A Dynamic Nuclear Polarization spectrometer at 95 GHz/144 MHz with EPR and NMR excitation and detection capabilities

A spectrometer specifically designed for systematic studies of the spin dynamics underlying Dynamic Nuclear Polarization (DNP) in solids at low temperatures is described. The spectrometer functions as a fully operational NMR spectrometer (144 MHz) and pulse EPR spectrometer (95 GHz) with a microwave (MW) power of up to 300 mW at the sample position, generating a MW B(1) field as high as 800 KHz. The combined NMR/EPR probe comprises of an open-structure horn-reflector configuration that functions as a low Q EPR cavity and an RF coil that can accommodate a 30-50 μl sample tube. The performance of the spectrometer is demonstrated through some basic pulsed EPR experiments, such as echo-detected EPR, saturation recovery and nutation measurements, that enable quantification of the actual intensity of MW irradiation at the position of the sample. In addition, DNP enhanced NMR signals of samples containing TEMPO and trityl are followed as a function of the MW frequency. Buildup curves of the nuclear polarization are recorded as a function of the microwave irradiation time period at different temperatures and for different MW powers.     

High-field/high-frequency EPR spectrometer operating in pulsed and continuous-wave mode at 180 GHz

A novel electron paramagnetic resonance (EPR) spectrometer is reported, which has been developed to allow pulsed EPR experiments with high sensitivity and time resolution at a microwave (MW) frequency of 180 GHz (G-band) and wavelengths of approximately 1.6 mm. This corresponds to a magnetic field of about 6.4 T forg ≈ 2 signals. The “hybrid” system architecture combines components of quasioptical as well as conventional MW techniques, making it possible to achieve excellent spectrometer performance with respect to sensitivity and time resolution. Quasioptical MW components have been used to design an MW circulator allowing high sensitivity and low bias operation in the reflection mode. A miniaturized, closed-type cylindrical cavity provides a high sample filling factor and an adequate MW field strength (B₁) enhancement and thus permits reasonably short MW pulses (60 ns for a π/2 pulse) even with a moderate MW input power (15 mW at the cavity). Commercial quartz capillaries (up to 0.5 mm internal diameter) can be used as sample holders for a broad range of applications.     

Theg-tensor anisotropy of the triplet state of the primary electron donor in the photosynthetic bacteriumRhodobacter sphaeroides by high-field (95 GHz) EPR

The anisotropy of theg-tensor of the light-induced triplet state of the primary electron donor (D) of the photosynthetic bacteriumRhodobacter sphaeroides is determined by electron-spin-echo-detected electron paramagnetic resonance at 95 GHz. Measurements on frozen solutions of quinone-depleted reaction centers yield g-values along the principal directions of the zero-field splitting tensor (Norris J.R., Budil D.E., Gast P., Chang C.H., ElKabbani O., Schiffer M.: Proc. Natl. Acad. Sci. USA86, 4335–4339, 1989).g-Values determined are: 2.00308, 2.00238, and 2.00138. The deviation from axial symmetry and thez-component of the g-tensor are smaller than observed in the cation radical of D.     

Dielectric waveguide modulators at 95 GHz using LiNbO3

We describe electro-optic modulators at 95 GHz using LiNbO₃ in an H-guide configuration. We have observed 70% amplitude modulation at l KHz in a bridge configuration, corresponding to an induced phase shift of ±29°. The prospects for improved device performance will be discussed.Supported in part by Subcontract #67-471915 with California Institute of Technology under Prime Contract N00014-79-C-0839 with Office of Naval Research.     

Dynamic nuclear polarization at 9T using a novel 250GHz gyrotron microwave source

In this communication, we report enhancements of nuclear spin polarization by dynamic nuclear polarization (DNP) in static and spinning solids at a magnetic field strength of 9T (250 GHz for g=2 electrons, 380 MHz for 1H). In these experiments, 1H enhancements of up to 170+/-50 have been observed in 1-13C-glycine dispersed in a 60:40 glycerol/water matrix at temperatures of 20K; in addition, we have observed significant enhancements in 15N spectra of unoriented pf1-bacteriophage. Finally, enhancements of approximately 17 have been obtained in two-dimensional 13C-13C chemical shift correlation spectra of the amino acid U-13C, 15N-proline during magic angle spinning (MAS), demonstrating the stability of the DNP experiment for sustained acquisition and for quantitative experiments incorporating dipolar recoupling. In all cases, we have exploited the thermal mixing DNP mechanism with the nitroxide radical 4-amino-TEMPO as the paramagnetic dopant. These are the highest frequency DNP experiments performed to date and indicate that significant signal enhancements can be realized using the thermal mixing mechanism even at elevated magnetic fields. In large measure, this is due to the high microwave power output of the 250 GHz gyrotron oscillator used in these experiments.     

