose-Einstein condensates

    SciTech Connect

    Perez-Garcia, Victor M.; Beitia, Juan Belmonte

    2005-09-15

    We show that bright solitons exist in quasi-one-dimensional heteronuclear multicomponent Bose-Einstein condensates with repulsive self-interaction and attractive interspecies interaction. They are remarkably robust to perturbations of initial data and collisions and can be generated by the mechanism of modulational instability. Some possibilities for control and the behavior of the system in fully three-dimensional scenarios are also discussed.

  2. 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

  3. (1)H, (15)N and (13)C resonance assignments of translationally-controlled tumor protein from photosynthetic microalga Nannochloropsis oceanica.

    PubMed

    Yao, Xingzhe; Xiao, Yan; Cui, Qiu; Feng, Yingang

    2015-10-01

    Translationally-controlled tumor protein (TCTP) is a eukaryote-conserved protein with crucial roles in cellular growth. It has also been proposed that plant TCTP has functions specific to plant, while no structure of TCTP from photosynthetic organism has been reported. Nannochloropsis is a photosynthetic microalga with high yield of lipid and high-value polyunsaturated fatty acid, which is promising for biodiesel production. Study of growth-related proteins may provide new clue for improving the yield of lipid. TCTP from Nannochloropsis oceanica shares low sequence identity with structure-known TCTPs. Here we reported the NMR resonance assignments of TCTP from N. oceanica for further structural and functional studies. PMID:25680850

  4. Backbone and sidechain 1H, 15N and 13C assignments of the KSR1 CA1 domain

    PubMed Central

    Koveal, Dorothy; Pinheiro, Anderson S.; Peti, Wolfgang; Page, Rebecca

    2014-01-01

    The backbone and side chain resonance assignments of the murine KSR1 CA1 domain have been determined based on triple-resonance experiments using uniformly [13C, 15N]-labeled protein. This assignment is the first step towards the determination of the three-dimensional structure of the unique KSR1 CA1 domain. PMID:20737253

  5. 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

  6. 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

  7. Strong-field ionization of a heteronuclear diatomic molecule

    SciTech Connect

    Ren, Xianghe; Nakajima, Takashi

    2010-12-15

    We theoretically study strong-field ionization of a heteronuclear diatomic molecule, CO, by calculating the photoelectron angular distributions (PADs) and the total ionization rates using linearly and circularly polarized laser fields. We find that, although the PADs of CO generally do not have inversion symmetry, they become more inversion symmetric as the photoelectron energy increases. Heteronuclear features of CO upon ionization are better understood by comparing the results with those of a representative of homonuclear molecules, N{sub 2}, in that, although there are some similarities between CO and N{sub 2} due to the same orbital symmetry, {sigma}{sub g}, there are some differences between them in terms of the ionization suppression and orientation dependence of the total ionization yield. Namely, CO behaves more like an atom in the low-intensity range in a sense that ionization takes place mainly from the neighborhood of the C core, while it behaves more like a double-core molecule in the high-intensity range since ionization takes place from the neighborhood of both C and O cores. This explains why ionization suppression of CO is not seen at the low intensity but it becomes more visible at the high intensity range.

  8. Highly Repeatable Dissolution Dynamic Nuclear Polarization for Heteronuclear NMR Metabolomics.

    PubMed

    Bornet, Aurélien; Maucourt, Mickaël; Deborde, Catherine; Jacob, Daniel; Milani, Jonas; Vuichoud, Basile; Ji, Xiao; Dumez, Jean-Nicolas; Moing, Annick; Bodenhausen, Geoffrey; Jannin, Sami; Giraudeau, Patrick

    2016-06-21

    At natural (13)C abundance, metabolomics based on heteronuclear NMR is limited by sensitivity. We have recently demonstrated how hyperpolarization by dissolution dynamic nuclear polarization (D-DNP) assisted by cross-polarization (CP) provides a reliable way of enhancing the sensitivity of heteronuclear NMR in dilute mixtures of metabolites. In this Technical Note, we evaluate the precision of this experimental approach, a critical point for applications to metabolomics. The higher the repeatability, the greater the likelihood that one can detect small biologically relevant differences between samples. The average repeatability of our state-of-the-art D-DNP NMR equipment for samples of metabolomic relevance (20 mg dry weight tomato extracts) is 3.6% for signals above the limit of quantification (LOQ) and 6.4% when all the signals above the limit of detection (LOD) are taken into account. This first report on the repeatability of D-DNP highlights the compatibility of the technique with the requirements of metabolomics and confirms its potential as an analytical tool for such applications. PMID:27253320

  9. Tailored real-time scaling of heteronuclear couplings

    NASA Astrophysics Data System (ADS)

    Schilling, Franz; Glaser, Steffen J.

    2012-10-01

    Heteronuclear couplings are a valuable source of molecular information, which is measured from the multiplet splittings of an NMR spectrum. Radiofrequency irradiation on one coupled nuclear spin allows to modify the effective coupling constant, scaling down the multiplet splittings in the spectrum observed at the resonance frequency of the other nuclear spin. Such decoupling sequences are often used to collapse a multiplet into a singlet and can therefore simplify NMR spectra significantly. Continuous-wave (cw) decoupling has an intrinsic non-linear offset dependence of the scaling of the effective J-coupling constant. Using optimal control pulse optimization, we show that virtually arbitrary off-resonance scaling of the J-coupling constant can be achieved. The new class of tailored decoupling pulses is named SHOT (Scaling of Heteronuclear couplings by Optimal Tracking). Complementing cw irradiation, SHOT pulses offer an alternative approach of encoding chemical shift information indirectly through off-resonance decoupling, which however makes it possible for the first time to achieve linear J scaling as a function of offset frequency. For a simple mixture of eight aromatic compounds, it is demonstrated experimentally that a 1D-SHOT {1H}-13C experiment yields comparable information to a 2D-HSQC and can give full assignment of all coupled spins.

  10. 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.

  11. 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. PMID:25327292

  12. 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.

  13. 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. PMID:26073419

  14. Two dimensional heteronuclear complexes with cyanide and 4-aminomethylpyridine ligands

    NASA Astrophysics Data System (ADS)

    Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Yeşilel, Okan Zafer; MuratTaş

    2014-09-01

    Two new cyano-bridged two-dimensional heteronuclear complexes, [Cd(NH3)2(μ-ampy)Ni(μ-CN)2(CN)2]n (1) and [Cd(H2O)2(μ-ampy)Pt(μ-CN)2(CN)2]n (2) (ampy = 4-aminomethylpyridine), were synthesized and characterized by FT-IR and Raman spectroscopic, thermal (TG, DTG and DTA) and elemental analyses and single crystal X-ray diffraction techniques. They crystallize in the triclinic system and P-1 space group. The Ni(II) or Pt(II) ions are four coordinate with four cyanide-carbon atoms in a square planar geometry and the Cd(II) ion exhibits a distorted octahedral coordination by two different N-atoms from two symmetrically equivalent ampy ligands, two ammine or aqua ligands and two bridging cyano groups.The most important features of the complexes are the presence of obvious M⋯π (M = Ni(II) or Pt(II)) interactions.

  15. 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.

  16. Mixed frequency/time domain optical analogues of heteronuclear multidimensional NMR.

    PubMed

    Pakoulev, Andrei V; Rickard, Mark A; Meyer, Kent A; Kornau, Kathryn; Mathew, Nathan A; Thompson, David E; Wright, John C

    2006-03-16

    Ultrafast spectroscopy is dominated by time domain methods such as pump-probe and, more recently, 2D-IR spectroscopies. In this paper, we demonstrate that a mixed frequency/time domain ultrafast four wave mixing (FWM) approach not only provides similar capabilities, but it also provides optical analogues of multiple- and zero-quantum heteronuclear nuclear magnetic resonance (NMR). The method requires phase coherence between the excitation pulses only over the dephasing time of the coherences. It uses twelve coherence pathways that include four with populations, four with zero-quantum coherences, and four with double-quantum coherences. Each pathway provides different capabilities. The population pathways correspond to those of two-dimensional (2D) time domain spectroscopies, while the double- and zero-quantum coherence pathways access the coherent dynamics of coupled quantum states. The three spectral and two temporal dimensions enable the isolation and characterization of the spectral correlations between different vibrational and/or electronic states, coherence and population relaxation rates, and coupling strengths. Quantum-level interference between the direct and free-induction decay components gives a spectral resolution that exceeds that of the excitation pulses. Appropriate parameter choices allow isolation of individual coherence pathways. The mixed frequency/time domain approach allows one to access any set of quantum states with coherent multidimensional spectroscopy. PMID:16526612

  17. Studies in protein dynamics using heteronuclear nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Vugmeyster, Liliya

    Dynamic processes in proteins are important for their biological function. Several issues in protein dynamics are addressed by applying existing NMR methodologies to investigate dynamics of several small proteins. Amide H/D exchange rates have been measured for the N-terminal domain of the ribosomal protein L9, residues 1--56. The results suggest that the structure of the domain is preserved in isolation and that the stability of the isolated domain is comparable to the stability of this domain in intact L9. Single domain proteins can fold in vitro at rates in excess of 1 x 104 s-1. Measurement of folding rates of this magnitude poses a considerable technical challenge. Off-resonance 15N R1rho measurements are shown to be capable of measuring such fast protein folding rates. The measurements were performed on a sample of the peripheral subunit-binding domain from the dihydrolopoamide acetyltransferase component of the pyruvate dehydrogenase multienzyme complex from Bacillus stearothermophilus 15N labeled at Ala 11. Fast intramolecular motions (on ps-ns time scale) can be studied by heteronuclear laboratory frame NMR relaxation. The temperature dependence of the backbone dynamics of the 36-resiude subdomain of the F-actin bundling protein villin has been investigated by studying the temperature dependence of order parameters obtained from 15N relaxation measurements. The results support the hypothesis that one of the possible mechanisms of thermostability is to lower the heat capacity difference between the folded and unfolded states by lowering the contribution from the backbone dynamics. A commonly used model-free approach for the interpretation of the relaxation data for macromolecules in solution is modified to correct for the decoupling approximation between the overall and internal motions.

  18. Heteronuclear three-body parameter pinned down by multichannel spinor model

    NASA Astrophysics Data System (ADS)

    Wang, Yujun; Julienne, Paul S.; Greene, Chris H.

    2015-05-01

    Although a quantitative study of ultracold three-body collisions has been recently performed for homonuclear atomic systems, a similar theoretical study for heteronuclear ones has not been available. In this work we show progress in predicting Efimov-like three-body resonances using multichannel spinor models. In particular, we show that our calculations correctly predict the experimental observed isotope dependence of the atom-diatomic resonances in 87Rb-87Rb-40K and 87Rb-87Rb-41K systems without fitting parameters. Our study demonstrates that with our simple spinor models, quantitative characterization of ultracold chemical processes for heteronuclear systems is in principle feasible. Application of our model to other heteronuclear alkali-metal systems is also discussed. The authors acknowledge the support of an AFOSR-MURI FA9550-09-1-0617, Y.W. also acknowledges the support of Department of Physics, Kansas State University.

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

    PubMed

    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 ((13)C and (1)H) at 12mT was investigated in this study. Nonlinear phase and amplitude modulated waveforms designed to simultaneously refocus magnetization at 128kHz ((13)C) and 510kHz ((1)H) 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

  20. 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

  1. Engineering of an all-heteronuclear 5-qubit NMR quantum computer.

    PubMed

    Marx, Raimund; Pomplun, Nikolas; Bermel, Wolfgang; Zeiger, Heinz; Engelke, Frank; Fahmy, Amr F; Glaser, Steffen J

    2015-06-01

    The realization of an all-heteronuclear 5-qubit nuclear magnetic resonance quantum computer is reported, from the design and synthesis of a suitable molecule through the engineering of a prototype 6-channel probe head. Full control over the quantum computer is shown by a benchmark experiment. PMID:25854330

  2. Homo- and heteronuclear 2D NMR approaches to analyse a mixture of deuterated unlike/like stereoisomers using weakly ordering chiral liquid crystals

    NASA Astrophysics Data System (ADS)

    Ben Ali, Karim; Lafon, Olivier; Zimmermann, Herbert; Guittet, Eric; Lesot, Philippe

    2007-08-01

    We describe several homo- and heteronuclear 2D NMR strategies dedicated to the analysis of anisotropic 2H spectra of a mixture of dideuterated unlike/like stereoisomers with two remote stereogenic centers, using weakly orienting chiral liquid crystals. To this end, we propose various 2D correlation experiments, denoted "D(H) nD" or "D(H) nC" (with n = 1, 2), that involve two heteronuclear polarization transfers of INEPT-type with one or two proton relays. The analytical expressions of correlation signals for four pulse sequences reported here were calculated using the product-operators formalism for spin I = 1 and S = 1/2. The features and advantages of each scheme are presented and discussed. The efficiency of these 2D sequences is illustrated using various deuterated model molecules, dissolved in organic solutions of polypeptides made of poly- γ-benzyl- L-glutamate (PBLG) or poly- ɛ-carbobenzyloxy- L-lysine (PCBLL) and NMR numerical simulations.

  3. Studying metal ion binding properties of a three-way junction RNA by heteronuclear NMR.

    PubMed

    Bartova, Simona; Pechlaner, Maria; Donghi, Daniela; Sigel, Roland K O

    2016-06-01

    Self-splicing group II introns are highly structured RNA molecules, containing a characteristic secondary and catalytically active tertiary structure, which is formed only in the presence of Mg(II). Mg(II) initiates the first folding step governed by the κζ element within domain 1 (D1κζ). We recently solved the NMR structure of D1κζ derived from the mitochondrial group II intron ribozyme Sc.ai5γ and demonstrated that Mg(II) is essential for its stabilization. Here, we performed a detailed multinuclear NMR study of metal ion interactions with D1κζ, using Cd(II) and cobalt(III)hexammine to probe inner- and outer-sphere coordination of Mg(II) and thus to better characterize its binding sites. Accordingly, we mapped (1)H, (15)N, (13)C, and (31)P spectral changes upon addition of different amounts of the metal ions. Our NMR data reveal a Cd(II)-assisted macrochelate formation at the 5'-end triphosphate, a preferential Cd(II) binding to guanines in a helical context, an electrostatic interaction in the ζ tetraloop receptor and various metal ion interactions in the GAAA tetraloop and κ element. These results together with our recently published data on Mg(II) interaction provide a much better understanding of Mg(II) binding to D1κζ, and reveal how intricate and complex metal ion interactions can be. PMID:26880094

  4. Heteronuclear NMR of DNA with the heteronucleus in natural abundance: facilitated assignment and extraction of coupling constants.

    PubMed Central

    Schmieder, P; Ippel, J H; van den Elst, H; van der Marel, G A; van Boom, J H; Altona, C; Kessler, H

    1992-01-01

    Two heteronuclear proton-carbon NMR experiments are applied to the DNA-octamer d(TTGGCCAA)2 with carbon in natural abundance. They lead to a complete assignment of the carbon resonances of the sugars and bases. In addition, several heteronuclear coupling constants, proton-carbon as well as proton-phosphorous and phosphorous-carbon, were determined. The information can be obtained in a reasonable measuring time and offers valuable information for a detailed picture of DNA structure. PMID:1408787

  5. 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.

  6. 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.

  7. The possibility of laser action in ionic heteronuclear molecules. I - Spectroscopy. II - Kinetics

    NASA Astrophysics Data System (ADS)

    Basov, N. G.; Voitik, M. G.; Zuev, V. S.; Kutakhov, V. P.

    1985-11-01

    A theoretical study is presented of the electronic structure of levels of ionic heteronuclear molecules (IHM) consisting of atoms and ions of inert gases, halogens, the oxygen group, and alkali metals. Electron transitions are found which are promising for the generation of laser action in the visible, UV, and far UV (greater than 70 nm). In addition, the feasibility of a new family of IHM gas lasers emitting in the above-mentioned ranges is demonstrated theoretically.

  8. 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.

  9. 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.

  10. 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. PMID:26272112

  11. High-order-harmonic generation in homonuclear and heteronuclear diatomic molecules: Exploration of multiple orbital contributions

    SciTech Connect

    Heslar, John; Telnov, Dmitry; Chu, Shih-I

    2011-04-15

    We present a time-dependent density functional theory (TDDFT) approach with proper asymptotic long-range potential for nonperturbative treatment of high-order harmonic generation (HHG) of diatomic molecules with their molecular axis parallel to the laser field polarization. A time-dependent two-center generalized pseudospectral method in prolate spheroidal coordinate system is used for accurate and efficient treatment of the TDDFT equations in space and time. The theory is applied to a detailed all-electron nonperturbative investigation of HHG processes of homonuclear (N{sub 2} and F{sub 2}) and heteronuclear (CO, BF, and HF) molecules in intense ultrashort laser pulses with the emphasis on the role of multiple molecular orbitals (MOs). The results reveal intriguing and substantially different nonlinear optical response behaviors for homonuclear and heteronuclear molecules. In particular, we found that the HHG spectrum for homonuclear molecules features a destructive interference of MO contributions while heteronuclear molecules show mostly constructive interference of orbital contributions.

  12. (1)H, (15)N and (13)C chemical shift assignment of the Gram-positive conjugative transfer protein TraHpIP501.

    PubMed

    Fercher, Christian; Keller, Walter; Zangger, Klaus; Helge Meyer, N

    2016-04-01

    Conjugative transfer of DNA represents the most important transmission pathway in terms of antibiotic resistance and virulence gene dissemination among bacteria. TraH is a putative transfer protein of the type IV secretion system (T4SS) encoded by the Gram-positive (G+) conjugative plasmid pIP501. This molecular machine involves a multi-protein core complex spanning the bacterial envelope thereby serving as a macromolecular secretion channel. Here, we report the near complete (1)H, (13)C and (15)N resonance assignment of a soluble TraH variant comprising the C-terminal domain. PMID:26559076

  13. Use of dipolar 1H-15N and 1H-13C couplings in the structure determination of magnetically oriented macromolecules in solution.

    PubMed

    Tjandra, N; Omichinski, J G; Gronenborn, A M; Clore, G M; Bax, A

    1997-09-01

    Anisotropy of the molecular magnetic susceptibility gives rise to a small degree of alignment. The resulting residual dipolar couplings, which can now be measured with the advent of higher magnetic fields in NMR, contain information on the orientation of the internuclear vectors relative to the molecular magnetic susceptibility tensor, thereby providing information on long range order that is not accessible by any of the solution NMR parameters currently used in structure determination. Thus, the dipolar couplings constitute unique and powerful restraints in determining the structures of magnetically oriented macromolecules in solution. The method is demonstrated on a complex of the DNA-binding domain of the transcription factor GATA-1 with a 16 base pair oligodeoxyribonucleotide. PMID:9303001

  14. Backbone and side-chain (1)H, (15)N, (13)C assignment and secondary structure of BPSL1445 from Burkholderia pseudomallei.

    PubMed

    Quilici, Giacomo; Berardi, Andrea; Gaudesi, Davide; Gourlay, Louise J; Bolognesi, Martino; Musco, Giovanna

    2015-10-01

    BPSL1445 is a lipoprotein produced by the Gram-negative bacterium Burkholderia pseudomallei (B. pseudomallei), the etiological agent of melioidosis. Immunodetection assays against sera patients using protein microarray suggest BPSL1445 involvement in melioidosis. Herein we report backbone, side chain NMR assignment and secondary structure for the recombinant protein. PMID:25893672

  15. NMR profiling of biomolecules at natural abundance using 2D 1H-15N and 1H-13C multiplicity-separated (MS) HSQC spectra

    NASA Astrophysics Data System (ADS)

    Chen, Kang; Freedberg, Darón I.; Keire, David A.

    2015-02-01

    2D NMR 1H-X (X = 15N or 13C) HSQC spectra contain cross-peaks for all XHn moieties. Multiplicity-edited1H-13C HSQC pulse sequences generate opposite signs between peaks of CH2 and CH/CH3 at a cost of lower signal-to-noise due to the 13C T2 relaxation during an additional 1/1JCH period. Such CHn-editing experiments are useful in assignment of chemical shifts and have been successfully applied to small molecules and small proteins (e.g. ubiquitin) dissolved in deuterated solvents where, generally, peak overlap is minimal. By contrast, for larger biomolecules, peak overlap in 2D HSQC spectra is unavoidable and peaks with opposite phases cancel each other out in the edited spectra. However, there is an increasing need for using NMR to profile biomolecules at natural abundance dissolved in water (e.g., protein therapeutics) where NMR experiments beyond 2D are impractical. Therefore, the existing 2D multiplicity-edited HSQC methods must be improved to acquire data on nuclei other than 13C (i.e.15N), to resolve more peaks, to reduce T2 losses and to accommodate water suppression approaches. To meet these needs, a multiplicity-separated1H-X HSQC (MS-HSQC) experiment was developed and tested on 500 and 700 MHz NMR spectrometers equipped with room temperature probes using RNase A (14 kDa) and retroviral capsid (26 kDa) proteins dissolved in 95% H2O/5% D2O. In this pulse sequence, the 1/1JXH editing-period is incorporated into the semi-constant time (semi-CT) X resonance chemical shift evolution period, which increases sensitivity, and importantly, the sum and the difference of the interleaved 1JXH-active and the 1JXH-inactive HSQC experiments yield two separate spectra for XH2 and XH/XH3. Furthermore we demonstrate improved water suppression using triple xyz-gradients instead of the more widely used z-gradient only water-suppression approach.

  16. Three-dimensional solution structure of mouse [Cd7]-metallothionein-1 by homonuclear and heteronuclear NMR spectroscopy.

    PubMed Central

    Zangger, K.; Oz, G.; Otvos, J. D.; Armitage, I. M.

    1999-01-01

    Sequential 1H-NMR assignments of mouse [Cd7]-metallothionein-1 (MT1) have been carried out by standard homonuclear NMR methods and the use of an accordion-heteronuclear multiple quantum correlation (HMQC) experiment for establishing the metal, 113Cd2+, to cysteine connectivities. The three-dimensional structure was then calculated using the distance constraints from two-dimensional nuclear Overhauser effect (NOE) spectroscopy spectra and the Cys-Cd connectivities as input for a distance geometry-dynamical simulated annealing protocol in X-PLOR 3.851. Similar to the mammalian MT2 isoforms, the homologous primary structure of MT1 suggested two separate domains, each containing one metal cluster. Because there were no interdomain constraints, the structure calculation for the N-terminal beta- and the C-terminal alpha-domain were carried out separately. The structures are based on 409 NMR constraints, consisting of 381 NOEs and 28 cysteine-metal connectivities. The only elements of regular secondary structure found were two short stretches of 3(10) helices along with some half-turns in the alpha-domain. Structural comparison with rat liver MT2 showed high similarity, with the beta-domain structure in mouse MT1 showing evidence of increased flexibility compared to the same domain in MT2. The latter was reflected by the presence of fewer interresidue NOEs, no slowly exchanging backbone amide protons, and enhanced cadmium-cadmium exchange rates found in the beta-domain of MT1. PMID:10631978

  17. 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.

  18. Selective charge asymmetric distribution in heteronuclear diatomic molecules in strong laser fields

    NASA Astrophysics Data System (ADS)

    Lai, Wei; Guo, Chunlei

    2015-07-01

    In this paper we study double-ionization-induced charge asymmetric dissociation (CAD) in heteronuclear diatomic molecules. In CO we find a selective charge distribution in two CAD channels, i.e., C2 ++O is abundantly produced but C +O2 + is nearly nonexistent. This cannot be explained by the ionization energy difference between the two channels alone. Our study shows that the C2 ++O channel is sequentially formed through an intermediate state C++O and the selective charge distribution is the result of electron distribution in CO when exposed to intense laser fields.

  19. Quantum atom-heteronuclear molecule dark state: Role of population imbalance

    SciTech Connect

    Jing Hui; Cui Shuai

    2010-08-15

    Recently, the finite-number effect of initial atoms in coherent atom-molecule conversion was investigated by Zhao et al. [Phys. Rev. Lett. 101, 010401 (2008)]. Here, by extending to the atom-heteronuclear molecule dark state, we find that the initial populations imbalance of the atoms plays a significant role in quantum conversion rate and adiabatic fidelity. In particular, even for the finite total number of imbalanced two-species atoms, the mean-field conversion rate, contrary to the general belief, still can be remarkably close to the exact quantum results.

  20. 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

  1. 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.

  2. 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.

  3. 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.}

  4. Preparation of 13C and 15N labelled RNAs for heteronuclear multi-dimensional NMR studies.

    PubMed

    Nikonowicz, E P; Sirr, A; Legault, P; Jucker, F M; Baer, L M; Pardi, A

    1992-09-11

    A procedure is described for the efficient preparation of isotopically enriched RNAs of defined sequence. Uniformly labelled nucleotide 5'triphosphates (NTPs) were prepared from E.coli grown on 13C and/or 15N isotopically enriched media. These procedures routinely yield 180 mumoles of labelled NTPs per gram of 13C enriched glucose. The labelled NTPs were then used to synthesize RNA oligomers by in vitro transcription. Several 13C and/or 15N labelled RNAs have been synthesized for the sequence r(GGCGCUUGCGUC). Under conditions of high salt or low salt, this RNA forms either a symmetrical duplex with two U.U base pairs or a hairpin containing a CUUG loop respectively. These procedures were used to synthesize uniformly labelled RNAs and a RNA labelled only on the G and C residues. The ability to generate milligram quantities of isotopically labelled RNAs allows application of multi-dimensional heteronuclear magnetic resonance experiments that enormously simplify the resonance assignment and solution structure determination of RNAs. Examples of several such heteronuclear NMR experiments are shown. PMID:1383927

  5. 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.

