A method for imaging of chemical shift or magnetic field distributions

A phase encoding method for imaging of chemical shift or magnetic field distributions is described. The method utilizes the spin-echo principle and the time period between signal collection and excitation is constant but the time period between excitation and the 180 degrees pulse is varied by constant steps. The method is relatively easy to apply with the Fourier or projection reconstruction methods.     

Band-Selective HSQC and HMBC Experiments Using Excitation Sculpting and PFGSE

Variants of the HSQC and HMBC experiments are described. They allow the restriction of the heteronuclear chemical shift domain without causing spectral folding. Selectivity is introduced in the HSQC experiment by means of excitation sculpting. The selective element of the pulse sequence is a double pulsed field gradient spin echo. It may be used either split by the t(1) evolution period, or not. The selectivity profile depends on the scheme used as well as on the number of protons attached to the heteronucleus. The selective HMBC experiment requires only a single echo sequence as no strict control of the signal phase is required. A complex glycoconjugate is used as a test compound for the new pulse sequences.     

Pure-phase selective excitation in fast-relaxing systems

Selective pulses have been used frequently for small molecules. However, their application to proteins and other macromolecules has been limited. The long duration of shaped-selective pulses and the short T(2) relaxation times in proteins often prohibited the use of highly selective pulses especially on larger biomolecules. A very selective excitation can be obtained within a short time by using the selective excitation sequence presented in this paper. Instead of using a shaped low-intensity radiofrequency pulse, a cluster of hard 90 degrees pulses, delays of free precession, and pulsed field gradients can be used to selectively excite a narrow chemical shift range within a relatively short time. Thereby, off-resonance magnetization, which is allowed to evolve freely during the free precession intervals, is destroyed by the gradient pulses. Off-resonance excitation artifacts can be removed by random variation of the interpulse delays. This leads to an excitation profile with selectivity as well as phase and relaxation behavior superior to that of commonly used shaped-selective pulses. Since the evolution of scalar coupling is inherently suppressed during the double-selective excitation of two different scalar-coupled nuclei, the presented pulse cluster is especially suited for simultaneous highly selective excitation of N-H and C-H fragments. Experimental examples are demonstrated on hen egg white lysozyme (14 kD) and the bacterial antidote ParD (19 kD).     

Velocity selective radiofrequency pulse trains

The incorporation of velocity-encoding gradient pulses in RF-pulse trains is proposed and examined. Velocity selective perturbation is shown to be analogous in many respects to the well established use of trains of short RF-pulses for chemical shift selective perturbation. Velocity selective perturbation is viable in a biomedical setting only if additional RF refocusing pulses are inserted between the individual RF-pulse elements. Aspects of velocity selective excitation saturation and inversion are examined, and new inversion pulse trains proposed. The selective perturbation of both flowing and stationary spins is demonstrated in phantoms and possible biomedical applications of these pulse trains are discussed.     

Simultaneous acquisition of phosphocreatine and inorganic phosphate images for Pi:PCr ratio mapping using a RARE sequence with chemically selective interleaving

The ratio of inorganic phosphate to phosphocreatine (Pi:PCr) is a validated marker of mitochondrial function in human muscle. The magnetic resonance imaging rapid acquisition with relaxation enhancement (RARE) pulse sequence can acquire phosphorus-31 (³¹P) images with higher spatial and temporal resolution than traditional spectroscopic methods, which can then be used to create Pi:PCr ratio maps of muscle regions. While the ³¹P RARE method produces images that reflect the content of the ³¹P metabolites, it has been limited to producing an image of only one chemical shift in a scan. This increases the scan time required to acquire images of multiple chemical shifts as well as the likelihood of generating inaccurate Pi:PCr maps due to gross motion. This work is a preliminary study to demonstrate the feasibility of acquiring Pi and PCr images in a single scan by interleaving Pi and PCr chemical shift acquisitions using a chemically selective radiofrequency excitation pulse. The chemical selectivity of the excitation pulse evaluated and the Pi:PCr maps generated using the interleaved Pi and PCr acquisition method with the subject at rest and during exercise are compared to those generated using separate Pi and PCr acquisition scans. A paired t test indicated that the resulting Pi:PCr ratios for the exercised forearm muscle regions were not significantly different between the separate Pi and PCr acquisition method (3.18±1.53) (mean±standard deviation) and the interleaved acquisition method (3.41±1.66). This work demonstrates the feasibility of creating Pi:PCr ratio maps in human muscle with Pi and PCr images acquired simultaneously by interleaving between the Pi and PCr resonances in a single scan.     

