Data processing in NMR relaxometry using the matrix pencil.

The matrix pencil method (MPM) is explored for stable, reproducible data processing in nuclear magnetic resonance (NMR) relaxometry. Data from one-dimensional and two-dimensional relaxometry experiments designed to measure transverse relaxation T2, longitudinal relaxation T1, diffusion coefficient D values, and their correlations in a standard olive oil/water mixture serve as a platform available to any NMR spectroscopist to compare the performance of the MPM to the benchmark inverse Laplace transform (ILT). The data from two practical examples, including the drying of a solvent polymer system and the enzymatic digestion of polysialic acid, were also explored with the MPM and ILT. In the cases considered here, the MPM appears to outperform the ILT in terms of resolution and stability in the determination of fundamental constants for complex materials and mixtures.

Experimental estimates of compression heating and decompression cooling in ethylene glycol.

The chemical shift difference, Δσ, between the methylene and hydroxyl protons in the high resolution 1 H nuclear magnetic resonance spectrum of ethylene glycol is shown to be pressure dependent. The equilibrium Δσ values for ethylene glycol are reported as a function of temperature and pressure between ambient conditions, 323 K and 2 kbar, respectively. This surface is used along with Δσ values measured in response to a rapid pressure increase to calculate a temperature rise that is used to infer a temperature change for water that is consistent with theoretical estimates. This work implies that compression heating and decompression cooling are not significant enough to interfere with pressure induced protein folding studies.

Analytical approximations to inhomogeneously broadened, radiation damped free precession and echo signals.

The Dirac-Frenkel-Maclachlan (DFM) variation of parameters approach to approximately solving the time dependent Schrödinger equation is used to generate free precession and echo signals from the Bloch equations corrected for the effects of radiation damping and inhomogeneous broadening. Following a brief description of how the DFM method can be applied to the non-linear Bloch equations, two figures of merit designed to evaluate how a DFM optimized approximation compares with the exact solution is provided. This framework is used to optimize and evaluate the performance of six trial functions describing inhomogeneously broadened, radiation damped free precession and echo signals. The trial functions are then used to analyze the resolution enhancement and signal attenuation produced by pulse sequences that suppress radiation damping.

Application of bivariate statistics to full wine bottle diamagnetic screening data.

A bivariate correlated Student distribution is applied to full wine bottle diamagnetic screening measurements. Previous work involving a limited number of rare wines indicated that like wines cluster in a plot of the first two principal component scores derived from a covariance matrix of the diamagnetic screening measurements. This study extends the approach to a much larger, statistically meaningful sixty bottle wine library where bivariate statistics are used to comment on the measured data. The full bottle diamagnetic screening of thirty-six identically labeled, sealed bottles of wine obtained from four different sources combined with principal component analysis data reduction followed by treatment with a bivariate distribution permit the effect of wine transport and storage to be observed. The usefulness and future success of the method towards the identification of counterfeit wines is mentioned.

A single coil radio frequency gradient probe for nuclear magnetic resonance applications.

A single coil nuclear magnetic resonance (NMR) probehead and associated electronics capable of asynchronously applying both homogeneous and inhomogeneous radio frequency (rf) pulses to solid, liquid, or gaseous samples is described. This equipment can be interfaced with a conventional single channel NMR spectrometer. Carefully placed PIN diodes on the NMR probehead are used to switch the coil between a homogeneous end tapped configuration and an inhomogeneous center tapped rf gradient configuration. This approach dramatically improves channel isolation in comparison to existing two coil designs. Descriptions of the new probehead, the transistor-transistor logic (TTL) controlled dc pulser for PIN diode gating, and the high power rf switch are provided. Several NMR pulse sequences are used to test the channel isolation and probe performance. Finally an application to liquid phase solvent suppression is provided.

The time dependent Dirac-Frenkel-McLachlan variation of parameters: an NMR application.

The time dependent variation of parameters solution to the time dependent Schrödinger equation pioneered by Dirac, Frenkel, and McLachlan is described in terms useful for immediate application to complex time dependent problems in magnetic resonance. A benchmark comparison of the theory to one dimensional images and spin echo envelope signals in simple spatially varying magnetic fields with molecular diffusion is provided.

Using low frequency full bottle diamagnetic screening to study collectible wine.