  6. 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. PMID:26296115

  7. Two-center interference in high-order harmonic generation from heteronuclear diatomic molecules.

    PubMed

    Zhu, Xiaosong; Zhang, Qingbin; Hong, Weiyi; Lan, Pengfei; Lu, Peixiang

    2011-01-17

    Two-center interference for heteronuclear diatomic molecules (HeDM) is investigated. The minimum in the high-order harmonic spectrum, as a consequence of the destructive interference, is shifted to lower harmonic orders compared with that in a homonuclear case. This phenomenon is explained by performing phase analysis. It is found that, for an HeDM, the high harmonic spectrum contains information not only on the internuclear separation but also on the properties of the two separate centers, which implies the potential application of estimating the asymmetry of molecules and judging the linear combination of atomic orbitals (LCAO) for the highest occupied molecular orbital (HOMO). Moreover, the possibility to monitor the evolution of HOMO itself in molecular dynamics is also promised. PMID:21263583

  8. 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.

  9. 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

  10. Epitope Mapping of Antigenic MUC1 Peptides to Breast Cancer Antibody Fragment B27.29: A Heteronuclear NMR Study

    SciTech Connect

    Grinstead, Jeffrey S.; Schuman, Jason T.; Campbell, Ann P.

    2003-11-13

    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], 1H 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 15N and 13C 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. 15N and 13C NMR relaxation parameters were measured for both peptides free in solution and bound to Fab B27.29. The 13CR T1 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 15N- and 13C-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 cancer vaccine design.

  11. 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.

  12. Measurement of hetero-nuclear distances using a symmetry-based pulse sequence in solid-state NMR.

    PubMed

    Chen, Lei; Wang, Qiang; Hu, Bingwen; Lafon, Olivier; Trébosc, Julien; Deng, Feng; Amoureux, Jean-Paul

    2010-08-28

    A Symmetry-based Resonance-Echo DOuble-Resonance (S-REDOR) method is proposed for measuring hetero-nuclear dipolar couplings between two different spin-1/2 nuclei, under fast magic-angle spinning. The hetero-nuclear dipolar couplings are restored by employing the SR4 sequence, which requires the rf-field strength to be only twice the spinning frequency. The S-REDOR experiment is extended to S-RESPDOR (Symmetry-based Resonance-Echo Saturation-Pulse DOuble-Resonance) for determining dipolar coupling between a spin-1/2 nucleus (e.g.(13)C) and (14)N. It is demonstrated that S-REDOR and S-RESPDOR methods suppress efficiently the homo-nuclear dipolar interaction of the irradiated nucleus and benefit from high robustness to the rf-field inhomogeneity, chemical shielding and dipolar truncation. Therefore, these methods allow the measurement of (13)C/(14,15)N distances, with (13)C observation, in uniformly (13)C-labeled samples. Furthermore, we provide analytical solutions for the S-REDOR and S-RESPDOR dephasing curves. These solutions facilitate the measurement of hetero-nuclear distances from experimental data. PMID:20577687

  13. Regulation of charge delocalization in a heteronuclear Fe2 ru system by a stepwise photochromic process.

    PubMed

    Xu, Guang-Tao; Li, Bin; Wang, Jin-Yun; Zhang, Dao-Bin; Chen, Zhong-Ning

    2015-02-16

    Heteronuclear complexes FeCp2 -DTE-C≡C-Ru(dppe)2 Cl (1 o; dppe=1,2-bis(diphenylphosphino)ethane, Cp=cyclopentadienyl, DTE=dithienylethene) and FeCp2-DTE-C≡C-Ru(dppe)2-C≡C-DTE-FeCp2 (2 oo), with redox-active ferrocenyl and ruthenium centers separated by a photochromic DTE moiety, were prepared to achieve photoswitchable charge delocalization and Fe⋅⋅⋅Ru electronic communication. Upon UV-light irradiation of 2 oo, the Fe⋅⋅⋅Ru heterometallic electronic interaction is increasingly facilitated with stepwise photocyclization, 2 oo→2 co→2 cc; this is ascribed to the gradual increase in π-conjugated systems. The near-infrared absorptions in mixed-valence species [2 oo](+) /[2 co](+) /[2 cc](+) are gradually intensified following the conversion of [2 oo](+) →[2 co](+) →[2 cc](+) , which demonstrates that the extent of charge delocalization shows progressive enhancement with stepwise photocyclization. As revealed by electrochemical, spectroscopic, and theoretical studies, complex 2 exhibits nine switchable states through stepwise photochromic and reversible redox processes. PMID:25640650

  14. 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. PMID:27306000

  15. 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.

  16. Structural dynamics and folding of beta-lactoglobulin probed by heteronuclear NMR.

    PubMed

    Sakurai, Kazumasa; Konuma, Tsuyoshi; Yagi, Masanori; Goto, Yuji

    2009-06-01

    Bovine beta-lactoglobulin (beta LG) has been one of the most extensively studied proteins in the history of protein science mainly because its abundance in cow's milk makes it readily available to researchers. However, compared to other textbook proteins, progress in the study of beta LG has been slow because of obstacles such as a low reversibility from denaturation linked with thiol-disulfide exchange or monomer-dimer equilibrium preventing a detailed NMR analysis. Recently, the expression of various types of recombinant beta LGs combined with heteronuclear NMR analysis has significantly improved understanding of the physico-chemical properties of beta LG. In this review, we address several topics including pH-dependent structural dynamics, ligand binding, and the complex folding mechanism with non-native intermediates. These unique properties might be brought about by conformational frustration of the beta LG structure, partly attributed to the relatively large molecular size of beta LG. We expect studies with beta LG to continue to reveal various important findings, difficult to obtain with small globular proteins, leading to a more comprehensive understanding of the conformation, dynamics and folding of proteins. PMID:19362581

  17. 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.

  18. Improved 1H amide resonance line narrowing in oriented sample solid-state NMR of membrane proteins in phospholipid bilayers

    NASA Astrophysics Data System (ADS)

    Lu, George J.; Park, Sang Ho; Opella, Stanley J.

    2012-07-01

    We demonstrate 1H amide resonance line widths <300 Hz in 1H/15N heteronuclear correlation (HETCOR) spectra of membrane proteins in aligned phospholipid bilayers. This represents a substantial improvement over typically observed line widths of ˜1 kHz. Furthermore, in a proton detected local field (PDLF) version of the experiment that measures heteronuclear dipolar couplings, line widths <130 Hz are observed. This dramatic line narrowing of 1H amide resonances enables many more individual signals to be resolved and assigned from uniformly 15N labeled membrane proteins in phospholipid bilayers under physiological conditions of temperature and pH. Finding that the decrease in line widths occurs only for membrane proteins that undergo fast rotational diffusion around the bilayer normal, but not immobile molecules, such as peptide single crystals, identifies a potential new direction for pulse sequence development that includes overall molecular dynamics in their design.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. Multiple acquisition/multiple observation separated local field/chemical shift correlation solid-state magic angle spinning NMR spectroscopy.

    PubMed

    Das, Bibhuti B; Opella, Stanley J

    2014-08-01

    Multiple acquisition spectroscopy (MACSY) experiments that enable multiple free induction decays to be recorded during individual experiments are demonstrated. In particular, the experiments incorporate separated local field spectroscopy into homonuclear and heteronuclear correlation spectroscopy. The measured heteronuclear dipolar couplings are valuable in structure determination as well as in enhancing resolution by providing an additional frequency axis. In one example four different three-dimensional spectra are obtained in a single experiment, demonstrating that substantial potential saving in experimental time is available when multiple multi-dimensional spectra are required as part of solid-state NMR studies. PMID:25023566

  4. Multiple Acquisition/Multiple Observation Separated Local Field/Chemical Shift Correlation Solid-state Magic Angle Spinning NMR Spectroscopy

    PubMed Central

    Das, Bibhuti B.; Opella, Stanley J.

    2014-01-01

    Multiple acquisition spectroscopy (MACSY) experiments that enable multiple free induction decays to be recorded during individual experiments are demonstrated. In particular, the experiments incorporate separated local field spectroscopy into homonuclear and heteronuclear correlation spectroscopy. The measured heteronuclear dipolar couplings are valuable in structure determination as well as in enhancing resolution by providing an additional frequency axis. In one example four different three-dimensional spectra are obtained in a single experiment, demonstrating that substantial potential saving in experimental time is available when multiple multi-dimensional spectra are required as part of solid-state NMR studies. PMID:25023566

  5. 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

  6. 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

  7. Matter-wave solitons in heteronuclear atomic Bose-Einstein condensates with synchronously controllable interactions and potentials

    SciTech Connect

    Ding, Cai-Ying; Zhang, Xiao-Fei; Liu, W. M.; Zhao, Dun; Luo, Hong-Gang

    2011-11-15

    We investigate exact matter-wave soliton pairs of two-component heteronuclear atomic Bose-Einstein condensates with tunable interactions and harmonic potentials by using a combination of the homogeneous balance principle and the F-expansion technique. Our results show that exact matter-wave soliton pairs are asymmetric where their existence requires some restrictive conditions corresponding to experimentally controllable interactions and harmonic potential parameters. In contrast to homonuclear systems, the potentials for two components in heteronuclear systems are different, which is due to the mass of two components being unequal. Considering two explicit situations of the interaction parameters, we further explore the collision dynamics of the soliton pairs with opposite velocities by synchronously controlling the interaction and potential parameters. The collision dynamics occur during and after the simultaneous evaporative cooling of two condensates. The results show that collisions are elastic and that the solitons after the collision can keep their identities. In addition, we find that the amplitudes of the soliton pairs periodically grow with time during the cooling process and, for the same initial conditions, the collision time of the soliton pair without gain is delayed compared with that with gain. We also discuss how to observe these new phenomena in future experiments.

  8. 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

  9. 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.

  10. Comprehensive description of NMR cross-correlated relaxation under anisotropic molecular tumbling and correlated local dynamics on all time scales

    NASA Astrophysics Data System (ADS)

    Vögeli, Beat

    2010-07-01

    A simple general expression for the NMR cross-correlated relaxation rate under anisotropic molecular tumbling is presented for globular proteins. The derivation includes effects of fast and slow motion of the interaction tensors and correlation between them. Expressions suitable for practical analysis are tailored in dependence of standard order parameters of the individual interactions. It is shown that these order parameters must be sensitive to slow motion (slower than molecular tumbling) for detection of slow correlated motion. Such order parameters are those obtained from residual dipolar couplings but not those obtained from T1, T2, and heteronuclear Nuclear Overhauser Enhancement measurements.

  11. 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

  12. Relative merits of rCWA and XiX heteronuclear spin decoupling in solid-state magic-angle-spinning NMR spectroscopy: A bimodal Floquet analysis

    NASA Astrophysics Data System (ADS)

    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.

  13. 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

  14. 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

  15. 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

  16. Simple, efficient protocol for enzymatic synthesis of uniformly 13C, 15N-labeled DNA for heteronuclear NMR studies.

    PubMed Central

    Masse, J E; Bortmann, P; Dieckmann, T; Feigon, J

    1998-01-01

    The use of uniformly 13C,15N-labeled RNA has greatly facilitated structural studies of RNA oligonucleotides by NMR. Application of similar methodologies for the study of DNA has been limited, primarily due to the lack of adequate methods for sample preparation. Methods for both chemical and enzymatic synthesis of DNA oligonucleotides uniformly labeled with 13C and/or 15N have been published, but have not yet been widely used. We have developed a modified procedure for preparing uniformly 13C,15N-labeled DNA based on enzymatic synthesis using Taq DNA polymerase. The highly efficient protocol results in quantitative polymerization of the template and approximately 80% incorporation of the labeled dNTPs. Procedures for avoiding non-templated addition of nucleotides or for their removal are given. The method has been used to synthesize several DNA oligonucleotides, including two complementary 15 base strands, a 32 base DNA oligonucleotide that folds to form an intramolecular triplex and a 12 base oligonucleotide that dimerizes and folds to form a quadruplex. Heteronuclear NMR spectra of the samples illustrate the quality of the labeled DNA obtained by these procedures. PMID:9592146

  17. 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

  18. 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.

  19. Interaction of yeast iso-1-cytochrome c with cytochrome c peroxidase investigated by [15N, 1H] heteronuclear NMR spectroscopy.

    PubMed

    Worrall, J A; Kolczak, U; Canters, G W; Ubbink, M

    2001-06-19

    The interaction of yeast iso-1-cytochrome c with its physiological redox partner cytochrome c peroxidase has been investigated using heteronuclear NMR techniques. Chemical shift perturbations for both 15N and 1H nuclei arising from the interaction of isotopically enriched 15N cytochrome c with cytochrome c peroxidase have been observed. For the diamagnetic, ferrous cytochrome c, 34 amides are affected by binding, corresponding to residues at the front face of the protein and in agreement with the interface observed in the 1:1 crystal structure of the complex. In contrast, for the paramagnetic, ferric protein, 56 amides are affected, corresponding to residues both at the front and toward the rear of the protein. In addition, the chemical shift perturbations were larger for the ferric protein. Using experimentally observed pseudocontact shifts the magnetic susceptibility tensor of yeast iso-1-cytochrome c in both the free and bound forms has been calculated with HN nuclei as inputs. In contrast to an earlier study, the results indicate that there is no change in the geometry of the magnetic axes for cytochrome c upon binding to cytochrome c peroxidase. This leads us to conclude that the additional effects observed for the ferric protein arise either from a difference in binding mode or from the more flexible overall structure causing a transmittance effect upon binding. PMID:11401551

  20. 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 O2O2‧ 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.

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

    PubMed

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

    2016-03-28

    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. PMID:27036444

  2. 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.

  3. 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

  4. 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.

  5. Heteronuclear NMR assignments and secondary structure of the coiled coil trimerization domain from cartilage matrix protein in oxidized and reduced forms.

    PubMed Central

    Wiltscheck, R.; Kammerer, R. A.; Dames, S. A.; Schulthess, T.; Blommers, M. J.; Engel, J.; Alexandrescu, A. T.

    1997-01-01

    The C-terminal oligomerization domain of chicken cartilage matrix protein is a trimeric coiled coil comprised of three identical 43-residue chains. NMR spectra of the protein show equivalent magnetic environments for each monomer, indicating a parallel coiled coil structure with complete threefold symmetry. Sequence-specific assignments for 1H-, 15N-, and 13C-NMR resonances have been obtained from 2D 1H NOESY and TOCSY spectra, and from 3D HNCA, 15N NOESY-HSQC, and HCCH-TOCSY spectra. A stretch of alpha-helix encompassing five heptad repeats (35 residues) has been identified from intra-chain HN-HN and HN-H alpha NOE connectivities. 3JHNH alpha coupling constants, and chemical shift indices. The alpha-helix begins immediately downstream of inter-chain disulfide bonds between residues Cys 5 and Cys 7, and extends to near the C-terminus of the molecule. The threefold symmetry of the molecule is maintained when the inter-chain disulfide bonds that flank the N-terminus of the coiled coil are reduced. Residues Ile 21 through Glu 36 show conserved chemical shifts and NOE connectivities, as well as strong protection from solvent exchange in the oxidized and reduced forms of the protein. By contrast, residues Ile 10 through Val 17 show pronounced chemical shift differences between the oxidized and reduced protein. Strong chemical exchange NOEs between HN resonances and water indicate solvent exchange on time scales faster than 10 s, and suggests a dynamic fraying of the N-terminus of the coiled coil upon reduction of the disulfide bonds. Possible roles for the disulfide crosslinks of the oligomerization domain in the function of cartilage matrix protein are proposed. PMID:9260286

  6. Mechanism of Solid-State Thermolysis of Ammonia Boraine: 15N NMR Study Using Fast Magic-Angle Spinning and Dynamic Nuclear Polarization

    SciTech Connect

    Kobayashi, Takeshi; Gupta, Shalabh; Caporini, Marc A; Pecharsky, Vitalij K; Pruski, Marek

    2014-08-28

    The solid-state thermolysis of ammonia borane (NH3BH3, AB) was explored using state-of-the-art 15N solid-state NMR spectroscopy, including 2D indirectly detected 1H{15N} heteronuclear correlation and dynamic nuclear polarization (DNP)-enhanced 15N{1H} cross-polarization experiments as well as 11B NMR. The complementary use of 15N and 11B NMR experiments, supported by density functional theory calculations of the chemical shift tensors, provided insights into the dehydrogenation mechanism of AB—insights that have not been available by 11B NMR alone. Specifically, highly branched polyaminoborane derivatives were shown to form from AB via oligomerization in the “head-to-tail” manner, which then transform directly into hexagonal boron nitride analog through the dehydrocyclization reaction, bypassing the formation of polyiminoborane.

  7. Diagonal free homonuclear correlation using heteronuclei at natural abundance.

    PubMed

    Baishya, Bikash

    2015-07-01

    Homonuclear correlated spectroscopy such as COSY and TOCSY provides crucial structural information. In all homonuclear correlation, the most intense peaks are represented by the diagonal. As a result, the useful cross peaks close to the diagonal get obscured by the huge tails of diagonal peaks. Herein, we show that by editing the proton magnetization by a 13C nucleus in natural abundance, it is possible to eliminate the inphase coherence or untransferred magnetization that leads to the diagonal peak while retaining the antiphase coherence or transferred magnetization required for creation of cross peak. After the coherence transfer step, the untransferred magnetization directly attached to 13C evolves under one bond heteronuclear coupling while the transferred transverse magnetization directly attached to remote 12C does not. As a result, the untransferred magnetization directly attached to 13C can be converted to an unobservable heteronuclear multiple quantum coherence leading to a diagonal free correlated spectrum with a sensitivity penalty of two orders of magnitude but comparable to HSQC kind of experiments at natural abundance. The method demonstrated for COSY and TOCSY allows all proton-proton correlations to be observed except the geminal proton-proton correlations. Further, protons directly attached to heteronuclei other than 13C must be scalar coupled to protons directly attached to 13C to have a detectable cross peak. PMID:26001137

  8. Distinct mechanistic differences in the hydrogen-atom transfer from methane and water by the heteronuclear oxide cluster [Ga2 MgO4](.).

    PubMed

    Li, Jilai; Wu, Xiao-Nan; Zhou, Shaodong; Tang, Shiya; Schlangen, Maria; Schwarz, Helmut

    2015-10-12

    The thermal reactions of the heteronuclear oxide cluster [Ga2 MgO4 ](.+) with methane and water have been studied using state-of-the-art gas-phase experiments in conjunction with quantum-chemical calculations. The significant reactivity differences, favoring activation of the strong OH bond, can be ascribed to a proton-coupled electron transfer (PCET) mechanism operative in the activation of water. This study deepens our mechanistic understanding on how inert RH bonds are cleaved by metal oxides. PMID:26136380

  9. 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.

  10. 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

  11. Unexpected effects of third-order cross-terms in heteronuclear spin systems under simultaneous radio-frequency irradiation and magic-angle spinning NMR

    NASA Astrophysics Data System (ADS)

    Tatton, Andrew S.; Frantsuzov, Ilya; Brown, Steven P.; Hodgkinson, Paul

    2012-02-01

    We recently noted [R. K. Harris, P. Hodgkinson, V. Zorin, J.-N. Dumez, B. Elena, L. Emsley, E. Salager, and R. Stein, Magn. Reson. Chem. 48, S103 (2010), 10.1002/mrc.2636] anomalous shifts in apparent 1H chemical shifts in experiments using 1H homonuclear decoupling sequences to acquire high-resolution 1H NMR spectra for organic solids under magic-angle spinning (MAS). Analogous effects were also observed in numerical simulations of model 13C,1H spin systems under homonuclear decoupling and involving large 13C,1H dipolar couplings. While the heteronuclear coupling is generally assumed to be efficiently suppressed by sample spinning at the magic angle, we show that under conditions typically used in solid-state NMR, there is a significant third-order cross-term from this coupling under the conditions of simultaneous MAS and homonuclear decoupling for spins directly bonded to 1H. This term, which is of the order of 100 Hz under typical conditions, explains the anomalous behaviour observed on both 1H and 13C spins, including the fast dephasing observed in 13C{1H} heteronuclear spin-echo experiments under 1H homonuclear decoupling. Strategies for minimising the impact of this effect are also discussed.

  12. Tuning the electronic properties and work functions of graphane/fully hydrogenated h-BN heterobilayers via heteronuclear dihydrogen bonding and electric field control.

    PubMed

    Liang, Qiuhua; Jiang, Junke; Meng, Ruishen; Ye, Huaiyu; Tan, Chunjian; Yang, Qun; Sun, Xiang; Yang, Daoguo; Chen, Xianping

    2016-06-28

    Using density functional theory calculations with van der Waals correction, we show that the electronic properties (band gap and carrier mobility) and work functions of graphane/fully hydrogenated hexagonal boron nitride (G/fHBN) heterobilayers can be favorably tuned via heteronuclear dihydrogen bonding (C-HH-B and C-HH-N) and an external electric field. Our results reveal that G/fHBN heterobilayers have different direct band gaps of ∼1.2 eV and ∼3.5 eV for C-HH-B and C-HH-N bonds, respectively. In particular, these band gaps can be effectively modulated by altering the direction and strength of the external electric field (E-field), and correspondingly exhibit a semiconductor-metal transition. The conformation and stability of G/fHBN heterobilayers show a strong dependence on the heteronuclear dihydrogen bonding. Fantastically, these bonds are stable enough under a considerable external E-field as compared with other van der Waals (vdW) 2D layered materials. The mobilities of G/fHBN heterobilayers we predicted are hole-dominated, reasonably high (improvable up to 200 cm(2) V(-1) s(-1)), and extremely isotropic. We also demonstrate that the work function of G/fHBN heterobilayers is very sensitive to the external E-field and is extremely low. These findings make G/fHBN heterobilayers very promising materials for field-effect transistors and light-emitting devices, and inspire more efforts in the development of 2D material systems using weak interlayer interactions and electric field control. PMID:27265511

  13. 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.}

  14. 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.

  15. 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.

  16. Correlation Spectroscopy with Two Simultaneous Soft Pulses (TSETSE)

    NASA Astrophysics Data System (ADS)

    Nuzillard, J. M.; Freeman, R.

    An analysis is presented of a new correlation experiment where two self-focusing soft pulses are applied simultaneously to two coupled spins I and S. It is shown that for a certain pulse duration, antiphase dispersion-mode doublets are observed at both sites, although the corresponding single-excitation experiment displays only in-phase absorption. At longer pulse durations appreciable amounts of multiple-quantum coherence are created. Simulations of this behavior are presented in the form of magnetization trajectories during a pair of soft E-BURP-2 pulses, and these predictions are compared with experiments on heteronuclear two-spin systems. The effect (called "TSETSE") shows promise as a one-dimensional correlation experiment and as a practical method of determining scalar coupling constants. An application to the determination of long-range C-H couplings in brucine is reported.

  17. Determination of NH proton chemical shift anisotropy with 14N-1H heteronuclear decoupling using ultrafast magic angle spinning solid-state NMR

    NASA Astrophysics Data System (ADS)

    Pandey, Manoj Kumar; Nishiyama, Yusuke

    2015-12-01

    The extraction of chemical shift anisotropy (CSA) tensors of protons either directly bonded to 14N nuclei (I = 1) or lying in their vicinity using rotor-synchronous recoupling pulse sequence is always fraught with difficulty due to simultaneous recoupling of 14N-1H heteronuclear dipolar couplings and the lack of methods to efficiently decouple these interactions. This difficulty mainly arises from the presence of large 14N quadrupolar interactions in comparison to the rf field that can practically be achieved. In the present work it is demonstrated that the application of on-resonance 14N-1H decoupling with rf field strength ∼30 times weaker than the 14N quadrupolar coupling during 1H CSA recoupling under ultrafast MAS (90 kHz) results in CSA lineshapes that are free from any distortions from recoupled 14N-1H interactions. With the use of extensive numerical simulations we have shown the applicability of our proposed method on a naturally abundant L-Histidine HCl·H2O sample.

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    Fifteen lanthanide-copper heteronuclear compounds, formulated as [CuLn2(pzdc)4(H2O)6]·xH2O (1-6(x=2), 8(x=3), 9-10(x=4); [CuLn2(pzdc)4(H2O)4]·xH2O (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); H2pzdc (C6H4N2O4)=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 {4.62}2{42.62.82}{63}2{65.8}2 topology. Using 1 mol cm-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.

  20. A molecular dynamics simulation-based interpretation of nuclear magnetic resonance multidimensional heteronuclear spectra of α-synuclein·dopamine adducts.

    PubMed

    Dibenedetto, Domenica; Rossetti, Giulia; Caliandro, Rocco; Carloni, Paolo

    2013-09-24

    Multidimensional heteronuclear nuclear magnetic resonance (NMR) spectroscopy provides valuable structural information about adducts between naturally unfolded proteins and their ligands. These are often highly pharmacologically relevant. Unfortunately, the determination of the contributions to observed chemical shifts changes upon ligand binding is complicated. Here we present a tool that uses molecular dynamics (MD) trajectories to help interpret two-dimensional (2D) NMR data. We apply this tool to the naturally unfolded protein human α-synuclein interacting with dopamine, an inhibitor of fibril formation, and with its oxidation products in water solutions. By coupling 2D NMR experiments with MD simulations of the adducts in explicit water, the tool confirms with experimental data that the ligands bind preferentially to (125)YEMPS(129) residues in the C-terminal region and to a few residues of the so-called NAC region consistently. It also suggests that the ligands might cause conformational rearrangements of distal residues located at the N-terminus. Hence, the performed analysis provides a rationale for the observed changes in chemical shifts in terms of direct contacts with the ligand and conformational changes in the protein. PMID:23964651

  1. Heteronuclear transverse and longitudinal relaxation in AX4 spin systems: Application to 15N relaxations in 15NH4+

    PubMed Central

    Werbeck, Nicolas D.; Hansen, D. Flemming

    2014-01-01

    The equations that describe the time-evolution of transverse and longitudinal 15N magnetisations in tetrahedral ammonium ions, 15NH4+, are derived from the Bloch-Wangsness-Redfield density operator relaxation theory. It is assumed that the relaxation of the spin-states is dominated by (1) the intra-molecular 15N–1H and 1H–1H dipole–dipole interactions and (2) interactions of the ammonium protons with remote spins, which also include the contribution to the relaxations that arise from the exchange of the ammonium protons with the bulk solvent. The dipole–dipole cross-correlated relaxation mechanisms between each of the 15N–1H and 1H–1H interactions are explicitly taken into account in the derivations. An application to 15N-ammonium bound to a 41 kDa domain of the protein DnaK is presented, where a comparison between experiments and simulations show that the ammonium ion rotates rapidly within its binding site with a local correlation time shorter than approximately 1 ns. The theoretical framework provided here forms the basis for further investigations of dynamics of AX4 spin systems, with ammonium ions in solution and bound to proteins of particular interest. PMID:25128779

  2. Opposite Dysregulation of Fragile-X Mental Retardation Protein and Heteronuclear Ribonucleoprotein C Protein Associates with Enhanced APP Translation in Alzheimer Disease.

