Proton spin relaxation in bisphenol-a polycarbonate,butyl rubber,and their composites

Proton spin-lattice relaxation times of bisphenol-A polycarbonate, butyl rubber, and blends of the two polymers were studied at 18 Mc/sec in the temperature range 90°-450°K. The proton spin-lattice relaxation is primarily dipolar in each polymer, due to methyl group reorientation and to reorientation of chain segments. In a blend of bisphenol-A polycarbonate with 7 and 10 wt of butyl, a nonexponential decay of magnetization was observed in the temperature range 280°-380°K. This was explained by the existence of two spin temperatures in these blends, indicating that processes which bring about the equilibrium within the spin system are slow compared to the spin-lattice relaxation times of the two components of the blend.     

N-正丁基苯胺的13C自旋晶格弛豫研究

本文采用反转回复法(180°-τ-90°-Τ)_n脉冲序列测定了N-正丁基苯胺在两种温度下,各¹³C核总的自旋-晶格弛豫时间T₁和NOE因子η_с值,通过计算估计了各种弛豫机理的贡献大小,并求出了分子无规则运动的相关时间τ_с,进一步讨论了此分子的动力学状况。     

Spin relaxation measurements using first-harmonic out-of-phase absorption EPR signals: rotational motion effects

A recent survey of nonlinear continuous-wave (CW) EPR methods revealed that the first-harmonic absorption EPR signal, detected 90 degrees out of phase with respect to the Zeeman modulation (V(1)(')-EPR), is the most appropriate for determining spin-lattice relaxation enhancements of spin labels (V. A. Livshits, T. Páli, and D. Marsh, 1998, J. Magn. Reson. 134, 113-123). The sensitivity of such V(1)(')-EPR spectra to molecular rotational motion is investigated here by spectral simulations for nitroxyl spin labels, over the entire range of rotational correlation times. Determination of the effective spin-lattice relaxation times is less dependent on rotational mobility than for other nonlinear CW EPR methods, especially at a Zeeman modulation frequency of 25 kHz which is particularly appropriate for spin labels. This relative insensitivity to molecular motion further enhances the usefulness of the V(1)(')-EPR method. Calibrations of the out-of-phase to in-phase spectral intensity (and amplitude) ratios are given as a function of spin-lattice relaxation time, for the full range of spin-label rotational correlation times. Experimental measurements on spin labels in the slow, intermediate, and fast motional regimes of molecular rotation are used to test and validate the method.     

Radiofrequency pulse sequences which compensate their own imperfections. 1980

Radiofrequency pulse sequences are described which have the same overall effect as a single 90° or 180° pulse but which compensate the undesirable effects of resonance offset and spatial inhomogeneity of the radiofrequency field H₁. These “composite” pulses are built up from a small number of conventional pulses which rotate the nuclear magnetization vectors about different axes in the rotating frame, while in the intervals between pulses a limited amount of free precession may be allowed to occur. Insight into the way in which pulse imperfections are compensated is obtained by computer simulation of trajectories of families of nuclear spin “isochromats” representing a distribution of H₁ intensity or resonance offset. Composite 90° pulses are suggested as a method of reducing systematic errors in spin-lattice relaxation times derived from progressive saturation or saturation-recovery experiments, and as the preparation pulse of a spin-locking experiment. A test of the effectiveness of the composite 180° pulse sequence has been made by using it for population inversion in a spin-lattice relaxation measurement, where T₁ is derived from the null point in the recovery curve, a technique known to be very sensitive to pulse imperfections.     

