Inhomogeneity-free heteronuclear iMQC

Intermolecular dipolar interactions between proton and carbon spins can be used to indirectly detect carbon spectra with high sensitivity. In this communication, we present a modified sequence that, in addition to the high sensitivity of heteronuclear intermolecular multiple quantum coherence (iMQC) experiments, retains the line narrowing capability characteristic of homonuclear zero-quantum coherences. We demonstrate that this sequence can be used to obtain high resolution (13)C spectra in the presence of magnetic field inhomogeneities, both for thermal and hyperpolarized samples, and discuss applications to water-hyperpolarized carbon imaging.     

Simultaneous acquisition of multiple orders of intermolecular multiple-quantum coherence images in vivo

Until recently, NMR imaging with intermolecular multiple-quantum coherences (iMQCs) has been based on the acquisition of a single echo. In vivo studies of iMQC image contrast would greatly benefit from a method that could acquire several orders of quantum coherence during the same acquisition. This would enable comparison of the image contrast for various orders and eliminate image coregistration problems between scans. It has previously been demonstrated that multiple orders of iMQC images can be simultaneously acquired of a simple phantom. Here, we examine the technique and its effect on biological tissue, both in vivo and in vitro. First, we establish the effectiveness of the iMQC sequence in vivo using earthworms as specimens. We then further show that the multi-CRAZED sequence enhances detection of next generation (nanoparticle) contrast agents on excised tumor tissue.     

Isolating quantum coherences in structural imaging using intermolecular double-quantum coherence MRI

Intermolecular multiple-quantum coherence (iMQC) MR imaging provides a fundamentally different contrast mechanism. It allows probing tissue microstructure by tuning the direction and strength of the correlation gradient. However, iMQC images of a specific quantum-coherence can easily be contaminated by leakage signals from undesired quantum coherences (zero, single, and triple quantum coherence in this work). Using a modified double-quantum CRAZED imaging sequence, we show that signals originating from various coherence orders (M=0, 1, 2, 3) can be predicted in k-space and effectively isolated by means of a four-step phase cycling scheme and judicious choice of flip angles. Finally, preliminary data suggest the method to be able to provide information on trabecular bone architecture such as regional mean trabecular plate separation.     

Simultaneous acquisition of multiple orders of intermolecular multiple-quantum coherence images

Recent studies have demonstrated the ability to detect images based on intermolecular multiple-quantum coherences (iMQCs) that correspond to flipping of two or more separated spins simultaneously, as opposed to conventional magnetic resonance where only one spin is flipped at a time. Until now, iMQC imaging has only acquired one coherence signal per pulse sequence. Here we report a new sequence that successfully detects five orders of coherence (2, 1, 0, −1, and −2-quantum coherence images) in one pulse sequence, with each signal having its full intensity. The simultaneous acquisition highlights substantial contrast differences between conventional and iMQC images, and between the different types of iMQC images.     

基于分子间多量子相干的矢量场磁共振成像模拟

对基于分子间多量子相干的矢量场成像进行了系统的模拟研究. 模拟结果表明：这类成像能够对几十微米量级的异质结构进行成像,并较好地抑制来自均匀介质的信号. 即使不存在梯度磁场情况下,通过相位循环该方法亦可实现对异质结构的成像. 这将有助于开拓基于分子间多量子相干成像的应用领域,深化对其成像机制的理解.     

Magnetic resonance microscopic imaging based on high-order intermolecular multiple-quantum coherences

Most imaging studies using intermolecular multiple-quantum coherences (iMQCs) have focused on the two-spin dipolar interactions--zero and double quantum coherences. Here, we report the results of various experimental studies to assess the feasibility of magnetic resonance microscopy with high-order iMQCs in model systems at 7 and 14 T. Experimental results demonstrated that the iMQC microscopic images with high coherence orders are readily observable at high field and have unique contrast depending on the sample microstructure and coherence order.     