A low frequency ν < 30 MHz spectrometer capable of noninvasively and nondestructively screening the diamagnetic properties of full intact bottles of wine is described, and along with principal component analysis, used to compare and contrast sealed bottles of wine. The sensitivity of this approach to various ionic and molecular wine solutes is established by analyzing standard solutions. The successful application of this full bottle method to a library of collectible wine is discussed and suggests that the method can be used to identify counterfeit wine without violating the bottle.

Using low frequency dielectric absorption to screen full intact wine bottles.

A ν<25 MHz low frequency spectrometer capable of noninvasively and nondestructively screening the dielectric properties of full intact bottles of wine is described, and along with principal component analysis, used to screen rare wine. The sensitivity of this full bottle method to various ionic and molecular wine solutes was established by analyzing standard solutions. Application of the approach to a library of collectible wine and the identification of counterfeit wine are discussed.

Cavity ring-down observation of Yb(3+) optical absorption in room temperature solution.

Cavity ring-down spectroscopy is used to probe the optical absorption of the optical pseudo-two level system [Xe]4f(13) Yb(3+) in room temperature solution, a situation where the two-color pump-probe luminescence approach commonly used to study the other [Xe]4f(n) (2 < or = n < or = 12) trivalent lanthanide ions fails. A 1m optical cavity constructed from two highly reflective mirrors is used to obtain ring-down signals as a function of wavelength from 1 mL samples contained in a quartz cuvette placed in the center of the cavity. Absorption spectra constructed from these signals characteristic of the (6)H(15/2)-->(4)F(9/2) [Xe]4f(5) Dy(3+) and the (7)F(0)-->(5)D(0) [Xe]4f(6) Eu(3+) transitions are presented and compared to the corresponding single pass absorption and two-color pump-probe luminescence spectra to obtain sensitivity estimates. Finally the spectrum for the (2)F(5/2)-->(2)F(7/2) [Xe]4f(13) Yb(3+) transition for a model Yb(3+) complex in room temperature solution is obtained using cavity ring-down spectroscopy for the first time.

Using liquid and solid state NMR and photoluminescence to study the synthesis and solubility properties of amine capped silicon nanoparticles.

Water soluble silicon nanoparticles were prepared by the reaction of bromine terminated silicon nanoparticles with 3-(dimethylamino)propyl lithium and characterized with liquid and solid state nuclear magnetic resonance (NMR) and photoluminescence (PL) spectroscopies. The surface site dependent 29Si chemical shifts and the nuclear spin relaxation rates from an assortment of 1H-29Si heteronuclear solid state NMR experiments for the amine coated reaction product are consistent with both the 1H and 13C liquid state NMR results and routine transmission electron microscopy, ultra-violet/visible, and Fourier transform infrared measurements. PL was used to demonstrate the pH dependent solubility properties of the amine passivated silicon nanoparticles.

Nuclear spin relaxation of sodium cations in bacteriophage Pf1 solutions.

The nuclear magnetic resonance (NMR) spectra for the I=3/2 23Na cation dissolved into filamentous bacteriophage Pf1 solutions display line splittings and relaxation times consistent with an interaction between the 23Na nuclear quadrupole moment and the electric field gradient produced by the negatively charged Pf1 particles. The 23Na NMR line splittings and relaxation rates corresponding to magnetization recovery and single, double, and triple quantum coherence decays are measured in Pf1 solutions and compared to theoretical values. The deviation of the observed dc spectral density J0 from the equal first harmonic J(omega0) and second harmonic J(2omega0) values as J(omega0)=J(2omega0) not equal to J0 in these solutions suggests that ion migration in the electric field gradient of the Pf1 particles produces an anisotropic relaxation mechanism. Correlation functions and thus spectral densities for this process are calculated from solutions to the Fokker-Planck equation for radial motion in an electric potential and used to estimate measured relaxation rates. Appropriate electric potentials are generated from the solutions to the Poisson-Boltzmann equation for a charged Pf1 particle in aqueous phase, functions that lead to theoretical estimates of NMR line splittings consistent with experimental observations.

Using NMR to study full intact wine bottles.

