Spin-state-selective excitation in selective 1D inverse NMR experiments

A general and very simple strategy for achieving clean spin-state-selective excitation with full sensitivity in carbon-selective gradient-enhanced 1D HMQC and HSQC pulse schemes is presented. The incorporation of an additional hard 90 degrees (13)C pulse applied along a specific orthogonal axis just prior to acquisition into the conventional sequences allows us to select a simultaneous coherence transfer pathway which usually is not detected. The superimposition of this resulting antiphase magnetization to the conventional in-phase magnetization gives the exclusive excitation of the directly attached proton showing only the alpha or beta spin state of the passive (13)C nucleus. The propagation of this particular spin state to other protons can be accomplished by adding any homonuclear mixing process just after this supplementary pulse. Such an approach affords a suite of powerful selective 1D (13)C-edited NMR experiments which are helpful for resonance assignment purposes in overcrowded proton spin systems and also for the accurate determination of the magnitude and sign of long-range proton-carbon coupling constants in CH spin sytems for samples at natural abundance. Such measurements are performed by measuring the relative displacement of relayed signals in the corresponding alpha and beta 1D subspectra.     

Analyses, extensions and comparison of three experimental schemes for measuring ((n)J(CH)+D(CH))-couplings at natural abundance

Three types of experiments for measuring (n)J(CH) heteronuclear long-range coupling constants are examined and extended with state-of-the-art pulse sequence building-blocks: The use of a HMBC with corresponding reference-HSQC for accurate coupling determination is combined with the constant time technique and the conversion of antiphase magnetization into ZQ/DQ-coherences; CPMG-based LR-CAHSQC and BIRD(r,X)-HSQMBC experiments are examined in detail with respect to their coherence transfer properties; finally, the HSQC-TOCSY-IPAP experiment is introduced, a sequence derived from previously published alpha and beta selective HSQC-TOCSYs using a different spin state selection technique and a recently developed ZQ-suppression method. The experiments are characterized with their advantages and disadvantages and compared using strychnine and menthol as standard molecules.     

The Observation and Dynamics of 1H NMR Spin Noise in Methanol

The observation of ¹H spin noise in relation to prior established magnetization and radiation damping has revealed a correlated dynamics. The spin noise of methyl satellites in ¹³C-enriched methanol was observed in the presence of an antiphase magnetization, created by the combination of ¹H–¹³C J coupling evolution and radiofrequency (RF) pulses. A gradient pulse was applied to remove residue spin coherence coming from the RF pulses, and as a result spin noise phenomena were uncovered. While magnetization was in an inverted metastable state, the spin–spin relaxation time was shortened to prevent a super radiation burst. The relation between magnetization, radiation damping, and absorption or emission of the spin noise of methyl satellites has been studied. In relation to magnetization and radiation damping, spin noise bump and dip have been observed simultaneously in the same molecule. Both can be created through a proper inversion of magnetization. The revealed spin noise dynamics of spin system coupling to the probe circuit via radiation damping allows performance of a transformation from dip into bump by proper application of pulses combined with ¹H–¹³C J coupling evolution.     

Application of biselective refocusing soft pulses to the simplification of heteronuclear correlation spectra

The biselective spin echo technique allows the signals of coupled proton pairs to be extracted from crowded liquid state proton NMR spectra. Its use as a preparation sequence in heteronuclear chemical shift correlation experiments requires the removal of the heteronuclear coupling interaction during the biselective echo time. The discrimination between coupled and uncoupled protons signals is achieved by double quantum filtration, which delivers antiphase magnetization states. The latter are not directly compatible with the design of an HSQC-like pulse sequence. The conversion of antiphase to in-phase magnetization states by a second biselective echo sequence solves this problem. The optimization of spin echo delays is also discussed. Lastly, the article presents modified HSQC and HMBC pulses sequences in which information is obtained solely for the biselectively selected proton pairs. A peracetylated trisaccharide was used as a test molecule.     

Sensitivity enhanced recoupling experiments in solid-state NMR by gamma preparation

In this paper, we introduce a class of dipolar recoupling experiments under magic angle spinning (MAS), which use gamma dependent antiphase polarization during the t1 evolution period. We show that this helps us to design dipolar recoupling experiments that transfer both components of the transverse magnetization of spin S to a coupled spin I in the mixing step of a 2D NMR experiment. We show that it is possible to design such transfer schemes and make them insensitive to the orientation dependency of the couplings in powders. This helps us to develop sensitivity enhanced 2D NMR experiments of powder samples under MAS.     

