Sensitivity gain by simultaneous acquisition of two coherence pathways: the HNCA(+) experiment

In most multidimensional nuclear magnetic resonance experiments a single and distinct coherence transfer pathway is selected by phase cycling or by pulsed field gradients. It was shown that simultaneously exploiting more than one coherence transfer pathway could increase the overall sensitivity of NMR experiments. However, sensitivity enhancement schemes described to date introduce additional delays in the pulse schemes, resulting in considerable decrease of the expected sensitivity gain when applied to biomolecules due their fast transverse relaxation. A novel sensitivity enhancement principle which increases sensitivity of an experiment by simultaneously exploiting two completely independent coherence pathways in a single NMR pulse scheme is presented in this paper. As an example an improved HNCA experiment, the HNCA(+), is presented, which combines the "out-and-back" coherence transfer pathway used in HNCA with an "out-and-stay" experiment, analogous to HCANH, without adding any time periods compared to the conventional HNCA pulse sequence. The applicability of the HNCA(+) was theoretically evaluated with regard to different sizes of peptides or proteins, which showed that the experimental time can be reduced twofold in ideal cases. The application of this novel experiment to a 7-kDa protein showed a 20% sensitivity gain of HNCA(+) when compared to conventional HNCA.     

Determination of structural and dynamic characteristics of biodegradable polymers by the NMR relaxation method

A theory of the NMR spectra of heterogeneous polymer systems is proposed that makes it possible to simulate signals observed over a wide temperature range with account of spectral diffusion. Based on this theory, a technique of rapid analysis of molecular structure parameters, including the degree of crystallinity and NMR line shape, is developed. The degree of crystallinity is demonstrated to be a linear function of the area under the NMR spectrum. It is shown that this dependence, universal for a given substance, makes it possible to reliably determine the degree of crystallinity over a wide temperature range (or the fraction of low-molecular additives in composites). The NMR spectra of chitosan is simulated and compared to experimental data. The universal dependence of the degree of crystallinity on the area under the spectrum of chitosan is calculated. A comparison with experimental signals allowed determining the degree of crystallinity.     

Detection of NMR signals with a radio-frequency atomic magnetometer

We demonstrate detection of proton NMR signals with a radio-frequency (rf) atomic magnetometer tuned to the NMR frequency of 62 kHz. High-frequency operation of the atomic magnetometer makes it relatively insensitive to ambient magnetic field noise. We obtain magnetic field sensitivity of 7 fT/Hz1/2 using only a thin aluminum shield. We also derive an expression for the fundamental sensitivity limit of a surface inductive pick-up coil as a function of frequency and find that an atomic rf magnetometer is intrinsically more sensitive than a coil of comparable size for frequencies below about 50 MHz.     

Numerical solution to the Bloch equations:paramagnetic solutions under wideband continuous radio frequency irradiation in a pulsed magnetic field

A novel nuclear magnetic resonance(NMR) experimental scheme,called wideband continuous wave NMR(WB-CW-NMR),is presented in this article.This experimental scheme has promising applications in pulsed magnetic fields,and can dramatically improve the utilization of the pulsed field.The feasibility of WB-CW-NMR scheme is verified by numerically solving modified Bloch equations.In the numerical simulation,the applied magnetic field is a pulsed magnetic field up to 80 T,and the wideband continuous radio frequency(RF) excitation is a band-limited(0.68-3.40 GHz) white noise.Furthermore,the influences of some experimental parameters,such as relaxation time,applied magnetic field strength and wideband continuous RF power,on the WB-CW-NMR signal are analyzed briefly.Finally,a multi-channel system framework for transmitting and receiving ultra wideband signals is proposed,and the basic requirements of this experimental system are discussed.Meanwhile,the amplitude of the NMR signal,the level of noise and RF interference in WB-CW-NMR experiments are estimated,and a preliminary adaptive cancellation plan is given for detecting WB-CW-NMR signal from large background interference.     

Resolution and sensitivity aspects of ultrafast J-resolved 2D NMR spectra

Recent ultrafast techniques enable nD NMR spectra to be obtained in a single scan. However, resolution enhancement in the ultrafast domain leads to important sensitivity losses and lineshape distortions. In order to understand better resolution and spatial encoding aspects of continuous phase-encoding schemes, a theoretical and experimental comparison of different excitation patterns is carried out. Molecular diffusion appears to be the main cause of signal-to-noise ratio decrease, and a multi-echo excitation scheme is proposed to limit its effects when a good resolution is needed. Results obtained on 2D J-resolved spectra are presented.     

