用于时延估计的一种相关峰内插算法

本文介绍一种基于余弦函数的相关峰内插算法，在时延估计系统中，为了减少运算量和增加观察时间，采用内插算法是必要的，因为在频率估算时应用了迭代算法，所以无论对于ｃｏｓｘ，ｓｉｘ／ｘ或实际的相关峰，都有相当高的内插精度。     

Methods for peak assignment in low-resolution multidimensional NMR cross-correlation relaxometry

Several NMR protocols are presented for assigning peaks in complex T1-T2 spectra, including the effects of varying the spectrometer frequency and the CPMG pulsing rate. Extensions into a third dimension based on chemical-shift; diffusion- and field-cycled weighted T1-T2 cross-correlation methods are also explored as a means of peak assignment. We illustrate the power of these novel techniques with reference to simple aqueous sucrose solutions, but the methodology should be generally applicable.     

Progress on the two-dimensional filter diagonalization method. An efficient doubling scheme for two-dimensional constant-time NMR

An efficient way to treat two-dimensional (2D) constant-time (CT) NMR data using the filter diagonalization method (FDM) is presented. In this scheme a pair of N- and P-type data sets from a 2D CT NMR experiment are processed jointly by FDM as a single data set, twice as large, in which the signal effectively evolves in time for twice as long. This scheme is related to "mirror-image" linear prediction, but with the distinction that the data are directly used, without any preprocessing such as Fourier transformation along one dimension, or point-by-point reflection. As the signal has nearly perfect Lorentzian line shape in the CT dimension, it can be efficiently handled by the FDM approach. Applied to model and experimental signals, the scheme shows significant resolution improvement, and appears to tolerate noise reasonably well. Other complex aspects of multidimensional FDM are discussed and illustrated.     

Easy interpretation of optical two-dimensional correlation spectra

We demonstrate that the value of the underlying frequency-frequency correlation function can be retrieved from a two-dimensional optical correlation spectrum through a simple relationship. The proposed method yields both intuitive clues and a quantitative measure of the dynamics of the system. The technique is applied to studying the effects of temperature and phase changes on liquid-glass solvent dynamics.     

Sequentially acquired two-dimensional NMR spectra from hyperpolarized sample

A scheme capable of acquiring heteronuclear 2D NMR spectra of hyperpolarized sample is described. Hyperpolarization, the preparation of nuclear spins in a polarized state far from thermal equilibrium, can increase the NMR signal by several orders of magnitude. It presents opportunities to apply NMR spectroscopy to dilute samples that would otherwise yield insufficient signal. However, conventional 2D NMR spectroscopy, which is commonly applied for the determination of molecular structure, relies on the recovery of the initial polarization after each transient. For this reason, it cannot be applied directly to a sample that has been hyperpolarized once. With appropriately modified pulse schemes, two-dimensional NMR spectra an however be acquired sequentially by utilizing a small portion of the hyperpolarized signal in every scan, while keeping the remaining polarization for future scans. We present heteronuclear multi-quantum spectra of single hyperpolarized samples using this technique, and discuss different options for distributing the polarization among different scans. This robust method takes full advantage of Fourier NMR to resolve overlapping chemical shifts, and may prove particularly useful for the structural elucidation of compounds in mass-limited samples.     

Robust baseline correction algorithm for signal dense NMR spectra

This paper outlines a fully automated algorithm for baseline correction. Based on our experience with NMR spectra of complex mixtures, this algorithm is designed to automatically differentiate signal points from baseline points. The algorithm's strength is its ability to accurately determine baseline points in very dense spectra, without destroying the line shapes of prominent peaks. The algorithm described is implemented in Chenomx NMR Suite 4.6. It is demonstrated here using two separate spectra acquired on two different NMR spectrometers.     

Three-dimensional correlation by combination of 2D NMR spectra

A method is proposed to make automatic structure elucidation and identification more reliable and unambiguous. Space correlation is utilized to map spin systems and to produce data banks on the basis of pattern recognition. The essence of the method presented is the mathematical combination of the measured 2D NMR spectra, but further extensions are also possible. From the correlation solid constructed in this way, the entire hidden information content of the individual 2D NMR spectra can be extracted.     

AssignFit: a program for simultaneous assignment and structure refinement from solid-state NMR spectra

AssignFit is a computer program developed within the XPLOR-NIH package for the assignment of dipolar coupling (DC) and chemical shift anisotropy (CSA) restraints derived from the solid-state NMR spectra of protein samples with uniaxial order. The method is based on minimizing the difference between experimentally observed solid-state NMR spectra and the frequencies back calculated from a structural model. Starting with a structural model and a set of DC and CSA restraints grouped only by amino acid type, as would be obtained by selective isotopic labeling, AssignFit generates all of the possible assignment permutations and calculates the corresponding atomic coordinates oriented in the alignment frame, together with the associated set of NMR frequencies, which are then compared with the experimental data for best fit. Incorporation of AssignFit in a simulated annealing refinement cycle provides an approach for simultaneous assignment and structure refinement (SASR) of proteins from solid-state NMR orientation restraints. The methods are demonstrated with data from two integral membrane proteins, one α-helical and one β-barrel, embedded in phospholipid bilayer membranes.     