Enhancement of magnetization transfer effects by inter-molecular multiple quantum filtered NMR

There are a number of methods that give MRI contrasts based on changes of the water M(z) magnetization as a result of magnetization transfer to macromolecules. In the present work we report that a combination of these methods with inter-molecular multiple quantum coherences (iMQC) gives enhanced effects. For the magnetization transfer contrast (MTC) method an effect of (M(z)/M(0)) becomes (M(z)/M(0))(l) where l is the rank of the tensors constituting the iMQC. A similar trend was found upon combining iMQC with the Goldman-Shen experiment. It is pointed out that the method is general for all magnetization transfer methods, including the nuclear Overhauser effect.     

Spin state selective coherence transfer: a method for discrimination and complete analyses of the overlapped and unresolved 1H NMR spectra of enantiomers

In general, the proton NMR spectra of chiral molecules aligned in the chiral liquid crystalline media are broad and featureless. The analyses of such intricate NMR spectra and their routine use for spectral discrimination of R and S optical enantiomers are hindered. A method is developed in the present study which involves spin state selective two dimensional correlation of higher quantum coherence to its single quantum coherence of a chemically isolated group of coupled protons. This enables the spin state selective detection of proton single quantum transitions based on the spin states of the passive nuclei. The technique provides the relative signs and magnitudes of the couplings by overcoming the problems of enantiomer discrimination, spectral complexity and poor resolution, permitting the complete analyses of the otherwise broad and featureless spectra. A non-selective 180 degrees pulse in the middle of MQ dimension retains all the remote passive couplings. This accompanied by spin selective MQ-SQ conversion leads to spin state selective coherence transfer. The removal of field inhomogeneity contributes to dramatically enhanced resolution. The difference in the cumulative additive values of chemical shift anisotropies and the passive couplings, between the enantiomers, achieved by detecting Nth quantum coherence of N magnetically equivalent spins provides enhanced separation of enantiomer peaks. The developed methodology has been demonstrated on four different chiral molecules with varied number of interacting spins, each having a chiral centre.     

High-resolution absorptive intermolecular multiple-quantum coherence NMR spectroscopy under inhomogeneous fields

Intermolecular multiple-quantum coherence (iMQC) is capable of improving NMR spectral resolution using a 2D shearing manipulation method. A pulse sequence termed CT-iDH, which combines intermolecular double-quantum filter (iDQF) with a modified constant-time (CT) scheme, is designed to achieve fast acquisition of high-resolution intermolecular zero-quantum coherences (iZQCs) and intermolecular double-quantum coherences (iDQCs) spectra without strong coupling artifacts. Furthermore, double-absorption lineshapes are first realized in 2D intermolecular multi-quantum coherences (iMQCs) spectra under inhomogeneous fields through a combination of iZQC and iDQC signals to double the resolution without loss of sensitivity. Theoretically the spectral linewidth can be further reduced by half compared to original iMQC high-resolution spectra. Several experiments were performed to test the feasibility of the new method and the improvements are evaluated quantitatively. The study suggests potential applications for in vivo spectroscopy.     

Quantum coherence and decoherence of protons and muons in condensed matter

The coherence in quantum superposition states of protons (and chemically similar particles, the positive muons) has been studied in some condensed matter environments. It is shown that if the proton systems and the experimental techniques used to study them are carefully selected, it is possible to observe quantum delocalization states of single particles and to understand the mechanisms for their loss of coherence. Quantum correlated two- and multiparticle states of protons lose coherence very fast when coupled to condensed matter environments, but new sub-femtosecond techniques have made them accessible to experimental studies. The degree of decoherence can be measured as function of time and the decoherence mechanisms can, at least in certain cases, be identified. Although less clean than in corresponding studies of quantum optical systems, these studies can be seen as a first step towards understanding the conditions for preservation of quantum correlation and entanglement in massive systems. Some consequences and some suggestions for future work are discussed. Received 28 August 2002 Published online 7 January 2003     

Direct observation of quantum coherence in single-molecule magnets

Direct evidence of quantum coherence in a single-molecule magnet in a frozen solution is reported with coherence times as long as T{2}=630+/-30 ns. We can strongly increase the coherence time by modifying the matrix in which the single-molecule magnets are embedded. The electron spins are coupled to the proton nuclear spins of both the molecule itself and, interestingly, also to those of the solvent. The clear observation of Rabi oscillations indicates that we can manipulate the spin coherently, an essential prerequisite for performing quantum computations.     