A nuclear magnetic resonance (NMR) probe and spectrometer capable of investigating full intact wine bottles is described and used to study a series of Cabernet Sauvignons with high resolution 1H NMR spectroscopy. Selected examples of full bottle 13C NMR spectra are also provided. The application of this full bottle NMR method to the measurement of acetic acid content, the detection of complex sugars, phenols, and trace elements in wine is discussed.

Magnetic resonance imaging of electroconvection in a polar organic solvent.

Molecular motion in the polar organic solvent nitrobenzene induced by an electric field is studied by magnetic resonance imaging. Rf pulse sequences that correlate images obtained at two different times under conditions of both continuous and pulsed electric fields are introduced. The resultant image correlation spectra indicate that the time scale of motion in a 9.6 kV/cm electric field is tens of milliseconds. Comparison of the results to an analytic solution for the Fokker-Planck probability function for one-dimensional bounded diffusion yields an electric field dependent effective diffusion coefficient for perdeuterated nitrobenzene of D = 1.08 x 10(-5) cm(2)/s + (3.33 x 10(-3) cm(4)/kV(2)s) E(2) at room temperature. Characteristics of this electroconvection and its consequences for combining multidimensional nuclear magnetic resonance with electrical orientation are also discussed.

Solid-state and high-resolution liquid 119Sn NMR spectroscopy of some monomeric, two-coordinate low-valent tin compounds: very large chemical shift anisotropies.

High-resolution liquid- and solid-state 119Sn NMR spectroscopy was used to study the bonding environment in the series of monomeric, two-coordinate Sn(II) compounds of formula Sn(X)C6H3-2,6-Trip2 (X = Cl, Cr(eta 5-C5H5)(CO)3, t-Bu, Sn(Me)2C6H3-2,6-Trip2; Trip = C6H2-2,4,6-i-Pr3). The trends in the principal components of the chemical shift tensor extracted from the solid-state NMR data were consistent with the structures determined by X-ray crystallography. Furthermore, the spectra for the first three compounds displayed the largest 119Sn NMR chemical shift anisotropies (up to 3798 ppm) of any tin compound for which data are currently available. Relaxation time based calculations for the dimetallic compound 2,6-Trip2H3C6Sn-Sn(Me)2C6H3-2,6-Trip2 suggests that the chemical shift anisotropy for the two-coordinate tin center may be as much as ca. 7098 ppm, which is as broad as the 1 MHz bandwidth of the NMR spectrometer.

SQUID detected NMR and NQR. Superconducting Quantum Interference Device.

The dc Superconducting QUantum Interference Device (SQUID) is a sensitive detector of magnetic flux, with a typical flux noise of the order 1 muphi0 Hz(-1/2) at liquid helium temperatures. Here phi0 = h/2e is the flux quantum. In our NMR or NQR spectrometer, a niobium wire coil wrapped around the sample is coupled to a thin film superconducting coil deposited on the SQUID to form a flux transformer. With this untuned input circuit the SQUID measures the flux, rather than the rate of change of flux, and thus retains its high sensitivity down to arbitrarily low frequencies. This feature is exploited in a cw spectrometer that monitors the change in the static magnetization of a sample induced by radio frequency irradiation. Examples of this technique are the detection of NQR in 27Al in sapphire and 11B in boron nitride, and a level crossing technique to enhance the signal of 14N in peptides. Research is now focused on a SQUID-based spectrometer for pulsed NQR and NMR, which has a bandwidth of 0-5 MHz. This spectrometer is used with spin-echo techniques to measure the NQR longitudinal and transverse relaxation times of 14N in NH4ClO4, 63+/-6 ms and 22+/-2 ms, respectively. With the aid of two-frequency pulses to excite the 359 kHz and 714 kHz resonances in ruby simultaneously, it is possible to obtain a two-dimensional NQR spectrum. As a third example, the pulsed spectrometer is used to study NMR spectrum of 129Xe after polariza-tion with optically pumped Rb. The NMR line can be detected at frequencies as low as 200 Hz. At fields below about 2 mT the longitudinal relaxation time saturates at about 2000 s. Two recent experiments in other laboratories have extended these pulsed NMR techniques to higher temperatures and smaller samples. In the first, images were obtained of mineral oil floating on water at room temperature. In the second, a SQUID configured as a thin film gradiometer was used to detect NMR in a 50 microm particle of 195Pt at 6 mT and 4.2 K.