    PubMed

    Borreca, Antonella; Gironi, Katia; Amadoro, Giusy; Ammassari-Teule, Martine

    2016-07-01

    Amyloid precursor protein (APP) is overexpressed in familiar and sporadic Alzheimer Disease (AD) patients suggesting that, in addition to abnormalities in APP cleavage, enhanced levels of APP full length might contribute to the pathology. Based on data showing that the two RNA binding proteins (RBPs), Fragile-X Mental Retardation Protein (FMRP) and heteronuclear Ribonucleoprotein C (hnRNP C), exert an opposite control on APP translation, we have analyzed whether expression and translation of these two RBPs vary in relation to changes in APP protein and mRNA levels in the AD brain at 1, 3, and 6 months of age. Here, we show that, as expected, human APP is overexpressed in hippocampal total extract from Tg2576 mice at all age points. APP overexpression, however, is not stable over time but reaches its maximal level in 1-month-old mutants in association with the stronger (i) reduction of FMRP and (ii) augmentation of hnRNP C. APP levels then decrease progressively as a function of age in close relationship with the gradual normalization of FMRP and hnRNP C levels. Consistent with the mouse data, expression of FMRP and hnRNP C are, respectively, decreased and increased in hippocampal synaptosomes from sporadic AD patients. Our findings identify two RBP targets that might be manipulated for reducing abnormally elevated levels of APP in the AD brain, with the hypothesis that acting upstream of amyloidogenic processing might contribute to attenuate the amyloid burden. PMID:26048669

  3. 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.

  4. 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

  5. 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.

  6. Selectively Labeling the Heterologous Protein in Escherichia coli for NMR Studies: A Strategy to Speed Up NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Almeida, F. C. L.; Amorim, G. C.; Moreau, V. H.; Sousa, V. O.; Creazola, A. T.; Américo, T. A.; Pais, A. P. N.; Leite, A.; Netto, L. E. S.; Giordano, R. J.; Valente, A. P.

    2001-01-01

    Nuclear magnetic resonance is an important tool for high-resolution structural studies of proteins. It demands high protein concentration and high purity; however, the expression of proteins at high levels often leads to protein aggregation and the protein purification step can correspond to a high percentage of the overall time in the structural determination process. In the present article we show that the step of sample optimization can be simplified by selective labeling the heterologous protein expressed in Escherichia coli by the use of rifampicin. Yeast thioredoxin and a coix transcription factor Opaque 2 leucine zipper (LZ) were used to show the effectiveness of the protocol. The 1H/15N heteronuclear correlation two-dimensional NMR spectrum (HMQC) of the selective 15N-labeled thioredoxin without any purification is remarkably similar to the spectrum of the purified protein. The method has high yields and a good 1H/15N HMQC spectrum can be obtained with 50 ml of M9 growth medium. Opaque 2 LZ, a difficult protein due to the lower expression level and high hydrophobicity, was also probed. The 15N-edited spectrum of Opaque 2 LZ showed only the resonances of the protein of heterologous expression (Opaque 2 LZ) while the 1H spectrum shows several other resonances from other proteins of the cell lysate. The demand for a fast methodology for structural determination is increasing with the advent of genome/proteome projects. Selective labeling the heterologous protein can speed up NMR structural studies as well as NMR-based drug screening. This methodology is especially effective for difficult proteins such as hydrophobic transcription factors, membrane proteins, and others.

  7. Origin of the step structure of molecular exchange-correlation potentials.

    PubMed

    Kohut, Sviataslau V; Polgar, Alexander M; Staroverov, Viktor N

    2016-08-21

    The exact exchange-correlation potential of a stretched heteronuclear diatomic molecule exhibits a localized upshift in the region around the more electronegative atom; by this device the Kohn-Sham scheme ensures that the molecule dissociates into neutral atoms. Baerends and co-workers showed earlier that the upshift originates in the response part of the exchange-correlation potential. We describe a reliable numerical method for constructing the response potential of a given many-electron system and report accurate plots of this quantity. We also demonstrate that the step feature itself can be obtained directly from the interacting wavefunction of the system by computing the so-called average local electron energy. These findings illustrate in previously unavailable detail the mechanism of the formation of the upshift and the role played by static correlation in this process. PMID:26983370

  8. 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

  9. 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

  10. Getting to know the nitrogen next door: HNMBC measurements of amino sugars

    NASA Astrophysics Data System (ADS)

    Limtiaco, John F. K.; Langeslay, Derek J.; Beni, Szabolcs; Larive, Cynthia K.

    2011-04-01

    Long-range 1H- 15N correlations detected by the heteronuclear multiple-bond correlation (HMBC) experiment are explored for the characterization of amino sugars. The gradient-enhanced HMBC, IMPACT-HMBC, and a modified pulse sequence with the 1J-filters removed, IMPACT-HNMBC, are compared for sensitivity and resolution. 15N chemical shifts and long-range proton correlations are reported using the IMPACT-HNMBC experiment for N-acetyl-glucosamine, N-acetyl-galactosamine, and for a series of glucosamine analogs with an N-sulfo substitution, unmodified amino group, and 6- O-sulfonation. As is common with sugars, for all the compounds examined both anomeric forms are present in solution. For each compound studied, the 15N chemical shifts of the α anomer are downfield of the β form. For the N-acetylated sugars, the β anomer has a unique long-range 15N correlation to the anomeric proton not observed for the α anomer. Though N-sulfonation results in a significant change in the 15N chemical shift of the glucosamine analogs, 6- O sulfo substitution has no significant effect on the local environment of the amino nitrogen. For N-acetylated sugars in D 2O solution, peaks in the 15N projection of the HMBC spectrum appear as triplets as a result of J-modulation due to 2H- 15N coupling.

  11. Synthesis of rhodium(III) complexes with tris/tetrakis-benzimidazoles and benzothiazoles--quick identification of cyclometallation by nuclear magnetic resonance spectroscopy.

    PubMed

    Chandrashekhar, N; Gayathri, V; Nanje Gowda, N M

    2009-08-01

    Reactions of rhodium(III) halides with multidentate N,S-heterocycles, (LH3) 1,3,5-tris(benzimidazolyl)benzene (L1H3; 1), 1,3,5-tris(N-methylbenzimidazolyl) benzene (L2H3; 2) and 1,3,5-tris(benzothiazolyl)benzene (L3H3; 3), in the molar ratio 1:1 in methanol-chloroform produced mononuclear cyclometallated products of the composition [RhX2(LH2)(H2O)] (X = Cl, Br, I; LH2 = L1H2, L2H2, L3H2). When the metal to ligand (1-3 or 1,2,4,5-tetrakis(benzothiazolyl)benzene [L4H2; 4]) molar ratio was 2:1, the reactions yielded binuclear complexes of the compositions [Rh2Cl5(LH2)(H2O)3] (LH2 = L1H2, L2H2, L3H2) and [Rh2X4(L4)(H2O)2] (X = Cl, Br, I). Elemental analysis, IR and 1H nuclear magnetic resonance (NMR) chemical shifts supported the binuclear nature of the complexes. Cyclometallation was detected by conventional 13C NMR spectra that showed a doublet around approximately 190 ppm. Cyclometallation was also detected by gradient-enhanced heteronuclear multiple bond correlation (g-HMBC) experiment that showed cross-peaks between the cyclometallated carbon and the central benzene ring protons of 1-3. Cyclometallation was substantiated by two-dimensional 1H-1H correlated experiments (gradient-correlation spectroscopy and rotating frame Overhauser effect spectroscopy) and 1H-13C single bond correlated two-dimensional NMR experiments (gradient-enhanced heteronuclear single quantum coherence). The 1H-15N g-HMBC experiment suggested the coordination of the heterocycles to the metal ion via tertiary nitrogen. PMID:19444858

  12. 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.

  13. Backbone dynamics of the oligomerization domain of p53 determined from 15N NMR relaxation measurements.

    PubMed

    Clubb, R T; Omichinski, J G; Sakaguchi, K; Appella, E; Gronenborn, A M; Clore, G M

    1995-05-01

    The backbone dynamics of the tetrameric p53 oligomerization domain (residues 319-360) have been investigated by two-dimensional inverse detected heteronuclear 1H-15N NMR spectroscopy at 500 and 600 MHz. 15N T1, T2, and heteronuclear NOEs were measured for 39 of 40 non-proline backbone NH vectors at both field strengths. The overall correlation time for the tetramer, calculated from the T1/T2 ratios, was found to be 14.8 ns at 35 degrees C. The correlation times and amplitudes of the internal motions were extracted from the relaxation data using the model-free formalism (Lipari G, Szabo A, 1982, J Am Chem Soc 104:4546-4559). The internal dynamics of the structural core of the p53 oligomerization domain are uniform and fairly rigid, with residues 327-354 exhibiting an average generalized order parameter (S2) of 0.88 +/- 0.08. The N- and C-termini exhibit substantial mobility and are unstructured in the solution structure of p53. Residues located at the N- and C-termini, in the beta-sheet, in the turn between the alpha-helix and beta-sheet, and at the C-terminal end of the alpha-helix display two distinct internal motions that are faster than the overall correlation time. Fast internal motions (< or = 20 ps) are within the extreme narrowing limit and are of uniform amplitude. The slower motions (0.6-2.2 ns) are outside the extreme narrowing limit and vary in amplitude.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7663341

  14. 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

  15. 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

  16. Characterization of proteins by in-cell NMR spectroscopy in cultured mammalian cells.

    PubMed

    Barbieri, Letizia; Luchinat, Enrico; Banci, Lucia

    2016-06-01

    In-cell NMR spectroscopy is a unique tool for characterizing biological macromolecules in their physiological environment at atomic resolution. Recent progress in NMR instruments and sample preparation methods allows functional processes, such as metal uptake, disulfide-bond formation and protein folding, to be analyzed by NMR in living, cultured human cells. This protocol describes the necessary steps to overexpress one or more proteins of interest inside human embryonic kidney 293T (HEK293T) cells, and it explains how to set up in-cell NMR experiments. The cDNA is transiently transfected as a complex with a cationic polymer (DNA:PEI (polyethylenimine)), and protein expression is carried on for 2-3 d, after which the NMR sample is prepared. (1)H and (1)H-(15)N correlation NMR experiments (for example, using band-selective optimized flip-angle short-transient heteronuclear multiple quantum coherence (SOFAST-HMQC)) can be carried out in <2 h, ensuring cell viability. Uniform (15)N labeling and amino-acid-specific (e.g., cysteine, methionine) labeling schemes are possible. The entire procedure takes 4 d from cell culture seeding to NMR data collection. PMID:27196722

  17. Pf1 bacteriophage hydration by magic angle spinning solid-state NMR

    NASA Astrophysics Data System (ADS)

    Sergeyev, Ivan V.; Bahri, Salima; Day, Loren A.; McDermott, Ann E.

    2014-12-01

    High resolution two- and three-dimensional heteronuclear correlation spectroscopy (1H-13C, 1H-15N, and 1H-13C-13C HETCOR) has provided a detailed characterization of the internal and external hydration water of the Pf1 virion. This long and slender virion (2000 nm × 7 nm) contains highly stretched DNA within a capsid of small protein subunits, each only 46 amino acid residues. HETCOR cross-peaks have been unambiguously assigned to 25 amino acids, including most external residues 1-21 as well as residues 39-40 and 43-46 deep inside the virion. In addition, the deoxyribose rings of the DNA near the virion axis are in contact with water. The sets of cross-peaks to the DNA and to all 25 amino acid residues were from the same hydration water 1H resonance; some of the assigned residues do not have exchangeable side-chain protons. A mapping of the contacts onto structural models indicates the presence of water "tunnels" through a highly hydrophobic region of the capsid. The present results significantly extend and modify results from a lower resolution study, and yield a comprehensive hydration surface map of Pf1. In addition, the internal water could be distinguished from external hydration water by means of paramagnetic relaxation enhancement. The internal water population may serve as a conveniently localized magnetization reservoir for structural studies.

  18. Water-Protein Interactions of an Arginine-Rich Membrane Peptide in Lipid Bilayers Investigated by Solid-State NMR Spectroscopy

    PubMed Central

    Li, Shenhui; Su, Yongchao; Luo, Wenbin; Hong, Mei

    2010-01-01

    The interaction of an arginine (Arg) residue with water in a transmembrane antimicrobial peptide, PG-1, is investigated by two-dimensional heteronuclear correlation (HETCOR) solid-state NMR spectroscopy. Using 13C and 15N dipolar-edited 1H-15N HETCOR experiments, we unambiguously assigned a water-guanidinium cross peak that is distinct from intramolecular protein-protein cross peaks. This water-Arg cross peak was detected within a short 1H spin diffusion mixing time of 1 ms, indicating that water is in close contact with the membrane-inserted guanidinium. Together with previously observed short guanidinium-phosphate distances, these solid-state NMR data suggest that the Arg sidechains of PG-1 are stabilized by both hydration water and neutralizing lipid headgroups. The membrane deformation that occurs when water and lipid headgroups are pulled into the hydrophobic region of the bilayer is symptomatic of the membrane-disruptive function of this antimicrobial peptide. The water-Arg interactions observed here provide direct experimental evidence for molecular dynamics simulations of the solvation of Arg sidechains of membrane proteins by deeply embedded water in lipid bilayers. PMID:20199036

  19. Washington Correlator

    NASA Technical Reports Server (NTRS)

    Hall, David M.; Boboltz, David

    2013-01-01

    This report summarizes the activities of the Washington Correlator for 2012. The Washington Correlator provides up to 80 hours of attended processing per week plus up to 40 hours of unattended operation, primarily supporting Earth Orientation and astrometric observations. In 2012, the major programs supported include the IVS-R4, IVS-INT, APSG, and CRF observing sessions.

  20. 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

  1. Interaction with DNA of a heteronuclear [Na2Cu4] coordination cluster obtained from the assembly of two hydroxo-bridged [Cu(II)2] units by a dimeric sodium nitrate template.

    PubMed

    Mandal, Debashree; Chauhan, Mala; Arjmand, Farukh; Aromí, Guillem; Ray, Debashis

    2009-11-14

    The heteronuclear [Na(2)Cu(4)(bemp)(2)(OH)(2)(NO(3))(2)(OH(2))(4)] x 5 H(2)O (1 x 5H(2)O; H(3)bemp: 2,6-bis-[(2-hydroxyethylimino)-methyl]-4-methyl-phenol) cluster has been synthesized in aqueous-methanol at room temperature and structurally characterized. The water soluble complex is obtained from the template assembly of two [Cu(2)(bemp)(OH)] neutral fragments through their weak oxophillic interactions with two interconnected NaNO(3) units as core. Four [Na(2)Cu(4)] units form a metal-organic cage arrangement in the crystal lattice that traps a (H(2)O)(7) cluster. Variable-temperature magnetic susceptibility measurements (2-300 K) reveals a strong antiferromagnetic coupling between the Cu(II) ions within the dimers with J = -124.1 cm(-1) (in the H = -2JS(1)S(2) convention). The interaction of complex 1 x 3H(2)O with calf thymus DNA (binding constant K(b), 4.6 x 10(4) M(-1)) in Tris buffer was studied by UV-visible and emission titration, and cyclic voltammetry. The hexanuclear Na(2)Cu(4) complex also binds double-stranded supercoiled plasmid pBR322 DNA and displays efficient hydrolytic cleavage. The hydrolytic mechanism is supported by evidence from DNA relegation employing T4 ligase assay and reactive oxygen species (ROS) quenching cleavage experiments. PMID:20449195

  2. Bond Functions and Core Correlation Energy Contributions To HeBe Potential

    NASA Astrophysics Data System (ADS)

    Shalabi, A. S.; Nour, E. M.; Abdel Halim, W. S.

    An empirical scheme for implementation of bond functions in heteronuclear diatomics is suggested and applied to HeBe using universal even-tempered functions. The effects of bond functions and core-correlation energy on the interaction potential of HeBe calculated at the uncorrelated (SCF) and correlated (MBPT and CC) levels are examined. The results confirm that an accuracy of sub μ Hartree level can be obtained using even-tempered functions with s-, p-, and d- symmetry and that bond functions of size {4s2p} for He and {6s3p} for Be recovers 100% of energy lowering obtained from the addition of 10d atom-centered functions to He and 13d atom centred functions to Be. The various treatments of the electron correlation, conclude that the system is interacting weakly with a well depth from 14.5-24.7 μEh at a separation near 9.1a0 compared with 20.7-25.5 μEh previously reported with a rather limited basis set. The most reliable well depth corrected for BSSE (19.0 μEh) was obtained at the CC-SD(T)level at separation of 8.71a0 taking into account the effects of bond functions and core correlation energy. Potential energy curves at the CC-SD(T) valence and CC-SD(T) valence + core correlation levels are analyzed in analytical forms in terms of exchange repulsion, induction and dispersion components.

  3. Backbone dynamics of barstar: a (15)N NMR relaxation study.

    PubMed

    Sahu, S C; Bhuyan, A K; Majumdar, A; Udgaonkar, J B

    2000-12-01

    Backbone dynamics of uniformly (15)N-labeled barstar have been studied at 32 degrees C, pH 6.7, by using (15)N relaxation data obtained from proton-detected 2D (1)H-(15)N NMR spectroscopy. (15)N spin-lattice relaxation rate constants (R(1)), spin-spin relaxation rate constants (R(2)), and steady-state heteronuclear (1)H-(15)N NOEs have been determined for 69 of the 86 (excluding two prolines and the N-terminal residue) backbone amide (15)N at a magnetic field strength of 14.1 Tesla. The primary relaxation data have been analyzed by using the model-free formalism of molecular dynamics, using both isotropic and axially symmetric diffusion of the molecule, to determine the overall rotational correlation time (tau(m)), the generalized order parameter (S(2)), the effective correlation time for internal motions (tau(e)), and NH exchange broadening contributions (R(ex)) for each residue. As per the axially symmetric diffusion, the ratio of diffusion rates about the unique and perpendicular axes (D( parallel)/D( perpendicular)) is 0.82 +/- 0.03. The two results have only marginal differences. The relaxation data have also been used to map reduced spectral densities for the NH vectors of these residues at three frequencies: 0, omega(H), and omega(N), where omega(H),(N) are proton and nitrogen Larmor frequencies. The value of tau(m) obtained from model-free analysis of the relaxation data is 5.2 ns. The reduced spectral density analysis, however, yields a value of 5.7 ns. The tau(m) determined here is different from that calculated previously from time-resolved fluorescence data (4.1 ns). The order parameter ranges from 0.68 to 0.98, with an average value of 0.85 +/- 0.02. A comparison of the order parameters with the X-ray B-factors for the backbone nitrogens of wild-type barstar does not show any considerable correlation. Model-free analysis of the relaxation data for seven residues required the inclusion of an exchange broadening term, the magnitude of which ranges from 2

  4. 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.

  5. HCCCH Experiment for Through-Bond Correlation of Thymine Resonances in 13C-Labeled DNA Oligonucleotides

    NASA Astrophysics Data System (ADS)

    Sklenář, Vladimír.; Masse, James E.; Feigon, Juli

    1999-04-01

    Application of heteronuclear magnetic resonance pulse methods to13C,15N-labeled nucleic acids is important for the accurate structure determination of larger RNA and DNA oligonucleotides and protein-nucleic acid complexes. These methods have been applied primarily to RNA, due to the availability of labeled samples. The two major differences between DNA and RNA are at the C2‧ of the ribose and deoxyribose and the additional methyl group on thymine versus uracil. We have enzymatically synthesized a13C,15N-labeled 32 base DNA oligonucleotide that folds to form an intramolecular triplex. We present two- and three-dimensional versions of a new HCCCH-TOCSY experiment that provides intraresidue correlation between the thymine H6 and methyl resonances via the intervening carbons (H6-C6-C5-Cme-Hme).

  6. 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.

  7. Correlative tomography.

    PubMed

    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

  8. 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

  9. Carbon-proton scalar couplings in RNA. 3D heteronuclear and 2D isotope-edited NMR of a [sup 13]C-labeled extra-stable hairpin

    SciTech Connect

    Hines, J.V.; Landry, S.M.; Varani, G.; Tinoco, I. Jr. Lawrence Berkeley Lab., CA )

    1994-06-29

    Long range carbon-proton scalar couplings were measured for an RNA hairpin of 12 nucleotides using 3D and [sup 13]C-edited 2D NMR. The large one-bond carbon-proton scalar couplings ([sup 1]J[sub CH]) and small n-bond couplings ([sup 1]J[sub CH]) produce ECOSY type cross-peaks, thus facilitating the determination of the sign and magnitude of the smaller [sup 2]J[sub CH] or [sup 3]J[sub CH]. The UUCGRNA hairpin (5[prime]-rGGACUUCGGUCC-3[prime]), whose structure has been determined by our laboratory, was uniformly [sup 13]C-labeled at 30% isotopic enrichment. The observed [sup 1]J[sub CH] couplings were then correlated to the known structure. The signs of [sup 2]J[sub C4[prime]H5[prime

  10. 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

  11. 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.

  12. Proton-detected 3D 14N/14N/1H isotropic shift correlation experiment mediated through 1H-1H RFDR mixing on a natural abundant sample under ultrafast MAS

    NASA Astrophysics Data System (ADS)

    Pandey, Manoj Kumar; Nishiyama, Yusuke

    2015-09-01

    In this contribution, we have demonstrated a proton detection-based approach on a natural abundant powdered L-Histidine HCl-H2O sample at ultrafast magic angle spinning (MAS) to accomplish 14N/14N correlation from a 3D 14N/14N/1H isotropic shift correlation experiment mediated through 1H finite-pulse radio frequency-driven recoupling (fp-RFDR). Herein the heteronuclear magnetization transfer between 14N and 1H has been achieved by HMQC experiment, whereas 14N/14N correlation is attained through enhanced 1H-1H spin diffusion process due to 1H-1H dipolar recoupling during the RFDR mixing. While the use of ultrafast MAS (90 kHz) provides sensitivity enhancement through increased 1H transverse relaxation time (T2), the use of micro-coil probe which can withstand strong 14N radio frequency (RF) fields further improves the sensitivity per unit sample volume.

  13. Backbone dynamics of free barnase and its complex with barstar determined by 15N NMR relaxation study.

    PubMed

    Sahu, S C; Bhuyan, A K; Udgaonkar, J B; Hosur, R V

    2000-10-01

    Backbone dynamics of uniformly 15N-labeled free barnase and its complex with unlabelled barstar have been studied at 40 degrees C, pH 6.6, using 15N relaxation data obtained from proton-detected 2D [1H]-15N NMR spectroscopy. 15N spin-lattice relaxation rate constants (R1), spin-spin relaxation rate constants (R2), and steady-state heteronuclear [1H]-15N NOEs have been measured at a magnetic field strength of 14.1 Tesla for 91 residues of free barnase and for 90 residues out of a total of 106 in the complex (excluding three prolines and the N-terminal residue) backbone amide 15N sites of barnase. The primary relaxation data for both the cases have been analyzed in the framework of the model-free formalism using both isotropic and axially symmetric models of the rotational diffusion tensor. As per the latter, the overall rotational correlation times (tau(m)) are 5.0 and 9.5 ns for the free and complexed barnase, respectively. The average order parameter is found to be 0.80 for free barnase and 0.86 for the complex. However, the changes are not uniform along the backbone and for about 5 residues near the binding interface there is actually a significant decrease in the order parameters on complex formation. These residues are not involved in the actual binding. For the residues where the order parameter increases, the magnitudes vary significantly. It is observed that the complex has much less internal mobility, compared to free barnase. From the changes in the order parameters, the entropic contribution of NH bond vector motion to the free energy of complex formation has been calculated. It is apparent that these motion's cause significant unfavorable contributions and therefore must be compensated by many other favorable contributions to effect tight complex formation. The observed variations in the motion and their different locations with regard to the binding interface may have important implications for remote effects and regulation of the enzyme action. PMID

  14. Synthesis, X-ray structure, and spectroscopic and electrochemical properties of novel heteronuclear ruthenium-osmium complexes with an asymmetric triazolate bridge

    SciTech Connect

    Hage, R.; Haasnoot, J.G.; Nieuwenhuis, H.A.; Reedijk, J. ); De Ridder, D.J.A. ); Vos, J.G. )

    1990-12-05

    The heterodinuclear compounds ((bpy){sub 2}Ru(bpt)Os(bpy){sub 2})(PF{sub 6}){sub 3} (RuOs) and ((bpy){sub 2}Os(bpt)Ru(bpy){sub 2})(PF{sub 6}){sub 3} (OsRu), where Hbpt = 3,5-bis(pyridin-2-yl)-1,2,4-triazole and bpy = 2,2{prime}-bipyridine, have been prepared and characterized. The crystal and molecular structures of ((Ru(bpy){sub 2}){sub 2}(bpt))(CF{sub 3}SO{sub 3}){sub 3}{center dot}4H{sub 2}O and ((bpy){sub 2}Ru(bpt)Os(bpy){sub 2})(CF{sub 3}SO{sub 3}){sub 3}{center dot}4H{sub 2}O have been determined. Only one of the two possible geometrical isomers of the ruthenium dinuclear compound was found in the crystal structure. The two metal centers are coordinated via N(1) and N(4) of the triazole ring. The metal-metal distance is 6.184 (2) {angstrom}. The NMR data revealed that the OsRu isomer has a similar structure, but with the osmium center bound via N(1) and the ruthenium ion coordinated via N(4) of the triazole ring. The electrochemical potentials of the two heterodinuclear compounds are significantly different; for the RuOs compound the oxidation potentials are 0.73 and 1.20 V, while for the OsRu isomer the oxidation potentials are at 0.65 and 1.30 V vs SCE. These differences in electrochemical behavior between the two isomeric RuOs and OsRu compounds suggest that the N(1) atom of the triazole ring is a better {sigma}-donor than N(4). The mixed-valence dinuclear systems all exhibit rather intense intervalence transition (IT) bands in the near-infrared region, suggesting a moderately strong metal-metal interaction for the bpt systems. A correlation between the energy of the IT bands of the mixed-valence dinuclear complexes and the oxidation potentials has been observed.