Dynamic nuclear polarization at 9T using a novel 250 GHz gyrotron microwave source. 2003

In this communication, we report enhancements of nuclear spin polarization by dynamic nuclear polarization (DNP) in static and spinning solids at a magnetic field strength of 9 T (250 GHz for g = 2 electrons, 380 MHz for ¹H). In these experiments, ¹H enhancements of up to 170 ± 50 have been observed in 1-¹³C-glycine dispersed in a 60:40 glycerol/water matrix at temperatures of 20 K; in addition, we have observed significant enhancements in ¹⁵N spectra of unoriented pf1-bacteriophage. Finally, enhancements of ∼17 have been obtained in two-dimensional ¹³C–¹³C chemical shift correlation spectra of the amino acid U–¹³C, ¹⁵N-proline during magic angle spinning (MAS), demonstrating the stability of the DNP experiment for sustained acquisition and for quantitative experiments incorporating dipolar recoupling. In all cases, we have exploited the thermal mixing DNP mechanism with the nitroxide radical 4-amino-TEMPO as the paramagnetic dopant. These are the highest frequency DNP experiments performed to date and indicate that significant signal enhancements can be realized using the thermal mixing mechanism even at elevated magnetic fields. In large measure, this is due to the high microwave power output of the 250 GHz gyrotron oscillator used in these experiments.     

Investigating magnetically aligned phospholipid bilayers with EPR spectroscopy at Q-band (35 GHz): optimization and comparison with X-band (9 GHz)

This paper presents the improvement and advantages of investigating magnetically aligned phospholipid bilayers (bicelles) utilizing electron paramagnetic resonance (EPR) spectroscopy at a microwave frequency of 35 GHz (Q-band) and at a high magnetic field strength of 1.25 T when compared to weaker magnetic fields for X-band EPR studies. The nitroxide spin label 3beta-doxyl-5alpha-cholestane (cholestane or CLS) was inserted into the bicelles and utilized to demonstrate the effects of macroscopic bilayer alignment through the measurement of orientational dependent hyperfine splittings. The effects of different lanthanide ions with varying degree of magnetic susceptibility anisotropy were examined. The requirement of minimal amounts of the Tm3+ and Dy3+ lanthanide ions for well-aligned bicelles were examined for Q-band and compared with amounts required for X-band bicelle alignment studies. At a magnetic field of 1.25 T (when compared to 0.63 T at X-band), the perpendicular and parallel orientation were aligned with lower concentrations of Dy3+ and Tm3+, respectively, and thereby eliminating/minimizing the unwanted effects associated with lanthanide-protein interactions. Thus, it is much easier to magnetically align phospholipid bilayers at Q-band when compared to X-band.     

Dual and broadband power dividers at microwave frequencies based on composite right/left handed (CRLH) lattice networks

This paper proposes a dual-band power divider operating at GHz frequencies and implemented by means of impedance transformers (also called inverters) based on lattice networks and transmission line sections. The dual-band functionality of the proposed device is achieved thanks to the composite right/left handed (CRLH) behavior of the impedance transformers, able to provide −90° and +90° phase shift at the first and second design frequencies, respectively, of the divider. By using such combination of transmission line sections and lattice networks, the characteristic impedance of the impedance transformers is roughly constant over wide bandwidths, with the results of broad operating bands. To demonstrate the possibilities of the approach, a prototype device is designed, fabricated and characterized.     

