H Spectroscopy without Solvent Suppression: Characterization of Signal Modulations at Short Echo Times

While most proton (¹H) spectra acquired in vivo utilize selective suppression of the solvent signal for more sensitive detection of signals from the dilute metabolites, recent reports have demonstrated the feasibility and advantages of collecting in vivo data without solvent attenuation. When these acquisitions are performed at short echo times, the presence of frequency modulations of the water resonance may become an obstacle to the identification and quantitation of metabolite resonances. The present report addresses the characteristics, origin, and elimination of these sidebands. Sideband amplitudes were measured as a function of delay time between gradient pulse and data collection, as a function of gradient pulse amplitude, and as a function of spatial location of the sample for each of the three orthogonal gradient sets. Acoustic acquisitions were performed to demonstrate the correlation between mechanical vibration resonances and the frequencies of MR sidebands. A mathematical framework is developed and compared with the experimental results. This derivation is based on the theory that these frequency modulations are induced by magnetic field fluctuations generated by the transient oscillations of gradient coils.     

Localized proton spectroscopy without water suppression: removal of gradient induced frequency modulations by modulus signal selection

Most Magnetic Resonance Spectroscopy (MRS) localization methods can generate gradient vibrations at acoustic frequencies and/or magnetic field oscillation, which can cause a time-varying magnetic field superimposed onto the static one. This effect can produce frequency modulations of the spectral resonances. When localized MRS data are acquired without water suppression, the associated frequency modulations are manifested as a manifold of spurious peaks, called sidebands, which occur symmetrically around the water resonance. These sidebands can be larger than the small metabolite resonances and can present a problem for the quantitation of the spectra, especially at short echo times. Furthermore, the resonance lineshapes may be distorted if any low frequency modulations are present. A simple solution is presented which consists of selecting the modulus of the acquired Free Induction Decay (FID) signal. Since the frequency modulations affect only the phase of the FID signal, the obtained real spectrum of the modulus is free from the spurious peaks where quantitative results may be directly obtained. Using this method, the distortions caused by the sidebands are removed. This is demonstrated by processing proton MRS spectra acquired without water suppression collected from a phantom containing metabolites at concentrations comparable to those in human brain and from a human subject using two different localization methods (PRESS and Chemical Shift Imaging PRESS-(CSI)). The results obtained illustrate the ability of this approach to remove the spurious peaks. The corrected spectra can then be fit accurately. This is confirmed by the results obtained from both the relative and the absolute metabolites concentrations in phantoms and in vivo.     

Coherent population trapping spectra in presence of ac magnetic fields

Experimental and theoretical investigations are reported on the effects induced by an alternating magnetic field on coherent population trapping resonances. We show that the ac magnetic field produces sidebands of these resonances in such a way that the spectrum observed is similar to those observed via the FM spectroscopic technique. Because of the very narrow linewidth of the resonances, sidebands are resolved even for ac field frequencies as low as a fraction of a kHz. The theoretical model developed, which takes into account a very simple atomic structure, fits the experimental data quite well.     

A two-dimensional experiment that separates decoupling sidebands from the main peaks.

Broadband decoupling techniques generate undesirable cycling sidebands. The new two-dimensional technique described here allows separation of these sidebands from the main peaks by spreading the sideband responses in the indirectly detected dimension (F(1)) according to their frequency separations from the parent peaks, leaving the main resonances at zero frequency in F(1). This trace at zero frequency shows a thousandfold suppression of the residual sidebands, making possible the detection of very weak signals from dilute constituents of the sample. The experimental results can be displayed as one-dimensional "quiet decoupling" spectra without any significant loss of sensitivity. The new technique (DESIRE-decoupling sideband resolved spectroscopy) is simple, robust, and straightforward to implement.     

Adiabatic decoupling sidebands

An analytical solution is given for amplitudes and phases of adiabatic decoupling sidebands as a function of spin inversion time tau. Since all the adiabatic decoupling phases theta(t, tau) refocus at two periods (2T) of the decoupling pulse, the sidebands are located at n/2T rather than at n/T as observed in other decoupling schemes. The real (R(n)(tau)) and imaginary (I(n)(tau)) amplitudes of the sidebands have symmetry R(n)(tau) = R(-n)(tau) and I(n)(tau) = -I(-n)(tau), forming a mirror image between the counterparts of the sidebands. When frequency sweep changes direction all I(n)(tau) are inverted while all R(n)(tau) remain unchanged, leading to pure absorption sidebands with two accumulations as demonstrated by Kupce and Freeman, and to an exchange of sidebands between counterparts. The sum of the real parts for sidebands n = 1 and 2 is almost a constant near on-resonance decoupling, and it increases substantially for large decoupling offsets. The phase defocusing can be minimized for all decoupling offsets by inserting an initial decoupling period with T(ini) = T/2, eliminating all sidebands located at n/2T (n = +/-1, +/-3, +/-5, ...).     