  15. Dynamics of GCN4 facilitate DNA interaction: a model-free analysis of an intrinsically disordered region.

    PubMed

    Gill, Michelle L; Byrd, R Andrew; Palmer Iii, Arthur G

    2016-02-17

    Intrinsically disordered proteins (IDPs) and proteins with intrinsically disordered regions (IDRs) are known to play important roles in regulatory and signaling pathways. A critical aspect of these functions is the ability of IDP/IDRs to form highly specific complexes with target molecules. However, elucidation of the contributions of conformational dynamics to function has been limited by challenges associated with structural heterogeneity of IDP/IDRs. Using NMR spin relaxation parameters ((15)N R1, (15)N R2, and {(1)H}-(15)N heteronuclear NOE) collected at four static magnetic fields ranging from 14.1 to 21.1 T, we have analyzed the backbone dynamics of the basic leucine-zipper (bZip) domain of the Saccharomyces cerevisiae transcription factor GCN4, whose DNA binding domain is intrinsically disordered in the absence of DNA substrate. We demonstrate that the extended model-free analysis can be applied to proteins with IDRs such as apo GCN4 and that these results significantly extend previous NMR studies of GCN4 dynamics performed using a single static magnetic field of 11.74 T [Bracken, et al., J. Mol. Biol., 1999, 285, 2133-2146] and correlate well with molecular dynamics simulations [Robustelli, et al., J. Chem. Theory Comput., 2013, 9, 5190-5200]. In contrast to the earlier work, data at multiple static fields allows the time scales of internal dynamics of GCN4 to be reliably quantified. Large amplitude dynamic fluctuations in the DNA-binding region have correlation times (τs ≈ 1.4-2.5 ns) consistent with a two-step mechanism in which partially ordered bZip conformations of GCN4 form initial encounter complexes with DNA and then rapidly rearrange to the high affinity state with fully formed basic region recognition helices. PMID:26661739

  16. Blocking the Interactions between Calcium-Bound S100A12 Protein and the V Domain of RAGE Using Tranilast.

    PubMed

    Chiou, Jian Wei; Fu, Brian; Chou, Ruey-Hwang; Yu, Chin

    2016-01-01

    The receptor for advanced glycation end products (RAGE), a transmembrane receptor in the immunoglobulin superfamily, is involved in several inflammatory processes. RAGE induces cellular signaling pathways upon binding with various ligands, such as advanced glycation end products (AGEs), β-amyloids, and S100 proteins. The solution structure of S100A12 and the V ligand-binding region of RAGE have been reported previously. Using heteronuclear NMR spectroscopy to conduct 1H-15N heteronuclear single quantum coherence (HSQC) titration experiments, we identified and mapped the binding interface between S100A12 and the V domain of RAGE. The NMR chemical shift data were used as the constraints for the High Ambiguity Driven biomolecular DOCKing (HADDOCK) calculation to generate a structural model of the S100A12-V domain complex. In addition, tranilast (an anti-allergic drug) showed strong interaction with S100A12 in the 1H-15N HSQC titration, fluorescence experiments, and WST-1 assay. The results also indicated that tranilast was located at the binding site between S100A12 and the V domain, blocking interaction between these two proteins. Our results provide the mechanistic details for a structural model and reveal a potential precursor for an inhibitor for pro-inflammatory diseases, which could be useful for the development of new drugs. PMID:27598566

  17. 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

  18. 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

  19. 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

  20. 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.

  1. [Structural analysis of vinorelbine in solution determined by nuclear magnetic resonance spectrometry].

    PubMed

    Ribet, J P; Zalavari, P; Commenges, G; Fahy, J; Duflos, A; Schambel, P

    1997-01-01

    An active partnership between the National Centre for Scientific Research (CNRS) and the laboratories Pierre Fabre is underpinning the development of a new molecule, vinorelbine, whose tartrate received marketing authorization in France in 1989, under the name of Navelbine. This medicine was first recommended for the treatment of bronchial cancer "not small cell", then, in 1991, for the treatment of metastatic breast cancer. In 1994, its registration in United States was granted for the treatment of bronchial cancer "not small cell". Vinorelbine is obtained by hemisynthesis using two antecedent monomeric alkaloids, catharanthine and vindoline, followed by a modification of the catharanthine nucleus, so as to produce the first 5' nor vinca-alkaloid. The chemical structure of vinorelbine has been examined in our laboratory using nuclear magnetic resonance spectrometry. Bearing in mind their complexity, the total attribution of the proton spectrum and the carbon-13 spectrum has required experiments for homonuclear (1H-1H) and heteronuclear (1H-13C and 1H-15N) correlation. These experiments have been carried out using a BRUKER spectrometer operating at the nominal proton frequency of 200 MHz in direct detection mode, then with a 400 MHz spectrometer equipped with the reverse detection mode. The chemical structure has thus been analyzed with no ambiguity. The results of this structural study will be presented in due course. We have also undertaken a comparative conformational study between base vinorelbine in chloroform solution and ditartrate vinorelbine (Navelbine) in methanolic solution. The conformation of the vinorelbine molecule in solution in these different solvents have been studied with NOESY (Nuclear Overhauser Effect Spectroscopy) experiments. The results of these experiments have been confirmed by data stemming from molecular modelization. PMID:9138318

  2. NMR Analysis of a Novel Enzymatically Active Unlinked Dengue NS2B-NS3 Protease Complex*

    PubMed Central

    Kim, Young Mee; Gayen, Shovanlal; Kang, CongBao; Joy, Joma; Huang, Qiwei; Chen, Angela Shuyi; Wee, John Liang Kuan; Ang, Melgious Jin Yan; Lim, Huichang Annie; Hung, Alvin W.; Li, Rong; Noble, Christian G.; Lee, Le Tian; Yip, Andy; Wang, Qing-Yin; Chia, Cheng San Brian; Hill, Jeffrey; Shi, Pei-Yong; Keller, Thomas H.

    2013-01-01

    The dengue virus (DENV) is a mosquito-borne pathogen responsible for an estimated 100 million human infections annually. The viral genome encodes a two-component trypsin-like protease that contains the cofactor region from the nonstructural protein NS2B and the protease domain from NS3 (NS3pro). The NS2B-NS3pro complex plays a crucial role in viral maturation and has been identified as a potential drug target. Using a DENV protease construct containing NS2B covalently linked to NS3pro via a Gly4-Ser-Gly4 linker (“linked protease”), previous x-ray crystal structures show that the C-terminal fragment of NS2B is remote from NS3pro and exists in an open state in the absence of an inhibitor; however, in the presence of an inhibitor, NS2B complexes with NS3pro to form a closed state. This linked enzyme produced NMR spectra with severe signal overlap and line broadening. To obtain a protease construct with a resolved NMR spectrum, we expressed and purified an unlinked protease complex containing a 50-residue segment of the NS2B cofactor region and NS3pro without the glycine linker using a coexpression system. This unlinked protease complex was catalytically active at neutral pH in the absence of glycerol and produced dispersed cross-peaks in a 1H-15N heteronuclear single quantum correlation spectrum that enabled us to conduct backbone assignments using conventional techniques. In addition, titration with an active-site peptide aldehyde inhibitor and paramagnetic relaxation enhancement studies demonstrated that the unlinked DENV protease exists predominantly in a closed conformation in solution. This protease complex can serve as a useful tool for drug discovery against DENV. PMID:23511634

  3. Sensitivity enhancement using paramagnetic relaxation in MAS solid-state NMR of perdeuterated proteins

    NASA Astrophysics Data System (ADS)

    Linser, Rasmus; Chevelkov, Veniamin; Diehl, Anne; Reif, Bernd

    2007-12-01

    Previously, Ishii et al., could show that chelated paramagnetic ions can be employed to significantly decrease the recycle delay of a MAS solid-state NMR experiment [N.P. Wickramasinghe, M. Kotecha, A. Samoson, J. Past, Y. Ishii, Sensitivity enhancement in C-13 solid-state NMR of protein microcrystals by use of paramagnetic metal ions for optimizing H-1 T-1 relaxation, J. Magn. Reson. 184 (2007) 350-356]. Application of the method is limited to very robust samples, for which sample stability is not compromised by RF induced heating. In addition, probe integrity might be perturbed in standard MAS PRE experiments due to the use of very short duty cycles. We show that these deleterious effects can be avoided if perdeuterated proteins are employed that have been re-crystallized from D 2O:H 2O = 9:1 containing buffer solutions. The experiments are demonstrated using the SH3 domain of chicken α-spectrin as a model system. The labeling scheme allows to record proton detected 1H, 15N correlation spectra with very high resolution in the absence of heteronuclear dipolar decoupling. Cu-edta as a doping reagent yields a reduction of the recycle delay by up to a factor of 15. In particular, we find that the 1H T1 for the bulk H N magnetization is reduced from 4.4 s to 0.3 s if the Cu-edta concentration is increased from 0 mM to 250 mM. Possible perturbations like chemical shift changes or line broadening due to the paramagnetic chelate complex are minimal. No degradation of our samples was observed in the course of the experiments.

  4. 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.

  5. HyperSPASM NMR: A new approach to single-shot 2D correlations on DNP-enhanced samples

    NASA Astrophysics Data System (ADS)

    Donovan, Kevin J.; Frydman, Lucio

    2012-12-01

    Dissolution DNP experiments are limited to a single or at most a few scans, before the non-Boltzmann magnetization has been consumed. 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 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 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.

  6. Codes with special correlation.

    NASA Technical Reports Server (NTRS)

    Baumert, L. D.

    1964-01-01

    Uniform binary codes with special correlation including transorthogonality and simplex code, Hadamard matrices and difference sets uniform binary codes with special correlation including transorthogonality and simplex code, Hadamard matrices and difference sets

  7. 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.

  8. Correlation in business networks

    NASA Astrophysics Data System (ADS)

    Souma, Wataru; Aoyama, Hideaki; Fujiwara, Yoshi; Ikeda, Yuichi; Iyetomi, Hiroshi; Kaizoji, Taisei

    2006-10-01

    This paper considers business networks. Through empirical study, we show that business networks display characteristics of small-world networks and scale-free networks. In this paper, we characterize firms as sales and bankruptcy probabilities. A correlation between sales and a correlation between bankruptcy probabilities in business networks are also considered. The results reveal that the correlation between sales depends strongly on the type of network, whereas the correlation between bankruptcy probabilities does so only weakly.

  9. 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…

  10. Reverse Correlation in Neurophysiology

    ERIC Educational Resources Information Center

    Ringach, Dario; Shapley, Robert

    2004-01-01

    This article presents a review of reverse correlation in neurophysiology. We discuss the basis of reverse correlation in linear transducers and in spiking neurons. The application of reverse correlation to measure the receptive fields of visual neurons using white noise and m-sequences, and classical findings about spatial and color processing in…

  11. Constrained Canonical Correlation.

    ERIC Educational Resources Information Center

    DeSarbo, Wayne S.; And Others

    1982-01-01

    A variety of problems associated with the interpretation of traditional canonical correlation are discussed. A response surface approach is developed which allows for investigation of changes in the coefficients while maintaining an optimum canonical correlation value. Also, a discrete or constrained canonical correlation method is presented. (JKS)

  12. VLBI Correlators in Kashima

    NASA Technical Reports Server (NTRS)

    Sekido, Mamoru; Takefuji, Kazuhiro

    2013-01-01

    Kashima Space Technology Center (KSTC) is making use of two kinds of software correlators, the multi-channel K5/VSSP software correlator and the fast wide-band correlator 'GICO3,' for geodetic and R&D VLBI experiments. Overview of the activity and future plans are described in this paper.

  13. 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.

  14. Complementarity and Correlations

    NASA Astrophysics Data System (ADS)

    Maccone, Lorenzo; Bruß, Dagmar; Macchiavello, Chiara

    2015-04-01

    We provide an interpretation of entanglement based on classical correlations between measurement outcomes of complementary properties: States that have correlations beyond a certain threshold are entangled. The reverse is not true, however. We also show that, surprisingly, all separable nonclassical states exhibit smaller correlations for complementary observables than some strictly classical states. We use mutual information as a measure of classical correlations, but we conjecture that the first result holds also for other measures (e.g., the Pearson correlation coefficient or the sum of conditional probabilities).

  15. Complementarity and correlations.

    PubMed

    Maccone, Lorenzo; Bruß, Dagmar; Macchiavello, Chiara

    2015-04-01

    We provide an interpretation of entanglement based on classical correlations between measurement outcomes of complementary properties: States that have correlations beyond a certain threshold are entangled. The reverse is not true, however. We also show that, surprisingly, all separable nonclassical states exhibit smaller correlations for complementary observables than some strictly classical states. We use mutual information as a measure of classical correlations, but we conjecture that the first result holds also for other measures (e.g., the Pearson correlation coefficient or the sum of conditional probabilities). PMID:25884117

  16. 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.

  17. Almost quantum correlations.

    PubMed

    Navascués, Miguel; Guryanova, Yelena; Hoban, Matty J; Acín, Antonio

    2015-01-01

    Quantum theory is not only successfully tested in laboratories every day but also constitutes a robust theoretical framework: small variations usually lead to implausible consequences, such as faster-than-light communication. It has even been argued that quantum theory may be special among possible theories. Here we report that, at the level of correlations among different systems, quantum theory is not so special. We define a set of correlations, dubbed 'almost quantum', and prove that it strictly contains the set of quantum correlations but satisfies all-but-one of the proposed principles to capture quantum correlations. We present numerical evidence that the remaining principle is satisfied too. PMID:25697645

  18. Local available quantum correlations

    NASA Astrophysics Data System (ADS)

    Mundarain, Douglas F.; de Guevara, María L. Ladrón

    2015-12-01

    In this work, local available quantum correlations are studied. They are defined in terms of mutual information of bipartite local measurements done over an optimal local basis complementary to the local basis which defines the respective classical correlations. For two qubits, it is always possible to choose the basis of classical correlations as the set of eigenvectors of σ _z (the third Pauli matrix) and complementary bases become the sets of eigenvectors of the observables orthogonal to σ _z. It is shown that all states with zero local available quantum correlations are separable but not necessarily strictly classical; this fact puts this kind of correlations in the middle between discord and entanglement. Since in many cases it may suffice to know whether a given state has quantum correlations, the structure of the states with zero local available quantum correlations is presented. It is also shown that there is a close connection between local available quantum correlations and the protocol of entanglement activation developed by Piani et al. (Phys Rev Lett 106:220403, 2011). If a state satisfies the sufficient condition for the entanglement swapping associated with this protocol, this state has nonzero local available quantum correlations.

  19. 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

  20. Correlates of Academic Procrastination.

    ERIC Educational Resources Information Center

    Milgram, Norman A.; And Others

    1993-01-01

    Investigated concurrent correlates of academic procrastination in Israeli college preparatory students (n=113). Procrastination in one course of study was found to be moderately correlated with procrastination in another but not to procrastination in routine tasks of daily living. Procrastination was weakly related to emotional upset about it and…

  1. 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.

  2. Harmonic electron correlation operator.

    PubMed

    Rassolov, Vitaly A

    2011-07-21

    An appealing way to model electron correlation within the single determinant wave function formalism is through the expectation value of a linear two-electron operator. For practical reasons, it is desirable for such an operator to be universal, i.e., not depend on the positions and types of nuclei in a molecule. We show how a perturbation theory applied to a hookium atom provides for a particular form of a correlation operator, hence called the harmonic correlation operator. The correlation operator approach is compared and contrasted to the traditional ways to describe electron correlation. To investigate the two-electron approximation of this operator, we apply it to many-electron hookium systems. To investigate the harmonic approximation, we apply it to the small atomic systems. Directions of future research are also discussed. PMID:21786991

  3. Strongly-correlated heterostructures

    SciTech Connect

    Okamoto, Satoshi

    2012-01-01

    Electronic phase behavior in correlated-electron systems is a fundamental problem of condensed matter physics. The change in the phase behavior near surfaces and interfaces, i.e., {\\em electronic reconstruction}, is therefore the fundamental issue of the correlated-electron surface or interface science. In addition to basic science, understanding of such a phase behavior is of crucial importance for potential devices exploiting the novel properties of the correlated systems. In this article, we present a general overview of the field, and then discuss the recent theoretical progress mainly focusing on the correlation effects. We illustrate the general concept of {\\em electronic reconstruction} by studying model heterostructures consisting of strongly-correlated systems. Future directions for research are also discussed.

  4. Correlation reflectometry at TEXTOR

    SciTech Connect

    Kraemer-Flecken, A.; Soldatov, S.; Vowinkel, B.; Mueller, P.

    2010-11-15

    In high temperature fusion plasmas the transport of energy and particles is commonly believed to be driven by turbulence. Turbulence quantities as correlation length and decorrelation time are important for the confinement properties of a plasma. Besides other diagnostics, correlation reflectometry has proven to be a suitable tool for the measurement of turbulence properties. At the medium sized Toroidal EXperiment for Technical Oriented Research (TEXTOR) the existing correlation reflectometry has been recently upgraded. A new reflectometer based on a microwave synthesizer has been developed and installed for the investigation of turbulence properties in a fusion plasma. Together with the existing reflectometer the measurement of radial correlation length and decorrelation time becomes available. Both reflectometers are computer controlled and allow to program individual frequency sequences and the duration of each frequency step. With the existing poloidal antenna array at {theta}=0 deg. and on top of the vacuum vessel, the system allows the measurement of radial correlation and poloidal correlations at the same time. First experiments have been performed and the results on the radial correlation length of density fluctuations in a fusion plasma are presented.

  5. Hadronic Correlations and Fluctuations

    SciTech Connect

    Koch, Volker

    2008-10-09

    We will provide a review of some of the physics which can be addressed by studying fluctuations and correlations in heavy ion collisions. We will discuss Lattice QCD results on fluctuations and correlations and will put them into context with observables which have been measured in heavy-ion collisions. Special attention will be given to the QCD critical point and the first order co-existence region, and we will discuss how the measurement of fluctuations and correlations can help in an experimental search for non-trivial structures in the QCD phase diagram.

  6. 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.

  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. PMID:27314718

  8. Entropic Nonsignaling Correlations

    NASA Astrophysics Data System (ADS)

    Chaves, Rafael; Budroni, Costantino

    2016-06-01

    We introduce the concept of entropic nonsignaling correlations, i.e., entropies arising from probabilistic theories that are compatible with the fact that we cannot transmit information instantaneously. We characterize and show the relevance of these entropic correlations in a variety of different scenarios, ranging from typical Bell experiments to more refined descriptions such as bilocality and information causality. In particular, we apply the framework to derive the first entropic inequality testing genuine tripartite nonlocality in quantum systems of arbitrary dimension and also prove the first known monogamy relation for entropic Bell inequalities. Further, within the context of complex Bell networks, we show that entropic nonlocal correlations can be activated.

  9. Statistics of atmospheric correlations.

    PubMed

    Santhanam, M S; Patra, P K

    2001-07-01

    For a large class of quantum systems, the statistical properties of their spectrum show remarkable agreement with random matrix predictions. Recent advances show that the scope of random matrix theory is much wider. In this work, we show that the random matrix approach can be beneficially applied to a completely different classical domain, namely, to the empirical correlation matrices obtained from the analysis of the basic atmospheric parameters that characterize the state of atmosphere. We show that the spectrum of atmospheric correlation matrices satisfy the random matrix prescription. In particular, the eigenmodes of the atmospheric empirical correlation matrices that have physical significance are marked by deviations from the eigenvector distribution. PMID:11461326

  10. Correlation Plenoptic Imaging

    NASA Astrophysics Data System (ADS)

    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.

  11. 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.

  12. Correlations and droplet growth

    NASA Technical Reports Server (NTRS)

    Marder, M.

    1985-01-01

    Consideration is given to the time development of a system in which small spheres of a stable phase grow out of a supersaturated melt. The spheres then grow and shrink in a manner similar to Ostwald ripening. The growth process of pairs of particles in an effective background accounts for can be used to explain the long time correlations which develop in the system. The correlations broaden the distribution of particles sizes, even for relatively dilute systems.

  13. Apoflavodoxin (un)folding followed at the residue level by NMR.

    PubMed Central

    van Mierlo, C. P.; van den Oever, J. M.; Steensma, E.

    2000-01-01

    The denaturant-induced (un)folding of apoflavodoxin from Azotobacter vinelandii has been followed at the residue level by NMR spectroscopy. NH groups of 21 residues of the protein could be followed in a series of 1H-15N heteronuclear single-quantum coherence spectra recorded at increasing concentrations of guanidinium hydrochloride despite the formation of protein aggregate. These NH groups are distributed throughout the whole apoflavodoxin structure. The midpoints of unfolding determined by NMR coincide with the one obtained by fluorescence emission spectroscopy. Both techniques give rise to unfolding curves with transition zones at significantly lower denaturant concentrations than the one obtained by circular dichroism spectroscopy. The NMR (un)folding data support a mechanism for apoflavodoxin folding in which a relatively stable intermediate is involved. Native apoflavodoxin is shown to cooperatively unfold to a molten globule-like state with extremely broadened NMR resonances. This initial unfolding step is slow on the NMR chemical shift timescale. The subsequent unfolding of the molten globule is faster on the NMR chemical shift timescale and the limited appearance of 1H-15N HSQC cross peaks of unfolded apoflavodoxin in the denaturant range studied indicates that it is noncooperative. PMID:10739257

  14. NMR characterization of structure, backbone dynamics, and glutathione binding of the human macrophage migration inhibitory factor (MIF).

    PubMed

    Mühlhahn, P; Bernhagen, J; Czisch, M; Georgescu, J; Renner, C; Ross, A; Bucala, R; Holak, T A

    1996-10-01

    Human macrophage migration inhibitory factor is a 114 amino acid protein that belongs to the family of immunologic cytokines. Assignments of 1H, 15N, and 13C resonances have enabled the determination of the secondary structure of the protein, which consists of two alpha-helices (residues 18-31 and 89-72) and a central four-stranded beta-sheet. In the beta-sheet, two parallel beta-sheets are connected in an antiparallel sense. From the total of three cysteines present in the primary structure of MIF, none was found to form disulfide bridges. 1H-15N heteronuclear T1, T2, and steady-state NOE measurements indicate that the backbone of MIF exists in a rigid structure of limited conformational flexibility (on the nanosecond to picosecond time scale). Several residues located in the loop regions and at the N termini of two helices exhibit internal motions on the 1-3 ns time scale. The capacity to bind glutathione was investigated by titration of a uniform 15N-labeled sample and led us to conclude that MIF has, at best, very low affinity for glutathione. PMID:8897610

  15. NMR characterization of structure, backbone dynamics, and glutathione binding of the human macrophage migration inhibitory factor (MIF).

    PubMed Central

    Mühlhahn, P.; Bernhagen, J.; Czisch, M.; Georgescu, J.; Renner, C.; Ross, A.; Bucala, R.; Holak, T. A.

    1996-01-01

    Human macrophage migration inhibitory factor is a 114 amino acid protein that belongs to the family of immunologic cytokines. Assignments of 1H, 15N, and 13C resonances have enabled the determination of the secondary structure of the protein, which consists of two alpha-helices (residues 18-31 and 89-72) and a central four-stranded beta-sheet. In the beta-sheet, two parallel beta-sheets are connected in an antiparallel sense. From the total of three cysteines present in the primary structure of MIF, none was found to form disulfide bridges. 1H-15N heteronuclear T1, T2, and steady-state NOE measurements indicate that the backbone of MIF exists in a rigid structure of limited conformational flexibility (on the nanosecond to picosecond time scale). Several residues located in the loop regions and at the N termini of two helices exhibit internal motions on the 1-3 ns time scale. The capacity to bind glutathione was investigated by titration of a uniform 15N-labeled sample and led us to conclude that MIF has, at best, very low affinity for glutathione. PMID:8897610

  16. Nonclassicality of Temporal Correlations.

    PubMed

    Brierley, Stephen; Kosowski, Adrian; Markiewicz, Marcin; Paterek, Tomasz; Przysiężna, Anna

    2015-09-18

    The results of spacelike separated measurements are independent of distant measurement settings, a property one might call two-way no-signaling. In contrast, timelike separated measurements are only one-way no-signaling since the past is independent of the future but not vice versa. For this reason some temporal correlations that are formally identical to nonclassical spatial correlations can still be modeled classically. We propose a new formulation of Bell's theorem for temporal correlations; namely, we define nonclassical temporal correlations as the ones which cannot be simulated by propagating in time the classical information content of a quantum system given by the Holevo bound. We first show that temporal correlations between results of any projective quantum measurements on a qubit can be simulated classically. Then we present a sequence of general measurements on a single m-level quantum system that cannot be explained by propagating in time an m-level classical system and using classical computers with unlimited memory. PMID:26430975

  17. Correlational Neural Networks.

    PubMed

    Chandar, Sarath; Khapra, Mitesh M; Larochelle, Hugo; Ravindran, Balaraman

    2016-02-01

    Common representation learning (CRL), wherein different descriptions (or views) of the data are embedded in a common subspace, has been receiving a lot of attention recently. Two popular paradigms here are canonical correlation analysis (CCA)-based approaches and autoencoder (AE)-based approaches. CCA-based approaches learn a joint representation by maximizing correlation of the views when projected to the common subspace. AE-based methods learn a common representation by minimizing the error of reconstructing the two views. Each of these approaches has its own advantages and disadvantages. For example, while CCA-based approaches outperform AE-based approaches for the task of transfer learning, they are not as scalable as the latter. In this work, we propose an AE-based approach, correlational neural network (CorrNet), that explicitly maximizes correlation among the views when projected to the common subspace. Through a series of experiments, we demonstrate that the proposed CorrNet is better than AE and CCA with respect to its ability to learn correlated common representations. We employ CorrNet for several cross-language tasks and show that the representations learned using it perform better than the ones learned using other state-of-the-art approaches. PMID:26654210

  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

    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.