Sensitivity losses and line shape modifications due to molecular diffusion in continuous encoding ultrafast 2D NMR experiments

Recent ultrafast techniques make it possible to obtain multidimensional (nD) NMR spectra in a single scan. These ultrafast methods rely on a spatial encoding process based on radiofrequency (RF) pulses applied simultaneously with magnetic field gradients. Numerous approaches have been proposed in the past few years to perform this excitation process, most of them relying on a continuous excitation of the spins throughout the whole sample. However, the resolution and sensitivity of ultrafast nD spectra are often reduced by molecular diffusion effects due to the presence of gradients during the excitation process. In particular, increasing the excitation period is necessary to improve the resolution in the ultrafast dimension, but it leads to high sensitivity losses due to diffusion. In order to understand better and to limit molecular diffusion effects, a detailed theoretical and experimental study of the various continuous ultrafast excitation processes is carried out in the present study. New numerical simulations of ultrafast echo line shapes are presented and compared to experimental data. The evolution of the signal intensity with the excitation process duration is also simulated and compared to experimental intensity losses. The different excitation schemes are compared in order to determine the best excitation conditions to perform 2D ultrafast experiments with optimum resolution and sensitivity. The experimental and theoretical results put in evidence the efficiency of the multi-echo scheme.     

Wave atom transform generated strong image hashing scheme

The rapid development of multimedia technology has resulted in a rising rate on digital unauthorized utilization and forgery, which makes the situation of image authentication increasingly severe. A novel strong image hashing scheme is proposed based on wave atom transform, which can better authenticate images by precisely distinguishing the malicious tampered images from the non-maliciously processed ones. Wave atom transform is employed since it has significantly sparser expansion and better characteristics of texture feature extraction than other traditional transforms. For better detection sensitivity, gray code is applied instead of natural binary code to optimize the hamming distance. Randomizations are also performed using Rényi chaotic map for the purposes of secure image hashing and key sensitivity. The experimental results show that the proposed strong scheme is robust to non-malicious content-preserving operations and also fragile to malicious content-altering operations. The scheme also outperforms DCT and DWT based schemes in terms of receiving operating characteristic (ROC) curves. Moreover, to provide an application-defined tradeoff, a security enhancement approach based on Rényi map is presented, which can further protect the integrity and secrecy of images.     

Temperature response of 129Xe depolarization transfer and its application for ultrasensitive NMR detection

Trapping xenon in functionalized cryptophane cages makes the sensitivity of hyperpolarized (HP) 129Xe available for specific NMR detection of biomolecules. Here, we study the signal transfer onto a reservoir of unbound HP xenon by gating the residence time of the nuclei in the cage through the temperature-dependant exchange rate. Temperature changes larger than approximately 0.6 K are detectable as an altered reservoir signal. The temperature response is adjustable with lower concentrations of caged xenon providing more sensitivity at higher temperatures. Ultrasensitive detection of functionalized cryptophane at 310 K is demonstrated with a concentration of 10 nM, corresponding to a approximately 4000-fold sensitivity enhancement compared to conventional detection. This makes HPNMR capable of detecting such constructs in concentrations far below the detection limit of benchtop uv-visible light absorbance.     

Simulations of information transport in spin chains

Transport of quantum information in linear spin chains has been the subject of much theoretical work. Experimental studies by NMR in solid state spin systems (a natural implementation of such models) is complicated since the dipolar Hamiltonian is not solely comprised of nearest-neighbor XY-Heisenberg couplings. We present here a similarity transformation between the XY Hamiltonian and the double-quantum Hamiltonian, an interaction which is achievable with the collective control provided by radio-frequency pulses. Not only can this second Hamiltonian simulate the information transport in a spin chain, but it also creates coherent states, whose intensities give an experimental signature of the transport. This scheme makes it possible to study experimentally the transport of polarization beyond exactly solvable models and explore the appearance of quantum coherence and interference effects.     

