Lifetimes of the singlet-states under coherent off-resonance irradiation in NMR spectroscopy

Singlet-states |S=(|alphabeta> - |betaalpha>)/sq.rt.2 can be excited in pairs of coupled spins I and S, first by preparing either a non-vanishing zero-quantum coherence I(+)S(-) or a state of longitudinal two-spin order I(z)S(z) and then by applying a coherent radio-frequency (RF) irradiation with a carrier frequency omega(rf) = (Omega(I) + Omega(S))/2 that lies half-way between the chemical shifts of the two spins involved. The life-times T(S) can be much longer than the spin-lattice relaxation time T(1) of longitudinal magnetization, but singlet-states are ultimately relaxed, not only by dipolar interactions between the active spins or with the external spins, but also as a result of a non-vanishing offset Deltaomega = omega(rf) - (Omega(I) + Omega(S))/2 or an insufficient amplitude of the RF irradiation that fails to fulfill the condition omega(1) > DeltaOmega = (Omega(I) - Omega(S)). In this work, the effect of off-resonance irradiation is explored and an approximate formula for the effective relaxation rate of the singlet population is provided on the basis of perturbation theory. The qualitative features of the dependence of the relaxation rate of the singlet population on the offset Deltaomega and on the difference DeltaOmega of the chemical shifts of the two spins are illustrated by comparison with numerical simulations.     

Magnetization transfer using inversion recovery during off-resonance irradiation

Estimation of magnetization transfer (MT) parameters in vivo can be compromised by an inability to drive the magnetization to a steady state using allowable levels of radiofrequency (RF) irradiation, due to safety concerns (tissue heating and specific absorption rate (SAR)). Rather than increasing the RF duration or amplitude, here we propose to circumvent the SAR limitation by sampling the formation of the steady state in separate measurements made with the magnetization initially along the -z and +z axis of the laboratory frame, i.e. with or without an on-resonance inversion pulse prior to the off-resonance irradiation. Results from human brain imaging demonstrate that this choice provides a tremendous benefit in the fitting procedure used to estimate MT parameters. The resulting parametric maps are characterized by notably increased tissue specificity as compared to those obtained with the standard MT acquisition in which magnetization is initially along the +z axis only.     

Sandwich-ELISE NMR: reducing the sample volume of NMR samples

We present Sandwich-ELISE, a concatenated version of our previously proposed Experimental LIquid SEaling (ELISE) protocol, in which an aqueous sample is effectively sealed by the addition of a small layer of mineral oil, or, alternatively, a chloroform sample was sealed by a water layer. With Sandwich-ELISE, a triple layered geometry composed of deuterated chloroform/aqueous buffer/mineral oil can be used to limit the sample to the active coil volume, effectively replacing the popular Shigemi tubes. Importantly, this procedure is readily applicable to smaller diameter tubes, for which no Shigemi tubes are available. We further present spectra of a 1 microl protein sample sandwiched between the chloroform and Nujol phases in a 1mm tube, demonstrating thereby that the volume of the aqueous phase of interest can be reduced even further.     

Simulation for internal energy deposition in sustained off-resonance irradiation collisional activation using a monte carlo method

This paper proposes a novel computational approach employing a Monte Carlo method, aimed at an improved understanding of the dynamics and energetics of activated ions in sustained off-resonance irradiation collisionally activated dissociation (SORI-CAD) experimental events of Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). In SORI-CAD events, internal energies of activated ions are complicatedly associated with their motion undergoing off-resonance excitation (i.e. alternate accelerations and decelerations) and inherently stochastic ion-neutral collisions. Several types of pseudo-random generators were adapted to probability density functions (PDFs) which characterize the ion-neutral collision process. Simulated ion trajectories involve the realistic feature of pressurized SORI-CAD events, such as a collisional damping and those which have not been illustrated in conventional analytical approaches. The proposed method can simulate the time-varying translational and internal energies of activated ions. The present result suggests that the internal energy of a SORI-activated ion should be inversely proportional to the cube of the SORI excitation frequency offset. Copyright 1999 John Wiley & Sons, Ltd.     

A Al MAS, MQMAS and off-resonance nutation NMR study of aluminium containing silica-based sol-gel materials

Aluminium containing hybrid materials were prepared via the sol-gel method using aluminium sec-butoxide complexed with ethylacetoacetate (Al(OBu^s)₂EAA or Al(OBu^s)₃/EAA mixtures). As silanes, phenyltrimethoxysilane (PhTMS) or phenyltriethoxysilane (PhTES), 3-glycidoxypropyl trimethoxysilane (Glymo) and tetraethylorthosilicate (TEOS) were used. After room temperature drying of the samples the ²⁷Al single pulse excitation (SPE) magic angle spinning (MAS) NMR shows that octahedral (5 ppm) and tetrahedral (55 ppm) coordinated aluminium species are present in the materials. The relative amount of these two species depends on the preparation method. However, the Al(IV)/Al(VI) ratio is lower than 3 (typically 2.3) in all materials, indicating the presence of a small amount of an aluminate phase. Annealing of the samples at 100, 150 and 200 °C results in the formation of an extra signal at 30 ppm (peak maximum measured at 11.7 T). Based on the resonance frequency this signal is generally assigned to a pentahedrally coordinated aluminium species. Hydration/dehydration processes of annealed samples were studied with ²⁷Al SPE MAS NMR, multiple-quantum MAS NMR (MQMAS) and off-resonance nutation NMR. Upon hydration of the annealed sample the signal intensity around 30 ppm decreases in intensity and at the same time the intensity of the signal around 55 ppm increases by the same amount (tetrahedrally coordinated aluminium). The MQMAS spectra reveal that the signal around 30 ppm is not caused by a fivefold-coordinated aluminium species but mainly by tetrahedrally coordinated aluminium species in a distorted environment, experiencing large quadrupole induced shifts and small chemical shifts due to conformational changes in the polymeric network. From the MQMAS NMR spectra it can be concluded that the linebroadening observed in the ²⁷A1 MAS NMR spectra is due to both a distribution in isotropic chemical shifts and a distribution in quadrupole coupling constants (C_qcc = e²qQ/h). Hydration of the sample results in a decrease of the average C_qcc for the tetrahedrally coordinated aluminium from 6 to 4 MHz, whereas the average C_qcc of the octahedrally coordinated aluminium is hardly influenced (4 MHz). These MQMAS results are confirmed by off-resonance nutation experiments.     