红宝石中自旋—晶格弛豫直接过程的计算

本文计算了在低温、低浓度下红宝石基态自旋-晶格弛豫的直接过程。应用强场耦合表象中基态的二级微扰波函数,在θ=90°,脉冲饱和法测量条件下,计算了基态四能级之间的无辐射跃迁几率。然后,用求解粒子数方程的方法,计算1.4°K的自旋-晶格弛豫时间。计算结果与Pace等人的实验结果较好地符合。     

Comparing continuous wave progressive saturation EPR and time domain saturation recovery EPR over the entire motional range of nitroxide spin labels

The measurement of spin-lattice relaxation rates from spin labels, such as nitroxides, in the presence and absence of spin relaxants provides information that is useful for determining biomolecular properties such as nucleic acid dynamics and the interaction of proteins with membranes. We compare X-band continuous wave (CW) and pulsed or time domain (TD) EPR methods for obtaining spin-lattice relaxation rates of spin labels across the entire range of rotational motion to which relaxation rates are sensitive. Model nitroxides and spin-labeled biological species are used to illustrate the potential complications that arise in extracting relaxation data under conditions typical to biological experiments. The effect of super hyperfine (SHF) structure is investigated for both CW and TD spectra. First and second harmonic absorption and dispersion CW spectra of the nitroxide spin label, TEMPOL, are all fit simultaneously to a model of SHF structure over a range of microwave amplitudes. The CW spectra are novel because all harmonics and microwave phases were acquired simultaneously using our homebuilt CW/TD spectrometer. The effect of the SHF structure on the pulsed free induction decay (FID) and pulsed saturation recovery spectrum is shown for both protonated and deuterated TEMPOL. We present novel pulsed saturation recovery measurements on biological molecules, including spin-lattice relaxation rates of spin-labeled proteins and spin-labeled double-stranded DNA. The impact of structure and dynamics on relaxation rates are discussed in the context of each of these examples. Collisional relaxation rates with oxygen and transition metal paramagnetic relaxants are extracted using both continuous wave and time domain methods. The extent of the errors inherent in the CW method and the advantages of pulsed methods for unambiguously measuring collisional relaxation rates are discussed. Spin-lattice relaxation rates, determined by both CW and pulsed methods, are used to determine the electrostatic potential on the surface of a protein.     

Low Field (10 mT) Pulsed Dynamic Nuclear Polarization

EPR irradiation by a train of inverting pulses has potential advantages over continuous-wave EPR irradiation in DNP applications; however, it has previously been used only at high field (5 T). This paper presents the design and testing of an apparatus for performing pulsed DNP experiments at 10 mT with large samples (17 ml). Experimental results using pulsed DNP with an aqueous solution of a narrow-linewidth paramagnetic probe are presented. A maximum DNP enhancement of about -36 with a train of inverting pulses (width 500 ns, repetition time 4 micros) was measured. A preliminary comparison showed that, when the same enhancement value is considered, the pulsed DNP technique requires an average power that is about three times higher than that required with the CW irradiation. However, for in vivo DNP applications it is very important to minimize the average power deposited in the sample. From the experimental results reported in this work, when considering the maximum enhancement, the pulsed technique requires only 2% of the average power necessary with the CW DNP technique. We believe that this reduction in the average power can be important for future DNP studies with large biological samples.     

Semiempirical analysis of spin-lattice relaxation in rare earth Kramers' doublets

The spin-lattice coupling constants of Kramers' doublet measured in uniaxial stress experiments, are used to calculate the spin-lattice relaxation times in the direct process range. A comparison with experimental data shows that a true spin lattice relaxation time was obtained only when T₁ was measured as a function of magnetic field at high fields. We suggest that the effect of the phonon bottleneck is important at lower fields.     

Spin relaxation of Mn ions in (CdMn)Te/(CdMg)Te quantum wells under picosecond optical pumping