High contrast atomic magnetometer based on coherent population trapping

We present an experimental and theoretical investigation of the coherent population trapping （CPT） resonance excited on the D1 line of 87Rb atoms by bichromatic linearly polarized laser light. The experimental results show that a lin｜｜lin tran- sition scheme is a promising alternative to the conventional circular-circular transition scheme for an atomic magnetometer. Compared with the circular light transition scheme, linear light accounts for high-contrast transmission resonances, which makes this excitation scheme promising for high-sensitivity magnetometers. We also use linear light and circular light to detect changes of a standard magnetic field, separately.     

Theoretical Evaluation and Comparison of Fast Chemical Shift Imaging Methods

Magnetic resonance chemical shift imaging (CSI) is becoming the method of choice for localized NMR spectroscopic examinations, allowing simultaneous detection of NMR spectra from a large number of voxels. The main limitation of these methods is their long experimental duration. A number of fast CSI experiments have been presented, promising to reduce that duration. In this contribution the criteria for evaluating and optimizing the sensitivity of fast CSI experiments are elaborated. For a typical experiment in the human brain, the performance of various methods is compared. While conventional CSI provides optimal sensitivity per unit time, it is shown in which circumstances fast sequences allow a shorter experimental duration. Using these results, the best method for any experimental requirements can be selected.     

Planar microcoil-based microfluidic NMR probes

Microfabricated small-volume NMR probes consisting of electroplated planar microcoils integrated on a glass substrate with etched microfluidic channels are fabricated and tested. 1H NMR spectra are acquired at 300 MHz with three different probes having observed sample volumes of respectively 30, 120, and 470 nL. The achieved sensitivity enables acquisition of an 1H spectrum of 160 microg sucrose in D2O, corresponding to a proof-of-concept for on-chip NMR spectroscopy. Increase of mass-sensitivity with coil diameter reduction is demonstrated experimentally for planar microcoils. Models that enable quantitative prediction of the signal-to-noise ratio and of the influence of microfluidic channel geometry on spectral resolution are presented and successfully compared to the experimental data. The main factor presently limiting sensitivity for high-resolution applications is identified as being probe-induced static magnetic field distortions. Finally, based on the presented model and measured data, future performance of planar microcoil-based microfluidic NMR probes is extrapolated and discussed.     

Sensitive and robust electrophoretic NMR: instrumentation and experiments

Although simple as a concept, electrophoretic NMR (eNMR) has so far failed to find wider application. Problems encountered are mainly due to disturbing and partly irreproducible convection-like bulk flow effects from both electro-osmosis and thermal convection. Additionally, bubble formation at the electrodes and rf noise pickup has constrained the typical sample geometry to U-tube-like arrangements with a small filling factor and a low resulting NMR sensitivity. Furthermore, the sign of the electrophoretic mobility cancels out in U-tube geometries. We present here a new electrophoretic sample cell based on a vertically placed conventional NMR sample tube with bubble-suppressing palladium metal as electrode material. A suitable radiofrequency filter design prevents noise pickup by the NMR sample coil from the high-voltage leads which extend into the sensitive sample volume. Hence, the obtained signal-to-noise ratio of this cell is one order of magnitude higher than that of our previous U-tube cells. Permitted by the retention of the sign of the displacement-related signal phase in the new cell design, an experimental approach is described where bulk flow effects by electro-osmosis and/or thermal convection are compensated through parallel monitoring of a reference signal from a non-charged species in the sample. This approach, together with a CPMG-like pulse train scheme provides a superior first-order cancellation of non-electrophoretic bulk flow effects.     

Semi-constant-time HMSQC (SCT-HMSQC-HA) for the measurement of (3)J(H(N))(H(alpha)) couplings in (15)N-labeled proteins

A simple method for accurately measuring (3)J(H(N))(H(alpha)) coupling constants in (15)N-labeled proteins is described. This semi-constant-time HMSQC-HA experiment combines the rapidity and convenience of the recently introduced CT-HMQC-HA scheme (Postingl and Otting, J. Biomol. NMR 12, 319-324 (1998)) with the high resolution and robustness of the HSQC experiment. The proposed method is demonstrated for the 76-residue human ubiquitin and Saccharopolyspora erythraea calerythrin (176 residues). Our results imply that the SCT-HMSQC-HA experiment is suitable also for proteins with less favorable NMR properties due to its good resolution and sensitivity.     

