Separation of Anisotropy and Exchange Broadening Using N CSA–N–H Dipole–Dipole Relaxation Cross-Correlation Experiments

Based on the measurement of cross-correlation rates between ¹⁵N CSA and ¹⁵N–¹H dipole–dipole relaxation we propose a procedure for separating exchange contributions to transverse relaxation rates (R₂ = 1/T₂) from effects caused by anisotropic rotational diffusion of the protein molecule. This approach determines the influence of anisotropy and chemical exchange processes independently and therefore circumvents difficulties associated with the currently standard use of T₁/T₂ ratios to determine the rotational diffusion tensor. We find from computer simulations that, in the presence of even small amounts of internal flexibility, fitting T₁/T₂ ratios tends to underestimate the anisotropy of overall tumbling. An additional problem exists when the N–H bond vector directions are not distributed homogeneously over the surface of a unit sphere, such as in helix bundles or β-sheets. Such a case was found in segment 4 of the gelation factor (ABP 120), an F-actin cross-linking protein, in which the diffusion tensor cannot be calculated from T₁/T₂ ratios. The ¹⁵N CSA tensor of the residues for this β-sheet protein was found to vary even within secondary structure elements. The use of a common value for the whole protein molecule therefore might be an oversimplification. Using our approach it is immediately apparent that no exchange broadening exists for segment 4 although strongly reduced T₂ relaxation times for several residues could be mistaken as indications for exchange processes.     

TheB (3) field as a link between gravitation and electromagnetism in the vacuum

The emergence of theB ⁽³⁾ field in vacuo has shown that electromagnetism is non-Abelian and similar in structure to gravitation. In this paper the Christoffel symbol used in general relativity is developed for electromagnetism in curvilinear coordinates: The former becomes describable as the antisymmetric part of the gravitational Ricci tensor. Therefore gravitation and electromagnetism are respectively the symmetric and antisymmetric parts of thesame Ricci tensor within a proportionality factor. Both fields are obtained from the Riemann curvature tensor, both are expressions of curvature in spacetime.     

Unification of electromagnetism and gravitation: The equations of electrodynamics derived from the Riemann tensor in general relativity

The equations of free-space electrodynamics are derived directly from the Riemann curvature tensor and the Bianchi identity of general relativity by contracting on two indices to give a novel antisymmetric Ricci tensor. Within a factore/h, this is the field-strength tensor G of free-space electrodynamics. The Bianchi identity for G describes free-space electrodynamics in a manner analogous to, but more general than, Maxwell's equations for electrodynamics, the critical difference being the existence in general and special relativity of the Evans-Vigier fieldB ⁽³⁾.     

Distinguishing new physics scenarios with polarized electron and positron beams

Contact-like nonstandard interactions can be revealed only through deviations of observables from the standard model (SM) predictions. We consider a number of such nonstandard scenarios, and discuss their identification as sources of deviations in fermion-pair production processes at the international linear collider (ILC), if they were observed. We emphasize the role of e ⁻ and e ⁺ polarization in enhancing the identification reaches.      

J Coupling between C and H across Hydrogen Bonds in Proteins

Two new two- or three-dimensional NMR methods for measuring ^3hJ_C′N and ^2hJ_C′H coupling constants across hydrogen bonds in proteins are presented. They are tailored to suit the size of the TROSY effect, i.e., the degree of interference between dipolar and chemical shift anisotropy relaxation mechanisms. The methods edit 2D or 3D spectra into two separate subspectra corresponding to the two possible spin states of the ¹H^N spin during evolution of ¹³CO coherences. This allows ^2hJ_C′H to be measured in an E.COSY-type way while ^3hJ_C′N can be measured in the so-called quantitative way provided a reference spectrum is also recorded. A demonstration of the new methods is shown for the ¹⁵N,¹³C-labeled protein chymotrypsin inhibitor 2.     

High-resolution emission spectroscopy of the AΠ–XΣ system of AlH

The emission spectrum of the A²Π–X²Σ⁺ system of the AlH⁺ ion was investigated in the range of 27 000–29 000 cm⁻¹ by using a conventional spectroscopic technique. The AlH⁺ molecules were formed and excited in an aluminium hollow-cathode lamp with two anodes, filled with a mixture of Ne carried gas and a trace of NH₃. The emission from the discharge was observed with a plane grating spectrograph and recorded by a photomultiplier tube. The full rotational structure of the 0-0 and 1-1 bands has been observed for the first time (12 branches up to J″ = 36.5) and many new constants of the X²Σ⁺ state have been derived from the analysis. For the A²Π, v = 0 and 1 state a considerable irregularities of the Λ-doubling have been observed. The most reasonable explanation for this anomaly is an interaction with unstableness rotational levels of X²Σ⁺ state and perturbing of the A²Π state by the nearly lyingB²Σ⁺ state.     

