Measuring the longitudinal NMR relaxation rates of fast relaxing nuclei using a signal eliminating relaxation filter

A new experiment for selective determination of the relaxation rates of fast relaxing NMR signals is presented. The experiment is derived from the conventional inversion recovery experiment by substituting the 180 degrees inversion pulse of this experiment with a signal eliminating relaxation filter (SERF) consisting of three 180 degrees pulses separated by two variable delays, Delta1 and Delta2. The SERF experiment allows a selective suppression of signals with relaxation rates below a given limit while monitoring the relaxation of faster relaxing signals. The experiment was tested on a sample of 20% oxidized plastocyanin from Anabaena variabilis, where the fast exchange of an electron between the reduced (diamagnetic) and the oxidized (paramagnetic) form results in a series of average signals with widely different relaxation rates. To ensure an optimum extraction of information from the experimental data, the relaxation rates were obtained from the SERF experiment by a simultaneous analysis of all the FIDs of the experiment using a fast linear prediction model method developed previously. The reliability of the relaxation rates obtained from the SERF experiment was confirmed by a comparison of the rates with the corresponding rates obtained from a conventional inversion recovery experiment.     

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.     

SERF-filtered experiments: new enantio-selective tools for deciphering complex spectra of racemic mixtures dissolved in chiral oriented media

The use of chiral liquid crystals as NMR solvent is a powerful tool to visualize and quantify enantiomers. This technique is much more robust than traditional liquid state techniques. Recent developments have been performed to simplify proton spectra obtained in these solvents which are usually complex to analyze. In the different published sequences the enantiomeric differentiation can be visualized but none of them rely the different (1)H-(1)H couplings to have a coherent set for each enantiomer especially in cases of racemic mixtures. In this work to overcome such limitations, we present a new NMR pulse sequence using semi-selective pulses to assign for each enantiomer the different (1)H-(1)H couplings. The aim is to obtain the signal of only one enantiomer, through a first Selective ReFocussing (SERF) filtering block implemented for the enantio-selection followed by a second SERF block for measuring a chosen coupling. The whole sequence is called (1)H SERF-filtered-SERF. These techniques permit for the first time to assign all dipolar couplings to each enantiomer of racemic mixtures dissolved in chiral oriented media. We demonstrate that using this experiment it is possible to visualize enantio-differentiation even in the case where the multiplets are not resolved in the SERF experiments, pushing back the limits of the enantiomeric visualization.     

Improved resolution using symmetrically shifted pulses.

An approach to Hadamard phase encode the two halves of the F(1) dimension of a gHSQC experiment is presented. The phase encoding is achieved by excitation sculpting of the F(1) dimension using symmetrically shifted pulses. This approach (IMPRESS-improved resolution using symmetrically shifted pulses) increases the resolution of the F(1) dimension by exploiting spectral folding, but the folding is coded in the fashion of a Hadamard H(2) matrix. Editing of the IMPRESS spectra during processing sorts out spectral crowding which is a typical consequence of F(1) spectral folding. It is shown that for the same total experiment time, the IMPRESS-gHSQC experiment provides narrower peaks along the F(1) dimension compared to the normal gHSQC experiment. As a consequence of decreased linewidth, the peak height (sensitivity) is also increased.     

负五阶非线性下预啁啾高斯光脉冲的啁啾和频谱

为探究光纤负五阶非线性和光脉冲预啁啾对高斯光脉冲频率啁啾和频谱的综合影响,在忽略光纤色散的情况下,利用包含三五阶非线性的扩展非线性薛定谔方程,计算和分析了啁啾高斯脉冲的频谱和总啁啾。结果表明,脉冲无预啁啾时,负五阶非线性的存在可使脉冲频率啁啾的形状由单“S”形变为双“S”形,并使脉冲的中心附近由正啁啾变为负啁啾。此外,负五阶非线性的存在使预啁啾对脉冲频谱的影响发生了较大的变化。预啁啾与非线性所致啁啾叠加后对脉冲频谱的谱峰数目影响较小,而对能量在各个谱峰上的分布影响较大,在某些最大非线性相移下,甚至会出现总啁啾减小使谱峰值数目增加的情况。该研究对光开关、光脉冲压缩以及光纤通信系统等领域的深入发展具有一定的指导意义。     