Multifrequency time-resolved EPR (9.5GHz and 95GHz) on covalently linked porphyrin-quinone model systems for photosynthetic electron transfer: effect of molecular dynamics on electron spin polarization

Covalently linked porphyrin–quinone model systems for photosynthetic electron transfer were examined by using time-resolved electron paramagnetic resonance (TREPR) at intermediate magnetic field and microwave frequency (0.34T/9.5GHz, X-band) and high field and frequency (3.4T/95GHz, W-band). The paramagnetic transients studied were the light-induced spin-correlated radical pair states of the donor–acceptor complex in polar solvents below the melting point and in the soft glass phase of a liquid crystal. It is shown that the systems form strongly exchange-coupled radical pairs, whose TREPR lineshapes are determined mainly by fast electron recombination together with both spin–lattice relaxation and modulation of the exchange interaction. Below the melting point the spin–lattice relaxation rate naturally slows down, but that of the spin on the quinone site is still of the order of 10⁶ s^-1. Most probably this is due to contributions from spin–rotation interaction, and dependent on the molecular orientation with respect to the magnetic field. This relaxation anisotropy is related to anisotropic motion of the quinone site in the solvent cage. The results allow conclusions to be drawn concerning the molecular dynamics and flexibility of the systems. To yield long-lived radical pair states that would mimic photosynthetic electron transfer, the two mechanisms described, modulation of exchange and spin–rotation interactions, have to be suppressed by reducing the molecular flexibility of the complex.     

A CW and pulse EPR spectrometer operating at 122 and 244 GHz using a quasi-optical bridge and a cryogen-free 12 T superconducting magnet

A high-field continuous-wave (CW) and pulse electron paramagnetic resonance spectrometer operating at 122 and 244 GHz is described. The instrument is based on a millimeter-wave bridge built from quasi-optical components. To improve the sensitivity, a cryo-cooled detector/mixer is used. The magnetic field is generated using a cryogen-free superconducting 12 T magnet (warm bore, 88 mm) equipped with a helium-flow cryostat for sample cooling. The advantages of this spectrometer are described and first results (obtained in CW mode) on different types of samples at 122 and 244 GHz are presented. The extensions to pulse operation as well as double resonance techniques (electron-electron and electron-nuclear) are briefly discussed.     

Evidence for Mn clustering in dilute CuMn alloys from high-field (40 T) magnetization curves at 4.2 K

Magnetization curves of CuMn alloys with Mn concentration between 1.5 and 10 at.% have been measured at 4.2 K in fields up to 40 T, using a pulsed-field method.The results found for different concentrations can be scaled upon one another, which is a clear indication for the occurance of magnetic clusters. Analysis of this universal curve in terms of Brillouin functions yields the values $\text{z}{}_{\mathrm{I}}\text{J}{}_{\mathrm{I}}\text{/k??44K}$, $\text{z}{}_{\mathrm{II}}\text{J}{}_{\mathrm{II}}\text{/k??10K}$ and $\text{z}{}_{\mathrm{III}}\text{J}{}_{\mathrm{III}}\text{/k??0.5K}$, for the largest three interactions within each cluster.     

Cryogenic Q-band (35GHz) probehead featuring large excitation microwave fields for pulse and continuous wave electron paramagnetic resonance spectroscopy: performance and applications

The construction and performance of a Q-band (35GHz) cryogenic probehead for pulse electron paramagnetic resonance and continuous wave electron paramagnetic resonance measurements with down-scaled loop gap resonators (LGRs) is presented. The advantage of the LGR in comparison to TE(012) resonators lies in the large B(1) microwave (mw) fields that can be generated with moderate input mw power. We demonstrated with several examples that this allows optimal performance for double-quantum electron coherence, HYSCORE, and hyperfine decoupling experiments employing matched and high turning angle mw pulses with high B(1)-fields. It is also demonstrated that with very low excitation power (i.e. 10-40 mW), B(1)-fields in LGRs are still sufficient to allow short mw pulses and thus experiments such as HYSCORE with high-spin systems to be performed with good sensitivity. A sensitivity factor Lambda(rs) of LGRs with different diameters and lengths is introduced in order to compare the sensitivity of different resonant structures. The electromagnetic field distribution, the B(1)-field homogeneity, the E(1)-field strength, and the microwave coupling between wave guide and LGRs are investigated by electromagnetic field calculations. The advantage and application range using LGRs for small sample diameters is discussed.     

