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991.
Sensitivity-enhanced IPAP-SOFAST-HMQC for fast-pulsing 2D NMR with reduced radiofrequency load 总被引:3,自引:1,他引:2
Kern T Schanda P Brutscher B 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2008,190(2):333-338
The SOFAST-HMQC experiment [P. Schanda, B. Brutscher, Very fast two-dimensional NMR spectroscopy for real-time investigation of dynamic events in proteins on the time scale of seconds, J. Am. Chem. Soc. 127 (2005) 8014-8015] allows recording two-dimensional correlation spectra of macromolecules such as proteins in only a few seconds acquisition time. To achieve the highest possible sensitivity, SOFAST-HMQC experiments are preferably performed on high-field NMR spectrometers equipped with cryogenically cooled probes. The duty cycle of over 80% in fast-pulsing SOFAST-HMQC experiments, however, may cause problems when using a cryogenic probe. Here we introduce SE-IPAP-SOFAST-HMQC, a new pulse sequence that provides comparable sensitivity to standard SOFAST-HMQC, while avoiding heteronuclear decoupling during (1)H detection, and thus significantly reducing the radiofrequency load of the probe during the experiment. The experiment is also attractive for fast and sensitive measurement of heteronuclear one-bond spin coupling constants. 相似文献
992.
Proton-detected scalar coupling based assignment strategies in MAS solid-state NMR spectroscopy applied to perdeuterated proteins 总被引:1,自引:0,他引:1
Assignment of proteins in MAS (magic angle spinning) solid-state NMR relies so far on correlations among heteronuclei. This strategy is based on well dispersed resonances in the 15N dimension. In many complex cases like membrane proteins or amyloid fibrils, an additional frequency dimension is desirable in order to spread the amide resonances. We show here that proton detected HNCO, HNCA, and HNCACB type experiments can successfully be implemented in the solid-state. Coherences are sufficiently long lived to allow pulse schemes of a duration greater than 70 ms before incrementation of the first indirect dimension. The achieved resolution is comparable to the resolution obtained in solution-state NMR experiments. We demonstrate the experiments using a triply labeled sample of the SH3 domain of chicken α-spectrin, which was re-crystallized in H2O/D2O using a ratio of 1/9. We employ paramagnetic relaxation enhancement (PRE) using EDTA chelated CuII to enable rapid data acquisition. 相似文献
993.
Hee-Kap Ahn Sang Won Bae Otfried Cheong Joachim Gudmundsson 《Discrete and Computational Geometry》2008,40(3):414-429
The aperture angle
α(x,Q) of a point x
∉
Q in the plane with respect to a convex polygon Q is the angle of the smallest cone with apex x that contains Q. The aperture angle approximation error of a compact convex set C in the plane with respect to an inscribed convex polygon Q⊂C is the minimum aperture angle of any x∈C∖Q with respect to Q. We show that for any compact convex set C in the plane and any k>2, there is an inscribed convex k-gon Q⊂C with aperture angle approximation error
. This bound is optimal, and settles a conjecture by Fekete from the early 1990s.
The same proof technique can be used to prove a conjecture by Brass: If a polygon P admits no approximation by a sub-k-gon (the convex hull of k vertices of P) with Hausdorff distance σ, but all subpolygons of P (the convex hull of some vertices of P) admit such an approximation, then P is a (k+1)-gon. This implies the following result: For any k>2 and any convex polygon P of perimeter at most 1 there is a sub-k-gon Q of P such that the Hausdorff-distance of P and Q is at most
.
This research was supported by the Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2006-311-D00763).
NICTA is funded through the Australian Government’s Backing Australia’s Ability initiative, in part through the Australian
Research Council. 相似文献
994.
A Hamiltonian model is analyzed for a one-dimensional inviscid compressible fluid. The space–time evolution of the fluid is
governed by the following system of the Hamilton–Jacobi and the continuity equations:
Here S and ρ designate the velocity potential and the mass density, respectively. Unless S
0 is convex, shocks form and the velocity S
x
becomes discontinuous in {0<ω
t<π/2}. It is demonstrated that there nevertheless exists a unique viscosity–measure solution (S,ρ) when S
0 is globally Lipschitz continuous and locally semi-concave while ρ
0 is a finite Borel measure. The structure of the velocity and the density is exhibited. For initial data correlated in a certain
sense, a class of classical solutions (S,ρ) is given. Negative time is also considered, and illustrating examples are given.
相似文献
995.
Distributed point source method (DPSM) is gradually gaining popularity in the field of non-destructive evaluation (NDE). DPSM is a semi-analytical technique that can be used to calculate the ultrasonic fields produced by transducers of finite dimension placed in homogeneous or non-homogeneous media. This technique has been already used to model ultrasonic fields in homogeneous and multi-layered fluid structures. In this paper the method is extended to model the ultrasonic fields generated in both fluid and solid media near a fluid-solid interface when the transducer is placed in the fluid half-space near the interface. Most results in this paper are generated by the newly developed DPSM technique that requires matrix inversion. This technique is identified as the matrix inversion based DPSM technique. Some of these results are compared with the results produced by the Rayleigh-Sommerfield integral based DPSM technique. Theory behind both matrix inversion based and Rayleigh-Sommerfield integral based DPSM techniques is presented in this paper. The matrix inversion based DPSM technique is found to be very efficient for computing the ultrasonic field in non-homogeneous materials. One objective of this study is to model ultrasonic fields in both solids and fluids generated by the leaky Rayleigh wave when finite size transducers are inclined at Rayleigh critical angles. This phenomenon has been correctly modelled by the technique. It should be mentioned here that techniques based on paraxial assumptions fail to model the critical reflection phenomenon. Other advantages of the DPSM technique compared to the currently available techniques for transducer radiation modelling are discussed in the paper under Introduction. 相似文献
996.
