Determination of the 14N quadrupole coupling constant of nitroxide spin probes by W-band ELDOR-detected NMR

Nitroxide spin probe electron paramagnetic resonance (EPR) has proven to be a very successful method to probe local polarity and solvent hydrogen bonding properties at the molecular level. The g(xx) and the (14)N hyperfine A(zz) principal values are the EPR parameters of the nitroxide spin probe that are sensitive to these properties and are therefore monitored experimentally. Recently, the (14)N quadrupole interaction of nitroxides has been shown to be also highly sensitive to polarity and H-bonding (A. Savitsky et al., J. Phys. Chem. B 112 (2008) 9079). High-field electron spin echo envelope modulation (ESEEM) was used successfully to determine the P(xx) and P(yy) principal components of the (14)N quadrupole tensor. The P(zz) value was calculated from the traceless character of the quadrupole tensor. We introduce here high-field (W-band, 95 GHz, 3.5 T) electron-electron double resonance (ELDOR)-detected NMR as a method to obtain the (14)N P(zz) value directly, together with A(zz). This is complemented by W-band hyperfine sublevel correlation (HYSCORE) measurements carried out along the g(xx) direction to determine the principal P(xx) and P(yy) components. Through measurements of TEMPOL dissolved in solvents of different polarities, we show that A(zz) increases, while |P(zz)| decreases with polarity, as predicted by Savitsky et al.     

High-Bandwidth Q-Band EPR Resonators

The emerging technology of ultra-wide-band spectrometers in electron paramagnetic resonance—enabled by recent technological advances—provides the means for new experimental schemes, a broader range of samples, and huge gains in measurement time. Broadband detection does, however, require that the resonator provides sufficient bandwidth and, despite resonator compensation schemes, excitation bandwidth is ultimately limited by resonator bandwidth. Here, we present the design of three resonators for Q-band frequencies (33–36 GHz) with a larger bandwidth than what was reported so far. The new resonators are of a loop-gap type with 4–6 loops and were designed for 1.6 mm sample tubes to achieve higher field homogeneity than in existing resonators for 3 mm samples, a feature that is beneficial for precise spin control. The loop-gap design provides good separation of the B ₁ and E field, enabling robust modes with powder samples as well as with frozen water samples as the resonant behavior is largely independent of the dielectric properties of the samples. Experiments confirm the trends in bandwidth and field strength and the increased B ₁ field homogeneity predicted by the simulations. Variation of the position of the coupling rod allows the adjustment of the quality factor Q and thus the bandwidth over a broad range. The increased bandwidth of the loop-gap resonators was exploited in double electron–electron resonance measurements of a Cu(II)-PyMTA ruler to yield significantly higher modulation depth and thus higher sensitivity.     

NMR at 900 MHz

An important factor in the development of solution state NMR has always been th e ability to produce stable and homogeneous magnetic fields. As higher and higher field strengths are reached the pressure is growing on manufacturers to produce NMR systems with greatly improved spectral resolution and signal to noise ratio. The introduction of the Varian 900 MHz INOVA system in August 2000 featuring Oxford Instruments 21.1 T magnet represents the latest pioneering development in NMR technology.     

Q-Band Loop-Gap Resonator for EPR Applications with Broadband-Shaped Pulses

Recently, Q-band-pulsed electron paramagnetic resonance spectroscopy has strongly advanced its performance by the introduction of high-power microwave amplifiers and the use of shaped pulses. For such applications, the resonator Q value has to be low enough to achieve sufficient bandwidth for short microwave pulses and to reduce the ring-down time after the pulses. However, a low Q value reduces the detection sensitivity as well as the conversion efficiency of the microwave input power to the magnetic field strength at the sample position. Therefore, the resonator Q value has to be optimized for a given microwave input power and specific application. We designed a three-loop/two-gap resonator using CST Microwave Studio for such applications, and tested its performance in comparison with a standard Bruker D2 Q-band microwave resonator by accomplishing broadband SIFTER experiments on a nitroxide model compound.     