The chemical shift interaction under weak radio frequency pulses

The chemical shift anisotropy of a nuclear spin system in a strong magnetic field can be comparable to the strength of the rf pulse (weak pulse condition). In this case, the commonly used assumption that the chemical shift interaction Hamiltonian in the duration of a rf pulse can be neglected is no longer effective. The rf response characteristics of a spin-1/2 system under a weak pulse condition is studied in detail. The relationships between the distortion of the chemical shift powder spectrum and the relative rf field amplitude under various conditions are given. The suppression of sidebands of a MAS spectrum is analysed as an example of solid multiple pulse experiments. The experimental results are in good agreement with computer simulations.     

Numerical simulation of PRESS localized MR spectroscopy

Numerical simulations of NMR spectra can provide a rapid and convenient method for optimizing acquisition sequence parameters and generating prior spectral information required for parametric spectral analysis. For spatially resolved spectroscopy, spatially dependent variables affect the resultant spectral amplitudes and phases, which must therefore be taken into account in any spectral simulation model. In this study, methods for numerical simulation of spectra obtained using the PRESS localization pulse sequence are examined. A comparison is made between three different simulation models that include different levels of detail regarding the spatial distributions of the excitation functions, and spin evolution during application of the pulses. These methods were evaluated for measurement of spectra from J-coupled spin systems that are of interest for in vivo proton spectroscopy and results compared with experimental data. It is demonstrated that for optimized refocusing pulses it is sufficient to account for chemical shift effects only, although there is some advantage to implementing a more general numerical simulation approach that includes information on RF pulse excitation profiles, which provides sufficient accuracy while maintaining moderate computational requirements and flexibility to handle different spin systems.     

Optical selectivity in optically dense media driven by optimized Gaussian-type ultrashort pulse pairs

We theoretically demonstrate that selective resonant excitation can be achieved in a dense collection of V-type three-level atoms by optimizing the pulse delay and peak intensity ratio of an applied phase-tailored ultrashort pulse pair. Near-dipole-dipole interaction plays an important role in the quantum control of selective excitations since it brings about an intrinsic frequency shift in the atomic resonance, which builds up various excitation pathways. As a consequence, we can control the quantum interference between various pathways by shaping the excitation pulse pair to steer the atomic excitation selectively toward a desired quantum state.     

A Streak Camera System for Time Resolved Fluorimetry

Presently, there are several techniques for measurement of fluorescence lifetimes of organic molecules. These techniques, reviewed by Ware,¹ can be divided into two basic groups, those based upon pulsed sources and those based on modulated sources and phase shift measurement. In the pulsed methods, repetitive, short pulse width, intense excitation pulses excite the fluorophor and the fluorescence decay is measured; the source temporal response must be deconvoluced from the fluorescence decay in order to evaluate the fluorescence signal and lifetime. Typical sources of excitation include nanosecond flashlamps and more recently nanosecond N₂-laser (with or without a dye laser) and mode-locked lasers with picosecond pulse widths^2-6. The modulated source phase shift methods,¹ involve sinusoidal excitation of the fluorophor and measurement of the phase shift between the modulated excitation source and the modulated flourescence. Because modulation frequencies are limited to approximately 20 MHz, fluorescence lifetimes are limited to ～.1 ns and above. In addition, in the phase shift methods, only “one point” lifetimes are obtained, i.e., the entire fluorescence decay curve is not obtained.     

采用532nm锁模激光研究量子阱中的带填充效应

采用532nm锁模脉冲激光和时间分辨测量系统测量了InGaAs/GaAa单量子阱在77K时,不同激发功率下的时间分辨光致发光谱.结果表明,在低激发功率时,阱中的发光峰的位置随时间变化不大.而在175mW激发时,发光峰在刚激发时就向短波移动10meV以上,然后随时间向长波移动.结果明确显示了存在于阱中的带填充效应.     

Raman gap solitons

We show that an intense pump pulse, detuned far from the Bragg resonance of a nonlinear periodic structure, can excite a gap soliton at a wavelength within the band gap that corresponds to the Raman shift of the medium. This Raman gap soliton is a stable, long-lived, quasistationary excitation that exists within the grating even after the pump pulse has passed. We find both stationary solitons as well as slow Raman gap solitons with velocities as low as 1% of the speed of light. The predicted phenomena should be observable in fiber Bragg gratings and other nonlinear photonic band gap structures.     