Spectral fine-structures of low-frequency modulated distortion product otoacoustic emissions

Biasing of the cochlear partition with a low-frequency tone can produce an amplitude modulation of distortion product otoacoustic emissions (DPOAEs) in gerbils. In the time domain, odd- versus even-order DPOAEs demonstrated different modulation patterns depending on the bias tone phase. In the frequency domain, multiple sidebands are presented on either side of each DPOAE component. These sidebands were located at harmonic multiples of the biasing frequency from the DPOAE component. For odd-order DPOAEs, sidebands at the even-multiples of the biasing frequency were enhanced, while for even-order DPOAEs, the sidebands at the odd-multiples were elevated. When a modulation in DPOAE magnitude was presented, the magnitudes of the sidebands were enhanced and even greater than the DPOAEs. The amplitudes of these sidebands varied with the levels of the bias tone and two primary tones. The results indicate that the maximal amplitude modulations of DPOAEs occur at a confined bias and primary level space. This can provide a guide for optimal selections of signal conditions for better recordings of low-frequency modulated DPOAEs in future research and applications. Spectral fine-structure and its unique relation to the DPOAE modulation pattern may be useful for direct acquisition of cochlear transducer nonlinearity from a simple spectral analysis.     

Two-dimensional one pulse MAS of half-integer quadrupolar nuclei

We show that the two-dimensional one pulse (TOP) representation of magic-angle spinning nuclear magnetic resonance data of half-integer quadrupolar nuclei has significant advantages over the conventional one-dimensional spectrum. The TOP spectrum, which correlates NMR frequency to spinning sideband order, provides a rapid determination of the number of sites as well as the size of the their quadrupolar coupling. Additionally, synchronous acquisition spectra of the central and satellite transition resonances can be separated by different projections of the TOP spectrum, with higher resolution spectra often found in the satellite transitions projection. A previously perceived problem of centerband aliasing in TOP can be eliminated with an algorithm that uses larger subspectral widths and the sideband order dimension to distinguish centerbands from sidebands.     

An analysis of the intrinsic resonance offset dependence of magnetization generated by stimulated echo pulse sequences for noncoupled spins.

It is demonstrated that the basic radiofrequency pulse train used to generate stimulated echoes (90x-tau TE-90x-tau TM-90x-tau TE-Acq.) is in general characterized by strong amplitude and phase modulations of the transverse magnetization as a function of the resonance offset. Two dephasing techniques which eliminate the modulations are investigated both theoretically and experimentally, and a simple formula is derived for calculating the relative modulation across a spectrum as a function of gradient strength and duration, echo delay, and spectral linewidth.     

Nonlinear spectroscopy with a vertical-cavity surface-emitting laser (VCSEL)

We have evaluated the suitability of a vertical-cavity surface-emitting laser diode (VCSEL) for spectroscopic applications. Despite its low output power it is possible to observe narrow resonances in a saturated absorption spectroscopy experiment on the cesium D ₂ transition at 852 nm, limited in width by the laser linewidth of several tens of MHz. High modulation efficiency of the VCSEL allows us to create modulation sidebands at 9.2 GHz frequency via direct modulation of the laser injection current. Using the carrier and either one of the sidebands coherent population trapping (CPT) resonances in a buffered cesium vapor can be prepared with linewidths below 130 Hz. With this very compact setup we have studied the dependence of CPT resonance position and linewidth as a function of optical detuning and find evidence of the influence of the excited state hyperfine structure. Received: 30 April 1999 / Revised version: 25 June 1999 / Published online: 30 November 1999     

A dynamic model to predict modulation sidebands of a planetary gear set having manufacturing errors

In this study, a nonlinear time-varying dynamic model is proposed to predict modulation sidebands of planetary gear sets. This discrete dynamic model includes periodically time-varying gear mesh stiffnesses and the nonlinearities associated with tooth separations. The model uses forms of gear mesh interface excitations that are amplitude and frequency modulated due to a class of gear manufacturing errors to predict dynamic forces at all sun-planet and ring-planet gear meshes. The predicted gear mesh force spectra are shown to exhibit well-defined modulation sidebands at frequencies associated with the rotational speeds of gears relative to the planet carrier. This model is further combined with a previously developed model that accounts for amplitude modulations due to rotation of the carrier to predict acceleration spectra at a fixed position in the planetary transmission housing. Individual contributions of each gear error in the form of amplitude and frequency modulations are illustrated through an example analysis. Comparisons are made to measured spectra to demonstrate the capability of the model in predicting the sidebands of a planetary gear set with gear manufacturing errors and a rotating carrier.     