Applications of pulsed ELDOR-detected NMR measurements to studies of photosystem II: Magnetic characterization of YD tyrosine radical and Mn2+ bound to the high-affinity site

The pulsed electron-electron double resonance (ELDOR)-detected nuclear magnetic resonance (NMR) technique has been applied to the investigation of the hyperfine structure of the oxidized radical of Y_D tyrosine (Y _D ^· ) and Mn²⁺ ion bound to the high-affinity site in photosystem II. The resulting ELDOR spectrum of Y _D ^· was found to correspond with the pulsed electron-nuclear double resonance (ENDOR) spectrum except for a slightly larger linewidth (by a factor of 1.7). The spectrum showed marked anisotropy and revealed three peaks which can be assigned to matrix protons, C-3 and ?5 protons and one of the β-protons in the tyrosine molecule. The results demonstrate that the pulsed ELDOR-detected NMR technique is applicable to the study of organic radicals in biological systems. The Mn²⁺ ion bound to the high-affinity site in photosystem II yielded well-resolved ELDOR signals spreading over ±1000 MHz. The magnetic properties of the Mn²⁺ were characterized on the basis of the calculation of the ENDOR transitions and the anisotropy of the ELDOR spectrum.     

NMR at very low fields

Although nuclear magnetic resonance in low fields around or below the Earth's magnetic field is almost as old as nuclear magnetic resonance itself, the recent years have experienced a revival of this technique that is opposed to the common trend towards higher and higher fields. The background of this development is the expectation that the low-field domain may open a new window for the study of molecular structure and dynamics. Here, we will give an overview on the specific features in the low-field domain, both from the technical and from the physical point of view. In addition, we present a short passage on the option of magnetic resonance imaging in fields of the micro-Tesla range.     

NMR at single crystal surfaces

15 sites on 1 cm². To overcome this for the important class of alkali adsorbates on metals and semiconductors, two methods are presented. Common to both is the preparation of a highly nuclear spin-polarized atomic beam of ⁶Li in the one case and ⁸Li in the other. The latter isotope is radioactive and undergoes a β-decay with a half-life of 0.84 s. Li adsorbed on the close-packed Ru(001) surface is investigated. The longitudinal relaxation time, T₁, is the main observable and is used to deduce the local electronic density of states [LDOS(E_F,r=0)] and Li diffusion barriers. The second experiment uses ⁶Li as an adsorbate, also studied on Ru(001). The nuclear polarization is measured by beam foil spectroscopy. A novel particle detected (photon counting) Fourier transform NMR technique is demonstrated. This is done by observing the time-dependent flux of circularly polarized light emitted behind the foil after a 90° pulse has been employed at the surface. Electric field gradients and transverse relaxation times, T₂, are thus determined. A large difference between T₁ and T₂ is traced to the dimensionality of the system. Received: 21 March 1997/Accepted: 12 August 1997     

A New Q-Band EPR Probe for Quantitative Studies of Even Electron Metalloproteins

Existing Q-band (35 GHz) EPR spectrometers employ cylindrical cavities for more intense microwave magnetic fields B₁, but are so constructed that only one orientation between the external field B and B₁is allowed, namely the B B₁orientation, thus limiting the use of the spectrometer to measurements on Kramers spin systems (odd electron systems). We have designed and built a Q-band microwave probe to detect EPR signals in even electron systems, which operates in the range 2 K ≤ T ≤ 300 K for studies of metalloprotein samples. The cylindrical microwave cavity operates in the TE₀₁₁mode with cylindrical wall coupling to the waveguide, thus allowing all orientations of the external magnetic field B relative to the microwave field B₁. Such orientations allow observation of EPR transitions in non-Kramers ions (even electron) which are either forbidden or significantly weaker for B B₁. Rotation of the external magnetic field also permits easy differentiation between spin systems from even and odd electron oxidation states. The cavity consists of a metallic helix and thin metallic end walls mounted on epoxy supports, which allows efficient penetration of the modulation field. The first quantitative EPR measurements from a metalloprotein (Hemerythrin) at 35 GHz with B₁ B are presented.     