  20. 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

  1. Sensory Correlations in Autism

    ERIC Educational Resources Information Center

    Kern, Janet K.; Trivedi, Madhukar H.; Grannemann, Bruce D.; Garver, Carolyn R.; Johnson, Danny G.; Andrews, Alonzo A.; Savla, Jayshree S.; Mehta, Jyutika A.; Schroeder, Jennifer L.

    2007-01-01

    This study examined the relationship between auditory, visual, touch, and oral sensory dysfunction in autism and their relationship to multisensory dysfunction and severity of autism. The Sensory Profile was completed on 104 persons with a diagnosis of autism, 3 to 56 years of age. Analysis showed a significant correlation between the different…

  2. CORRELATION AND REGRESSION

    EPA Science Inventory

    Webcast entitled Statistical Tools for Making Sense of Data, by the National Nutrient Criteria Support Center, N-STEPS (Nutrients-Scientific Technical Exchange Partnership. The section "Correlation and Regression" provides an overview of these two techniques in the context of nut...

  3. Multivariate Intraclass Correlation.

    ERIC Educational Resources Information Center

    Wiley, David E.; Hawkes, Thomas H.

    This paper is an explication of a statistical model which will permit an interpretable intraclass correlation coefficient that is negative, and a generalized extension of that model to cover a multivariate problem. The methodological problem has its practical roots in an attempt to find a statistic which could indicate the degree of similarity or…

  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. 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)…

  6. Correlates of Adolescent Parenting.

    ERIC Educational Resources Information Center

    Reis, Janet S.; Herz, Elicia J.

    1987-01-01

    Studied correlates of teenage parenting in self-selected sample of 177 teenage parents. Parental race, punitive attitudes toward child rearing, and parental age were statistically significant predictors of total Home Observation for Measurement of the Environment scores. Older, white adolescent mothers with less punitive attitudes toward child…

  7. HIM Correlational Study

    ERIC Educational Resources Information Center

    Powell, Evan R.

    1977-01-01

    This study uses two methods of analysis to examine the degree to which items within the cells of the Hill Interaction Matrix correlate. It is found that the table of specifications does not hold up. But the author recommends caution in interpreting this finding. (Author/BP)

  8. 1H, 13C and 15N resonance assignments of URNdesign, a computationally redesigned RRM protein

    SciTech Connect

    Dobson, Neil; Dantas, Gautam; Varani, Gabriele

    2005-10-01

    Protein design represents one of the great challenges of computational structural biology. The ability to successfully design new proteins would allow us to generate new reagents and enzymes, while at the same time providing us with an understanding of the principles of protein stability. Here we report 1H, 15N and 13C resonance assignments of a redesigned U1A protein, URNdesign. U1A has been studied extensively by our group and hence was chosen as a design target. For the assignments we sued 2D and 3D heteronuclearNMR experiments with uniformly 13C, 15N-labeled URNdesign. The assignments for the backbone NH, CO,Ca and Cb nuclei are 94%complete. Sidechain 1Hand13C, aromatic andQ/NNH2 resonances are essentially complete with guanidinium and K NH3 residues unassigned. BMRB deposit with accession number 6493

  9. 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.

  10. Multi baseline Grid Software Correlator

    NASA Astrophysics Data System (ADS)

    Moritaka, Kimura; Nakajima, Junichi; Kondo, Tetsuro

    Software VLBI correlation is regarded as a solution for next generation VLBI. With a flexibility of the software correlation programming, appropriate scientific correlations by scientists are possible as well as the post processing. As the first experiment to handle Gbps VLBI data, multi baseline Grid correlator have been developing at CRL. The performance of software correlation adopted multi CPUs, SIMD architectures and Grid computing technology has nearly reached hardware correlator performance.

  11. 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.

  12. Correlations and Ostwald ripening

    NASA Technical Reports Server (NTRS)

    Marder, M.

    1987-01-01

    A previously developed model (Weins and Cahn, 1973) describing the growth of spheres of a second phase in metal alloys (Ostwald coarsening) is slightly modified to make it possible to study the complete time evolution of the system rather than simply the late-stage scaling behavior. Closed equations are obtained which describe the time evolution of two-particle correlations in the system. The development of the correlations is analyzed, and simpler expressions are found and solved numerically. The results are compared with experimental data for different systems (e.g., Ni-Al, Ni-Cr-Al, Co-Ni-Cr-Ti, Cu-Co, and MgO-Fe), alternate methods, and existing theories.

  13. 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.

  14. Correlation dimension Wonderland theorems

    NASA Astrophysics Data System (ADS)

    Carvalho, Silas L.; de Oliveira, César R.

    2016-06-01

    Existence of generic sets of self-adjoint operators, related to correlation dimensions of spectral measures, is investigated in separable Hilbert spaces. Typical results say that, given an orthonormal basis, the set of operators whose corresponding spectral measures are both 0-lower and 1-upper correlation dimensional is generic. The proofs rely on details of the relations among Fourier transform of spectral measures and Hausdorff and packing measures on the real line. Then such results are naturally combined with the Wonderland theorem. Applications are to classes of discrete one-dimensional Schrödinger operators and general (bounded) self-adjoint operators as well. Physical consequences include a proof of exotic dynamical behavior of singular continuous spectrum in some settings.

  15. 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.

  16. Correlative pediatric imaging

    SciTech Connect

    Garty, I.; Delbeke, D.; Sandler, M.P.

    1989-01-01

    Nuclear medicine, ultrasound, and magnetic resonance imaging (MRI) are considered ideal imaging modalities for pediatric patients. The future is even more promising for pediatric imaging with the development of newer and improved radiopharmaceuticals, instrumentation and diagnostic modalities such as positron emission tomography, labeled monoclonal antibodies, and faster dynamic and contrast enhanced MRI methods. However, correlation of more conventional imaging modalities with nuclear medicine, ultrasound and MRI remain essential for optimal patient care. 43 references.

  17. 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

  18. Cots Correlator Platform

    NASA Astrophysics Data System (ADS)

    Schaaf, Kjeld; Overeem, Ruud

    2004-06-01

    Moore’s law is best exploited by using consumer market hardware. In particular, the gaming industry pushes the limit of processor performance thus reducing the cost per raw flop even faster than Moore’s law predicts. Next to the cost benefits of Common-Of-The-Shelf (COTS) processing resources, there is a rapidly growing experience pool in cluster based processing. The typical Beowulf cluster of PC’s supercomputers are well known. Multiple examples exists of specialised cluster computers based on more advanced server nodes or even gaming stations. All these cluster machines build upon the same knowledge about cluster software management, scheduling, middleware libraries and mathematical libraries. In this study, we have integrated COTS processing resources and cluster nodes into a very high performance processing platform suitable for streaming data applications, in particular to implement a correlator. The required processing power for the correlator in modern radio telescopes is in the range of the larger supercomputers, which motivates the usage of supercomputer technology. Raw processing power is provided by graphical processors and is combined with an Infiniband host bus adapter with integrated data stream handling logic. With this processing platform a scalable correlator can be built with continuously growing processing power at consumer market prices.

  19. 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

  20. Energy calibration via correlation

    NASA Astrophysics Data System (ADS)

    Maier, Daniel; Limousin, Olivier

    2016-03-01

    The main task of an energy calibration is to find a relation between pulse-height values and the corresponding energies. Doing this for each pulse-height channel individually requires an elaborated input spectrum with an excellent counting statistics and a sophisticated data analysis. This work presents an easy to handle energy calibration process which can operate reliably on calibration measurements with low counting statistics. The method uses a parameter based model for the energy calibration and concludes on the optimal parameters of the model by finding the best correlation between the measured pulse-height spectrum and multiple synthetic pulse-height spectra which are constructed with different sets of calibration parameters. A CdTe-based semiconductor detector and the line emissions of an 241Am source were used to test the performance of the correlation method in terms of systematic calibration errors for different counting statistics. Up to energies of 60 keV systematic errors were measured to be less than ~ 0.1 keV. Energy calibration via correlation can be applied to any kind of calibration spectra and shows a robust behavior at low counting statistics. It enables a fast and accurate calibration that can be used to monitor the spectroscopic properties of a detector system in near realtime.

  1. 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

  2. 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.

  3. 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.

  4. 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…

  5. 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.

  6. 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.

  7. Correlative Measurements Program

    NASA Technical Reports Server (NTRS)

    Parsons, C. L.

    1988-01-01

    The GSFC Correlative Measurements Program at the Wallops Flight Facility was represented on the Satellite/Satellite Intercomparisons Working Group. The Correlative Measurements Program uses the Rocket Ozonesonde (ROCOZ-A) and the Electrochemical Concentration Cell (ECC) balloon borne ozonesonde to measure the vertical profile of ozone amount in the atmosphere. The balloon work is described in a separate report. The ROCOZ-A instrument was used for many years to provide in situ truth data for various satellite ozone measuring systems, such as SBUV on Nimbus-7, SAGE-II, SBUV-II on the NOAA series of polar orbiting satellites, SME, LIMS, etc. The particular data sets of interest to the Ozone Trends Panel Working Group were collected at Natal, Brazil. The major results produced for and used by the Ozone Trends Panel are shown. The ROCOZ-A average ozone density profile is plotted versus altitude on the left. ECC ozonesondes were used for the portion of the profile below 20 km, the lower limit for ROCOZ-A. The difference between SAGE-II and ROCOZ-A average density profiles is shown.

  8. Grayscale Optical Correlator Workbench

    NASA Technical Reports Server (NTRS)

    Hanan, Jay; Zhou, Hanying; Chao, Tien-Hsin

    2006-01-01

    Grayscale Optical Correlator Workbench (GOCWB) is a computer program for use in automatic target recognition (ATR). GOCWB performs ATR with an accurate simulation of a hardware grayscale optical correlator (GOC). This simulation is performed to test filters that are created in GOCWB. Thus, GOCWB can be used as a stand-alone ATR software tool or in combination with GOC hardware for building (target training), testing, and optimization of filters. The software is divided into three main parts, denoted filter, testing, and training. The training part is used for assembling training images as input to a filter. The filter part is used for combining training images into a filter and optimizing that filter. The testing part is used for testing new filters and for general simulation of GOC output. The current version of GOCWB relies on the mathematical software tools from MATLAB binaries for performing matrix operations and fast Fourier transforms. Optimization of filters is based on an algorithm, known as OT-MACH, in which variables specified by the user are parameterized and the best filter is selected on the basis of an average result for correct identification of targets in multiple test images.

  9. 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

  10. 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

  11. Strongly correlated electronic materials

    SciTech Connect

    Bedell, K.; Albers, R.; Balatsky, A.; Bishop, A.; Bonca, J.; Gubernatis, J.; Gulasci, M.; Silver, R.; Trugman, S.

    1996-04-01

    This is the final report of a 3-year project. Novel electronic materials characterized by strong electronic correlations display a number of unexpected, often extraordinary, properties. These are likely to play a major role in purpose-specific high-technology electronic materials of the future developed for electronic, magnetic, and optical applications. This project sought to develop predictive control of the novel properties by formulating, solving and applying many-body models for the underlying microscopic physics. This predictive control required the development of new analytical and numerical many-body techniques and strategies for materials of varying strengths of interactions, dimensionality and geometry. Results are compared with experiment on classes of novel materials, and the robust techniques are used to predict additional properties and motivate key additional experiments.

  12. Flatbands under Correlated Perturbations

    NASA Astrophysics Data System (ADS)

    Bodyfelt, Joshua D.; Leykam, Daniel; Danieli, Carlo; Yu, Xiaoquan; Flach, Sergej

    2014-12-01

    Flatband networks are characterized by the coexistence of dispersive and flatbands. Flatbands (FBs) are generated by compact localized eigenstates (CLSs) with local network symmetries, based on destructive interference. Correlated disorder and quasiperiodic potentials hybridize CLSs without additional renormalization, yet with surprising consequences: (i) states are expelled from the FB energy EFB, (ii) the localization length of eigenstates vanishes as ξ ˜1 /ln (E -EFB) , (iii) the density of states diverges logarithmically (particle-hole symmetry) and algebraically (no particle-hole symmetry), and (iv) mobility edge curves show algebraic singularities at EFB . Our analytical results are based on perturbative expansions of the CLSs and supported by numerical data in one and two lattice dimensions.

  13. Flatbands under correlated perturbations.

    PubMed

    Bodyfelt, Joshua D; Leykam, Daniel; Danieli, Carlo; Yu, Xiaoquan; Flach, Sergej

    2014-12-01

    Flatband networks are characterized by the coexistence of dispersive and flatbands. Flatbands (FBs) are generated by compact localized eigenstates (CLSs) with local network symmetries, based on destructive interference. Correlated disorder and quasiperiodic potentials hybridize CLSs without additional renormalization, yet with surprising consequences: (i) states are expelled from the FB energy E_{FB}, (ii) the localization length of eigenstates vanishes as ξ∼1/ln(E-E_{FB}), (iii) the density of states diverges logarithmically (particle-hole symmetry) and algebraically (no particle-hole symmetry), and (iv) mobility edge curves show algebraic singularities at E_{FB}. Our analytical results are based on perturbative expansions of the CLSs and supported by numerical data in one and two lattice dimensions. PMID:25526142

  14. Paths correlation matrix.

    PubMed

    Qian, Weixian; Zhou, Xiaojun; Lu, Yingcheng; Xu, Jiang

    2015-09-15

    Both the Jones and Mueller matrices encounter difficulties when physically modeling mixed materials or rough surfaces due to the complexity of light-matter interactions. To address these issues, we derived a matrix called the paths correlation matrix (PCM), which is a probabilistic mixture of Jones matrices of every light propagation path. Because PCM is related to actual light propagation paths, it is well suited for physical modeling. Experiments were performed, and the reflection PCM of a mixture of polypropylene and graphite was measured. The PCM of the mixed sample was accurately decomposed into pure polypropylene's single reflection, pure graphite's single reflection, and depolarization caused by multiple reflections, which is consistent with the theoretical derivation. Reflection parameters of rough surface can be calculated from PCM decomposition, and the results fit well with the theoretical calculations provided by the Fresnel equations. These theoretical and experimental analyses verify that PCM is an efficient way to physically model light-matter interactions. PMID:26371930

  15. 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.

  16. Understanding Correlations: Two Computer Exercises.

    ERIC Educational Resources Information Center

    Goldstein, Miriam D.; Strube, Michael J.

    1995-01-01

    Describes two QuickBASIC programs that provide students direct experience with interpreting correlation scatter-plots. Maintains that the programs can be used in classroom exercises to highlight factors that influence the size of a Pearson correlation coefficient. (CFR)

  17. 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.

  18. Standard Errors for Matrix Correlations.

    ERIC Educational Resources Information Center

    Ogasawara, Haruhiko

    1999-01-01

    Derives the asymptotic standard errors and intercorrelations for several matrix correlations assuming multivariate normality for manifest variables and derives the asymptotic standard errors of the matrix correlations for two factor-loading matrices. (SLD)

  19. 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.

  20. 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.

  1. 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)

  2. 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

  3. Self-assembly of highly luminescent heteronuclear coordination cages.

    PubMed

    Schmidt, Andrea; Hollering, Manuela; Han, Jiaying; Casini, Angela; Kühn, Fritz E

    2016-08-01

    Exo-functionalized Pd2L4 cage compounds with attached Ru(ii) pyridine complexes were prepared via coordination-driven self-assembly. Unlike most of the previously reported palladium(ii) cages, one of these metallocages exhibits an exceptionally high quantum yield of 66%. The presented approach is promising to obtain luminescent coordination complexes for various applications. PMID:27436541

  4. 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

  5. Correlational effect size benchmarks.

    PubMed

    Bosco, Frank A; Aguinis, Herman; Singh, Kulraj; Field, James G; Pierce, Charles A

    2015-03-01

    Effect size information is essential for the scientific enterprise and plays an increasingly central role in the scientific process. We extracted 147,328 correlations and developed a hierarchical taxonomy of variables reported in Journal of Applied Psychology and Personnel Psychology from 1980 to 2010 to produce empirical effect size benchmarks at the omnibus level, for 20 common research domains, and for an even finer grained level of generality. Results indicate that the usual interpretation and classification of effect sizes as small, medium, and large bear almost no resemblance to findings in the field, because distributions of effect sizes exhibit tertile partitions at values approximately one-half to one-third those intuited by Cohen (1988). Our results offer information that can be used for research planning and design purposes, such as producing better informed non-nil hypotheses and estimating statistical power and planning sample size accordingly. We also offer information useful for understanding the relative importance of the effect sizes found in a particular study in relationship to others and which research domains have advanced more or less, given that larger effect sizes indicate a better understanding of a phenomenon. Also, our study offers information about research domains for which the investigation of moderating effects may be more fruitful and provide information that is likely to facilitate the implementation of Bayesian analysis. Finally, our study offers information that practitioners can use to evaluate the relative effectiveness of various types of interventions. PMID:25314367

  6. Spectral correlates lexical prosody

    NASA Astrophysics Data System (ADS)

    Okobi, Anthony

    2005-09-01

    The purpose of this study is to derive a quantitative acoustic model of lexical-prosodic characteristics of stressed vowels by looking at several spectral properties associated with the articulatory mechanisms used in speech production. Native speakers of American English were asked to name disyllabic visualizable nouns. Words containing liquids or glides were not used in this study because of their effect on the spectra of adjacent vowels. Subjects uttered short phrases in which the target word was pitch accent half of the time and unaccented the other half. Results show that within the category of full vowels, unstressed and stressed vowels can be distinguished by syllable/vowel durations and spectral tilt. Spectral tilt (SpT) is an acoustic measure related to the degree of glottal spreading. Stressed full vowels had longer duration and less SpT. Distinction between unaccented and accented stressed vowels can be made by amplitude of voicing (AV), F0 (pitch), and intensity contour differences. Accented stressed vowels have higher pitch, and greater AV and intensity. These results suggest that there are acoustic correlates to lexical stress that can be used to determine the stressed syllable of a word, regardless of whether or not it is pitch accented. [Work supported by NIH T32-DC00038.

  7. Effects of ion binding on the backbone dynamics of calbindin D9k determined by 15N NMR relaxation.

    PubMed

    Akke, M; Skelton, N J; Kördel, J; Palmer, A G; Chazin, W J

    1993-09-21

    The backbone dynamics of apo- and (Cd2+)1-calbindin D9k have been characterized by 15N nuclear magnetic resonance spectroscopy. Spin-lattice and spin-spin relaxation rate constants and steady-state [1H]-15N nuclear Overhauser effects were measured at a magnetic field strength of 11.74 T by two-dimensional, proton-detected heteronuclear NMR experiments using 15N-enriched samples. The relaxation parameters were analyzed using a model-free formalism that characterizes the dynamics of the N-H bond vectors in terms of generalized order parameters and effective correlation times. The data for the apo and (Cd2+)1 states were compared to those for the (Ca2+)2 state [Kördel, J., Skelton, N. J., Akke, M., Palmer, A. G., & Chazin, W. J. (1992) Biochemistry 31, 4856-4866] to ascertain the effects on ion ligation on the backbone dynamics of calbindin D9k. The two binding loops respond differently to ligation by metal ions: high-frequency (10(9)-10(12) s-1) fluctuations of the N-terminal ion-binding loop are not affected by ion binding, whereas residues G57, D58, G59, and E60 in the C-terminal ion-binding loop have significantly lower order parameters in the apo state than in the metal-bound states. The dynamical responses of the four helices to binding of ions are much smaller than that for the C-terminal binding loop, with the strongest effect on helix III, which is located between the linker loop and binding site II. Significant fluctuations on slower time scales also were detected in the unoccupied N-terminal ion-binding loop of the apo and (Cd2+)1 states; the apparent rates were greater for the (Cd2+)1 state. These results on the dynamical response to ion binding in calbindin D9k provide insights into the molecular details of the binding process and qualitative evidence for entropic contributions to the cooperative phenomenon of calcium binding for the pathway in which the ion binds first in the C-terminal site. PMID:8373781

  8. Direct measure of quantum correlation

    SciTech Connect

    Yu, Chang-shui; Zhao, Haiqing

    2011-12-15

    The quantumness of the correlation known as quantum correlation is usually measured by quantum discord. So far various quantum discords can be roughly understood as indirect measure by some special discrepancy of two quantities. We present a direct measure of quantum correlation by revealing the difference between the structures of classically and quantum correlated states. Our measure explicitly includes the contributions of the inseparability and local nonorthogonality of the eigenvectors of a density matrix. Besides its relatively easy computability, our measure can provide a unified understanding of quantum correlation of all the present versions.

  9. 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…

  10. 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.

  11. Closed sets of nonlocal correlations

    SciTech Connect

    Allcock, Jonathan; Linden, Noah; Brunner, Nicolas; Popescu, Sandu; Skrzypczyk, Paul; Vertesi, Tamas

    2009-12-15

    We present a fundamental concept - closed sets of correlations - for studying nonlocal correlations. We argue that sets of correlations corresponding to information-theoretic principles, or more generally to consistent physical theories, must be closed under a natural set of operations. Hence, studying the closure of sets of correlations gives insight into which information-theoretic principles are genuinely different, and which are ultimately equivalent. This concept also has implications for understanding why quantum nonlocality is limited, and for finding constraints on physical theories beyond quantum mechanics.

  12. Why Are Experts Correlated? Decomposing Correlations between Judges

    ERIC Educational Resources Information Center

    Broomell, Stephen B.; Budescu, David V.

    2009-01-01

    We derive an analytic model of the inter-judge correlation as a function of five underlying parameters. Inter-cue correlation and the number of cues capture our assumptions about the environment, while differentiations between cues, the weights attached to the cues, and (un)reliability describe assumptions about the judges. We study the relative…

  13. Canonical Correlation: Terms and Descriptions.

    ERIC Educational Resources Information Center

    Pugh, Richard C.; Hu, Yuehluen

    The use of terms to describe and interpret results from canonical correlation analysis has been inconsistent across research studies. This study assembled the terminology related to the use and interpretation of canonical correlation analysis from research articles, textbooks, and computer manuals. Research articles using canonical correlation…

  14. 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…

  15. 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…

  16. 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.

  17. 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.

  18. Correlation filters for orientation estimation

    NASA Technical Reports Server (NTRS)

    Kumar, B. V. K. Vijaya; Lee, Andrew J.; Connelly, James M.

    1988-01-01

    An important task in many vision applications is that of rapidly estimating the orientation of an object with respect to some frame of reference. Because of their speed and parallel processing capabilities, optical correlators should prove valuable in this application. This paper considers two algorithms for object orientation estimation based on optical correlations and presents some initial simulation results.

  19. 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…

  20. 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.

  1. Correlation transfer: Development and application

    NASA Astrophysics Data System (ADS)

    Dougherty, R. L.; Ackerson, B. J.; Reguigui, N. M.; Dorri-Nowkoorani, F.; Nobbmann, U.

    1994-12-01

    A correlation transfer equation for multiple scattering of light through suspensions of diffusing particles is derived from multiple scattering theory. Because of the formal similarity between the correlation equation and the radiative transfer equation, radiative transport solution techniques are applied to obtain solutions for the field correlation function in isotropic one-dimensional media. A three-term Legendre expansion for the angularly dependent single scattering function (g(sup 1)) in the correlation integral equation is used to obtain approximate numerical solutions for the correlation function. Graphical results are presented for the correlation in both the forward and backward directions for a finite medium and for backscattering in the case of an infinite medium. Experimental results are also presented and they show improved agreement with the three-term Legendre expansion of g(sup 1) as compared to the one or two-term expansions. Correlation transfer results are shown to agree well with both the diffusion limit and the single scattering limit predictions.

  2. 25 ns software correlator for photon and fluorescence correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Magatti, Davide; Ferri, Fabio

    2003-02-01

    A 25 ns time resolution, multi-tau software correlator developed in LABVIEW based on the use of a standard photon counting unit, a fast timer/counter board (6602-PCI National Instrument) and a personal computer (PC) (1.5 GHz Pentium 4) is presented and quantitatively discussed. The correlator works by processing the stream of incoming data in parallel according to two different algorithms: For large lag times (τ⩾100 μs), a classical time-mode (TM) scheme, based on the measure of the number of pulses per time interval, is used; differently, for τ⩽100 μs a photon-mode (PM) scheme is adopted and the time sequence of the arrival times of the photon pulses is measured. By combining the two methods, we developed a system capable of working out correlation functions on line, in full real time for the TM correlator and partially in batch processing for the PM correlator. For the latter one, the duty cycle depends on the count rate of the incoming pulses, being ˜100% for count rates ⩽3×104 Hz, ˜15% at 105 Hz, and ˜1% at 106 Hz. For limitations imposed by the fairly small first-in, first-out (FIFO) buffer available on the counter board, the maximum count rate permissible for a proper functioning of the PM correlator is limited to ˜105 Hz. However, this limit can be removed by using a board with a deeper FIFO. Similarly, the 25 ns time resolution is only limited by maximum clock frequency available on the 6602-PCI and can be easily improved by using a faster clock. When tested on dilute solutions of calibrated latex spheres, the overall performances of the correlator appear to be comparable with those of commercial hardware correlators, but with several nontrivial advantages related to its flexibility, low cost, and easy adaptability to future developments of PC and data acquisition technology.