Experimental aspects of an NMR quantum computer with CeP

An NMR quantum computer based on an integrated device with CeP has been proposed by Yamaguchi and Yamamoto [Appl. Phys. A 68 1 (1999)]. We point out two problems in their scheme. We also investigate experimentally the ³¹P NMR spectra for our CeP. From the line width, we find that improvement of the sample quality is necessary to satisfy the experimental conditions for a quantum computer.     

Ultrafast 2D NMR spectroscopy using a continuous spatial encoding of the spin interactions

A new protocol for acquiring multidimensional NMR spectra within a single scan is introduced and illustrated. The approach relies on applying a pair of frequency-chirped excitation and storage pulses in combination with echoing magnetic field gradients, in order to impart the kind of linear spatial encoding of the NMR interactions that is required by ultrafast 2D NMR spectroscopy. It is found that when dealing with 2D NMR experiments involving a t1 amplitude-modulation of the spin evolution, such continuous encoding scheme presents a number of advantages over alternatives employing discrete excitation pulses. From an experimental standpoint this is mainly reflected by the use of a single pair of bipolar gradients during the course of the indirect-domain encoding, as opposed to the numerous (and more intense) gradient echoes required so far. In terms of the spectral outcome, main advantages of the continuous spatial encoding scheme are the avoidance of "ghost peaks" and of "enveloping effects" associated to the discrete excitation mode. The principles underlying this new spatial encoding protocol are derived, and its applicability is demonstrated with homo- and heteronuclear 2D ultrafast NMR applications on small molecule and on protein samples.     

Accurate non-relativistic density functional theory predictions for 77Se NMR shielding parameters

A reoptimized density functional theory (DFT) hybrid functional gives orbitals and energies which when substituted into the uncoupled generalized gradient approximation (GGA) sum-over-states expressions gives NMR shielding constants of high accuracy for first- and second-row nuclei. This procedure is validated further and its performance compared against well established exchange-correlation (XC) functionals for the prediction of the third-row ⁷⁷Se NMR shielding constants, in a series of challenging molecules where both accurate theoretical and experimental data are available. The shielding parameters obtained from this new mixed hybrid GGA scheme provide a significant improvement over conventional XC functionals. and are competitive with the benchmark coupled-cluster singles and doubles (CCSD) methods. From these results together with previous studies it is now apparent that this new GGA shielding scheme provides high accuracy NMR shielding constants for first-, second-and third-row atoms (excluding transition-metal atoms) even in molecules exhibiting large correlation effects.     

Quantum limits and symphotonic states in free-mass gravitational-wave antennae

Quantum mechanics sets severe limits on the sensitivity and required circulating energy in traditional free-mass gravitational-wave antennae. One possible way to avoid these restrictions is the use of intracavity QND measurements. We analyze a new QND observable, which possesses a number of features that make it a promising candidate for such measurements, and propose a practical scheme for the realization of this measurement. In combination with an advanced coordinate meter, this scheme makes it possible to lower substantially the requirements on the circulating power.     

Signal enhancement in 5QMAS spectra of spin-5/2 quadrupolar nuclei

5QMAS experiments on spin-5/2 systems display a low sensitivity compared with their 3QMAS counterparts. Nevertheless, the superior resolution of 5QMAS over 3QMAS makes these experiments a favorable choice for many materials. We report an enhancement scheme for the 5QMAS experiment, using an improved five-quantum excitation pulse scheme combined with a FAM-II conversion pulse. The results are verified experimentally on a polycrystalline sample of gamma-(27)Al(2)O(3), showing an enhancement factor of 2.4 over the simple two-pulse (CW) 5QMAS scheme. Numerical computations of the efficiency parameter epsilon support these results.     

Experimental implementation of a fixed-point duality quantum search algorithm in the nuclear magnetic resonance quantum system

In this work, we demonstrated a fixed-point quantum search algorithm in the nuclear magnetic resonance (NMR) system. We constructed the pulse sequences for the pivotal operations in the quantum search protocol. The experimental results agree well with the theoretical predictions. The generalization of the scheme to the arbitrary number of qubits has also been given.