Spin state selective Hadamard encoding during transfer periods using multiple selective CW-HCP

Hadamard spectroscopy today represents an alternative to conventional Fourier transform spectroscopy. The selective inversion of several narrow frequency bands is typically achieved by taylored inversion pulses in place of t1-evolution periods. However, band-selective inversion can also be achieved during coherence transfer steps, thereby shortening the period during which the magnetization is in the transverse plane. Using CW heteronuclear cross polarization (CW-HCP) as an example for highly selective coherence transfer, the implementation of Hadamard encoding within a transfer step is presented. Transfer characteristics, the preparation of multiple frequency selective CW-HCP and the possibility of acquiring spin state selective spectra are discussed in detail. The theoretical results are verified on two examples involving a cyclic pentapeptide and ubiquitin.     

Recoupling in solid state NMR using γ prepared states and phase matching

The paper describes two-dimensional solid state NMR experiments that use powdered dephased antiphase coherence (γ preparation) to encode chemical shifts in the indirect dimension. Both components of this chemical shift encoded gamma-prepared states can be refocused into inphase coherence by a recoupling element. This helps to achieve sensitivity enhancement in 2D NMR experiments by quadrature detection. The powder dependence of the gamma-prepared states allows for manipulating them by suitable insertion of delays in the recoupling periods. This helps to design experiments that suppress diagonal peaks in 2D spectra, leading to improved resolution. We describe some new phase modulated heteronuclear and homonuclear recoupling pulse sequences that simplify the implementation of the described experiments based on γ prepared states. Recoupling in the heteronuclear spin system is achieved by matching the difference in the amplitude of the sine/cosine modulated phase on the two rf-channels to the spinning frequency while maintaining the same power on the two rf-channels.     

The CLIP/CLAP-HSQC: pure absorptive spectra for the measurement of one-bond couplings

Heteronuclear residual dipolar one-bond couplings of organic molecules at natural abundance are most easily measured using t2 coupled HSQC spectra. However, inevitably mismatched transfer delays result in phase distortions due to residual dispersive antiphase coherences in such experiments. In this article, slightly modified t2 coupled HSQC experiments with clean inphase (CLIP) multiplets are introduced which also reduce the intensities of undesired long-range cross peaks. With the corresponding antiphase (CLAP) experiment, situations where alpha and beta components overlap can be resolved for all multiplicities in an IPAP manner. A comparison of the experiments using hard pulses and shaped broadband excitation and inversion pulses on the heteronucleus is given and potential spectral artefacts are discussed in detail.     

Amino-acid selective experiments on uniformly 13C and 15N labeled proteins by MAS NMR: Filtering of lysines and arginines

Amino-acid selective magic-angle spinning (MAS) NMR experiments can aid the assignment of ambiguous cross-peaks in crowded spectra of solid proteins. In particular for larger proteins, data analysis can be hindered by severe resonance overlap. In such cases, filtering techniques may provide a good alternative to site-specific spin-labeling to obtain unambiguous assignments that can serve as starting points in the assignment procedure. In this paper we present a simple pulse sequence that allows selective excitation of arginine and lysine residues. To achieve this, we make use of a combination of specific cross-polarization for selective excitation [M. Baldus, A.T. Petkova, J. Herzfeld, R.G. Griffin, Cross polarization in the tilted frame: assignment and spectral simplification in heteronuclear spin systems, Mol. Phys. 95 (1998) 1197-1207.] and spin diffusion for transfer along the amino-acid side-chain. The selectivity of the filter is demonstrated with the excitation of lysine and arginine side-chain resonances in a uniformly 13C and 15N labeled protein preparation of the alpha-spectrin SH3 domain. It is shown that the filter can be applied as a building block in a 13C-13C lysine-only correlation experiment.     

Magnetic-field induced transition to the 1/2 magnetization plateau state in the geometrically frustrated magnet CdCr2O4

The magnetization of the geometrically frustrated spinel CdCr2O4 was measured in pulsed fields of up to 47 T. We found a metamagnetic transition to a very wide magnetization plateau state with one half of the full moment of S=3/2 Cr3+ at 28 T, independent of the field direction. This is the first observation of magnetization plateau state realized in Heisenberg pyrochlore magnet. The plateau state can be ascribed to a collinear spin configuration with three-up and one-down spins out of four spins of each Cr tetrahedron. A large magnetostriction is observed at the transition in spite of the negligible spin-orbit couplings. We argue that spin frustration plays a vital role in this large spin-lattice coupling.     

选择性激发技术在偶合常数精确测量中的应用

采用基于简单Gaussian软脉冲的选择性激发技术来获得自旋系统的一维反相磁化分裂峰,并结合J-Doubling方法来精确测量该分裂峰的J偶合常数,对于重叠分裂峰或者线宽大、偶合分裂小的谱峰的J偶合常数的精确测量,该方法尤其适合.     