Resolving ambiguities in two-dimensional NMR spectra: the 'TILT' experiment

Ambiguities in two-dimensional nuclear magnetic resonance spectra due to overlap are usually resolved by recording a three-dimensional version of the experiment. It is shown that a simpler solution is to record a tilted projection of the three-dimensional spectrum, derived by Fourier transformation of the time-domain signal acquired while the two evolution parameters are varied simultaneously at the appropriate rates. By avoiding the need to record the full three-dimensional spectrum, this saves an order of magnitude in measurement time. The tilt technique is illustrated by reference to degenerate responses in the TOCSY and NOESY spectra of a small protein, agitoxin, where the 1H and 15N frequencies are incremented in tandem.     

NMR assignment of protein side chains using residue-correlated labeling and NOE spectra

A new approach for the isotopic labeling of proteins is proposed that aims to facilitate side chain resonance assignments. Residue-correlated (RC) labeling is achieved by the expression of a protein on a medium containing a mixture of labeled, e.g., [U-13C,15N]amino acids, and NMR silent, [U-2H]amino acids. De novo synthesis of amino acids was suppressed by feedback inhibition by the amino acids in the growth medium and by the addition of beta-chloro-L-alanine, a transaminase inhibitor. Incorporation of these amino acids into synthesized proteins results in a relative diminution of inter-residue NOE interactions and a relative enhancement of intra-residue NOEs. Comparison of the resulting NOE spectra with those obtained from a uniformly labeled sample allows identification of intra-residue NOE peaks. Thus, this approach provides direct information for sidechain assignments in the NOE spectra, which are subsequently used for structural analysis. We have demonstrated the feasibility of this strategy for the 143 amino acid nuclease inhibitor NuiA, both at 35 degrees C, corresponding to a rotational correlation time of 9.5 ns, and at 5 degrees C, corresponding to a rotational correlation time of 22 ns.     

Pulsed field gradients in simulations of one- and two-dimensional NMR spectra

A method for the inclusion of the effects of z-axis pulsed field gradients in computer simulations of an arbitrary pulsed NMR experiment with spin (1/2) nuclei is described. Recognizing that the phase acquired by a coherence following the application of a z-axis pulsed field gradient bears a fixed relation to its order and the spatial position of the spins in the sample tube, the sample is regarded as a collection of volume elements, each phase-encoded by a characteristic, spatially dependent precession frequency. The evolution of the sample's density matrix is thus obtained by computing the evolution of the density matrix for each volume element. Following the last gradient pulse, these density matrices are combined to form a composite density matrix which evolves through the rest of the experiment to yield the observable signal. This approach is implemented in a program which includes capabilities for rigorous inclusion of spin relaxation by dipole-dipole, chemical shift anisotropy, and random field mechanisms, plus the effects of arbitrary RF fields. Mathematical procedures for accelerating these calculations are described. The approach is illustrated by simulations of representative one- and two-dimensional NMR experiments.     

Spectral editing of 13C NMR spectra via two-dimensional pulse techniques

Two-dimensional pulse techniques for subspectral editing in ¹³C NMR spectroscopy are described. The experiments are compared with existing one-dimensional editing methods with respect to sensitivity, information content, and practical performance. In combination with a computer program for fully automatic extraction of one-dimensional edited subspectra and radiofrequency field strength information, the two-dimensional presented experiments are useful as setup experiments in ¹³C NMR.     

An efficient multi-domain spectral algorithm for the simulation of dispersive metallic structures in the time domain

In this article, we present a multi-domain formulation of the spectral time domain algorithm for the simulation of dispersive materials. We propose a leap-frog time-stepping scheme similar to the finite-difference time domain method in order to minimize memory usage. Dispersive material behavior is modelled in the frequency domain and used in our time-domain algorithm by introducing auxiliary differential equations for the macroscopic polarization. Absorbing boundary conditions are presented that can be used with dispersive materials. The numerical investigation of structures with material parameters fitted to experimental data shows excellent agreement with theoretical calculations.     

An efficient multi-resolution SPH framework for multi-phase fluid-structure interactions

Applying different spatial and temporal resolutions for different sub-systems is an effective approach to increase computational efficiency for particle-based methods. However, it still has many challenges in terms of achieving an optimized computational efficiency and maintaining good numerical robustness and accuracy for the simulation of multi-phase flows involving large density ratio and interacting with rigid or flexible structures. In the present work, based on the multi-resolution smoothe...     

Obtaining absorptive line shapes in two-dimensional infrared vibrational correlation spectra

Absorptive line shapes in two-dimensional infrared (2D IR) vibrational spectra are important for an intuitive interpretation of molecular structure and dynamics. We obtain an absorptive 2D IR correlation spectrum by summing complementary spectra from experiments sampling vibrational coherences that oscillate with conjugate frequencies in the initial evolution time period. The 2D correlation spectrum of a coupled vibrational system reveals certain spectral features with tilted line shapes that are explained in terms of unequal contributions of Liouville-space pathways.