Variable-frequency EPR study of Mn(2+)-doped NH(4)Cl(0.9)I(0.1) single crystal at 9.6, 36, and 249.9 GHz: structural phase transition

Multifrequency electron paramagnetic resonance studies on the Mn(2+) impurity ion in a mixed single crystal NH(4)Cl(0.9)I(0.1) were carried out at 9.62 (X-band) in the range 120-295 K, at 35.87 (Q-band) at 77 and 295 K, and at 249.9 GHz (far-infrared band) at 253 K. The high-field EPR spectra at 249.9 GHz are well into the high-field limit leading to a considerable simplification of the spectra and their interpretation. Three magnetically inequivalent, but physically equivalent, Mn(2+) ions with their respective magnetic Z-axes oriented along the crystallographic [100], [010], [001] axes were observed. Simultaneous fitting of EPR line positions observed at X-, Q-, and far infra-red bands was performed using a least-squares procedure and matrix diagonalization to estimate accurately the Mn(2+) spin-Hamiltonian parameters. The temperature variation of the linewidth and peak-to-peak intensities of the EPR lines indicate the presence of lambda-transitions in the mixed NH(4)Cl(0.9)I(0.1) crystal at 242 and 228 K consistent with those observed in the pure NH(4)Cl and NH(4)I crystals, respectively. A superposition-model analysis of the spin-Hamiltonian parameters reveals that the local environment of the Mn(2+) ion is considerably reorganized to produce axially symmetric crystal fields about the respective Z-axes of the three magnetically inequivalent ions as a consequence of the vacancy created due to charge-compensation when the divalent Mn(2+) ion substitutes for a monovalent NH(4)(+) ion in the NH(4)Cl(0.9)I(0.1) crystal. This reorganization is almost the same as that observed in NH(4)Cl and NH(4)I single crystals, although the latter two are characterized by different, simple cubic and face-centered cubic, structures.     

A variable temperature EPR study of Mn(2+)-doped NH(4)Cl(0.9)I(0.1) single crystal at 170 GHz: zero-field splitting parameter and its absolute sign

EPR measurements have been carried out on a single crystal of Mn(2+)-doped NH(4)Cl(0.9)I(0.1) at 170-GHz in the temperature range of 312-4.2K. The spectra have been analyzed (i) to estimate the spin-Hamiltonian parameters; (ii) to study the temperature variation of the zero-field splitting (ZFS) parameter; (iii) to confirm the negative absolute sign of the ZFS parameter unequivocally from the temperature-dependent relative intensities of hyperfine sextets at temperatures below 10K; and (iv) to detect the occurrence of a structural phase transition at 4.35K from the change in the structure of the EPR lines with temperature below 10K.     

Quantifying cortical bone free water using short echo time (STE-MRI) at 1.5 T

PurposeThe purpose of our study was to use Dual-TR STE-MR protocol as a clinical tool for cortical bone free water quantification at 1.5 T and validate it by comparing the obtained results (MR-derived results) with dehydration results.MethodsHuman studies were compliant with HIPPA and were approved by the institutional review board. Short Echo Time (STE) MR imaging with different Repetition Times (TRs) was used for quantification of cortical bone free water T₁ (T₁free) and concentration (ρ_free). The proposed strategy was compared with the dehydration technique in seven bovine cortical bone samples. The agreement between the two methods was quantified by using Bland and Altman analysis. Then we applied the technique on a cross-sectional population of thirty healthy volunteers (18F/12M) and examined the association of the biomarkers with age.ResultsThe mean values of ρ_free for bovine cortical bone specimens were quantified as 4.37% and 5.34% by using STE-MR and dehydration techniques, respectively. The Bland and Altman analysis showed good agreement between the two methods along with the suggestion of 0.99% bias between them. Strong correlations were also reported between ρ_free (r² = 0.62) and T_1free and age (r² = 0.8). The reproducibility of the method, evaluated in eight subjects, yielded an intra-class correlation of 0.95.ConclusionSTE-MR imaging with dual-TR strategy is a clinical solution for quantifying cortical bone ρ_free and T_1free.     