强激光啁啾脉冲中原子的高次谐波辐射

数值计算了强激光啁啾脉冲中原子的谐波辐射。啁啾效应使谐波发生移动和展宽，即相对于无啁啾冲情形，负啁啾脉冲中谐波平台的前半部分发生兰移，而后半部分谐波谱则发生红移。     

Spin dynamics of the potassium magnetometer in spin-exchange relaxation free regime

The laser-pumped potassium spin-exchange relaxation free(SERF) magnetometer is the most sensitive detector of magnetic field and has many important applications. We present the experimental results of our potassium SERF magnetometer. A pump–probe approach is used to identify the unique spin dynamics of the atomic ensemble in the SERF regime.A single channel sensitivity of 8 f·THz-1/2is achieved with our SERF magnetometer.     

3D HSQC-HSQMBC--increasing the resolution of long-range proton-carbon correlation experiments

A 3D HSQC-HSQMBC experiment is proposed for increasing the separation of proton-carbon long-range correlation cross peaks, the lack of which is occasionally seen in corresponding 2D experiments. It is aimed at complex molecules with many protonated carbons exhibiting a narrow spread of 13C chemical shifts e.g., complex carbohydrates. It does not yield long-range correlation of quaternary carbons. An extra indirectly detected 1H dimension of this experiment provides additional separation of long-range correlation cross peaks by utilising the chemical shifts of protons directly attached to 13C. Evolution of single-quantum coherences throughout the entire pulse sequence ensures that the cross peaks are inphase pure absorption singlets in both indirectly detected dimensions, thus maximising the resolution and sensitivity of the experiment. Partial signal cancellation can be expected due to the antiphase character of peaks in the directly detected dimension. The intensity of cross peaks depends on the length of a single long-range evolution interval and values of both active and passive long-range coupling constants of each carbon. The 3D HSQC-HSQMBC experiment provided high quality long-range correlation spectra of a 2 mg pentasaccharide sample in 27 h. The technique can also be used for measurement of long-range heteronuclear coupling constants from pure antiphase multiplets in the directly detected dimension.     

Two-dimensional J-spectra with absorption-mode lineshapes

Two-dimensional J-spectroscopy offers the possibility of a complete separation of chemical shifts and J-couplings. However, the usefulness of the experiment is considerably reduced by the fact that peaks in the spectra have the phase-twist lineshape. We present a simple new spectroscopic method for recording J-spectra in which the peaks are both in the absorption mode and retain their natural intensities, albeit at the cost of a considerable reduction in the signal-to-noise ratio. No special data-processing is required. The method is tested on quinine, and the steroid dehydroisoandrosterone.     

Composition analysis of single semiconductor nanowires using pulsed-laser atom probe tomography

We report the composition analysis of single InAs and Si semiconductor nanowires using pulsed-laser atom probe tomography. The experimental conditions and sample geometries needed to realize 3-D composition mapping are described in detail. InAs mass spectra obtained using voltage pulses and laser pulses are compared, and are found to be superior for pulsed-laser evaporation. The ability to analyze intrinsic Si nanowires using pulsed laser evaporation is demonstrated. No peaks associated with the gold catalyst used were found in the InAs or the Si nanowire mass spectra. PACS 68.70.+w; 61.82.Fk; 61.72.Ss     