Spin relaxation of Mn ions in a Cd_0.97Mn_0.03Te/Cd_0.75Mg_0.25Te quantum well with photogenerated quasi-two-dimensional electron-hole plasma at liquid helium temperatures in an external magnetic field has been investigated. Heating of Mn ions by photogenerated carriers due to spin and energy exchange between the hot electron-hole plasma and Mn ions through direct sd-interaction between electron and Mn spins has been detected. This process has a short characteristic time of about 4 ns, which leads to appreciable heating of the Mn spin subsystem in about 0.5 ns. Even under uniform excitation of a dense electron-hole plasma, the Mn heating is spatially nonuniform, and leads to formation of spin domains in the quantum well magnetic subsystem. The relaxation time of spin domains after pulsed excitation is measured to be about 70 ns. Energy relaxation of excitons in the random exchange potential due to spin domains results from exciton diffusion in magnetic field B=14 T with a characteristic time of 1 to 4 ns. The relaxation time decreases with decreasing optical pump power, which indicates smaller dimensions of spin domains. In weak magnetic fields (_B=2 T) a slow down in the exciton diffusion to 15 ns has been detected. This slow down is due to exciton binding to neutral donors (formation of bound excitons) and smaller spin domain amplitudes in low magnetic fields. The optically determined spin-lattice relaxation time of Mn ions in a magnetic field of 14 T is 270±10 and 16±7 ns for Mn concentrations of 3% and 12%, respectively. Zh. éksp. Teor. Fiz. 112, 1440–1463 (October 1997)     

Development of the Earth’s Field NMR Spectrometer for Liquid Screening

Earth??s field nuclear magnetic resonance (NMR) can be used for non-destructive in-bottle liquid screening by evaluating the spin?Clattice relaxation times of protons in various liquids. An Earth??s field NMR apparatus has been developed and optimized to measure the spin?Clattice relaxation times of various liquids contained in 500?ml PET bottles. Two methods to generate 90-degree readout pulses using transient oscillating signals generated in a resonator are reported. The lower detection limit of pure water was 1?ml. The minimum measurable spin?Clattice relaxation time was 50?ms.     

Study of the effect of a low-frequency magnetic field on the spin-lattice relaxation in water and in aqueous solutions

The spin-lattice relaxation times in water and NaCl aqueous solutions in a low-frequency magnetic field have been measured on natural-concentration ¹⁷O nuclei. The activation energies have been calculated. The differences in the temperature dependences of the spin-lattice relaxation time and the changes in the relaxation with the magnetic field frequency are established.     

Electron spin-lattice relaxation time and spectral diffusion in γ-irradiated l-alanine

We performed continuous (CW) wave and pulsed ESR experiments to obtain information on the relaxation behavior of the l-alanine radical in an irradiated single crystal. The analysis of the CW saturation behavior gives a relaxation time of 2.8 μs. The echo detected saturation recovery was obtained for a number of different experimental conditions. In any case only a portion of the 120 G wide ESR spectrum can be affected by the microwave (MW) pulses, spectral diffusion is active and a multi-exponential decay is therefore obtained. We measured characteristic spectral diffusion times of 1–10 and 20–50 μs. We found that a long time of about 200 μs can be measured only by using a train of long selective saturating pulses and short detecting pulses. The stimulated echo decay is bi-exponential, and the characteristic times are very short. A variable temperature investigation in the range 200 to 290 K showed that the decay is governed by the spectral diffusion and by the transverse nuclear spin relaxation timeT _2n of the methyl protons.     

Nuclear spin-lattice relaxation in the mixed state of superconducting niobium

Pulsed NMR measurements of the spin-lattice relaxation timeT ₁ have been carried out in niobium metal, in order to investigate the elementary excitation spectrum in the superconducting mixed state. The dependences ofT ₁ on temperature, external field, and mean free path were determined. The results below ～5°K were in agreement with the theory of field-induced gapless superconductivity. The best fit was obtained with a scale factor 0.35±0.2, in agreement with recent ultrasonic attenuation results. Anomalously fast relaxation was observed above ～5°K, which could not be interpreted in terms of the present theory of thermal vortex fluctuations.     

31P and 11B NMR in amorphous NiPB alloys near the paramagnetic-ferromagnetic transition

Knight-shift and nuclear spin-lattice relaxation time measurements have been performed between 4.2°K and room temperature on ¹¹B and ³¹P in amorphous NiPB alloys near the para-ferromagnetic transition. The EFG parameters on ¹¹B were found to be ν_Q=200(±20)kHz and η = 0.35 (±0.10). Knight-shift and Korringa spin-lattice relaxation are mainly due to mechanisms involving p electrons. The effect of Ni magnetic clouds results in a broadening of the linewidth. We observed also the occurence of a Giovannini-Heeger-like contribution to the spin-lattice relaxation rate.     