Selective averaging for high-resolution solid-state NMR spectroscopy of aligned samples

Solid-state NMR experiments benefit from being performed at high fields, and this is essential in order to obtain spectra with the resolution and sensitivity required for applications to protein structure determination in aligned samples. Since the amount of rf power that can be applied is limited, especially for aqueous protein samples, the most important pulse sequences suffer from bandwidth limitations resulting from the same spread in chemical shift frequencies that aids resolution. SAMPI4 is a pulse sequence that addresses these limitations. It yields separated local field spectra with narrower and more uniform linewidths over the entire spectrum than the currently used PISEMA and SAMMY experiments. In addition, it is much easier to set up on commercial spectrometers and can be incorporated as a building block into other multidimensional pulse sequences. This is illustrated with a two-dimensional HETCOR experiment, where it is crucial to transfer polarization from the amide protons to their directly bonded nitrogens over a wide range of chemical shift frequencies. A quantum-mechanical treatment of the spin Hamiltonians under high-power rf pulses is presented which gives the scaling factor for SAMPI4 as well as the durations of the rf pulses to achieve optimal decoupling.     

Carrier recombination kinetics in (3 1 1)A InGaAs sidewall quantum wires

We present a study of the optical properties and carrier dynamics in strained InGaAs sidewall quantum wires (QWR) on patterned GaAs (3 1 1)A substrates by means of picosecond time-resolved photoluminescence (PL). A pronounced dynamical red shift of the QWR-PL band when increasing the delay time after the pulse excitation is observed. In addition, time-resolved data show a significant shortening of the PL decay time from the wire at short delay and when high excitation power is used. The data are compared with theoretical predictions. The results, i.e. the dynamical red shift observed in the wire emission and the shortening of the PL decay with increasing the excitation density, are interpreted in terms of a dynamical screening effect of the piezoelectric field.     

In phase selective excitation of overlapping multiplets by gradient-enhanced chemical shift selective filters

We have developed gradient-enhanced chemical shift selective filters (ge-CSSF) for inphase excitation of overlapping multiplets 1H. This method relies on the constructive addition of on resonance signal while off resonance magnetization is eliminated by destructive interference due to variable chemical shift evolution. This is achieved by co-addition of several FIDs acquired with a gradually incremented chemical shift evolution period. Two variable-time and one constant-time ge-CSSFs are proposed that can be combined with TOCSY, NOESY, and ROESY mixing schemes yielding highly selective 1D experiments. Analytical and numerical expressions are derived to calculate the excitation profiles of the ge-CSSFs and to examine the effects of spin-spin relaxation, the length of the CSSF increment, and selective inversion pulses. We demonstrate, both theoretically and experimentally, that CSSFs yield fast signal separation for compounds with a range of spin-spin relaxation times and chemical shift differences as small as 1-2 Hz. The use of pulsed field gradients ensures that very clean spectra are obtained. The main application of these techniques lies in analysis of mixtures where severe spectral overlap prevents the use of simple 1D selective methods.     

Criteria to average out the chemical shift anisotropy in solid-state NMR when irradiated with BABA I,BABA II,and C7 radiofrequency pulse sequences

Floquet–Magnus expansion is used to study the effect of chemical shift anisotropy in solid-state NMR of rotating solids. The chemical shift interaction is irradiated with two types of radiofrequency pulse sequences: BABA and C7. The criteria for the chemical shift anisotropy to be averaged out in each rotor period are obtained.     

A chemical-shift-insensitive slice-selective RF pulse (CHISS)

In NMR imaging and in vivo spectroscopy, slice selection is usually achieved by applying a frequency-selective RF pulse in the presence of a magnetic field gradient. A serious limitation of this method of slice selection is that, in a system with many different chemical shifts, the selected slice is offset in space for each chemically shifted resonance. In the present study, a composite RF pulse that is insensitive to chemical-shift differences has been developed. The pulse involves applying a RF pulse of desired shape in the presence of an alternating magnetic field gradient, together with hard 180° pulses at each gradient transition. Calculations are presented to show that excitation with the proposed pulse averages the chemical-shift term to zero. An exact calculation for a rectangular RF excitation shape verifies this. Experiments based on observing the RF excitation profiles have been performed to demonstrate the validity of the proposed pulse.     