Two-dimensional ENDOR-ESEEM correlation spectroscopy

A two-dimensional (2D) experiment that correlates electron-nuclear double resonance (ENDOR) and electron spin-echo envelope modulation (ESEEM) frequencies, useful for unraveling and assigning ENDOR and ESEEM spectra from different paramagnetic centers with overlapping EPR spectra, is presented. The pulse sequence employed is similar to the Davies ENDOR experiment with the exception that the two-pulse echo detection is replaced by a stimulated echo detection in order to enhance the resolution in the ESEEM dimension. The two-dimensional data set is acquired by measuring the ENDOR spectrum as a function of the time interval T between the last two microwave pulses of the stimulated echo detection scheme. This produces a series of ENDOR spectra with amplitudes that are modulated with T. Fourier transformation (FT) with respect to T then generates a 2D spectrum with cross peaks connecting spectral lines of the ESEEM and ENDOR spectra that belong to the same paramagnetic center. Projections along the vertical and horizontal axes give the three-pulse FT-ESEEM and ENDOR spectra, respectively. The feasibility of the experiment was tested by simulating 2D ENDOR-ESEEM correlation spectra of a system consisting of an electron spin (S = (1/2)) coupled to two nuclei (I(1) = I(2) = (1/2)), taking into account experimental conditions such as pulse durations and off-resonance irradiation frequencies. The experiment is demonstrated on a single crystal of Cu(2+) doped l-histidine (Cu-His), containing two symmetrically related Cu(2+) sites that at an arbitrary orientation exhibit overlapping ESEEM and ENDOR spectra. While the ESEEM spectrum is relatively simple and arises primarily from one weakly coupled (14)N, the ENDOR spectrum is very crowded due to contributions from two nonequivalent nitrogens, two chlorides, and a relatively large number of protons. The simple ESEEM projection of the 2D ENDOR-ESEEM correlation spectrum is then used to disentangle the ENDOR spectrum and resolve two sets of lines corresponding to the different sites. Copyright 2000 Academic Press.     

Ultrafast 2D NMR spectroscopy using a continuous spatial encoding of the spin interactions

A new protocol for acquiring multidimensional NMR spectra within a single scan is introduced and illustrated. The approach relies on applying a pair of frequency-chirped excitation and storage pulses in combination with echoing magnetic field gradients, in order to impart the kind of linear spatial encoding of the NMR interactions that is required by ultrafast 2D NMR spectroscopy. It is found that when dealing with 2D NMR experiments involving a t1 amplitude-modulation of the spin evolution, such continuous encoding scheme presents a number of advantages over alternatives employing discrete excitation pulses. From an experimental standpoint this is mainly reflected by the use of a single pair of bipolar gradients during the course of the indirect-domain encoding, as opposed to the numerous (and more intense) gradient echoes required so far. In terms of the spectral outcome, main advantages of the continuous spatial encoding scheme are the avoidance of "ghost peaks" and of "enveloping effects" associated to the discrete excitation mode. The principles underlying this new spatial encoding protocol are derived, and its applicability is demonstrated with homo- and heteronuclear 2D ultrafast NMR applications on small molecule and on protein samples.     

双色高频激光作用下原子低阶次谐波的理论研究

通过数值求解含时薛定谔方程,研究了高频双色激光脉冲与原子相互作用产生的光辐射.研究表明,光辐射谱中既有基频光的谐波,又可观测到谐波能量附近的多个频率的光辐射产生,且辐射的峰值强度随着入射激光强度的提高呈指数增强,相邻辐射频率差值为入射的两束激光脉冲频率差.     

Enantiomeric excess measurements in weakly oriented chiral liquid crystal solvents through 2D H selective refocusing experiments

In this article, a simple and robust method is proposed for simplifying the analysis of proton spectra of molecules dissolved in weakly oriented chiral media. The NMR approach investigated is based on the use of proton selective refocusing 2D experiments (SERF) to measure proton–proton dipolar couplings from unresolved lines. This technique is applied to the case of enantiomers dissolved in chiral polypeptide liquid crystals. It is shown that an accurate determination of enantiomeric excess is possible within a short experimental time.     

Identification of isomers and control of ionization and dissociation processes using dual-mass-spectrometer scheme and genetic algorithm optimization

Identification of acetone and its two isomers, and the control of their ionization and dissociation processes are performed using a dual-mass-spectrometer scheme. The scheme employs two sets of time of flight mass spectrometers to simultaneously acquire the mass spectra of two different molecules under the irradiation of identically shaped femtosecond laser pulses. The optimal laser pulses are found using closed-loop learning method based on a genetic algorithm. Compared with the mass spectra of the two isomers that are obtained with the transform limited pulse, those obtained under the irradiation of the optimal laser pulse show large differences and the various reaction pathways of the two molecules are selectively controlled. The experimental results demonstrate that the scheme is quite effective and useful in studies of two molecules having common mass peaks, which makes a traditional single mass spectrometer unfeasible.     