A Homebuilt ESE Spectrometer on the Basis of a High-Power Q-Band Microwave Bridge

We present a Q-band spectrometer which was built recently at the Institute of Physical Chemistry of the University of Stuttgart. It allows us to perform the field-sweep electron spin echo (ESE), pulsed electron–nuclear double resonance (ENDOR), relaxation and electron spin echo envelope modulation experiments both at room and low (down to 1.5 K) temperatures. The spectrometer consists of an electromagnet, digital field controller, pulsed microwave bridge, probehead, cryostat, radio frequency unit, pulse programmer and data acquisition electronics. The Q-band microwave bridge with 10.8 W output power is based on a two-stage IMPATT-diode pulse amplifier. The commercial Varian electromagnet system is controlled by a 24-bit home-built digital controller. The external devices are interfaced to the two PCs via GPIB and LAN. The spectrometer control software was developed in Visual C++. It consists of two programs running synchronously on the control PCs. The spectrometer is equipped with a cylindrical TE₀₁₁ cavity constructed both for ESE and for pulsed ENDOR. The cavity fits into a liquid He cryostat thus allowing low-temperature experiments. An 8-bit data acquisition digitizer is used to collect the echo signals, and the PBESR-PRO-400 digital word generator orchestrates the pulse experiments and sets pulse sequences of the microwave bridge. The spectrometer performance is demonstrated on nitrogen impurities in a polycrystalline synthetic diamond, on silver clusters supported on NaA zeolite and electron-irradiated tooth enamel. Authors' address: Igor Tkach, Institute of Physical Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany     

NMR measurement of bitumen at different temperatures

Heavy oil (bitumen) is characterized by its high viscosity and density, which is a major obstacle to both well logging and recovery. Due to the lost information of T2 relaxation time shorter than echo spacing (TE) and interference of water signal, estimation of heavy oil properties from NMR T2 measurements is usually problematic. In this work, a new method has been developed to overcome the echo spacing restriction of NMR spectrometer during the application to heavy oil (bitumen). A FID measurement supplemented the start of CPMG. Constrained by its initial magnetization (M0) estimated from the FID and assuming log normal distribution for bitumen, the corrected T2 relaxation time of bitumen sample can be obtained from the interpretation of CPMG data. This new method successfully overcomes the TE restriction of the NMR spectrometer and is nearly independent on the TE applied in the measurement. This method was applied to the measurement at elevated temperatures (8-90 degrees C). Due to the significant signal-loss within the dead time of FID, the directly extrapolated M0 of bitumen at relatively lower temperatures (<60 degrees C) was found to be underestimated. However, resulting from the remarkably lowered viscosity, the extrapolated M0 of bitumen at over 60 degrees C can be reasonably assumed to be the real value. In this manner, based on the extrapolation at higher temperatures (> or = 60 degrees C), the M0 value of bitumen at lower temperatures (<60 degrees C) can be corrected by Curie's Law. Consequently, some important petrophysical properties of bitumen, such as hydrogen index (HI), fluid content and viscosity were evaluated by using corrected T2.     

First2H NMR at 58 T

The first nuclear magnetic resonance (NMR) experiments in pulsed field magnets at fields up to 58 T are reported. The basic features of the pulsed field source and the strategy to observe the first spectra are described. A²H NMR spectrum at 58 T is shown and the first results are discussed.     

Feasibility of Q-Band EPR Dosimetry in Biopsy Samples of Dental Enamel, Dentine and Bone

Electron paramagnetic resonance (EPR) dosimetry of tooth enamel in X-band has been established as a suitable method for individual reconstruction of doses 0.1 Gy and higher. The objective was to demonstrate the feasibility of using Q-band EPR in small biopsy tooth enamel samples to provide accurate measurements of radiation doses. Q-band spectra of small (<10 mg) irradiated samples of dentine and bone were studied to investigate the possibility of using Q-band EPR for dose measurements in those materials if there are limited amounts of enamel available, and there is no time for the chemical sample preparation required for accurate X-band measurements in dental enamel. Our results have shown that Q-band provides accurate measurements of radiation doses higher than 0.5 Gy in tooth enamel biopsy samples as small as 2 mg. Q-band EPR spectra in powdered dentine and bone demonstrated significantly higher resolution and sensitivity than in conventional X-band measurements.     