A simple method for analyzing 51V solid-state NMR spectra of complex systems

Five vanadium complexes as models for biological systems were investigated using ⁵¹V-MAS–NMR spectroscopy. All spectra show an uncommon line shape, which can be attributed to a shorter relaxation time of the satellite transition in contrast to the central one. A method for the reliable analysis of such kind of spectra is presented for the first time and the most important NMR parameters of the investigated complexes (quadrupolar coupling constant C_Q, asymmetry of the EFG tensor η_Q, isotropic chemical shift δ_iso, chemical shift anisotropy δ_σ and asymmetry of the CSA tensor η_σ) are presented. These results are of particular importance with respect to the analysis of the ⁵¹V-MAS–NMR spectra of vanadium moieties in biological matrices such as vanadium chloroperoxidase, which show hitherto unexplained low intensity of the satellite sideband pattern.     

More line narrowing in TROSY by decoupling of long-range couplings: shift correlation and JNC′ coupling constant measurements

Since the introduction of RDCs in high-resolution NMR studies of macromolecules, there is a growing interest in the development of accurate, and sensitive methods for determining coupling constants. Most methods for extracting these couplings are based on the measurement of the splitting between multiplet components in J-coupled spectra. However, these methods are often unreliable since undesired multiple-bond couplings can considerably broaden the multiplet components and consequently make accurate determination of their position difficult. To demonstrate one approach to this problem, G-BIRD^(r) decoupled TROSY sequences are proposed for the measurement of ¹J_NH and ¹J_NC′ coupling constants. Resolved or unresolved splittings due to remote protons are removed by a G-BIRD^(r) module employed during t₁ and as a result, spectra with narrow, well-resolved peaks are obtained from which heteronuclear one-bond couplings can be accurately measured. Moreover, introduction of a spin-state-selective α/β-filter in the TROSY sequence allows the separation of the ¹J_NC′ doublet components into two subspectra which contain the same number of peaks as the regular TROSY spectrum. The ¹J_NC′ couplings are obtained from the displacement between the corresponding peaks in the subspectra.     

Breakup of 8B and the 7Be(p, γ)8B reaction

The calculated rate of events in some of the existing solar neutrino detectors is directly proportional to the rate of the ⁷Be(p, γ)⁸B reaction measured in the laboratory at low energies. However, the low-energy cross sections of this reaction are quite uncertain as various measurements differ from each other by 30–40%. The Coulomb dissociation process which reverses the radiative capture by the dissociation of ⁸B in the Coulomb field of a target, provides an alternate way of accessing this reaction. While this method has several advantages (like large breakup cross sections and flexibility in the kinematics), the difficulties arise from the possible interference by the nuclear interactions, uncertainties in the contributions of the various multipoles and the higher order effects, which should be considered carefully. We review the progress made so far in the experimental measurements and theoretical analysis of the breakup of ⁸B and discuss the current status of the low-energy cross sections (or the astrophysical S-factor) of the ⁷Be(p, γ)⁸B reaction extracted therefrom. The future directions of the experimental and theoretical investigations are also suggested. Work supported by EPSRC, UK, grant nos J/95867 and L/94574.     

Structure and Ionic Conductivity of Halocomplexes of Main Group Metallic Elements Studied by NMR and NQR

Li₃InBr₆ undergoes phase transition to a lithium superionic conductor at T _tr = 314 K (σ = 5.0 × 10⁻⁴ S cm⁻¹ at 330 K). The Rietveld analysis and the DSC measurement suggested that the positional disorder is introduced at the cationic sites above T _tr. The X-ray powder diffraction pattern at the superionic phase changes gradually with temperature and finally shows a simple powder pattern at 420 K which is quite similar to that of LiBr. This rock salt structure contains intrinsic vacancies because one In³⁺ and two vacancies substitute for three Li⁺. ⁷Li and ¹¹⁵In NMR support the rapid diffusion of the Li⁺ and the introduction of the In³⁺ into the rock salt structure. On the other hand, the ionic conductivity for Na₃InCl₆ was 10⁻⁵ S cm⁻¹ even at 500 K. Conduction path for the sodium ions could be proposed by means of the Rietveld analysis and the NMR experiment using a single crystal.     