  3. 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.

  4. 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

  5. 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.

  6. Largescale QSO - Galaxy Correlations Revisited

    NASA Astrophysics Data System (ADS)

    Bartelmann, M.; Schneider, P.

    1993-04-01

    Fugmann (1990) claimed indications for correlations between Lick galaxies and high-redshift, radio-loud background sources. We re- analyze these correlations using an improved statistical method based on Spearman's rank-order test, which we have introduced recently (Bartelmann & Schneider 1993). To our surprise, we are not able to reproduce Fugmann's results, but we detect a significant correlation between moderate-redshift sources from the 1-Jansky catalog and Lick galaxies, which increases when we apply an optical flux limit to the source sample. We interpret these empirical results in terms of an amplification bias caused by gravitational light deflection by dark matter; in particular, we argue that the observed large-scale QSO-galaxy correlations can provide a proof for the association of luminous matter (galaxies) with dark matter.

  7. 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. PMID:27145916

  8. 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.

  9. 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.

  10. Correlated Lloyd model: Exact solution

    NASA Astrophysics Data System (ADS)

    Kozlov, G. G.

    2014-11-01

    We describe an exactly solvable model of a disordered system that is a generalized Lloyd model; it differs from the classical model because the random potential is not a δ-correlated random process. We show that the exact average Green's function in this case is independent of the correlation radius of the random potential and, as in the classical Lloyd model, is a crystal Green's function whose energy argument acquires an imaginary part dependent on the disorder degree.

  11. NASA SERC digital correlator projects

    NASA Technical Reports Server (NTRS)

    Canaris, John

    1992-01-01

    Interest in custom digital correlator processors is growing, in both the radio astronomy and earth sensing communities, as scientists realize that VLSI technology is available to them. This paper presents three digital correlator projects currently underway at the NASA SERC for VLSI Systems Design. The projects are as follows: a 60MHz chip for the ESTAR satellite; a 100MHz, 1024 channel autocorrelator; and a 64 MHz, VLSI system consisting of 8 32- channel complex crosscorrelators including phase rotators.

  12. 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

  13. 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.

  14. The Murchison Widefield Array Correlator

    NASA Astrophysics Data System (ADS)

    Ord, S. M.; Crosse, B.; Emrich, D.; Pallot, D.; Wayth, R. B.; Clark, M. A.; Tremblay, S. E.; Arcus, W.; Barnes, D.; Bell, M.; Bernardi, G.; Bhat, N. D. R.; Bowman, J. D.; Briggs, F.; Bunton, J. D.; Cappallo, R. J.; Corey, B. E.; Deshpande, A. A.; deSouza, L.; Ewell-Wice, A.; Feng, L.; Goeke, R.; Greenhill, L. J.; Hazelton, B. J.; Herne, D.; Hewitt, J. N.; Hindson, L.; Hurley-Walker, N.; Jacobs, D.; Johnston-Hollitt, M.; Kaplan, D. L.; Kasper, J. C.; Kincaid, B. B.; Koenig, R.; Kratzenberg, E.; Kudryavtseva, N.; Lenc, E.; Lonsdale, C. J.; Lynch, M. J.; McKinley, B.; McWhirter, S. R.; Mitchell, D. A.; Morales, M. F.; Morgan, E.; Oberoi, D.; Offringa, A.; Pathikulangara, J.; Pindor, B.; Prabu, T.; Procopio, P.; Remillard, R. A.; Riding, J.; Rogers, A. E. E.; Roshi, A.; Salah, J. E.; Sault, R. J.; Udaya Shankar, N.; Srivani, K. S.; Stevens, J.; Subrahmanyan, R.; Tingay, S. J.; Waterson, M.; Webster, R. L.; Whitney, A. R.; Williams, A.; Williams, C. L.; Wyithe, J. S. B.

    2015-03-01

    The Murchison Widefield Array is a Square Kilometre Array Precursor. The telescope is located at the Murchison Radio-astronomy Observatory in Western Australia. The MWA consists of 4 096 dipoles arranged into 128 dual polarisation aperture arrays forming a connected element interferometer that cross-correlates signals from all 256 inputs. A hybrid approach to the correlation task is employed, with some processing stages being performed by bespoke hardware, based on Field Programmable Gate Arrays, and others by Graphics Processing Units housed in general purpose rack mounted servers. The correlation capability required is approximately 8 tera floating point operations per second. The MWA has commenced operations and the correlator is generating 8.3 TB day-1 of correlation products, that are subsequently transferred 700 km from the MRO to Perth (WA) in real-time for storage and offline processing. In this paper, we outline the correlator design, signal path, and processing elements and present the data format for the internal and external interfaces.

  15. Nonglobal correlations in collider physics

    DOE PAGESBeta

    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

  16. Nonglobal correlations in collider physics

    NASA Astrophysics Data System (ADS)

    Larkoski, Andrew J.; Moult, Ian

    2016-01-01

    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 nonglobal 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 nonglobal 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 it is more widely applicable. The procedure exploits the sensitivity of soft radiation at large angles to nonglobal correlations, and we calculate these correlations through next-to-leading logarithmic accuracy. The bulk of these nonglobal correlations are found to be described in Monte Carlo simulation. They increase by the inclusion of nonperturbative effects, which we show can be incorporated in our calculation through the use of a model shape function. This procedure illuminates the source of nonglobal correlations and has connections more broadly to fundamental quantities in quantum field theory.

  17. 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.

  18. 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.

  19. 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.

  20. Electronic correlations in Hund metals

    NASA Astrophysics Data System (ADS)

    Fanfarillo, L.; Bascones, E.

    2015-08-01

    To clarify the nature of correlations in Hund metals and its relationship with Mott physics we analyze the electronic correlations in multiorbital systems as a function of intraorbital interaction U , Hund's coupling JH, and electronic filling n . We show that the main process behind the enhancement of correlations in Hund metals is the suppression of the double occupancy of a given orbital, as it also happens in the Mott insulator at half-filling. However, contrary to what happens in Mott correlated states the reduction of the quasiparticle weight Z with JH can happen in spite of increasing charge fluctuations. Therefore, in Hund metals the quasiparticle weight and the mass enhancement are not good measurements of the charge localization. Using simple energetic arguments we explain why the spin polarization induced by Hund's coupling produces orbital decoupling. We also discuss how the behavior at moderate interactions, with correlations controlled by the atomic spin polarization, changes at large U and JH due to the proximity to a Mott insulating state.

  1. 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

  2. Biometric verification with correlation filters

    NASA Astrophysics Data System (ADS)

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

    2004-01-01

    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.

  3. Sequence correlations shape protein promiscuity

    NASA Astrophysics Data System (ADS)

    Lukatsky, David B.; Afek, Ariel; Shakhnovich, Eugene I.

    2011-08-01

    We predict analytically that diagonal correlations of amino acid positions within protein sequences statistically enhance protein propensity for nonspecific binding. We use the term "promiscuity" to describe such nonspecific binding. Diagonal correlations represent statistically significant repeats of sequence patterns where amino acids of the same type are clustered together. The predicted effect is qualitatively robust with respect to the form of the microscopic interaction potentials and the average amino acid composition. Our analytical results provide an explanation for the enhanced diagonal correlations observed in hubs of eukaryotic organismal proteomes [J. Mol. Biol. 409, 439 (2011)], 10.1016/j.jmb.2011.03.056. We suggest experiments that will allow direct testing of the predicted effect.

  4. 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.

  5. Correlated optical and isotopic nanoscopy

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    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.

  6. 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

  7. Quantum correlation via quantum coherence

    NASA Astrophysics Data System (ADS)

    Yu, Chang-shui; Zhang, Yang; Zhao, Haiqing

    2014-06-01

    Quantum correlation includes quantum entanglement and quantum discord. Both entanglement and discord have a common necessary condition—quantum coherence or quantum superposition. In this paper, we attempt to give an alternative understanding of how quantum correlation is related to quantum coherence. We divide the coherence of a quantum state into several classes and find the complete coincidence between geometric (symmetric and asymmetric) quantum discords and some particular classes of quantum coherence. We propose a revised measure for total coherence and find that this measure can lead to a symmetric version of geometric quantum correlation, which is analytic for two qubits. In particular, this measure can also arrive at a monogamy equality on the distribution of quantum coherence. Finally, we also quantify a remaining type of quantum coherence and find that for two qubits, it is directly connected with quantum nonlocality.

  8. Minimum Bayes risk image correlation

    NASA Technical Reports Server (NTRS)

    Minter, T. C., Jr.

    1980-01-01

    In this paper, the problem of designing a matched filter for image correlation will be treated as a statistical pattern recognition problem. It is shown that, by minimizing a suitable criterion, a matched filter can be estimated which approximates the optimum Bayes discriminant function in a least-squares sense. It is well known that the use of the Bayes discriminant function in target classification minimizes the Bayes risk, which in turn directly minimizes the probability of a false fix. A fast Fourier implementation of the minimum Bayes risk correlation procedure is described.

  9. Top Quark Spin Correlations - Theory

    SciTech Connect

    Parke, Stephen J.; /Fermilab

    2012-02-01

    The top quark decay width (G{sub F}m{sub t}{sup 3} {approx} 1 GeV) is much larger than the QCD hadronization scale ({Lambda}{sub QCD} {approx} 0.1 GeV) and much larger than the spin decorrelation scale ({Lambda}{sub QCD}{sup 2}/m{sub t} {approx} 0.1 MeV). Therefore, spin correlations in top quark pair production are reflected in angular correlations of the decay products, see [1] and [2].

  10. Petascale cross correlation in software

    NASA Astrophysics Data System (ADS)

    Barsdell, Benjamin R.; Clark, M. A.; Greenhill, L. J.

    2014-04-01

    The exascale computational demands of back-end processing in the era of the SKA and HERA, headlined by the needs of cross-correlation, are likely to require solutions that differ significantly from traditional approaches on smaller arrays. The rapid growth of massively-parallel general-purpose computing hardware presents an alternative to ASIC- or FPGA-based designs and promises several advantages. In this talk we present strong scaling results for an FX correlator that runs entirely in software on GPU-based off-the-shelf HPC clusters.

  11. 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.

  12. 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.

  13. Reveal quantum correlation in complementary bases

    PubMed Central

    Wu, Shengjun; Ma, Zhihao; Chen, Zhihua; Yu, Sixia

    2014-01-01

    An essential feature of genuine quantum correlation is the simultaneous existence of correlation in complementary bases. We reveal this feature of quantum correlation by defining measures based on invariance under a basis change. For a bipartite quantum state, the classical correlation is the maximal correlation present in a certain optimum basis, while the quantum correlation is characterized as a series of residual correlations in the mutually unbiased bases. Compared with other approaches to quantify quantum correlation, our approach gives information-theoretical measures that directly reflect the essential feature of quantum correlation. PMID:24503595

  14. 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

  15. 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

  16. 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,…

  17. 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…

  18. Echoes in correlated neural systems

    NASA Astrophysics Data System (ADS)

    Helias, M.; Tetzlaff, T.; Diesmann, M.

    2013-02-01

    Correlations are employed in modern physics to explain microscopic and macroscopic phenomena, like the fractional quantum Hall effect and the Mott insulator state in high temperature superconductors and ultracold atoms. Simultaneously probed neurons in the intact brain reveal correlations between their activity, an important measure to study information processing in the brain that also influences the macroscopic signals of neural activity, like the electroencephalogram (EEG). Networks of spiking neurons differ from most physical systems: the interaction between elements is directed, time delayed, mediated by short pulses and each neuron receives events from thousands of neurons. Even the stationary state of the network cannot be described by equilibrium statistical mechanics. Here we develop a quantitative theory of pairwise correlations in finite-sized random networks of spiking neurons. We derive explicit analytic expressions for the population-averaged cross correlation functions. Our theory explains why the intuitive mean field description fails, how the echo of single action potentials causes an apparent lag of inhibition with respect to excitation and how the size of the network can be scaled while maintaining its dynamical state. Finally, we derive a new criterion for the emergence of collective oscillations from the spectrum of the time-evolution propagator.

  19. 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.

  20. 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.

  1. Resistant multiple sparse canonical correlation.

    PubMed

    Coleman, Jacob; Replogle, Joseph; Chandler, Gabriel; Hardin, Johanna

    2016-04-01

    Canonical correlation analysis (CCA) is a multivariate technique that takes two datasets and forms the most highly correlated possible pairs of linear combinations between them. Each subsequent pair of linear combinations is orthogonal to the preceding pair, meaning that new information is gleaned from each pair. By looking at the magnitude of coefficient values, we can find out which variables can be grouped together, thus better understanding multiple interactions that are otherwise difficult to compute or grasp intuitively. CCA appears to have quite powerful applications to high-throughput data, as we can use it to discover, for example, relationships between gene expression and gene copy number variation. One of the biggest problems of CCA is that the number of variables (often upwards of 10,000) makes biological interpretation of linear combinations nearly impossible. To limit variable output, we have employed a method known as sparse canonical correlation analysis (SCCA), while adding estimation which is resistant to extreme observations or other types of deviant data. In this paper, we have demonstrated the success of resistant estimation in variable selection using SCCA. Additionally, we have used SCCA to find multiple canonical pairs for extended knowledge about the datasets at hand. Again, using resistant estimators provided more accurate estimates than standard estimators in the multiple canonical correlation setting. R code is available and documented at https://github.com/hardin47/rmscca. PMID:26963062

  2. 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.)

  3. Time correlators from deferred measurements

    NASA Astrophysics Data System (ADS)

    Oehri, D.; Lebedev, A. V.; Lesovik, G. B.; Blatter, G.

    2016-01-01

    Repeated measurements that typically occur in two-time or multitime correlators rely on von Neumann's projection postulate, telling how to restart the system after an intermediate measurement. We invoke the principle of deferred measurement to describe an alternative procedure in which coevolving quantum memories extract system information through entanglement, combined with a final readout of the memories described by Born's rule. Our approach to repeated quantum measurements respects the unitary evolution of quantum mechanics during intermediate times, unifies the treatment of strong and weak measurements, and reproduces the projected and (anti)symmetrized correlators in the two limits. As an illustration, we apply our formalism to the calculation of the electron charge correlator in a mesoscopic physics setting, where single electron pulses assume the role of flying memory qubits. We propose an experimental setup that reduces the measurement of the time correlator to the measurement of currents and noise, exploiting the (pulsed) injection of electrons to cope with the challenge of performing short-time measurements.

  4. 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…

  5. Dynamics of electricity market correlations

    NASA Astrophysics Data System (ADS)

    Alvarez-Ramirez, J.; Escarela-Perez, R.; Espinosa-Perez, G.; Urrea, R.

    2009-06-01

    Electricity market participants rely on demand and price forecasts to decide their bidding strategies, allocate assets, negotiate bilateral contracts, hedge risks, and plan facility investments. However, forecasting is hampered by the non-linear and stochastic nature of price time series. Diverse modeling strategies, from neural networks to traditional transfer functions, have been explored. These approaches are based on the assumption that price series contain correlations that can be exploited for model-based prediction purposes. While many works have been devoted to the demand and price modeling, a limited number of reports on the nature and dynamics of electricity market correlations are available. This paper uses detrended fluctuation analysis to study correlations in the demand and price time series and takes the Australian market as a case study. The results show the existence of correlations in both demand and prices over three orders of magnitude in time ranging from hours to months. However, the Hurst exponent is not constant over time, and its time evolution was computed over a subsample moving window of 250 observations. The computations, also made for two Canadian markets, show that the correlations present important fluctuations over a seasonal one-year cycle. Interestingly, non-linearities (measured in terms of a multifractality index) and reduced price predictability are found for the June-July periods, while the converse behavior is displayed during the December-January period. In terms of forecasting models, our results suggest that non-linear recursive models should be considered for accurate day-ahead price estimation. On the other hand, linear models seem to suffice for demand forecasting purposes.

  6. Separating Spike Count Correlation from Firing Rate Correlation

    PubMed Central

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

    2016-01-01

    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. PMID:26942746

  7. 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.

  8. 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. PMID:26942746

  9. Correlates of hysterectomy in Australia.

    PubMed

    Santow, G; Bracher, M

    1992-04-01

    With around one in five women undergoing hysterectomy by the age of 50, the prevalence of hysterectomy in Australia is greater than in Europe but less than in the United States. In this paper, data from a nationally representative sample survey of 2547 Australian women aged 20-59 years are employed to identify correlates of hysterectomy and tubal sterilization over the last 30 years. Physiological, socio-economic and supply-side factors all influence the propensity to undergo hysterectomy, and a comparison with the correlates of tubal sterilization reveals parallels and contrasts between the determinants of the two operations. Age and parity are important predictors of hysterectomy. In addition, use of oral contraceptives for at least five years reduces the risk of hysterectomy, as do tubal sterilization, tertiary education and birthplace in Southern Europe. Conversely, risk increases after experiencing side effects with the IUD or repeated foetal losses, or after bearing a third child before the age of 25. PMID:1604382

  10. 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.

  11. 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.

  12. 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.

  13. Correlations in avalanche critical points.

    PubMed

    Cerruti, Benedetta; Vives, Eduard

    2009-07-01

    Avalanche dynamics and related power-law statistics are ubiquitous in nature, arising in phenomena such as earthquakes, forest fires, and solar flares. Very interestingly, an analogous behavior is associated with many condensed-matter systems, such as ferromagnets and martensites. Bearing it in mind, we study the prototypical random-field Ising model at T=0. We find a finite correlation between waiting intervals and the previous avalanche size. This correlation is not found in other models for avalanches but it is experimentally found in earthquakes and in forest fires. Our study suggests that this effect occurs in critical points that are at the end of a first-order discontinuity separating two regimes: one with high activity from another with low activity. PMID:19658651

  14. Supercritical Angle Fluorescence Correlation Spectroscopy

    PubMed Central

    Ries, Jonas; Ruckstuhl, Thomas; Verdes, Dorinel; Schwille, Petra

    2008-01-01

    We explore the potential of a supercritical angle (SA) objective for fluorescence correlation spectroscopy (FCS). This novel microscope objective combines tight focusing by an aspheric lens with strong axial confinement of supercritical angle fluorescence collection by a parabolic mirror lens, resulting in a small detection volume. The tiny axial extent of the detection volume features an excellent surface sensitivity, as is demonstrated by diffusion measurements in model membranes with an excess of free dye in solution. All SA-FCS measurements are directly compared to standard confocal FCS, demonstrating a clear advantage of SA-FCS, especially for diffusion measurements in membranes. We present an extensive theoretical framework that allows for accurate and quantitative evaluation of the SA-FCS correlation curves. PMID:17827221

  15. Velocity correlations of galaxy clusters

    NASA Technical Reports Server (NTRS)

    Cen, Renyue; Bahcall, Neta A.; Gramann, Mirt

    1994-01-01

    We determine the velocity correlation function, pairwise peculiar velocity difference, and rms pairwise peculiar velocity dispersion of rich clusters of galaxies, as a function of pair separation, for three cosmological models: Omega = 1 and Omega = 0.3 cold dark matter (CDM), and Omega = 0.3 primeval baryonic isocurvature (PBI) models (all flat and Cosmic Background Explorer (COBE)-normalized). We find that close cluster pairs, with separation r is less than or equal to 10/h Mpc, exhibit strong attractive peculiar velocities in all models; the cluster pairwise velocities depend sensitively on the model. The mean pairwise attractive velocity of clusters on 5/h Mpc scale ranges from approximately 1700 km/s for Omega = 1 CDM to approximately 1000 km/s for PBI to approximately 700 km/s for Omega = 0.3 CDM. The small-scale pairwise velocities depend also on cluster mass: richer, more massive clusters exhibit stronger attractive velocities than less massive clusters. On large scales, from approximately 20 to 200/h Mpc, the cluster peculiar velocities are increasingly dominated by bulk and random motions; they are independent of cluster mass. The cluster velocity correlation function is negative on small scales for Omega = 1 and Omega = 0.3 CDM, indicating strong pairwise motion relative to bulk motion on small scales; PBI exhibits relatively larger bulk motions. The cluster velocity correlation function is positive on very large scales, from r approximately 10/h Mpc to r approximately 200/h Mpc, for all models. These positive correlations, which decrease monotonically with scale, indicate significant bulk motions of clusters up to approximately 200/h Mpc. The strong dependence of the cluster velocity functions on models, especially at small separations, makes them useful tools in constraining cosmological models when compared with observations.

  16. 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.

  17. Correlation and simple linear regression.

    PubMed

    Eberly, Lynn E

    2007-01-01

    This chapter highlights important steps in using correlation and simple linear regression to address scientific questions about the association of two continuous variables with each other. These steps include estimation and inference, assessing model fit, the connection between regression and ANOVA, and study design. Examples in microbiology are used throughout. This chapter provides a framework that is helpful in understanding more complex statistical techniques, such as multiple linear regression, linear mixed effects models, logistic regression, and proportional hazards regression. PMID:18450049

  18. 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.

  19. Neuropsychological correlates of domestic violence.

    PubMed

    Cohen, R A; Rosenbaum, A; Kane, R L; Warnken, W J; Benjamin, S

    1999-01-01

    Neuropsychological functioning was assessed in 39 males who had committed domestic violence (batterers) and compared to 63 nonviolent (both maritally discordant and satisfied) subjects recruited by advertisement. Subjects were subsequently divided into two groups (head injured, nonhead injured) and these groups were also contrasted as a function of batterer status. Tests were administered to assess for cognitive and behavioral functions, including executive dysfunction, hypothesized to be a factor contributing to propensity for violence. Questionnaires and structured clinical interviews were used to assess marital discord, emotional distress, and violent behaviors. Batterers differed from nonbatterers across several cognitive domains: executive, learning, memory, and verbal functioning. Batterers were reliably discriminated from nonbatterers based on three neuropsychological tasks: Digit Symbol, Recognition Memory Test-Words, Wisconsin Card Sorting Test. Neuropsychological performance was the strongest correlate of domestic violence of all clinical variables measured. However, the inclusion of two other variables, severity of emotional distress and history of head injury, together with the neuropsychological indices provided the strongest correlation with batterers status. Among batterers, neuropsychological performance did not vary as a function of head injury status, indicating that while prior head injury was correlated with batterer status, it was not the sole basis for their impairments. The findings suggest that current cognitive status, prior brain injury, childhood academic problems, as well as psychosocial influences, contribute along with coexisting emotional distress to a propensity for domestic violence. PMID:10751047

  20. 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.

  1. Correlated genotypes in friendship networks

    PubMed Central

    Fowler, James H.; Settle, Jaime E.; Christakis, Nicholas A.

    2011-01-01

    It is well known that humans tend to associate with other humans who have similar characteristics, but it is unclear whether this tendency has consequences for the distribution of genotypes in a population. Although geneticists have shown that populations tend to stratify genetically, this process results from geographic sorting or assortative mating, and it is unknown whether genotypes may be correlated as a consequence of nonreproductive associations or other processes. Here, we study six available genotypes from the National Longitudinal Study of Adolescent Health to test for genetic similarity between friends. Maps of the friendship networks show clustering of genotypes and, after we apply strict controls for population stratification, the results show that one genotype is positively correlated (homophily) and one genotype is negatively correlated (heterophily). A replication study in an independent sample from the Framingham Heart Study verifies that DRD2 exhibits significant homophily and that CYP2A6 exhibits significant heterophily. These unique results show that homophily and heterophily obtain on a genetic (indeed, an allelic) level, which has implications for the study of population genetics and social behavior. In particular, the results suggest that association tests should include friends’ genes and that theories of evolution should take into account the fact that humans might, in some sense, be metagenomic with respect to the humans around them. PMID:21245293

  2. Wolfram syndrome: a clinicopathologic correlation

    PubMed Central

    Merchant, Saumil N.; Adams, Joe C.; Joseph, Jeffrey T.

    2009-01-01

    Wolfram syndrome or DIDMOAD (diabetes insipidus, diabetes mellitus, optic atrophy and deafness) is a neurodegenerative disorder characterized by diabetes mellitus and optic atrophy as well as diabetes insipidus and deafness in many cases. We report the post-mortem neuropathologic findings of a patient with Wolfram syndrome and correlate them with his clinical presentation. In the hypothalamus, neurons in the paraventricular and supraoptic nuclei were markedly decreased and minimal neurohypophyseal tissue remained in the pituitary. The pontine base and inferior olivary nucleus showed gross shrinkage and neuron loss, while the cerebellum was relatively unaffected. The visual system had moderate to marked loss of retinal ganglion neurons, commensurate loss of myelinated axons in the optic nerve, chiasm and tract, and neuron loss in the lateral geniculate nucleus but preservation of the primary visual cortex. The patient’s inner ear showed loss of the organ of Corti in the basal turn of the cochleae and mild focal atrophy of the stria vascularis. These findings correlated well with the patient’s high-frequency hearing loss. The pathologic findings correlated closely with the patient’s clinical symptoms and further support the concept of Wolfram syndrome as a neurodegenerative disorder. Our findings extend prior neuropathologic reports of Wolfram syndrome by providing contributions to our understanding of eye, inner ear and olivopontine pathology in this disease. PMID:19449020

  3. 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

  4. Manifest and concealed correlations in quantum mechanics

    NASA Astrophysics Data System (ADS)

    de la Torre, A. C.; Iguain, J. L.

    1998-11-01

    The quantum covariance function is used to study correlations in quantum systems. Besides the obvious correlations due to the conservation of some quantity, the appearance of concealed quantum correlations like non-locality or non-separability is studied. The choice of an appropriate basis allows a complete analysis relating correlations with conservation laws and factorizability.

  5. 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.

  6. 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.

  7. 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.