基于氧化镁晶体中级联四波混频过程的紫外飞秒光脉冲产生

紫外波段飞秒激光脉冲是研究超快化学和超快物理相关过程的重要工具,实现波长可调谐的宽带紫外飞秒光脉冲将有助于推动超快动力学及相关领域的研究.本文报道了以两束400 nm的飞秒光脉冲作为级联四波混频的抽运源,在氧化镁晶体中产生9阶频率上转换和5阶频率下转换边带信号的实验结果.边带波长范围从350 nm到450 nm连续可调谐,这些边带信号的发散角和波长与级联四波混频理论预测结果吻合.紫外边带相对于入射光的整体转化效率约为1.2%.同时,高阶边带的光谱形状呈现高斯型,其谱宽理论上支持傅里叶转换极限脉宽为20—50 fs.本文展示了一种高效产生波长可连续调谐的紫外飞秒光脉冲的便捷方法,为基于紫外超短脉冲的相关研究提供了有效工具.     

A Six-Pulse PASS MAS-NMR Technique Solved by a Phasor Method

The PASS MAS-NMR technique is capable of recovering full intensities of the central resonances of a spectrum by phase adjusting the spinning sidebands. This variant of the original PASS sequence by Dixon uses six π pulses instead of four. The addition of two π pulses provides more flexibility in choosing the spacing between pulses and therefore eliminates pulse overlap and receiver dead-time problems. The nonlinear, underdetermined PASS equations were solved using a graphical phasor method. All PASS sequences were successfully tested. A table of the six pulse delay times for different pitches is presented.     

Removal of sidebands in double-rotation NMR in real time

Double-rotation (DOR) is the only technique generally capable of yielding high-resolution NMR spectra of half-integer quadrupolar nuclei in one dimension for solids without the need for sophisticated coherence pathway selection. Unfortunately, due to the low outer rotor spinning frequencies currently available, the spectra often contain a large number of spinning sidebands which may overlap with the resonances of interest. We implement a simple, robust, and easy to use family of pulse sequences, which in practice are fully analogous to the 'total suppression of sidebands' (TOSS) sequences, to suppress all sidebands arising from the spinning of the outer rotor in DOR experiments. By removing the rotor phase dependence of the evolution of the sidebands, the sidebands destructively interfere with one another during the course of signal averaging to yield 'solution-like' spectra of half-integer quadrupolar nuclei in solids. Advantages and shortcomings of the method compared to other DOR sideband suppression methods are explored with the aid of simulations.     

Time-dependent electron transport in HgTe/CdTe quantum wells

Based on the Floquet theory and Keldysh's nonequilibrium Green's function methods, we study the electron transport through the HgTe/CdTe quantum wells (QWs) irradiated by a monochromatic laser field. We find that when the laser field is applied, the edge states are split into a series of sidebands. When the Fermi level lies among these sidebands, the quantized plateau of the conductance is destroyed. Instead, the conductance versus the radiation frequency exhibits the successive oscillation peaks corresponding to the resonant tunneling through the sidebands of the edge states. The resonant interaction between the quasiparticles and the radiation field opens the gaps in the crossing region of the sidebands, which can be tuned by the radiation strength and frequency. This leads to the shift of the oscillation peaks in the conductance. We also show that the amplitudes of the oscillation peaks in the conductance are governed by the radiation strength and frequency.     

Cross-phase-modulation-induced instabilities and frequency shifts in a photonic-crystal fiber

Copropagating fundamental-wavelength and second-harmonic femtosecond pulses of Cr: forsterite laser radiation are used to study cross-phase-modulation-induced instabilities and frequency shifts in a photonic-crystal fiber. Parametric instability of the second-harmonic probe pulse induced through cross-phase modulation by the fundamental-wavelength pump pulse gives rise to distinct sidebands in the spectrum of the probe field transmitted through the fiber. The wavelength of these sidebands was tuned in our experiments within approximately 100 nm by varying the peak power and the delay time of the pump pulse, suggesting a convenient way of controlled parametric spectral transformation of ultrashort laser pulses.This revised version was published online in March 2005. In the previous version, the published online date was missing     

Solvent-localized NMR spectroscopy using the distant dipolar field: a method for NMR separations with a single gradient