Detection and Characterization of Boric Acid and Borate Ion Binding to Cytochrome c Using Multiple Quantum Filtered NMR

The application of multiple quantum filtered (MQF) NMR to the identification and characterization of the binding of ligands containing quadrupolar nuclei to proteins is demonstrated. Using relaxation times measured by MQF NMR multiple binding of boric acid and borate ion to ferri and ferrocytochrome c was detected. Borate ion was found to have two different binding sites. One of them was in slow exchange, k_diss = 20 ± 3 s⁻¹ at 5°C and D₂O solution, in agreement with previous findings by ¹H NMR (G. Taler et al., 1998, Inorg. Chim. Acta 273, 388–392). The triple quantum relaxation of the borate in this site was found to be governed by dipolar interaction corresponding to an average B–H distance of 2.06 ± 0.07 Å. Other, fast exchanging sites for borate and boric acid could be detected only by MQF NMR. The binding equilibrium constants at these sites at pH 9.7 were found to be 1800 ± 200 M⁻¹ and 2.6 ± 1.5 M⁻¹ for the borate ion and boric acid, respectively. Thus, detection of binding by MQF NMR proved to be sensitive to fast exchanging ligands as well as to very weak binding that could not be detected using conventional methods.     

N2O+离子A2Σ+电子态高振动能级的转动结构分析

利用一束波长为36055nm的激光,通过(3+1)共振多光子电离方法制备纯净的且处于X²Π_1/2,3/2(000)态的N₂O⁺离子,用另一束激光激发所制备的离子到第一电子激发态A²Σ⁺的不同振动能级,然后解离,通过检测解离碎片NO⁺强度随光解光波长的变化,得到了转动分辨的N₂ 关键词： 2O⁺离子A²Σ⁺电子态')" href="#">N₂O⁺离子A²Σ⁺电子态 共振增强多光子电离 光解碎片激发光谱 光谱常数     

On the observability of the fieldB (3): Relativistic effects in magneto-optics

It is shown that the novel vacuum fieldB ⁽³⁾ is an experimental observable, and several methods of observation are suggested: these include the pulsed microwave magnetization of a plasma, the optical Aharonov-Bohm effect, and the microwave frequency optical Faraday effect. The effect ofB ⁽³⁾ is presented in the form of relativistically corrected semi-classical theory.     

(π +,p) Reaction in12C

Hartree-Fock wave functions obtained from realistic nucleon-nucleon interaction are employed to calculate cross-sections for the reaction¹² C(π ⁺,p)¹¹ C(g.s.). These wave functions take into account central correlations between nucleons inside the nucleus. This itself is found to change the cross-section by more than an order of magnitude. The incoming pion is represented by a plane wave while proton-distortion is taken into account in the high-energy or semi-classical approximation, thereby determining the proton optical well parameters. These values agree well with those obtained by more conventional methods. Variation of the cross-section with the oscillator well parameter is also studied. Calculations have been made using the one-nucleon mechanism for the pion-absorption process.     

Resolved photon processes

We review high-energy scattering processes that are sensitive to the hadronic structure of the photon, describing theoretical predictions as well as recent experimental results. These processes include deep-inelastic electron-photon scattering ate ⁺ e ⁻ colliders; and the production of jets, heavy quarks and isolated photons in the collision of real photons ate ⁺ e ⁻ colliders, as well as in photon-photon collisions atep colliders. We also comment on minijet based calculations of totalγp andγγ cross-sections, and discuss the possibility that future lineare ⁺ e ⁻ colliders might produce very large photon fluxes due to the beamstrahlung phenomenon; in the most extreme cases, we predict more than one hadronicγγ event to occur at every bunch crossing.     

() reaction studies of Dy and Hf

Angular distributions for the ¹⁶³Dy(t,p) and ¹⁷⁷Hf(t,p) reactions were measured using 17 MeV tritons from the McMaster University Tandem Van de Graaff accelerator. Reaction products were analyzed with a magnetic spectrograph and detected with photographic emulsions. Favored L=0 transitions confirmed assignments of the 5/2⁻[523] band in ¹⁶⁵Dy and 7/2⁻[514] band in ¹⁷⁹Hf. Additional L=0 transitions in each nuclide identified previously unknown 5/2⁻ levels in ¹⁶⁵Dy and 7/2⁻ ones in ¹⁷⁹Hf. Overall trends of L=0 strengths support the existence of subshell closures at neutron numbers 98 and 108. On the basis of a relatively strong L=2 transition, the K^π=11/2⁻ γ-vibration based on the 7/2⁻[514] state is identified at 1689 keV in ¹⁷⁹Hf, about 440 keV above its previously-assigned K^π=3/2⁻ partner.     