Selective Decoupling

Low-power broadband decoupling sequences WALTZ-16 and GARP-1 generate large far-from-resonance frequency modulations which preclude selectivity. The framework developed to construct these broadband sequences is modified to permit selective spin decoupling. Selective-decoupling sequences are created from shaped 90° pulses combined consecutively using WALTZ permutations and supercycle symmetry while shaped 180° pulses are combined in supercycle symmetry to make inversion-based decoupling sequences. Simulations and experiments compare the decoupling bandwidth, frequency selectivity, and quality of near-resonance decoupling for broadband and selective-decoupling sequences.     

Optical parametric oscillator pumped by relaxation oscillation pulses of a mechanically Q-switched Nd:YAG laser

We report the generation of mid-infrared pulsed radiation between 2.2 and 3 μm range using a singly-resonant optical parametric oscillator (SR-OPO) based on a 40-mm-long crystal of periodically-poled LiNbO₃ (PPLN) pumped by mechanically Q-switched pulses from a Nd:YAG laser, obtained by chopping the beam inside the laser resonator over a 1–10 kHz duty cycle. An appreciable reduction in pulse width as well as the number of relaxation oscillation pulses of the Nd:YAG pump laser is observed when the frequency of the Q-switch chopper is increased up to 10 kHz. Sub-nanosecond relaxation oscillation pulses of about 170–210 ns duration are generated under the width of the idler envelope varying from 4.6 to 8.55 μs. The same behavior is observed for the signal wave. A maximum extraction efficiency of 22 % is obtained for the idler, corresponding to 785 mW of output power at 10 kHz. The tuning of the signal and idler beams were performed by temperature variation of the PPLN crystal within 100–200 °C range.     

Electron spin relaxation via vibronic level of rhodium(II) hexacyanide complex in KCl crystal

Electron spin-lattice relaxation rates for the low-spin [Rh(CN)(6)](4-) complex in KCl were measured by the inversion recovery and saturation recovery techniques, in the range of 5 to 30 K. Angular variation experiments indicate that electron spin-lattice relaxation times present axial symmetry. The data fit very well to a relaxation process involving localized anharmonic vibration modes, also responsible for the g tensor temperature dependence.     

Measurement of spin-lattice relaxation times with longitudinal detection

New experimental schemes to measure spin-lattice relaxation times T₁ on the basis of inversion-recovery and saturation-recovery experiments with longitudinal detection are introduced. With this approach, paramagnetic species with T₁ values as short as 20 ns can be measured. Possibilities to reduce unwanted signals and instrumental artifacts are analyzed. An experiment where the signal is induced directly by the time-dependent M₂ magnetization is also proposed. Experimental results for organic radicals and defect centers are presented and compared with data obtained with conventional techniques, and a metal complex at 250 K is analyzed where it is very difficult to get information about relaxation times with established methods because of fast spin-spin relaxation.     

Broadband and narrowband composite excitation sequences

Novel broadband and narrowband composite 90° pulses are derived for use in NMR spectroscopy. The broadband pulses excite transverse magnetization with nearly constant amplitude and phase over a very wide range of values of the radiofrequency field strength. These composite pulses are therefore suitable models for designing improved broadband multiple-pulse techniques. Broadband INEPT and Jeener-Broekaert experiments are demonstrated.     

Cross-polarisation method for improvement of 14N NQR signal detectability

This is a study of the cross-polarization effects in the case of 14N quadrupolar spin-system with a long spin-lattice relaxation time. Two important benefits of the cross-polarization technique were demonstrated for PETN: (i) a polarization transfer resulting in increased NQR single shot signal response and (ii) a dynamic reduction in recovery time of the NQR system allowing scan repetition on a much shorter timescale. It was proved that this technique can reduce the optimal waiting time between pulse sequences up to 60 times through a significant reduction of the relaxation time of the quadrupolar spin-system. All experiments were carried out at room temperature using spin-locking multi-pulse sequences and small external magnetic field.