Solvent-localized NMR (SOLO) is a new method which allows the separation of NMR spectra of substances dissolved in different solvents. It uses the selective HOMOGENIZED pulse sequence to produce a two-dimensional NMR spectrum resulting from intermolecular zero-quantum coherences in one distinct solvent. The detected signal is locally refocused by the action of the distant dipolar field, which is created by a frequency selective pulse only in regions containing the selected solvent. The prerequisites are that the different solvents have sufficiently different chemical shifts to be excited separately and that compartments with different solvents are spatially separated by more than the typical diffusion distance. Here, the method is demonstrated for the solvents water and DMSO on a length scale of 0.5 mm. Because signal in the spectra is refocused locally, SOLO is insensitive to variations in the magnetic field which may result from inhomogeneities or structures in the sample. This makes applications in strongly structured samples possible. SOLO is the first method that achieves localization of NMR signal with a single gradient pulse. Therefore, it can be used in conventional NMR spectrometers with one-axis gradient systems and lends itself to a wide range of applications including in vivo NMR.     

Singular spectrum analysis for an automated solvent artifact removal and baseline correction of 1D NMR spectra

NMR spectroscopy in biology and medicine is generally performed in aqueous solutions, thus in (1)H NMR spectroscopy, the dominant signal often stems from the partly suppressed solvent and can be many orders of magnitude larger than the resonances of interest. Strong solvent signals lead to a disappearance of weak resonances of interest close to the solvent artifact and to base plane variations all over the spectrum. The AUREMOL-SSA/ALS approach for automated solvent artifact removal and baseline correction has been originally developed for multi-dimensional NMR spectroscopy. Here, we describe the necessary adaptations for an automated application to one-dimensional NMR spectra. Its core algorithm is still based on singular spectrum analysis (SSA) applied on time domain signals (FIDs) and it is still combined with an automated baseline correction (ALS) in the frequency domain. However, both steps (SSA and ALS) have been modified in order to achieve optimal results when dealing with one-dimensional spectra. The performance of the method has been tested on one-dimensional synthetic and experimental spectra including the back-calculated spectrum of HPr protein and an experimental spectrum of a human urine sample. The latter has been recorded with the typically used NOESY-type 1D pulse sequence including water pre-saturation. Furthermore, the fully automated AUREMOL-SSA/ALS procedure includes the managing of oversampled, digitally filtered and zero-filled data and the correction of the frequency domain phase shift caused by the group delay time shift from the digital finite response filtering.     

Laser-assisted photoelectric effect from surfaces

We report the first observation of the laser-assisted photoelectric effect from a solid surface. By illuminating a Pt(111) sample simultaneously with ultrashort 1.6 eV and 42 eV pulses, we observe sidebands in the extreme ultraviolet photoemission spectrum. The magnitude of these sidebands as a function of time delay between the laser and extreme ultraviolet pulses represents a cross-correlation measurement of the extreme ultraviolet pulse. This effect promises to be useful to extend extreme ultraviolet pulse duration measurements to higher photon energies, as well as opening up femtosecond-to-attosecond time-scale electron dynamics in solid and surface-adsorbate systems.     

Lactate observation in vivo by spectral editing in real time

We have developed a novel in vivo proton MR spectroscopy magnetization transfer method for detection of lactate in ischemic tissue in the presence of interfering fat proton resonances. Pyruvate is magnetically labeled with a saturation pulse and, when converted to lactate, the lactate retains the label. Difference of spectra obtained with and without a saturation pulse contain no fat resonances. High-resolution spectra (determined with a GE 1.5 T Signa) of low lactate levels were obtained in vivo by water suppression using a 2662 composite RF pulse and slice-selective gradients. Spectral subtraction was performed in real time allowing the monitoring of a buildup of the intensity of the lactate peak. Pyruvate-lactate saturation transfer techniques should find wide applicability in the study of ischemia.     

A new decoupling method for accurate quantification of polyethylene copolymer composition and triad sequence distribution with 13C NMR

(13)C NMR is a powerful analytical tool for characterizing polyethylene copolymer composition and sequence distribution. Accurate characterization of the composition and sequence distribution is critical for researchers in industry and academia. Some common composite pulse decoupling (CPD) sequences used in polyethylene copolymer (13)C NMR can lead to artifacts such as modulations of the decoupled (13)C NMR signals (decoupling sidebands) resulting in systematic errors in quantitative analysis. A new CPD method was developed, which suppresses decoupling sidebands below the limit of detection (less than 1:40,000 compared to the intensity of the decoupled signal). This new CPD sequence consists of an improved Waltz-16 CPD, implemented as a bilevel method. Compared with other conventional CPD programs this new decoupling method produced the cleanest (13)C NMR spectra for polyethylene copolymer composition and triad sequence distribution analyses.