•Passive shimming using paramagnetic shim pieces is proposed.•Paramagnetic shimming works over a wide range of magnetic fields.•There is no need to change shim configuration with field strength.•This work opens a way toward high-resolution variable-field NMR.We propose a new passive shimming strategy for variable-field NMR experiments, in which the magnetic field produced by paramagnetic shim pieces placed inside the magnet bore compensates the inhomogeneity of a variable-field magnet for a wide range of magnet currents. Paramagnetic shimming is demonstrated in 7Li, 87Rb, and 45Sc NMR of a liquid solution sample in magnetic fields of 3.4, 4.0, and 5.4 T at a fixed carrier frequency of 56.0 MHz. Since both the main-field inhomogeneity and the paramagnetic magnetization are proportional to the main-magnet current, the resonance lines are equally narrowed by the improved field homogeneity with an identical configuration of the paramagnetic shim pieces. Paramagnetic shimming presented in this work opens the possibility of high-resolution variable-field NMR experiments.Download high-res image (171KB)Download full-size image

Two-dimensional (2D) covariance NMR spectroscopy, which has originally been established to extract homonuclear correlations (HOMCOR), is extended to include heteronuclear correlations (HETCOR). In a 13C/15N 2D chemical shift correlation experiment, 13C and 15N signals of a polycrystalline sample of 13C, 15N-labeled amino acid are acquired simultaneously using a dual-receiver NMR system. The data sets are rearranged for the covariance data processing, and the 13C–15N heteronuclear correlations are obtained together with the 13C–13C and 15N–15N homonuclear correlations. The present approach retains the favorable feature of the original covariance HOMCOR that the spectral resolution along the indirect dimension is given by that of the detection dimension. As a result, much fewer amounts of data are required to obtain a well-resolved 2D spectrum compared to the case of the conventional 2D Fourier-Transformation (FT) scheme. Hence, one can significantly save the experimental time, or enhance the sensitivity by increasing the number of signal averaging within a given measurement time.

Recent reports on microcoils are reviewed. The first part of the review includes a discussion of how the geometries of the sample and coil affect the NMR signal intensity. In addition to derivation of the well-known result that the signal intensity increases as the coil size decreases, the prediction that dilution of a small sample with magnetically inert matter leads to better sensitivity if a tiny coil is not available is given. The second part of the review focuses on the issues specific to solid-state NMR. They include realization of magic-angle spinning (MAS) using a microcoil and harnessing of such strong pulses that are feasible only with a microcoil. Two strategies for microcoil MAS, the piggyback method and magic-angle coil spinning (MACS), are reviewed. In addition, MAS of flat, disk-shaped samples is discussed in the context of solid-state NMR of small-volume samples. Strong RF irradiation, which has been exploited in wide-line spectral excitation, multiple-quantum MAS (MQMAS), and dipolar decoupling experiments, has been accompanied by new challenges regarding the Bloch–Siegert effect, the minimum time resolution of the spectrometer, and the time scale of pulse transient effects. For a possible solution to the latter problem, recent reports on active compensation of pulse transients are described.Graphical abstractHighlights► Microcoils used in solid-state NMR are overviewed. ► Relation between the sample geometry and the signal intensity is described. ► Strong RF irradiation can be utilized in a number of scenes. ► The challenges associated with the strong RF irradiation are pointed out. ► The hints for overcoming them are suggested.

In this work we propose an approach to reduce the digitization noise for a given dynamic range, i.e., the number of bits, of an analog to digital converter used in an NMR receiver. In this approach, the receiver gain is dynamically increased so that the free induction decay is recorded in such an emphasized way that the decaying signal is digitized using as many number of bits as possible, and at the stage of data processing, the original signal profile is restored by applying the apodization that compensates the effect of the preemphasis. This approach, which we call APodization after Receiver gain InCrement during Ongoing sequence with Time (APRICOT), is performed in a solid-state system containing a pair of 13C spins, one of which is fully isotopically labeled and the other is naturally abundant. It is demonstrated that the exceedingly smaller peak buried in the digitization noise in the conventional approach can be revealed by employing APRICOT.Graphical abstractBy dynamically increasing the receiver gain during acquisition, small peaks buried in the digitization noise can be revealed.Research highlights► Dynamic modulation of the receiver gain eliminates digitization noise. ► This idea is useful when the peaks under interest show large contrast in intensity. ► An exceedingly small peak buried in the noise is shown to be revealed.

We present an extension of magic angle coil spinning (MACS) solid-state NMR spectroscopy to double-resonance experiments, enabling implementation of powerful double-resonance solid-state NMR methodologies including cross polarization, proton decoupling, and two-dimensional correlation spectroscopy etc., while still enjoying the merits that are intrinsic to MACS, such as high concentration sensitivity, eliminated magnetic susceptibility-induced field distortion, and an easy-to-use approach with the conventional and widespread hardware.

A new approach to compensate rf-pulse transients is proposed. Based on the idea of the response theory of a linear system, a formula is derived to obtain the required excitation voltage profile back from the intended target rf-pulse shape. The validity of the formula is experimentally confirmed by monitoring the rf-field created inside the sample coil with a pickup coil. Since this approach realizes accurate rf-pulse shapes without reducing the Q-factor of the tank circuit of the probe, it can be used not only to suppress the transient tail of the rf-pulse, but also as a general concept for accurate rf-pulsing.

A tool kit for implementing an integrated FPGA-based NMR spectrometer [K. Takeda, A highly integrated FPGA-based nuclear magnetic resonance spectrometer, Rev. Sci. Instrum. 78 (2007) 033103], referred to as the OPENCORE NMR spectrometer, is open to public. The system is composed of an FPGA chip and several peripheral boards for USB communication, direct-digital synthesis (DDS), RF transmission, signal acquisition, etc. Inside the FPGA chip have been implemented a number of digital modules including three pulse programmers, the digital part of DDS, a digital quadrature demodulator, dual digital low-pass filters, and a PC interface. These FPGA core modules are written in VHDL, and their source codes are available on our website. This work aims at providing sufficient information with which one can, given some facility in circuit board manufacturing, reproduce the OPENCORE NMR spectrometer presented here. Also, the users are encouraged to modify the design of spectrometer according to their own specific needs. A home-built NMR spectrometer can serve complementary roles to a sophisticated commercial spectrometer, should one comes across such new ideas that require heavy modification to hardware inside the spectrometer. This work can lower the barrier of building a handmade NMR spectrometer in the laboratory, and promote novel and exciting NMR experiments.

Two-dimensional (2D) covariance NMR spectroscopy, which has originally been established to extract homonuclear correlations (HOMCOR), is extended to include heteronuclear correlations (HETCOR). In a 13C/15N 2D chemical shift correlation experiment, 13C and 15N signals of a polycrystalline sample of 13C, 15N-labeled amino acid are acquired simultaneously using a dual-receiver NMR system. The data sets are rearranged for the covariance data processing, and the 13C–15N heteronuclear correlations are obtained together with the 13C–13C and 15N–15N homonuclear correlations. The present approach retains the favorable feature of the original covariance HOMCOR that the spectral resolution along the indirect dimension is given by that of the detection dimension. As a result, much fewer amounts of data are required to obtain a well-resolved 2D spectrum compared to the case of the conventional 2D Fourier-Transformation (FT) scheme. Hence, one can significantly save the experimental time, or enhance the sensitivity by increasing the number of signal averaging within a given measurement time.