Practical methods for biological NMR sample handling

The ability of NMR parameters T₁ and T₂ to be used to distinguish one tissue from another and diseased from normal tissues has wide application in diagnostic medicine. Measurement of such values in vitro on excised tissues and fluids was the basis for fundamental discoveries which provided the impetus for the development of in vivo clinical whole body NMR imagers. Therefore, as in vivo imaging grows, the need for screening and testing of new ideas in vitro will grow. The success of data collection in vitro depends greatly on the care and understanding with which biological samples are processed. This paper summarizes proven methods for handling of soft and firm biopsy material, blood components, body fluids, and culture cells. The effects of temperature variation and storage parameters are discussed for animal and human samples. The paper is a practical guide to the hows and whys of biological sample handling for NMR.     

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.     

A sample of active galactic nuclei with strong soft X-ray variabilities

Large-amplitude X-ray variation is a special feature of AGN,reflecting possible extreme change in the central engine or the absorption along the line of sight.Till now there are only a few relevant studies on individual sources or rather small samples.In this work we aim to perform a systematic study of AGNs with strong soft X-ray variations at timescale of 10 years.To build the sample,we compare the soft X-ray fluxes of AGNs measured in ROSAT All-Sky Survey(RASS)during 1990–1991 with those measured by XMM-Newton during 2000–2009.This investigation bings forth to a sample of 13 AGNs,which appeared bright in RASS era,and went into low states(flux dropped by a factor of 10)when they were caught by XMM-Newton.Most of the 13sources are type I Seyfert galaxies.5 of them are noticed to have strong X-ray variation for the first time.We study the nature of their variations through performing XMM-Newton spectral analyses and by collecting reports from the existing literature.We find the sample could be divided into three categories according to the possible causes of the strong X-ray variations.The variations in MRK 0478 and 1H 0419-557 are consistent with strong light-bending effect,i.e.,the observed X-ray flux drops significantly as the X-ray emitting corona gets much closer to the central black hole.The variations in ESO 140-G043 and NGC 7158 are caused by absorption changes along the line of sight.For one special case MRK 0335,the variation can be explained by either light-bending or absorption variation.In the rest 8 sources(～60%),the strong soft X-ray variations are likely to exist due to intrinsic changes in the activities of the corona,although in some of them without high quality X-ray spectra we are unable to rule out alternative models.This sample provides good targets for future monitoring campaigns with more extensive studies.     

Heteronuclear spin decoupling in solid-state NMR under magic-angle sample spinning

Achieving high spectral resolution is an important prerequisite for the application of solid-state NMR to biological molecules. Higher spectral resolution allows to resolve a larger number of resonances and leads to higher sensitivity. Among other things, heteronuclear spin decoupling is one of the important factors which determine the resolution of a spectrum. The process of heteronuclear spin decoupling under magic-angle sample spinning is analyzed in detail. Continuous-wave RF irradiation leads only in a zeroth-order approximation to a full decoupling of heteronuclear spin systems in solids under magic-angle spinning (MAS). In a higher-order approximation, a cross-term between the dipolar-coupling tensor and the chemical-shielding tensor is reintroduced, providing a scaled coupling term between the heteronuclear spins. In strongly coupled spin systems this second-order recoupling term is partially averaged out by the proton spin-diffusion process, which leads to exchange-type narrowing of the line by proton spin flips. This process can be described by a spin-diffusion type superoperator, allowing the efficient simulation of strongly coupled spin systems under heteronuclear spin decoupling. Low-power continuous-wave decoupling at fast MAS frequencies offers an alternative to high-power irradiation by reversing the order of the averaging processes. At fast MAS frequencies low-power continuous-wave decoupling leads to significantly narrower lines than high-power continuous-wave decoupling while at the same time reducing the power dissipated in the sample by several orders of magnitude. The best decoupling is achieved by multiple-pulse sequences at high RF fields and under fast MAS. Two such sequences, two-pulse phase-modulated decoupling (TPPM) and X-inverse-X decoupling (XiX), are discussed and their properties analyzed and compared.     

Resonator with reduced sample heating and increased homogeneity for solid-state NMR

In the application of solid-state NMR to many systems, the presence of radiofrequency (rf) electric fields inside classical solenoidal coils causes heating of lossy samples. In particular, this is critical for proteins in ionic buffers. Rf sample heating increases proportional to frequency which may result in the need to reduce the rf pulse power to prevent partial or total sample deterioration. In the present paper, we propose a multifrequency-tunable NMR resonator where the sample is electrically shielded from the NMR coil by a conductive sheet that increases the magneto-electric ratio. Expressions for the B1 efficiency as function of magnetic and electric filling factors are derived that allow a direct comparison of different resonators. Rf efficiency, homogeneity, signal-to-noise, and rf sample heating are compared. NMR spectra at 700MHz on ethylene glycol, glycine, and a model protein were acquired to compare the resonators under realistic experimental conditions.