Measuring fast hydrogen exchange rates by NMR spectroscopy

We introduce a method to measure hydrogen exchange rates based on the observation of the coherence of a neighboring spin S such as (15)N that has a scalar coupling J(IS) to the exchanging proton I. The decay of S(x) coherence under a Carr-Purcell-Meiboom-Gill (CPMG) multiple echo train is recorded in the presence and absence of proton decoupling. This method allows one to extract proton exchange rates up to 10(5)s(-1). We could extend the pH range for the study of the indole proton in tryptophan, allowing the determination of the exchange constants of the cationic, zwitterionic, and anionic forms of tryptophan.     

Analysis of homonuclear RF gradient NMR spectroscopy

A formalism for describing the spin dynamics of radio frequency (RF) gradient experiments is introduced. It has the advantage over the most straight-forward applications of product operator methods of cleanly separating the steps of coherence transformation and gradient evolution which become confused in many RF gradient methods. The analysis is used to explore the dynamics of RF gradient homonuclear multiple quantum filtering experiments. Experimental results of these new sequences are included.     

量子相干

量子相干不仅是量子力学中的一个基本概念,同时也是重要的量子信息处理的物理资源.随着基于资源理论框架的量子相干度量方案的提出,量子相干度的量化研究成为近年来人们关注的一个热点问题.量子相干作为一种物理资源也十分脆弱,极容易受到环境噪声的影响而产生退相干,因此开放系统中的量子相干演化和保持也是人们广泛关注的课题.另外,量子相干在量子多体系统、量子热动力学、量子生物学等领域也有着潜在的应用价值.本文介绍量子相干度量的资源理论框架和基于该框架定义的相对熵相干性、l1范数相干性、基于量子纠缠的相干性、基于凸顶结构的相干性和相干鲁棒性等量子相干度量函数,概述开放系统中量子相干演化的动力学行为、典型信道的量子相干产生和破坏能力以及量子相干的冻结等现象,同时例举量子相干在Deutsch-Jozsa算法、Grover算法以及量子多体系统相变问题研究等方面的重要应用.量子相干研究仍处于快速发展之中,期望本综述能为该领域的发展带来启示.     

Mapping Highly Congested Proton NMR Spin Systems of Natural Products Using Two-Dimensional Proton Double Quantum Coherence

Highly congested terpenoid proton NMR spectra are generally intractable to detailed analysis and assignment. Analyses of the proton-proton connectivity networks in such spectra are, however, possible using the proton double quantum coherence two-dimensional NMR experiment. Natural cycloseychellene, which contains resonances for twenty four protons within a 1.2 ppm wide region is used as an example to demonstrate this technique.     

Quantum coherence and ground-state phase transition in a four-chain Bose–Hubbard model

We study the quantum coherence and ground-state phase transition of a four-chain Bose–Hubbard model with the long-range interaction. In a special four-chain Bose–Hubbard model,i.e., each chain only has one optical potential, four types of the ground-state phases are discovered. The effects of the disorder, the on-site interaction and the long-range interaction on the quantum coherence are studied. For the system without the long-range interaction, the quantum coherence changes from one periodic oscillation to two periodic oscillations as the onsite interaction increases. By considering the long-range interaction, the quantum coherence goes back to one periodic oscillation again. The on-site interaction itself suppresses the quantum coherence, both the on-site interaction and long-range interaction together enhance the quantum coherence with the weak disorder. If the disorder strength is increased beyond a critical value,they start to suppress the quantum coherence. In a regular four-chain Bose–Hubbard model, i.e.,each chain has many optical potentials, the ground-state phase transitions are obtained by using the cluster Gutzwiller mean-field method. Exotic ground-state phases are found, i.e., superfluid phase, integer Mott insulator phase, supersolid phase and loophole insulator phase. The combination of the loophole insulator phase and the supersolid phase expands the lobes with the half-integer filling per site for the small ratio β = t_■/t_⊥.     