Validity of the equivalent-photon approximation for the production of massive spin-1 particles

We point out that the equivalent-photon approximation (EPA) for processes with massive spin-1 particles in the final state would have validity in a more restricted kinematic domain than for processes where it is commonly applied, viz., those with spin-1/2 or spin-0 particles in the final state. We obtain the criterion for the validity ofEPA for the two-photon production of a pair of charged, massive, point-like spin-1 particlesV ^±, each of massM and with a standard magnetic moment (κ=1). In a process in which one of the photons is real and the other virtual with four-momentumq, the condition for the validity ofEPA is |q ²|≪M ², in addition to the usual condition |q ²|≪W ²,W being theV ⁺ V ⁻ invariant mass. In a process in which both photons are virtual (with four-momentaq andq′), our condition is |q ²||q′²|W ⁴ ≪ 16M ⁸, in addition to |q ²| ≪M ², |q′²| ≪M ² and |q ²| ≪W ², |q′²| ≪W ². Even when these extra conditions permitting the use ofEPA are not fulfilled, convenient approximate expressions may still be obtained assuming merely |q ²| ≪W ² and |q′²| ≪W ². We also discuss how the extra conditions are altered when the vector bosons are incorporated in a spontaneously broken gauge theory. Examples ofW boson production in Weinberg-Salam model are considered for which the condition |q ²||q′²|W ⁴ ≪ 16M ⁸ is shown to be removed.     

Production of hypernuclei with the reaction

We present results on the production of bound states of Θ⁺ in nuclei using the (K⁺,π⁺) reaction. By taking into account the states obtained within a wide range of strength of the Θ⁺ nucleus optical potential, plus the possibility to replace different nucleons of the nucleus, we obtain an excitation spectra with clearly differentiated peaks. The magnitude of the calculated cross sections is well within reachable range.     

Covariant tensor formalism for partial-wave analyses of ψ decays into γB¯, γγV and ψ(2s)↦γχ<Subscript>c0,1,2</Subscript> with χ<Subscript>c0,1,2</Subscript>↦K¯πand 2π<Superscript>+</Superscript>2π<Superscript>-</Superscript>

With accumulation of high statistics data at BES and CLEO-c, many new interesting channels can get enough statistics for partial-wave analysis (PWA). Among them, ψ↦γpˉ,γΛˉ,γΣˉ,γΞˉ channels provide a good place for studying baryon-antibaryon interactions; the double radiative decays ψ↦γγV with V ≡ ρ,ω,φ have a potential to provide information on the flavor content of any meson resonances (R) with positive charge parity (C = +) and mass above 1 GeV through ψ↦γR↦γγV; ψ(2s)↦γχ_c0,1,2 with χ_c0,1,2↦Kˉπ⁺π^- and 2π⁺2π^- decays are good processes to study χ_cJ charmonium decays. Using the covariant tensor formalism, here we provide theoretical PWA formulae for these channels.     

Proton Diffusion andT1Relaxation in Polyacrylamide Gels: A Unified Approach Using Volume Averaging

The structure of polyacrylamide gels was studied using proton spin–lattice relaxation and PFG diffusion methods. Polyacrylamide gels, with total polymer concentrations ranging from 0.25 to 0.35 g/ml and crosslinker concentrations from 0 to 10% by weight, were studied. The data showed no effect of the crosslinker concentration on the diffusion of water molecules. The Ogston–Morris and Mackie–Meares models fit the general trends observed for water diffusion in gels. The diffusion coefficients from the volume averaging method also fit the data, and this theory was able to account for the effects of water-gel interactions that are not accounted for in the other two theories. The averaging theory also did not require the physically unrealistic assumption, required in the other two theories, that the acrylamide fibers are of similar size to water molecules. Contrary to the diffusion data,T₁relaxation measurements showed a significant effect of crosslinker concentration on the relaxation of water in gels. The model developed using the Bloch equations and the volume averaging method described the effects of water adsorption on the gel medium on both the diffusion coefficients and the relaxation measurements. In the proposed model the gel medium was assumed to consist of three phases (i.e., bulk water, uncrosslinked acrylamide fibers, and a bisacrylamide crosslinker phase). The effects of the crosslinker concentration were accounted for by introducing the proton partition coefficient,K^eq, between the bulk water and crosslinker phase. The derived relaxation equations were successful in fitting the experimental data. The partition coefficient,K^eq, decreased significantly as the crosslinker concentration increased from 5 to 10% by weight. This trend is consistent with the idea that bisacrylamide tends to form hydrophobic regions with increasing crosslinker concentration.