  8. Correlates of increased sexual satisfaction.

    PubMed

    Haavio-Mannila, E; Kontula, O

    1997-08-01

    Comparisons of nationally representative survey data of the population ages 18-54 years in 1971 (N = 2252) and 1992 (N = 1718) from Finland show that sexual satisfaction has greatly increased particularly among women. Some predictors of sexual satisfaction of men and women are examined on the basis of the 1992 survey data on people ages 18-74 years (N = 2250). Correlations between social background factors, sexual ideas and assertiveness, optional relationships, sexual practices, organism, and satisfaction with sexual intercourse were calculated. To control the simultaneous effect of the variables explaining satisfaction, path analyses were conducted. Results show that young age, a sexually unreserved and a nonreligious childhood home, early start of sexual life, high education, sexual assertiveness, considering sexuality important in life, reciprocal feeling of love, use of sex materials, frequent intercourse, many-sided (versatile) sexual techniques, and frequent orgasm correlate with finding sexual intercourse pleasurable. There were some gender differences in the connections between the independent factors and satisfaction with coitus. The importance of sexuality in life, love, and the use of sexual materials were connected directly to physical sexual satisfaction among men but only indirectly among women. For women, but not for men, young age and early start of sexual life correlated with enjoyment of intercourse. The greater sexual dissatisfaction of women compared to men, which still prevails, may be due to their late start of sexual life, conservative sexual attitudes, unimportance of sexuality in life, lack of sexual assertiveness, and use of restricted sexual techniques. The emancipation of women may change these ideas and practices of women. This might lessen the gender gap in physical sexual satisfaction. PMID:9251837

  9. Correlation-induced spectral changes

    NASA Astrophysics Data System (ADS)

    Wolf, Emil; James, Daniel F. V.

    1996-06-01

    This paper presents a review of research, both theoretical and experimental, concerning the influence of coherence properties of fluctuating light sources and of correlation properties of scattering media on the spectra of radiated and scattered fields. Much of this research followed a discovery made in 1986, that the spectrum of light may change on propagation, even in free space. More than 100 papers on this topic have been published to date and many of them are reviewed, or at least mentioned, in this article. After an introduction and a summary of some of the main mathematical results relating to second-order coherence theory of statistically stationary optical fields, spectral changes that may take place on superposing fields produced by two partially correlated sources are discussed. Spectral effects in fields produced by two-dimensional secondary sources and by three-dimensional primary sources are then considered. The section which follows describes spectral changes that may arise when polychromatic light is scattered on media whose physical properties vary randomly either in space and/or in time. A review is also presented of recent research, which has revealed that under certain circumstances the changes in the spectrum of light scattered on random media may imitate the Doppler effect, even though the source, the medium and the observer are all at rest with respect to one another. In the final section a brief review is given of a new emerging technique sometimes called spatial-coherence spectroscopy. It is based on the discovery that it is possible, under certain circumstances, to determine field correlations from spectral measurements.

  10. Precision protection through indirect correlations

    NASA Astrophysics Data System (ADS)

    Jin, Yao

    2016-04-01

    The dynamics of the quantum Fisher information of the parameters of the initial atomic state is studied, in the framework of open quantum systems, for a pair of static two-level atoms coupled to a bath of fluctuating vacuum scalar fields. Our results show that the correlations between the two atoms as well as the precision limit in quantum metrology are determined by the separation between the two atoms. Remarkably, when the separation between the two atoms approaches zero, the quantum Fisher information, thus the precision limit of the estimation of the parameters of the initial atomic state will be survived from the vacuum fluctuations after long time evolution.

  11. 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.

  12. Speeding up local correlation methods

    NASA Astrophysics Data System (ADS)

    Kats, Daniel

    2014-12-01

    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.

  13. 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.

  14. Biological correlates of binge eating.

    PubMed

    Yanovski, S Z

    1995-01-01

    Eating disorders are associated with numerous biological perturbations; however, sorting out cause from effect is difficult. Neuroendocrine and metabolic abnormalities are seen in both anorexia nervosa and bulimia nervosa, but they have not been described in binge eating disorder, in which neither starvation nor compensatory behaviors are present. Although these findings may reflect biologic differences among subgroups of binge eaters, an alternative explanation is that many of the biological correlates of binge eating are the result of metabolic derangement secondary to starvation and/or purging. The identification of binge eating disorder provides an opportunity to study the causes and concomitants of binge eating in the absence of compensatory behaviors. PMID:8820523

  15. 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.

  16. Short Range Correlations in Nuclei

    SciTech Connect

    L. B. Weinstein

    2006-11-01

    Short range correlations (SRC) are an extremely important part of nuclear structure. They are responsible for the high momentum part of the nuclear wavefunction. Instantaneous densities can significantly exceed the average neutron star density. Recent (e,e[prime]) measurements at Jefferson Lab have shown that SRC are universal in nuclei from deuterium to gold, that the probability of two-nucleon SRC is 5-25%, and that the probability of three-nucleon SRC is less than 1%. Recent (e,e[prime]pn) measurements have measured the SRC probabilities as a function of proton momentum and have measured the joint NN momentum distributions.

  17. Development of "active correlation" technique

    NASA Astrophysics Data System (ADS)

    Tsyganov, Yu. S.

    2016-01-01

    With reaching to extremely high intensities of heavy-ion beams new requirements for the detection system of the Dubna Gas-Filled Recoil Separator (DGFRS) will definitely be set. One of the challenges is how to apply the "active correlations" method to suppress beam associated background products without significant losses in the whole long-term experiment efficiency value. Different scenarios and equations to develop the method according this requirement are under consideration in the present paper. The execution time to estimate the dead time parameter associated with the optimal choice of the life-time parameter is presented.

  18. 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. PMID:23679650

  19. 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.

  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. 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

  2. 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.

  3. Correlated metals as transparent conductors.

    PubMed

    Zhang, Lei; Zhou, Yuanjun; Guo, Lu; Zhao, Weiwei; Barnes, Anna; Zhang, Hai-Tian; Eaton, Craig; Zheng, Yuanxia; Brahlek, Matthew; Haneef, Hamna F; Podraza, Nikolas J; Chan, Moses H W; Gopalan, Venkatraman; Rabe, Karin M; Engel-Herbert, Roman

    2016-02-01

    The fundamental challenge for designing transparent conductors used in photovoltaics, displays and solid-state lighting is the ideal combination of high optical transparency and high electrical conductivity. Satisfying these competing demands is commonly achieved by increasing carrier concentration in a wide-bandgap semiconductor with low effective carrier mass through heavy doping, as in the case of tin-doped indium oxide (ITO). Here, an alternative design strategy for identifying high-conductivity, high-transparency metals is proposed, which relies on strong electron-electron interactions resulting in an enhancement in the carrier effective mass. This approach is experimentally verified using the correlated metals SrVO3 and CaVO3, which, despite their high carrier concentration (>2.2 × 10(22) cm(-3)), have low screened plasma energies (<1.33 eV), and demonstrate excellent performance when benchmarked against ITO. A method is outlined to rapidly identify other candidates among correlated metals, and strategies are proposed to further enhance their performance, thereby opening up new avenues to develop transparent conductors. PMID:26657329

  4. Correlated metals as transparent conductors

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Zhou, Yuanjun; Guo, Lu; Zhao, Weiwei; Barnes, Anna; Zhang, Hai-Tian; Eaton, Craig; Zheng, Yuanxia; Brahlek, Matthew; Haneef, Hamna F.; Podraza, Nikolas J.; Chan, Moses H. W.; Gopalan, Venkatraman; Rabe, Karin M.; Engel-Herbert, Roman

    2016-02-01

    The fundamental challenge for designing transparent conductors used in photovoltaics, displays and solid-state lighting is the ideal combination of high optical transparency and high electrical conductivity. Satisfying these competing demands is commonly achieved by increasing carrier concentration in a wide-bandgap semiconductor with low effective carrier mass through heavy doping, as in the case of tin-doped indium oxide (ITO). Here, an alternative design strategy for identifying high-conductivity, high-transparency metals is proposed, which relies on strong electron-electron interactions resulting in an enhancement in the carrier effective mass. This approach is experimentally verified using the correlated metals SrVO3 and CaVO3, which, despite their high carrier concentration (>2.2 × 1022 cm-3), have low screened plasma energies (<1.33 eV), and demonstrate excellent performance when benchmarked against ITO. A method is outlined to rapidly identify other candidates among correlated metals, and strategies are proposed to further enhance their performance, thereby opening up new avenues to develop transparent conductors.

  5. A correlated nickelate synaptic transistor

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

    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.

  6. CCD correlated quadruple sampling processor

    NASA Technical Reports Server (NTRS)

    Gaalema, S. D. (Inventor)

    1981-01-01

    A correlated quadruple sampling processor for improved signal-to-noise ratio in the output of a charge-coupled device (CCD) is comprised of: switching means for momentarily clamping a CCD signal line at a first reference level A before a CCD data pulse and then obtaining a first data sample B with respect to the reference A during a CCD data pulse, and storing the positive sample B-A; switching means for momentarily clamping the CCD signal line a second time at the level C during the presence of the CCD data pulse and then obtaining a second data sample D with respect to the reference level C after the CCD data pulse, and storing the negative sample D-C; and means for obtaining the difference between the stored samples +(B-A) and -(D-C), thus increasing the net signal amplitude by a factor of about 2 while the noise would be increased by only a factor of square root of 2 since there will be no correlation in the noise between the double samples +(B-A) and -(D-C) effectively added.

  7. PREFACE: Correlation Dynamics in Nuclei

    NASA Astrophysics Data System (ADS)

    Suzuki, Toshio; Otsuka, Takaharu; Ichimura, Munetake

    2005-01-01

    The International Symposium on `Correlation Dynamics in Nuclei' was held at the Sanjo Kaikan, the University of Tokyo, from the 31 January to 4 February 2005. This symposium was organized on the occasion of the 50th anniversary of the Configuration Mixing theory of Arima and Horie. The symposium was hosted by the University of Tokyo, and supported by the Inoue Foundation for Science, the Japan Atomic Energy Research Institute and the Ministry of Education, Culture, Sports, Science and Technology. The purpose of the symposium was to discuss theoretical and experimental developments and future prospects in physics of correlation dynamics in nuclei, including topics such as effective interactions, shell model studies of configuration mixing and spin-isospin modes in nuclei. It was shown in many ways and angles that the Arima-Horie theory has been a starting point of a variety of developments of the studies in these fields over many decades. The developments have been enhanced by the expansion of computational capabilities and the progress in accelerators, detectors and radioactive beam facilities. We enjoyed 28 excellent and lively invited talks and 30 oral presentations in the symposium with about 90 participants. A special session was dedicated to celebrate the 80th birthday of Professor Igal Talmi, who made invaluable and pioneering works in the shell model theory. Finally, we would like to thank all the speakers and the participants as well as the other organizers for their contributions which made the symposium very successful.

  8. 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.

  9. 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.

  10. 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

  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. 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

  13. Correlations in cosmic density fields

    NASA Technical Reports Server (NTRS)

    Bromley, B. C.

    1994-01-01

    A method is proposed to place constraints on the functional form of the high-order correlation functions zeta(sub n) that arise in cosmic density fields at large scales. This technique is based on a mass-in-cell statistic and a difference of mass in partitions of a cell. The relationship between these measures is sensitive to the formal structure of the zeta(sub n) as well as their amplitudes. This relationship is quantified in several theoretical models of structure, based on the hierarchical clustering paradigm. The results lead to a test for specific types of hierarchical clustering that is sensitive to correlations of all orders. The method is applied to examples of simulated large-scaled structure dominated by cold dark matter. In the preliminary study, the hierarchical paradigm appears to be a realistic approximation over a broad range of the scales. Furthermore, there is evidence that graphs of low-order vertices are dominant. On the basis of simulated data a phenomological model is specified that gives a good representation of clustering from linear scales to the strongly clustered regime (zeta(sub 2) approximately 500).

  14. 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.

  15. 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

  16. Exact exchange for correlated electrons

    NASA Astrophysics Data System (ADS)

    Novák, P.; Kune?, J.; Chaput, L.; Pickett, W. E.

    The cover picture is taken from the article by Pavel Novák that was chosen as Editor's Choice of this issue [1]. The figure shows the density of minority spin states in nickel oxide calculated by three commonly used approximations (LSDA, GGA, LDA+U) as well as using the newly proposed ?Exact Exchange for Correlated Electrons? (EECE) method. The EECE method treats the interactions between correlated electrons in a Hartree-Fock way, while all other interactions are described by the density functional theory. EECE is a promising starting point for the improvement of orbital-dependent functionals within the density functional theory.Pavel Novák is the head of the ?Spectroscopy of Magnetic Oxides? group at the Institute of Physics of ASCR, Prague, Czech Republic. Most of his scientific activity is devoted to the calculation of the electronic structure of solids, but he also closely cooperates with several experimental groups. Particular attention is focused on the nuclear magnetic resonance and electronic structure of magnetic oxides with mixed valency of the cations

  17. 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.

  18. Holographic lens for optical correlator

    NASA Astrophysics Data System (ADS)

    Semenov, G. B.; Koreshev, S. N.; Pavlov, A. V.; Shubnikov, Y. I.

    1984-08-01

    Aberrations in holographic optics place limitations on the information capacity of the data that can be processed by holographic optical correlators. Nonetheless, the aberrations can be reduced sufficiently for an extensive class of devices such as those for real time data input using space-time light modulators and a TV channel. This paper analyzes the aberrations of holographic lenses, demonstrating the feasibility of an off-axis lens for correlation image analysis with aberrations similar to an axial lens. A requirement that the wave aberrations not exceed a quarter-wavelength was placed on the lens. Equations are solved for coma and astigmatism, and used to plot the maximum wave aberrations as a function of the spatial frequency of the proposed signal for three cases: (1) normal propagation of a diverging beam and oblique propagation of a plane beam; (2) oblique propagation of diverging and parallel beams, symmetrical with respect to the normal to the photographic plate; (3) oblique propagation of the diverging beam and normal propagation of the parallel beam. The angle between the beam axes was 45 deg in all cases, with a lens focal length of 350 mm and an operture of 32 mm.

  19. Development of Software Correlator for KJJVC

    NASA Astrophysics Data System (ADS)

    Yeom, J. H.; Oh, S. J.; Roh, D. G.; Kang, Y. W.; Park, S. Y.; Lee, C. H.; Chung, H. S.

    2009-12-01

    Korea-Japan Joint VLBI Correlator (KJJVC) is being developed by collaborating KASI (Korea Astronomy and Space Science Institute), Korea, and NAOJ(National Observatory of Japan), Japan. In early 2010, KJJVC will work in normal operation. In this study, we developed the software correlator which is based on VCS (VLBI Correlation Subsystem) hardware specification as the core component of KJJVC. The main specification of software correlator is 8 Gbps, 8192 output channels, and 262,144-points FFT (Fast Fourier Transform) function same as VCS. And the functional algorithm which is same as specification of VCS and arithmetic register are adopted in this software correlator. To verify the performance of developed software correlator, the correlation experiments were carried out using the spectral line and continuum sources which were observed by VERA (VLBI Exploration of Radio Astrometry), NAOJ. And the experimental results were compared to the output of Mitaka FX correlator by referring spectrum shape, phase rate, and fringe detection and so on. Through the experimental results, we confirmed that the correlation results of software correlator are the same as Mitaka FX correlator and verified the effectiveness of it. In future, we expect that the developed software correlator will be the possible software correlator of KVN (Korean VLBI Network) with KJJVC by introducing the correlation post-processing and modifying the user interface as like GUI (Graphic User Interface).

  20. 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"…

  1. 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…

  2. 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.

  3. 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.

  4. Neural correlates of face detection.

    PubMed

    Xu, Xiaokun; Biederman, Irving

    2014-06-01

    Although face detection likely played an essential adaptive role in our evolutionary past and in contemporary social interactions, there have been few rigorous studies investigating its neural correlates. MJH, a prosopagnosic with bilateral lesions to the ventral temporal-occipital cortices encompassing the posterior face areas (fusiform and occipital face areas), expresses no subjective difficulty in face detection, suggesting that these posterior face areas do not mediate face detection exclusively. Despite his normal contrast sensitivity and visual acuity in foveal vision, the present study nevertheless revealed significant face detection deficits in MJH. Compared with controls, MJH showed a lower tolerance to noise in the phase spectrum for faces (vs. cars), reflected in his higher detection threshold for faces. MJH's lesions in bilateral occipito-temporal cortices thus appear to have produced a deficit not only in face individuation, but also in face detection. PMID:23365211

  5. Correlation functions in stochastic inflation

    NASA Astrophysics Data System (ADS)

    Vennin, Vincent; Starobinsky, Alexei A.

    2015-09-01

    Combining the stochastic and formalisms, we derive non-perturbative analytical expressions for all correlation functions of scalar perturbations in single-field, slow-roll inflation. The standard, classical formulas are recovered as saddle-point limits of the full results. This yields a classicality criterion that shows that stochastic effects are small only if the potential is sub-Planckian and not too flat. The saddle-point approximation also provides an expansion scheme for calculating stochastic corrections to observable quantities perturbatively in this regime. In the opposite regime, we show that a strong suppression in the power spectrum is generically obtained, and we comment on the physical implications of this effect.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. Multiagency VLBI Correlator Facility opens

    NASA Astrophysics Data System (ADS)

    Carter, William E.

    A new $1.2 million facility to process geodetic Very Long Baseline Interferometry (VLBI) observational data was dedicated August 25, 1986, at the U.S. Naval Observatory headquarters, Washington, D.C., by representatives of the National Oceanic and Atmospheric Administration (NOAA), the Naval Research Laboratory (NRL), the U.S. Naval Observatory (USNO), and the National Aeronautics and Space Administration (NASA). The new facility will provide timely correlation of the data tapes produced by the POLARIS (Polar (Motion) Analysis by Radio Interferometric Surveying) earth orientation monitoring network. The new facility will also be used to process VLBI data collected by the NASA Crustal Dynamics Project (CDP) and by NRL and USNO programs in astrometry and basic research.

  12. 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.

  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. Arousal and Anxiety Correlates of Gymnastic Performance

    ERIC Educational Resources Information Center

    Basler, Marilyn L.; And Others

    1976-01-01

    Tests on a women's gymnastic team to explore correlation between arousal, anxiety, and performance, revealed limited relationships between performance and arousal/anxiety measures and indicated that gymnastic ability is the best correlate of gymnastic performance. (JD)

  15. 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.

  16. Structural dynamics analyses testing and correlation

    NASA Technical Reports Server (NTRS)

    Caughey, T. K.

    1982-01-01

    Some aspects of the lack of close correlation between the predictions of analytical modeling of dynamic structures and the results of vibration tests on such structures are examined. Ways in which the correlation may be improved are suggested.

  17. Quantum Correlations, Chaos and Information

    NASA Astrophysics Data System (ADS)

    Madhok, Vaibhav

    Quantum chaos is the study of quantum systems whose classical description is chaotic. How does chaos manifest itself in the quantum world? In this spirit, we study the dynamical generation of entanglement as a signature of chaos in a system of periodically kicked coupled-tops, where chaos and entanglement arise from the same physical mechanism. The long-time entanglement as a function of the position of an initially localized wave packet very closely correlates with the classical phase space surface of section - it is nearly uniform in the chaotic sea, and reproduces the detailed structure of the regular islands. The uniform value in the chaotic sea is explained by the random state conjecture. As classically chaotic dynamics take localized distributions in phase space to random distributions, quantized versions take localized coherent states to pseudo-random states in Hilbert space. Such random states are highly entangled, with an average value near that of the maximally entangled state. For a map with global chaos, we derive that value based on new analytic results for the entropy of random states. For a mixed phase space, we use the Percival conjecture to identify a "chaotic subspace" of the Hilbert space. The typical entanglement, averaged over the unitarily invariant Haar measure in this subspace, agrees with the long-time averaged entanglement for initial states in the chaotic sea. In all cases the dynamically generated entanglement is that of a random complex vector, even though the system is time-reversal invariant, and the Floquet operator is a member of the circular orthogonal ensemble. Continuing on our journey to find the footprints of chaos in the quantum world, we explore quantum signatures of classical chaos by studying the rate of information gain in quantum tomography. The measurement record is obtained as a sequence of expectation values of a Hermitian operator evolving under repeated application of the Floquet operator of the quantum kicked top on

  18. 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.

  19. Survey of current correlators and applications

    NASA Technical Reports Server (NTRS)

    Lahmeyer, C. R.; Brokl, S. S.

    1987-01-01

    With this summary an attempt is made to contact as many users as possible so as to provide summary data on correlation systems, both in use and as planned. Data on currently available very large scale integration (VLSI) chips and complete systems are included. Also, several planned correlator systems are described and summarized in tabular form. Finally, a description is given of the work being done in the Communications Systems Research Section on VLSI correlator chips and complete correlator systems.

  20. 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.

  1. Wavelet correlations in the [ital p] model

    SciTech Connect

    Greiner, M. Institut fuer Theoretische Physik, Justus Liebig Universitaet, 35392 Geien ); Lipa, P.; Carruthers, P. )

    1995-03-01

    We suggest applying the concept of wavelet transforms to the study of correlations in multiparticle physics. Both the usual correlation functions as well as the wavelet transformed ones are calculated for the [ital p] model, which is a simple but tractable random cascade model. For this model, the wavelet transform decouples correlations between fluctuations defined on different scales. The advantageous properties of factorial moments are also shared by properly defined factorial wavelet correlations.

  2. 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…

  3. 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…

  4. Economic and Educational Correlates of TIMSS Results

    ERIC Educational Resources Information Center

    Mikk, Jaan

    2005-01-01

    The good knowledge of the correlates of educational achievement highlights the ways to the efficient use of economic and human capital in raising the efficiency of education. The present paper investigates the correlates and compares the values of the correlates for the Republic of Lithuania with the average international values. The data for the…

  5. Structural Correlates of Prospective Memory

    PubMed Central

    Gordon, Brian A; Shelton, Jill T; Bugg, Julie M; McDaniel, Mark A; Head, Denise

    2011-01-01

    Prospective memory (PM) includes the encoding and maintenance of an intention, and the retrieval and execution of this intention at the proper moment in the future. The present study expands upon previous behavioral, electrophysiological, and functional work by examining the association between grey matter volume and PM. Estimates of grey matter volume in theoretically relevant regions of interest (prefrontal, parietal, and medial temporal) were obtained in conjunction with performance on two PM tasks in a sample of 39 cognitively normal and very mildly demented older adults. The first PM task, termed focal in the literature, is supported by spontaneous retrieval of the PM intention whereas the second, termed non-focal, relies on strategic monitoring processes for successful intention retrieval. A positive relationship was observed between medial temporal volume and accuracy on the focal PM task. An examination of medial temporal lobe subregions revealed that this relationship was strongest for the hippocampus, which is considered to support spontaneous memory retrieval. There were no significant structure-behavior associations for the non-focal PM task. These novel results confirm a relationship between behavior and underlying brain structure proposed by the multiprocess theory of PM, and extend findings on cognitive correlates of medial temporal lobe integrity. PMID:21982698

  6. Magnetoencephalographic correlates of audiotactile interaction.

    PubMed

    Lütkenhöner, B; Lammertmann, C; Simões, C; Hari, R

    2002-03-01

    To seek for correlates of an interaction between auditory and somatosensory processing, the brain's magnetic field in response to simultaneously presented auditory (A) and tactile (T) stimuli was compared with the sum of the respective unimodal responses (A+T). The stimuli were binaural 1047-Hz tone bursts of 60 dB sensation level and tactile pressure pulses to the right thumb. The mean interval between two stimuli of the same modality was 1.95 s. The magnetic field was recorded using a 306-channel whole-scalp neuromagnetometer. A clear audiotactile interaction was revealed in the hemisphere contralateral to the side of tactile stimulation in six of eight subjects, whereas in the ipsilateral hemisphere an interaction was noticed in only three subjects. The time courses of these audiotactile interaction fields typically showed major deflections of opposite polarities around 140 and 220 ms. The first deflection appeared to arise in the region of the secondary somatosensory cortex (SII). The polarity of this interaction was consistent with the view that the auditory stimulus resulted in a partial inhibition in SII. In two subjects, strong indications of auditory contributions to the interaction were available, although in different hemispheres. The relatively high interindividual variability of the observed interaction, which represents potential neural substrates for multisensory integration, could indicate that the way subjects perceive the simultaneous presentation of auditory and tactile stimuli differs. PMID:11848694

  7. 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.