3D HSQC-HSQMBC—increasing the resolution of long-range proton–carbon correlation experiments

A 3D HSQC-HSQMBC experiment is proposed for increasing the separation of proton–carbon long-range correlation cross peaks, the lack of which is occasionally seen in corresponding 2D experiments. It is aimed at complex molecules with many protonated carbons exhibiting a narrow spread of ¹³C chemical shifts e.g., complex carbohydrates. It does not yield long-range correlation of quaternary carbons. An extra indirectly detected ¹H dimension of this experiment provides additional separation of long-range correlation cross peaks by utilising the chemical shifts of protons directly attached to ¹³C. Evolution of single-quantum coherences throughout the entire pulse sequence ensures that the cross peaks are inphase pure absorption singlets in both indirectly detected dimensions, thus maximising the resolution and sensitivity of the experiment. Partial signal cancellation can be expected due to the antiphase character of peaks in the directly detected dimension. The intensity of cross peaks depends on the length of a single long-range evolution interval and values of both active and passive long-range coupling constants of each carbon. The 3D HSQC-HSQMBC experiment provided high quality long-range correlation spectra of a 2 mg pentasaccharide sample in 27 h. The technique can also be used for measurement of long-range heteronuclear coupling constants from pure antiphase multiplets in the directly detected dimension.     

Shaped pulses for selective inversion of magnetization in solids spinning at the magic angle

In order to achieve selective inversion of a chosen family of sidebands in NMR spectra of solids rotating at the magic angle (MAS spectra), a sequence of so-called DANTE pulses can be applied in synchronization with the sample rotation period. It is shown by simulation and experiment that the profiles of the offset dependence can be greatly improved by varying the amplitudes of the DANTE pulses, so that the envelope corresponds to that of a G³ Gaussian cascade. Alternatively, the DANTE pulses may be replaced by sandwiches composed of four hard pulses, adjusted so that the time-dependence of the nutation angles matches the envelope of a G³ Gaussian cascade. It is shown by simulations that in solids the profiles are affected by homogeneous decay of magnetization, in analogy to the influence of transverse relaxation in liquids. Applications to the intramolecular rearrangement (tautomerism) of polycrystalline tropolone illustrate that dynamic processes in the solid state can be monitored with great accuracy.     

Magnetostatic-Wave-Based Magneto-Optic Pulse Compression by Control of Phase Mismatching

Microwave magnetostatic waves (MSWs) as moving gratings in magneto-optic (MO) film can lead to the Bragg diffraction of guided optical waves (GOWs). The MO coupling characteristics are responsible for the amplitude and phase frequency spectra of diffracted pulses and even result in the compression of chirped optical pulses in time domain. We theoretically investigate the noncollinear diffraction of linearly chirped Gaussian optical pulses by continuous magnetostatic forward volume waves in detail. For a given chirped optical pulse, with the increase of phase-mismatching slopes, the compression efficiency (CE) is gradually improved up to the maximum followed by the transition of diffracted pulses from single peak to multi peaks. The larger the chirp parameter is, the smaller the required phase-mismatching slope to achieve the maximal CE is. However, the rise of the chirp parameter or phase-mismatching slope reduces the relative peak intensity of the diffracted pulse. Lastly, it is pointed out that the phase-mismatching slope can be greatly increased by using the high-order modes of MSWs and GOWs.     

The study of high-order harmonic generation using ellipticity-modulated laser pulse

The high-order harmonic generation using ellipticity-modulated laser field is investigated experimentally and theoretically. The laser field with time-varying ellipticity is obtained using two quarter wave plates. The harmonic spectral intensity peaks appear periodic for the localization induced by the ellipticity modulation of the laser pulse. We calculate the single-atom response to the driving laser field using the Lewenstein model and compare the calculated and measured harmonic spectra generated with ellipticity-modulated driving laser pulses. The theoretical simulation and the experiment results agree well with each other.