Fast high-resolution 2D correlation spectroscopy in inhomogeneous fields via Hadamard intermolecular multiple quantum coherences technique

Recently, a method based on intermolecular multiple quantum coherences (iMQCs) has been proposed to obtain high-resolution 2D COSY spectra in inhomogeneous fields via 3D acquisitions. However, the very long acquisition time prevents its practical application. To overcome this shortage, the Hadamard technique was applied for the iMQC method in this paper. For the new pulse sequence, the direct frequency-domain excitation is used in the first indirect detection dimension, so the 3D acquisition was replaced by an array of 2D acquisitions. The acquisition time can be reduced to 10 min. The resulting spectra retain useful structural information including chemical shifts and multiplet patterns of J coupling even when the inhomogeneous line broadening leads to overlap of neighboring diagonal resonances in the conventional COSY spectrum. The experimental results are consistent with the theoretical predictions and computer simulations. The new sequence may provide a time-efficient way for the studies of chemical solution in inhomogeneous fields.     

Intermolecular double-quantum coherence imaging without coherence selection gradients and its application in in vivo MRI

In the COSY Revamped with Asymmetric Z-gradient Echo Detection (CRAZED) experiments, magnetization is modulated by the distant dipolar field (DDF) generated by coherence selection gradient (CSG) commonly in sinusoidal wave-form and results in detectable intermolecular multiple-quantum coherence (iMQC) signal. IMQCs have some attractive features, but their intrinsic weak signal intensity prevents their widespread applications. In this paper, a new phase cycling scheme was applied to obtain intermolecular double-quantum coherence (iDQC) signal. It is found that DDF can arise from nonspherical sample geometry or background inhomogeneous field in the absence of CSGs, which is more efficient than that created from CSGs. The experimental results show that the resulting DDF can refocus the ± iDQC signals simultaneously and thus enhance the signal intensity to about two folds of that from the conventional CRAZED sequence. Theoretical prediction and experiments give coincident results.     

Toward a superconducting quantum computer: Harnessing macroscopic quantum coherence

Intensive research on the construction of superconducting quantum computers has produced numerous important achievements. The quantum bit (qubit), based on the Josephson junction, is at the heart of this research. This macroscopic system has the ability to control quantum coherence. This article reviews the current state of quantum computing as well as its history, and discusses its future. Although progress has been rapid, the field remains beset with unsolved issues, and there are still many new research opportunities open to physicists and engineers.     

1H,15N,13C-triple resonance NMR of very large systems at 900 MHz

We provide quantitative signal to noise data and feasibility study at 900 MHz for 1H-15N-13C triple resonance backbone assignment pulse sequences obtained from a medium sized 2H, 13C, 15N labeled protein slowed down in glycerol-water solution to mimic relaxation and spectroscopic properties of a much larger protein system with macromolecular tumbling correlation time of 52 and 80 ns, respectively, at 296 and 283 K (corresponding to molecular weights of 130 and 250 kDa). Comparisons of several different schemes for transferring magnetization from proton to nitrogen and back to proton confirms Yang and Kay's 1999 prediction that avoiding the unfavorable relaxation properties of 1H-15N multiple quantum coherence in the TROSY phase cycle of the final 15N-1H transfer before acquisition is crucial for maximal sensitivity from these very large molecular weight systems. We also show results which confirm some predictions regarding the superiority of TROSY at 900 MHz vs. 800 MHz especially as the molecular weights become very large.