Development of 394.6 GHz CW Gyrotron (Gyrotron FU CW II) for DNP/Proton-NMR at 600 MHz

Gyrotron FU CW II with an 8 T liquid He free superconducting magnet, the second gyrotron of the THz Gyrotron FU CW Series, has been constructed and the operation test was successfully carried out. It will be used for enhancing the sensitivity of 600 MHz proton-NMR by use of Dynamic Nuclear Polarization (DNP). The designed operation mode of the gyrotron is TE_2,6 at the second harmonic. The corresponding frequency is 394.6 GHz. The real operation frequency is 394.3 GHz at TE₀₆ mode, because of fabrication error of the diameter of the cavity. The operation is in complete CW at the output power of around 30 W or higher at the TE₀₆ cavity mode. There are many other operation modes at the fundamental and the second harmonic. Typical output power of the fundamental and the second harmonic are higher than 100 W and 20 W, respectively. The highest frequency observed up to the present is 443.5 GHz at the second harmonic operation of TE_6,5 mode. The measured results are compared with the theoretical consideration.     

31P/1H WALTZ-4 broadband decoupling at 1.5 T: different versions of the composite pulse and consequences when using a surface coil

Two derivatives of the wideband alternating-phase low-power technique for zero-residual splitting (WALTZ)-4 decoupling sequence for broadband decoupling named WALTZ-4a and WALTZ-4b were compared for their proton decoupling performance in ³¹P nuclear magnetic resonance (NMR) spectroscopy using a Siemens Magnetom SP 1.5 T whole-body imager. Version WALTZ-4a originally implemented by the manufacturer doubles and triples the transmitter amplitude of the 90° pulse to achieve the 180° and 270° flip angle required for one composite pulse R in the WALTZ sequence. WALTZ-4b follows the sequence reported from Shaka et al. and leaves the transmitter amplitude constant but increases the durations of the 180° and 270° pulses. The decoupling performance of WALTZ-4b is superior because it requires less transmitter power and, therefore, it is advantageous in all in vivo studies where a low specific absorption rate is desired. When WALTZ-4 is used in combination with a surface coil for transmission the theoretically required flip angles cannot be achieved in the entire sensitive volume of the coil. The decoupling performance was therefore investigated at lower and higher flip angles. Again, WALTZ-4b is advantageous and provides, in certain ranges that are off-resonant from the decoupling frequency, a good decoupling quality even for flip angles that are only 60% of the theoretically required.     

Fourier-transform microwave spectroscopy of the deuterated acetylene dimers: The interconversion tunneling motions of (DCCD)2, (DCCH)2, DCCD---DCCH, DCCH---DCCD, HCCH---DCCD, and HCCH---DCCH

Microwave spectra of the deuterated acetylene dimers, produced in a molecular beam at 1 K from samples of HCCH, DCCH, and DCCD, were observed using a Fourier transform microwave spectrometer. We observed all variations of deuterated acetylene dimers in which a deuterium atom participates in the hydrogen bond; i.e., (DCCD)₂, (DCCH)₂, DCCD---DCCH, DCCH---DCCD, HCCH---DCCD, and HCCH---DCCH. Deuterated acetylene dimers with the hydrogen atom located in the hydrogen bond could not be detected. Precise molecular constants were determined for each species. Among the dimers identified, (DCCD)₂, (DCCH)₂, DCCD---DCCH, and DCCH---DCCD showed evidence of an interconversion tunneling motion like the tunneling observed for (HCCH)₂. The tunneling potential of (DCCD)₂ was analyzed using a one-coordinate model and the potential depth was determined to be V₄ = 35.577 cm⁻¹, which is 2.371 cm⁻¹ deeper than that of (HCCH)₂ studied by Fraser et al. (J. Chem. Phys. 89, 6028–6045 (1988)). A one-coordinate model was also applied to the other deutered acetylene dimers by adopting a further assumption of a composite potential.     

Rapid preparation of Mg（B1-xCx）2 superconductor using hybrid microwave method

The crystal structure and the superconductivity for samples Mg（B1-xCx）2 （0〈 x 〈0.09） prepared by a hybrid microwave synthesis have been investigated. The starting material B10C is also obtained by using the microwave method. The carbon can distribute uniformly in the Mg（B1-xCx）2 samples because boron and carbon are mixed on an atomic scale in the staring material B10C. The dependences of both lattice parameters and superconducting transition temperature Tc on carbon content accord with those reported in the literature. The upper critical field He2 at 20 K can be enhanced from about 4.3 T for x = 0 to 10 T for x = 0.05. The critical current density Jc of Mg（B0.95 C0.05）2 is 1.05×10^4 A/cm^2 at 20 K and 1 T.