  8. Oscillatory correlates of autobiographical memory.

    PubMed

    Knyazev, Gennady G; Savostyanov, Alexander N; Bocharov, Andrey V; Dorosheva, Elena A; Tamozhnikov, Sergey S; Saprigyn, Alexander E

    2015-03-01

    Recollection of events from one's own life is referred to as autobiographical memory. Autobiographical memory is an important part of our self. Neuroimaging findings link self-referential processes with the default mode network (DMN). Much evidence coming primarily from functional magnetic resonance imaging studies shows that autobiographical memory and DMN have a common neural base. In this study, electroencephalographic data collected in 47 participants during recollection of autobiographical episodes were analyzed using temporal and spatial independent component analyses in combination with source localization. Autobiographical remembering was associated with an increase of spectral power in alpha and beta and a decrease in delta band. The increase of alpha power, as estimated by sLORETA, was most prominent in the posterior DMN, but was also observed in visual and motor cortices, prompting an assumption that it is associated with activation of DMN and inhibition of irrelevant sensory and motor areas. In line with data linking delta oscillations with aversive states, decrease of delta power was more pronounced in episodes associated with positive emotions, whereas episodes associated with negative emotions were accompanied by an increase of delta power. Vividness of recollection correlated positively with theta oscillations. These results highlight the leading role of alpha oscillations and the DMN in the processes accompanying autobiographical remembering. PMID:25523347

  9. 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

  10. Neural Correlates of Predictive Saccades.

    PubMed

    Lee, Stephen M; Peltsch, Alicia; Kilmade, Maureen; Brien, Donald C; Coe, Brian C; Johnsrude, Ingrid S; Munoz, Douglas P

    2016-08-01

    Every day we generate motor responses that are timed with external cues. This phenomenon of sensorimotor synchronization has been simplified and studied extensively using finger tapping sequences that are executed in synchrony with auditory stimuli. The predictive saccade paradigm closely resembles the finger tapping task. In this paradigm, participants follow a visual target that "steps" between two fixed locations on a visual screen at predictable ISIs. Eventually, the time from target appearance to saccade initiation (i.e., saccadic RT) becomes predictive with values nearing 0 msec. Unlike the finger tapping literature, neural control of predictive behavior described within the eye movement literature has not been well established and is inconsistent, especially between neuroimaging and patient lesion studies. To resolve these discrepancies, we used fMRI to investigate the neural correlates of predictive saccades by contrasting brain areas involved with behavior generated from the predictive saccade task with behavior generated from a reactive saccade task (saccades are generated toward targets that are unpredictably timed). We observed striking differences in neural recruitment between reactive and predictive conditions: Reactive saccades recruited oculomotor structures, as predicted, whereas predictive saccades recruited brain structures that support timing in motor responses, such as the crus I of the cerebellum, and structures commonly associated with the default mode network. Therefore, our results were more consistent with those found in the finger tapping literature. PMID:27054397

  11. 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

  12. Fully exponentially correlated wavefunctions for small atoms

    SciTech Connect

    Harris, Frank E.

    2015-01-22

    Fully exponentially correlated atomic wavefunctions are constructed from exponentials in all the interparticle coordinates, in contrast to correlated wavefunctions of the Hylleraas form, in which only the electron-nuclear distances occur exponentially, with electron-electron distances entering only as integer powers. The full exponential correlation causes many-configuration wavefunctions to converge with expansion length more rapidly than either orbital formulations or correlated wavefunctions of the Hylleraas type. The present contribution surveys the effectiveness of fully exponentially correlated functions for the three-body system (the He isoelectronic series) and reports their application to a four-body system (the Li atom)

  13. Energetics of correlations in interacting systems

    NASA Astrophysics Data System (ADS)

    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.

  14. Nature of light correlations in ghost imaging

    PubMed Central

    Ragy, Sammy; Adesso, Gerardo

    2012-01-01

    We investigate the nature of correlations in Gaussian light sources used for ghost imaging. We adopt methods from quantum information theory to distinguish genuinely quantum from classical correlations. Combining a microscopic analysis of speckle-speckle correlations with an effective coarse-grained description of the beams, we show that quantum correlations exist even in ‘classical'-like thermal light sources, and appear relevant for the implementation of ghost imaging in the regime of low illumination. We further demonstrate that the total correlations in the thermal source beams effectively determine the quality of the imaging, as quantified by the signal-to-noise ratio. PMID:22973501

  15. Optical correlators: systems and domains of applications

    NASA Astrophysics Data System (ADS)

    Dragulinescu, Andrei; Cojoc, Dan

    2005-08-01

    The paper presents the basic concepts of the optical correlators. In our knowledge, it is the first systematic presentation of the applications of optical correlators. The main three types of optical correlators: the optical correlator in incoherent light, the optical correlator in coherent light (VanderLugt) and the joint transform correlator are presented. The optical correlators are very powerll systems used for image recognition, that perform a correlation between a bidimensional function which represents a Scene that must be analyzed and another bidimensional function that contains information about the reference function. This correlation is optically realized by a Fourier transform between the two functions. The optical Correlators have found a lot of applications for image recognition and target detection in various fields, such as the military field, robotics, medical field, industry a.s.o. Among the various applications of the optical correlators we can mention: digital fingerprints identification, credit card security, antique scripts recognition, determination of the cosmic ships and satellites behavior, amelioration of cancer tests precision, quality control etc.

  16. 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.

  17. Performance highlights of the ALMA correlators

    NASA Astrophysics Data System (ADS)

    Baudry, Alain; Lacasse, Richard; Escoffier, Ray; Webber, John; Greenberg, Joseph; Platt, Laurence; Treacy, Robert; Saez, Alejandro F.; Cais, Philippe; Comoretto, Giovanni; Quertier, Benjamin; Okumura, Sachiko K.; Kamazaki, Takeshi; Chikada, Yoshihiro; Watanabe, Manabu; Okuda, Takeshi; Kurono, Yasutake; Iguchi, Satoru

    2012-09-01

    Two large correlators have been constructed to combine the signals captured by the ALMA antennas deployed on the Atacama Desert in Chile at an elevation of 5050 meters. The Baseline correlator was fabricated by a NRAO/European team to process up to 64 antennas for 16 GHz bandwidth in two polarizations and another correlator, the Atacama Compact Array (ACA) correlator, was fabricated by a Japanese team to process up to 16 antennas. Both correlators meet the same specifications except for the number of processed antennas. The main architectural differences between these two large machines will be underlined. Selected features of the Baseline and ACA correlators as well as the main technical challenges met by the designers will be briefly discussed. The Baseline correlator is the largest correlator ever built for radio astronomy. Its digital hybrid architecture provides a wide variety of observing modes including the ability to divide each input baseband into 32 frequency-mobile sub-bands for high spectral resolution and to be operated as a conventional 'lag' correlator for high time resolution. The various observing modes offered by the ALMA correlators to the science community for 'Early Science' are presented, as well as future observing modes. Coherently phasing the array to provide VLBI maps of extremely compact sources is another feature of the ALMA correlators. Finally, the status and availability of these large machines will be presented.

  18. Robustness of quantum correlations against linear noise

    NASA Astrophysics Data System (ADS)

    Guo, Zhihua; Cao, Huaixin; Qu, Shixian

    2016-05-01

    Relative robustness of quantum correlations (RRoQC) of a bipartite state is firstly introduced relative to a classically correlated state. Robustness of quantum correlations (RoQC) of a bipartite state is then defined as the minimum of RRoQC of the state relative to all classically correlated ones. It is proved that as a function on quantum states, RoQC is nonnegative, lower semi-continuous and neither convex nor concave; especially, it is zero if and only if the state is classically correlated. Thus, RoQC not only quantifies the endurance of quantum correlations of a state against linear noise, but also can be used to distinguish between quantum and classically correlated states. Furthermore, the effects of local quantum channels on the robustness are explored and characterized.

  19. 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

  20. Correlative feature analysis on FFDM

    SciTech Connect

    Yuan Yading; Giger, Maryellen L.; Li Hui; Sennett, Charlene

    2008-12-15

    Identifying the corresponding images of a lesion in different views is an essential step in improving the diagnostic ability of both radiologists and computer-aided diagnosis (CAD) systems. Because of the nonrigidity of the breasts and the 2D projective property of mammograms, this task is not trivial. In this pilot study, we present a computerized framework that differentiates between corresponding images of the same lesion in different views and noncorresponding images, i.e., images of different lesions. A dual-stage segmentation method, which employs an initial radial gradient index (RGI) based segmentation and an active contour model, is applied to extract mass lesions from the surrounding parenchyma. Then various lesion features are automatically extracted from each of the two views of each lesion to quantify the characteristics of density, size, texture and the neighborhood of the lesion, as well as its distance to the nipple. A two-step scheme is employed to estimate the probability that the two lesion images from different mammographic views are of the same physical lesion. In the first step, a correspondence metric for each pairwise feature is estimated by a Bayesian artificial neural network (BANN). Then, these pairwise correspondence metrics are combined using another BANN to yield an overall probability of correspondence. Receiver operating characteristic (ROC) analysis was used to evaluate the performance of the individual features and the selected feature subset in the task of distinguishing corresponding pairs from noncorresponding pairs. Using a FFDM database with 123 corresponding image pairs and 82 noncorresponding pairs, the distance feature yielded an area under the ROC curve (AUC) of 0.81{+-}0.02 with leave-one-out (by physical lesion) evaluation, and the feature metric subset, which included distance, gradient texture, and ROI-based correlation, yielded an AUC of 0.87{+-}0.02. The improvement by using multiple feature metrics was statistically

  1. Sensitivity of adjustment to parameter correlations and to response-parameter correlations

    SciTech Connect

    Wagschal, J.J.

    2011-07-01

    The adjusted parameters and response, and their respective posterior uncertainties and correlations, are presented explicitly as functions of all relevant prior correlations for the two parameters, one response case. The dependence of these adjusted entities on the various prior correlations is analyzed and portrayed graphically for various valid correlation combinations on a simple criticality problem. (authors)

  2. 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

  3. 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.

  4. Image correlation method for DNA sequence alignment.

    PubMed

    Curilem Saldías, Millaray; Villarroel Sassarini, Felipe; Muñoz Poblete, Carlos; Vargas Vásquez, Asticio; Maureira Butler, Iván

    2012-01-01

    The complexity of searches and the volume of genomic data make sequence alignment one of bioinformatics most active research areas. New alignment approaches have incorporated digital signal processing techniques. Among these, correlation methods are highly sensitive. This paper proposes a novel sequence alignment method based on 2-dimensional images, where each nucleic acid base is represented as a fixed gray intensity pixel. Query and known database sequences are coded to their pixel representation and sequence alignment is handled as object recognition in a scene problem. Query and database become object and scene, respectively. An image correlation process is carried out in order to search for the best match between them. Given that this procedure can be implemented in an optical correlator, the correlation could eventually be accomplished at light speed. This paper shows an initial research stage where results were "digitally" obtained by simulating an optical correlation of DNA sequences represented as images. A total of 303 queries (variable lengths from 50 to 4500 base pairs) and 100 scenes represented by 100 x 100 images each (in total, one million base pair database) were considered for the image correlation analysis. The results showed that correlations reached very high sensitivity (99.01%), specificity (98.99%) and outperformed BLAST when mutation numbers increased. However, digital correlation processes were hundred times slower than BLAST. We are currently starting an initiative to evaluate the correlation speed process of a real experimental optical correlator. By doing this, we expect to fully exploit optical correlation light properties. As the optical correlator works jointly with the computer, digital algorithms should also be optimized. The results presented in this paper are encouraging and support the study of image correlation methods on sequence alignment. PMID:22761742

  5. 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.

  6. Spatial Correlations in Monte Carlo Criticality Simulations

    NASA Astrophysics Data System (ADS)

    Dumonteil, E.; Malvagi, F.; Zoia, A.; Mazzolo, A.; Artusio, D.; Dieudonné, C.; De Mulatier, C.

    2014-06-01

    Temporal correlations arising in Monte Carlo criticality codes have focused the attention of both developers and practitioners for a long time. Those correlations affects the evaluation of tallies of loosely coupled systems, where the system's typical size is very large compared to the diffusion/absorption length scale of the neutrons. These time correlations are closely related to spatial correlations, both variables being linked by the transport equation. Therefore this paper addresses the question of diagnosing spatial correlations in Monte Carlo criticality simulations. In that aim, we will propose a spatial correlation function well suited to Monte Carlo simulations, and show its use while simulating a fuel pin-cell. The results will be discussed, modeled and interpreted using the tools of branching processes of statistical mechanics. A mechanism called "neutron clustering", affecting simulations, will be discussed in this frame.

  7. Holographic thermalization with initial long range correlation

    NASA Astrophysics Data System (ADS)

    Lin, Shu

    2016-01-01

    We studied the evolution of the Wightman correlator in a thermalizing state modeled by AdS3 -Vaidya background. We gave a prescription for calculating the Wightman correlator in coordinate space without using any approximation. For equal-time correlator ⟨ O (v ,x )O (v ,0 )⟩ , 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. 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 correlator 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.

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

    PubMed

    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. PMID:16905346

  9. Removal of t1 noise from metabolomic 2D 1H- 13C HSQC NMR spectra by Correlated Trace Denoising

    NASA Astrophysics Data System (ADS)

    Poulding, Simon; Charlton, Adrian J.; Donarski, James; Wilson, Julie C.

    2007-12-01

    The presence of t1 noise artefacts in 2D phase-cycled Heteronuclear Single Quantum Coherence (HSQC) spectra constrains the use of this experiment despite its superior sensitivity. This paper proposes a new processing algorithm, working in the frequency-domain, for reducing t1 noise. The algorithm has been developed for use in contexts, such as metabolomic studies, where existing denoising techniques cannot always be applied. Two test cases are presented that show the algorithm to be effective in improving the SNR of peaks embedded within t1 noise by a factor of more than 2, while retaining the intensity and shape of genuine peaks.

  10. 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.

  11. 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.

  12. 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.

  13. Correlated edge overlaps in multiplex networks.

    PubMed

    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. PMID:27575144

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. Classical and quantum correlations under decoherence

    SciTech Connect

    Maziero, J.; Celeri, L. C.; Serra, R. M.; Vedral, V.

    2009-10-15

    Recently some authors have pointed out that there exist nonclassical correlations which are more general, and possibly more fundamental, than entanglement. For these general quantum correlations and their classical counterparts, under the action of decoherence, we identify three general types of dynamics that include a peculiar sudden change in their decay rates. We show that, under suitable conditions, the classical correlation is unaffected by decoherence. Such dynamic behavior suggests an operational measure of both classical and quantum correlations that can be computed without any extremization procedur000.

  19. 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

  20. 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.

  1. Degree of correlation inside a financial market

    NASA Astrophysics Data System (ADS)

    Mantegna, Rosario Nunzio

    1997-05-01

    I present an empirical study of the correlations observed between pairs of time series of stock prices in the New York Stock Exchange. I verify that various degrees of correlations or anti-correlations are present inside a financial market and I study the time evolution of these correlations. I briefly discuss how these empirical observations might be consistent with the well accepted hypothesis of absence of arbitrage in an efficient financial market (i.e. that there is no way of extracting money from the market in a continuous way without risk).

  2. Multireference explicitly correlated F12 theories

    NASA Astrophysics Data System (ADS)

    Shiozaki, Toru; Werner, Hans-Joachim

    2013-03-01

    We review our recent developments in multireference explicitly correlated F12 theories (explicitly correlated internally contracted multireference perturbation and multireference configuration interaction theories) that achieve near-basis-set-limit accuracy of the underlying multireference electron correlation methods with basis sets of medium size. The applicability of the multireference F12 theories is the same as that of their non-F12 counterpart, and therefore it is a computational tool with predictive accuracy for complicated electronic structures with strong correlation. A comparison with the earlier developments by others is also discussed.

  3. 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.

  4. 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.

  5. Ascertaining the uncertainty relations via quantum correlations

    NASA Astrophysics Data System (ADS)

    Li, Jun-Li; Du, Kun; Qiao, Cong-Feng

    2014-02-01

    We propose a new scheme to express the uncertainty principle in the form of inequality of the bipartite correlation functions for a given multipartite state, which provides an experimentally feasible and model-independent way to verify various uncertainty and measurement disturbance relations. By virtue of this scheme, the implementation of experimental measurement on the measurement disturbance relation to a variety of physical systems becomes practical. The inequality in turn, also imposes a constraint on the strength of correlation, i.e. it determines the maximum value of the correlation function for two-body system and a monogamy relation of the bipartite correlation functions for multipartite system.

  6. 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

  7. Study of adaptive correlation filter synthesis guided by the peak and shape of the correlation output

    NASA Astrophysics Data System (ADS)

    Campos Trujillo, Oliver G.; Díaz Blancas, Gerardo

    2014-09-01

    In recent years, many proposals that consider an adaptive perspective had been developed to solve some drawbacks, such as geometric distortions, background noise and target discrimination. The metrics are based only in the correlation peak output for the filter synthesis. In this paper, the correlation shape is studied to implement adaptive correlation filters guided by the peak and shape of the correlation output. Furthermore, the shape of correlation output is studied to improve the search in the filters bank. In addition, parallel algorithms are developed for accelerated the search in the filters bank. Some results are shown, such as time of synthesis, filter performance and comparisons with other adaptive correlation filter proposals.

  8. Correlating the DIAL and the BTBC.

    ERIC Educational Resources Information Center

    Sarachan-Deily, Ann Beth; And Others

    1983-01-01

    The degree of correlation of the "concept" subtest of the Developmental Indicators of the Assessment of Learning (DIAL) with the Boehm Test of Basic Concepts (BTBC) was studied with 95 beginning kindergarten children. Both measures were highly correlated, indicating the evaluation of similar abilities. (Author/SEW)

  9. 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…

  10. 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.

  11. On the insignificance of Herschel's sunspot correlation

    NASA Astrophysics Data System (ADS)

    Love, Jeffrey J.

    2013-08-01

    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. A Primer on Partial Correlation Coefficients.

    ERIC Educational Resources Information Center

    Waliczek, Tina M.

    Part and partial correlation coefficients are used to measure the strength of a relationship between a dependent variable and an independent variable while controlling for one or more other variables. The present paper discusses the uses and limitations of partial correlations and presents a small heuristic data set to illustrate the discussion.…

  13. 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.

  14. 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…

  15. Uses and Misuses of the Correlation Coefficient.

    ERIC Educational Resources Information Center

    Onwuegbuzie, Anthony J.; Daniel, Larry G.

    The purpose of this paper is to provide an in-depth critical analysis of the use and misuse of correlation coefficients. Various analytical and interpretational misconceptions are reviewed, beginning with the egregious assumption that correlational statistics may be useful in inferring causality. Additional misconceptions, stemming from…

  16. Transformation of stimulus correlations by the retina

    NASA Astrophysics Data System (ADS)

    Prentice, Jason; Simmons, Kristina; Tkacik, Gasper; Homann, Jan; Yee, Heather; Palmer, Stephanie; Nelson, Phillip; Balasubramanian, Vijay

    2014-03-01

    Correlations in the responses of sensory neurons seem to waste neural resources, but can carry cues about structured stimuli and help the brain correct for response errors. To assess how the retina negotiates this tradeoff, we measured simultaneous responses from many retinal ganglion cells presented with natural and artificial stimuli that varied in correlation structure. Responding to spatio-temporally structured stimuli such as natural movies, pairs of ganglion cells were more correlated than in response to white noise checkerboards, but 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 correlations across stimuli.

  17. Marital Adjustment Correlates in Young Couples.

    ERIC Educational Resources Information Center

    Haskell, Samuel D.

    The Locke-Wallace Marital Adjustment Scale was administered to 35 Caucasian, Protestant couples who were married an average of nine years, largely middle class, and lived in Knoxville, Tennessee. Significant correlates of marital adjustment were organized into groups of similar variables. Correlate groups that were the same for the husband and…

  18. 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 ...

  19. 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…

  20. 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

  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. 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.

  3. Correlation function studies for snow and ice

    NASA Technical Reports Server (NTRS)

    Vallese, F.; Kong, J. A.

    1981-01-01

    The random medium model is used to characterize snow and ice fields in the interpretation of active and passive microwave remote sensing data. A correlation function is used to describe the random permittivity fluctuations with the associated mean and variance and correlation lengths; and several samples are investigated to determine typical correlation functions for snow and ice. It is shown that correlation functions are extracted directly from appropriate ground truth data, and an exponential correlation function is observed for snow and ice with lengths corresponding to the actual size of ice particles or air bubbles. Thus, given that a medium has spatially stationary statistics and a small medium, the random medium model can interpret remote sensing data where theoretical parameters correspond to actual physical parameters of the terrain.

  4. 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.

  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. 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.

  7. 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.

  8. Norman Rostoker and strongly correlated plasmas

    NASA Astrophysics Data System (ADS)

    Ichimaru, Setsuo

    2016-03-01

    If Norman were alive and attended this symposium, he might have quipped: "Setsuo! What are you talking about! A plasma is, after all, a strongly correlated object, and there is nothing so special about it!" "Yes, Norman, you are so correct! A statistical system consisting of mutually non-interacting and thus uncorrelated particles may be an "ideal-gas" system from a physics teacher's pedagogical point of view, but real systems do consist of mutually interacting and thus strongly correlated particles; a plasma is definitely one of them.Here, in the memory of Professor Rostoker's outstanding contributions to strongly correlated plasmas for the past 60 years, we wish to survey on "Scattering of Electromagnetic Waves by a Strongly Correlated Plasma" and "Multi-particle Correlation, Equations of State, and Phase Diagrams" in what follows.

  9. Norm-based measurement of quantum correlation

    SciTech Connect

    Wu Yuchun; Guo Guangcan

    2011-06-15

    In this paper we derived a necessary and sufficient condition for classical correlated states and proposed a norm-based measurement Q of quantum correlation. Using the max norm of operators, we gave the expression of the quantum correlation measurement Q and investigated the dynamics of Q in Markovian and non-Markovian cases, respectively. Q decays exponentially and vanishes only asymptotically in the Markovian case and causes periodical death and rebirth in the non-Markovian case. In the pure state, the quantum correlation Q is always larger than the entanglement, which was different from other known measurements. In addition, we showed that locally broadcastable and broadcastable are equivalent and reproved the density of quantum correlated states.

  10. Holographic thermalization with initial long range correlation

    DOE PAGESBeta

    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

  11. Communication Strength of Correlations Violating Monogamy Relations

    NASA Astrophysics Data System (ADS)

    Kłobus, Waldemar; Oszmaniec, Michał; Augusiak, Remigiusz; Grudka, Andrzej

    2016-05-01

    In any theory satisfying the no-signaling principle correlations generated among spatially separated parties in a Bell-type experiment are subject to certain constraints known as monogamy relations. Recently, in the context of the black hole information loss problem it was suggested that these monogamy relations might be violated. This in turn implies that correlations arising in such a scenario must violate the no-signaling principle and hence can be used to send classical information between parties. Here, we study the amount of information that can be sent using such correlations. To this aim, we first provide a framework associating them with classical channels whose capacities are then used to quantify the usefulness of these correlations in sending information. Finally, we determine the minimal amount of information that can be sent using signaling correlations violating the monogamy relation associated to the chained Bell inequalities.

  12. Quantum correlations in connected multipartite Bell experiments

    NASA Astrophysics Data System (ADS)

    Tavakoli, Armin

    2016-04-01

    Bell experiments measure correlations between outcomes of a number of observers measuring on a shared physical state emitted from a single source. Quantum correlations arising in such Bell experiments have been intensively studied over the last decades. Much less is known about the nature of quantum correlations arising in network structures beyond Bell experiments. Such networks can involve many independent sources emitting states to observers in accordance with the network configuration. Here, we will study classical and quantum correlations in a family of networks which can be regarded as compositions of several independent multipartite Bell experiments connected together through a central node. For such networks we present tight Bell-type inequalities which are satisfied by all classical correlations. We study properties of the violations of our inequalities by probability distributions arising in quantum theory.

  13. Interpreting Canonical Correlation Analysis through Biplots of Structure Correlations and Weights.

    ERIC Educational Resources Information Center

    ter Braak, Cajo J. F.

    1990-01-01

    Canonical weights and structure correlations are used to construct low dimensional views of the relationships between two sets of variables. These views, in the form of biplots, display familiar statistics: correlations between pairs of variables, and regression coefficients. (SLD)

  14. Theory of correlations in stochastic neural networks

    NASA Astrophysics Data System (ADS)

    Ginzburg, Iris; Sompolinsky, Haim

    1994-10-01

    One of the main experimental tools in probing the interactions between neurons has been the measurement of the correlations in their activity. In general, however, the interpretation of the observed correlations is difficult since the correlation between a pair of neurons is influenced not only by the direct interaction between them but also by the dynamic state of the entire network to which they belong. Thus a comparison between the observed correlations and the predictions from specific model networks is needed. In this paper we develop a theory of neuronal correlation functions in large networks comprising several highly connected subpopulations and obeying stochastic dynamic rules. When the networks are in asynchronous states, the cross correlations are relatively weak, i.e., their amplitude relative to that of the autocorrelations is of order of 1/N, N being the size of the interacting populations. Using the weakness of the cross correlations, general equations that express the matrix of cross correlations in terms of the mean neuronal activities and the effective interaction matrix are presented. The effective interactions are the synaptic efficacies multiplied by the gain of the postsynaptic neurons. The time-delayed cross-correlation matrix can be expressed as a sum of exponentially decaying modes that correspond to the (nonorthogonal) eigenvectors of the effective interaction matrix. The theory is extended to networks with random connectivity, such as randomly dilute networks. This allows for a comparison between the contribution from the internal common input and that from the direct interactions to the correlations of monosynaptically coupled pairs. A closely related quantity is the linear response of the neurons to external time-dependent perturbations. We derive the form of the dynamic linear response function of neurons in the above architecture in terms of the eigenmodes of the effective interaction matrix. The behavior of the correlations and the

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Secrecy extraction from no-signaling correlations

    SciTech Connect

    Scarani, Valerio; Gisin, Nicolas; Brunner, Nicolas; Masanes, Lluis; Pino, Sergi; Acin, Antonio

    2006-10-15

    Quantum cryptography shows that one can guarantee the secrecy of correlation on the sole basis of the laws of physics, that is, without limiting the computational power of the eavesdropper. The usual security proofs suppose that the authorized partners, Alice and Bob, have a perfect knowledge and control of their quantum systems and devices; for instance, they must be sure that the logical bits have been encoded in true qubits and not in higher dimensional systems. In this paper, we present an approach that circumvents this strong assumption. We define protocols, both for the case of bits and for generic d-dimensional outcomes, in which the security is guaranteed by the very structure of the Alice-Bob correlations, under the no-signaling condition. The idea is that if the correlations cannot be produced by shared randomness, then Eve has poor knowledge of Alice's and Bob's symbols. The present study assumes on the one hand that the eavesdropper Eve performs only individual attacks (this is a limitation to be removed in further work), and on the other hand that Eve can distribute any correlation compatible with the no-signaling condition (in this sense her power is greater than what quantum physics allows). Under these assumptions, we prove that the protocols defined here allow extracting secrecy from noisy correlations, when these correlations violate a Bell-type inequality by a sufficiently large amount. The region in which secrecy extraction is possible extends within the region of correlations achievable by measurements on entangled quantum states.