New methods for the acquisition of ultra-wideline solid-state NMR spectra of spin-1/2 nuclides

The Wideband Uniform Rate Smooth Truncation - Carr-Purcell Meiboom-Gill (WURST-CPMG) pulse sequence was recently introduced as a new method of acquiring ultra-wideline solid-state NMR (SSNMR) patterns of quadrupolar nuclei (Chem. Phys. Lett. 464 (2008) 97). Herein, we describe the application of the WURST-CPMG pulse sequence to stationary samples (i.e., non-spinning or "static" samples) of various spin-1/2 nuclides ((119)Sn, (207)Pb, (199)Hg and (195)Pt) in order to examine its effectiveness for acquiring ultra-wideline SSNMR patterns. WURST-CPMG is compared to the CPMG and Cross Polarization (CP)-CPMG pulse sequences in select cases ((119)Sn and (207)Pb, respectively), and its usefulness in obtaining ultra-wideline SSNMR spectra in a piecewise fashion is explored. In addition, a preliminary investigation of pulses generated using optimal control theory (OCT) for the purpose of wideline excitation is presented; spectra acquired using these pulses are compared with standard, rectangular pulses of similar pulse powers. Both methods show much promise for acquiring high quality wideline patterns dominated by chemical shift anisotropy, with minimal distortions and significantly reduced experimental times.     

Selective excitation in Fourier transform nuclear magnetic resonance. 1978

The applications of frequency-selective excitation methods in Fourier transform NMR are discussed, and a simple technique is described for selective excitation of a narrow frequency region of a high-resolution NMR spectrum in a Fourier transform spectrometer. A regular sequence of identical radiofrequency pulses of small flip angle exerts a strong cumulative effect on magnetizations close to resonance with the transmitter frequency or one of a set of equally spaced sidebands separated by the pulse repetition rate. All other magnetizations precess through an incomplete number of full rotations between pulses, and are caught by successive pulses at an ever changing phase of their precession, which destroys the cumulative effect. The motion of the various nuclear magnetization vectors may be described pictorially according to the Bloch equations, neglecting relaxation during the pulse sequence. A general theory is presented for selective or “tailored” excitation by an arbitrary modulation of the radiofrequency transmitter signal. It confirms earlier conclusions that the frequency-domain excitation spectrum corresponds to the Fourier transform of the transmitter modulation pattern, provided that the NMR response remains linear. The excitation spectra calculated for the selective pulse sequence by these two alternative approaches show good agreement within their respective limitations. A number of practical applications of selective excitation are explored, including solvent peak suppression, the detection of partial spectra from individual chemical sites, selective studies of relaxation and slow chemical exchange, and holeburning or localized saturation.     

Toroid cavity detectors for high-resolution NMR spectroscopy and rotating frame imaging: capabilities and limitations

The capabilities of toroid cavity detectors for simultaneous rotating frame imaging and NMR spectroscopy have been investigated by means of experiments and computer simulations. The following problems are described: (a) magnetic field inhomogeneity and subsequent loss of chemical shift resolution resulting from bulk magnetic susceptibility effects, (b) image distortions resulting from off-resonance excitation and saturation effects, and (c) distortion of lineshapes and images resulting from radiation damping. Also, special features of signal analysis including truncation effects and the propagation of noise are discussed. B(0) inhomogeneity resulting from susceptibility mismatch is a serious problem for applications requiring high spectral resolution. Image distortions resulting from off-resonance excitation are not serious within the rather narrow spectral range permitted by the RF pulse lengths required to read out the image. Incomplete relaxation effects are easily recognized and can be avoided. Also, radiation damping produces unexpectedly small effects because of self-cancellation of magnetization and short free induction decay times. The results are encouraging, but with present designs only modest spectral resolution can be achieved.     

Artifacts in chemical shift selective imaging.

The role of susceptibility effects in the production of artifacts in chemical shift images generated by the selective excitation technique is discussed. The effects are demonstrated in images of phantom samples of agarose gels containing small air bubbles. The artifacts can lead to erroneous interpretations, in which the resonances to be resolved exhibit a relatively small chemical shift separation, such as that between water and soluble carbohydrates (sugars).