NMR spectra under skin-effect conditions at ultralow temperatures

An investigation based on the coupled Maxwell-Bloch equations for a system of equivalent exchange-coupled spins is performed in order to explain a number of features of NMR spectra obtained in metals by Fourier-transforming of the free-induction decay at ultralow temperatures. Small angles of tilting of the nuclear magnetization by the exciting rf field are considered. It is shown that the free precession inherits the nonuniformity in the distribution of the rf field and the magnetization produced at the excitation stage inside the sample on account of the skin effect. As a result, the NMR spectrum is found to consist of a set of peaks—signals due to standing spin waves. However, such a spectrum can be observed only when the detuning of the exciting rf field is sufficiently large relative to the Larmor frequency of the spins. Otherwise, the rf field does not penetrate into the sample because of strong absorption by the spins. If the detuning is large, the dispersion signal and part of the NMR absorption signal are proportional to the equilibrium magnetization to the power 3/2. Such behavior is expected at low temperatures so that the coupling of the magnetization with the rf field is strong. The results obtained qualitatively explain the experimentally observed characteristics of the NMR spectra: the presence of kinks and structure of the NMR lines, the dependence of the shape and intensity of the spectrum on the detuning of the exciting rf field, and the nonlinear dependence of the nuclear susceptibility on the reciprocal of the sample temperature. Zh. éksp. Teor. Fiz. 114, 1836–1847 (November 1998)     

Noise figure characterization of preamplifiers at NMR frequencies

A method for characterizing the noise figure of preamplifiers at NMR frequencies is presented. The noise figure of preamplifiers as used for NMR and MRI detection varies with source impedance and with the operating frequency. Therefore, to characterize a preamplifier's noise behavior, it is necessary to perform noise measurements at the targeted frequency while varying the source impedance with high accuracy. At high radiofrequencies, such impedance variation is typically achieved with transmission-line tuners, which however are not available for the relatively low range of typical NMR frequencies. To solve this issue, this work describes an alternative approach that relies on lumped-element circuits for impedance manipulation. It is shown that, using a fixed-impedance noise source and suitable ENR correction, this approach permits noise figure characterization for NMR and MRI purposes. The method is demonstrated for two preamplifiers, a generic BF998 MOSFET module and an MRI-dedicated, integrated preamplifier, which were both studied at 128MHz, i.e., at the Larmor frequency of protons at 3 Tesla. Variations in noise figure of 0.01dB or less over repeated measurements reflect high precision even for small noise figures in the order of 0.4dB. For validation, large sets of measured noise figure values are shown to be consistent with the general noise-parameter model of linear two-ports. Finally, the measured noise characteristics of the superior preamplifier are illustrated by SNR measurements in MRI data.     

NMR at earth's magnetic field using para-hydrogen induced polarization

A method to achieve NMR of dilute samples in the earth's magnetic field by applying para-hydrogen induced polarization is presented. Maximum achievable polarization enhancements were calculated by numerically simulating the experiment and compared to the experimental results and to the thermal equilibrium in the earth's magnetic field. Simultaneous 19F and 1H NMR detection on a sub-milliliter sample of a fluorinated alkyne at millimolar concentration (～10(18) nuclear spins) was realized with just one single scan. A highly resolved spectrum with a signal/noise ratio higher than 50:1 was obtained without using an auxiliary magnet or any form of radio frequency shielding.     

Rotor-synchronized dipolar-filter sequence at fast MAS in solid-state NMR

Dipolar filters are of considerable importance for eliminating the ¹H NMR signal of the rigid components of heterogeneous compounds while selecting the signal of their mobile parts. On the basis of such filters, structural and dynamical information of these compounds can often be acquired through further manipulations (e.g. spin diffusion) on the spin systems. To overcome the destructive interferences between the magic angle spinning (MAS) speed and the cycle-time of the widely-used Rotor-Asynchronized Dipolar Filter (RADF) sequence, we introduce a new method called Rotor-Synchronized Dipolar Filter (RSDF). This communication shows that this sequence does not present any interference with the spinning speed and is more compatible than RADF with high MAS frequencies (ν_R > 12 kHz). This new pulse sequence will potentially contribute to future researches on heterogeneous materials, such as multiphase polymer and membrane systems.     

High-pressure,high-resolution NMR probe working at 400 MHZ

Abstract

A probe for obtaining high-resolution multinuclear NMR spectra at elevated pressures with a Bruker AM-400 spectrometer is described. The probe is designed for pressures up to 200 MPa and has been used between -40 to 150°C. We obtain routinely a resolution of about 1 Hz for proton (400 MHz) spectra using deuterium as an internal field lock. This probe is easily interchangeable with a commercial probe. We also describe a simple sample tube made of a 5 mm commercial NMR tube and a machinable glass cap with a total volume of about 1 cm³.