Long-lived quantum memory with nuclear atomic spins

We propose to store nonclassical states of light into the macroscopic collective nuclear spin (10(18) atoms) of a 3He vapor, using metastability exchange collisions. These collisions, commonly used to transfer orientation from the metastable state 2 3S1 to the ground state of 3He, can also transfer quantum correlations. This gives a possible experimental scheme to map a squeezed vacuum field state onto a nuclear spin state with very long storage times (hours).     

结合脉冲梯度场(PFG)的选择性形状脉冲的相位特性研究

从转动矩阵理论与实验两方面研究了结合脉冲梯度场的选择性形状脉冲的相位特性,结果表明:单梯度自旋回波(SPFGSE)和双梯度自旋回波(DPFGSE)对于对称和反对称的形状脉冲,都能很好地克服其相位畸变;而双梯度自旋回波(DPFGSE)对于非对称的形状脉冲也能克服其相位畸变;双选择性单梯度自旋回波无法克服形状脉冲的相位畸变.     

Dependence of switching process on the perpendicular magnetic anisotropy constant in P-MTJ

We investigate the dependence of the switching process on the perpendicular magnetic anisotropy(PMA) constant in perpendicular spin transfer torque magnetic tunnel junctions(P-MTJs) using micromagnetic simulations. It is found that the final stable states of the magnetization distribution of the free layer after switching can be divided into three different states based on different PMA constants: vortex, uniform, and steady. Different magnetic states can be attributed to a trade-off among demagnetization, exchange, and PMA energies. The generation of the vortex state is also related to the non-uniform stray field from the polarizer, and the final stable magnetization is sensitive to the PMA constant. The vortex and uniform states have different switching processes, and the switching time of the vortex state is longer than that of the uniform state due to hindrance by the vortex.     

用于指导仲氢诱导核极化状态保存的己烯分子中五自旋的单重态制备和寿命研究

仲氢诱导核极化（PHIP）技术能极大地增强核磁共振（NMR）信号的灵敏度,已被应用于磁共振成像、原位化学反应监测等领域．除了不断提高不同分子极化后的灵敏度外,延长和保存高极化度状态对PHIP技术的应用也至关重要,其中将极化后的状态制备成核自旋单重态是目前被研究较多的一种方法．本文以能被PHIP技术极化的己烯分子为研究对象,通过设计优化控制脉冲,对分子中的一个五自旋体系进行操控,制备了多种核自旋单重态,结果表明：己烯分子的碳-碳双键上存在三种不同的核自旋单重态,它们的寿命均长于仲氢极化后产生的初始态的寿命,可以作为延缓极化度衰减的一种中间态;通过对比单重态的寿命与相应自旋的纵向弛豫时间发现,将极化后己烯的状态转化为纵向磁化可能也是一种保存极化度的有效方法．     

A New Two-Dimensional Pulse Sequence for T2* Measurements of Protons in C Isotopomers

A new two-dimensional pulse sequence for T₂* measurement of protons directly coupled to ¹³C spins is proposed. The sequence measures the tranverse relaxation time of heteronuclear proton single-quantum coherence under conditions of free precession and is therefore well suited to evaluate relaxation losses of proton magnetization during preparation delays of heteronuclear pulse experiments in analytical NMR. The relevant part of the pulse sequence can be inserted as a “building block” into any direct or inverse detecting H,C correlation pulse sequence if proton spin–spin relaxation is to be investigated. In this contribution, the building block is inserted into a HETCOR as well as into a HMQC pulse sequence. Experimental results for the HETCOR-based sequence are given.     

Solid-state NMR spectroscopy using the lost I spin magnetization in polarization transfer experiments

A variation of the cross polarization (CP) experiment is discussed. The method requires two scans where the difference signal is equivalent to the I spin magnetization that is transferred to the S spins. The acquired signal is equivalent to F1 sum projection of a two-dimensional (2D) heteronuclear correlation experiment and is obtained by just two scans without the need to increment the indirect time domain t(1). Any polarization transfer method and any kind of spin manipulations during the t(1) incrementation period of a 2D NMR experiment can be applied. The method allows fast measurements of the CP transfer, particularly if various S spins signal overlap and is good for spectral editing of I spin signals with contact to S spins. Various examples for biomaterials are presented. Most importantly, this novel approach is ideal for detailed investigations of organic-mineral interfaces in bone, here demonstrated for O-phospho-l-serine as simple model compound.     

Current driven magnetization dynamics in helical spin density waves

A mechanism is proposed for manipulating the magnetic state of a helical spin density wave using a current. It is shown that a current through a bulk metal with a helical spin density wave induces a spin transfer torque, which gives rise to a rotation of the order parameter. The use of spin transfer torque to manipulate the magnetization in bulk systems does not suffer from the obstacles seen for magnetization reversal using interface spin transfer torque in multilayered systems. The effect is demonstrated by a quantitative calculation of the current induced magnetization dynamics of a rare earth metal, Er. Finally, we propose a setup for experimental verification.