Abstract The heat capacities of the title compound (C3H11,O—C6H4,- CH=N—C6H4,—C4H9, abbreviation 5O ? 4) with a purity of 99.92 mole percent have been measured with an adiabatic-type calorimeter between 11 and 393 K. The transition temperature and the enthalpy and entropy of phase transition for stable crystal → SG, SG → N and N → isotropic liquid were T c = 299.69 K/ΔH = 22.68 kJ mol?1/ΔS = 75.70 JK?1 mol?1, 325.72/7.11/21.79 and 342.48/1.78/5.22, respectively. The crystal which melts at 285.5 K is a metastable modification. The SA phase hitherto reported in between SG and N does not exist. The glassy So state was realized by rapid cooling of the specimen from the So phase. The molar enthalpy of the glassy SG state at 0 K was by (10.1±0.1) kJ mol?1 higher than that of the stable crystalline state and the residual entropy of the glassy state was (9.40±0.83) JK?1 mol?1. The relaxational heat-capacity anomaly was observed from as low as 100 K and double glass transition phenomenon occurred around 200 K; a quite unusual phenomenon which has never been observed for the glassy states of nematic and cholesteric liquid crystals. The present results give a fair evidence that the unusual glass transition phenomenon previously found for the SG state of 6O?4 (a homologous compound) is not exceptional at all but common to the smectic glasses; at least common to the glassy SG states. Two possible origins responsible for the double glass transitions have been discussed. 相似文献
997.
Measurements of the pressure and temperature dependence of the a-axis resistivity of (TMTSF) 2ReO4, are presented. The metal-insulator transition seen in this material at the remarkably high temperature of ~180 K at ambient pressure and which is associated with an ordering of the ReO4, anions is suppressed under pressure. For pressures above ~9.5 kbar we observe a superconducting transition near 1.3 K. There is a narrow intermediate pressure regime about 2.5 kbar in width in which both superconductivity and effects of anion ordering are observed. In this regime (i) a superconducting transition is seen near 1.3 K even though ρ just above the transition can be up to 10-100 times greater than ρ(300 K), and (ii) there is an extraordinarily large hysteresis in p below ~ 100 K with the possibility of varying the resistance of the low temperature state by several orders of magnitude by appropriate temperature cycling. These results establish the first order character of the transition. We suggest that at high pressures the anions remain frozen in a metastable disordered state to low temperatures. 相似文献
998.
Abstract The HCl and DCl salts of pheny1-4-pyridyldiazomethane were prepared and irradiated at 6 K to generate the carbenes. Their ESR spectra indicated presence of plural triplet carbenes with slightly-different zero-field splitting constants. Besides the triplet species, we found a quintet species whose signal intensity decreases with increasing temperature. The quintet spin state was concluded to be a ground state which was produced by an intermolecular ferromagnetic interaction of the triplet carbenes. The ferromagnetic interaction would be explained by the McConnell mechanism, judging from the crystal structure of the HCl salt of phenyl-4-pyridylketone. 相似文献
999.
M. Kimura S. Okutani T. Churiki T. Akahane H. Toriumi T. Tadokoro 《Molecular Crystals and Liquid Crystals》2013,570(1):681-689
Abstract The birefringence, the twist angle and the thickness of the nematic liquid crystal sample were determined by means of the renormalized transmission ellipsometry. It was proposed that conventional sandwich-type cell is applicable to this ellipsometry measurement and the simplified numerical fitting procedure based on the 4 × 4 matrix method can provide the dispersion of the ordinary and the extraordinary refractive indices. The resolution of the twist angle and cell thickness measurement reaches to 0.05 deg. and 0.05 μm, respectively. 相似文献
1000.
María del Mar Castro López M.C. Cela PérezMaría Sonia Dopico García José Manuel López VilariñoMaría Victoria González Rodríguez Luis F. Barral Losada 《Analytica chimica acta》2012
Molecularly imprinted polymer (MIP) for solid extraction and preconcentration of catechins have been successfully prepared by a thermal polymerization method using quercetin as template, 4-vinylpyridine as functional monomer and ethylene glycol dimethacrylate as crosslinker. A solution mixture of acetone and acetonitrile was used as porogen. Systematic investigations of the influence of monomer, cross-linker, porogen, as well as polymerization conditions on the properties of the MIPs were carried out. The quercetin MIPs were evaluated according to their selective recognition properties for quercetin, structurally related compounds (catechin, epigallocatechin gallate and epicatechin) and a unrelated compound of similar molecular size (α-tocopherol). Good binding was observed for quercetin, catechin and epigallocatechin gallate with an optimized MIP in a solid phase extraction system. Adsorption and kinetic characteristics were evaluated for catechins which indicated that the synthesized polymer had high adsorption capacity and contained homogeneous binding sites. Chemical and morphological characterization of the MIP was investigated by FTIR, SEM and BET, which confirmed a high degree of polymerization. Finally, the MIP was successfully applied to the clean-up and preconcentration of catechins from several natural samples. 相似文献