Using MRI to Study High Pressure Assisted Nutrient Infusion.

High pressure assisted infusion of nutrients into food was in situ monitored with magnetic resonance imaging (MRI). Modification of an off-the-shelf pressure reactor with an MRI detection circuit provided a large enough volume to accommodate food. The model food used here was peeled apple flesh as it is considered as a good mimic for fibrous food. The nuclear spin relaxation properties of the water surrounding the apple flesh were enhanced by adding paramagnetic manganese cations. In this way, MRI relaxation contrast can be used to monitor the location of doped bulk water in and around the apple flesh during pressurization. This work tracked the efficiency of pressure induced nutrient infusion in situ, demonstrating that pressure gating and ramping offer no nutrient mass transport advantage over operation at constant pressure and that the presence of a peel expectedly disrupts solute transport into the fruit. High pressure assisted infusion, with all pressurization strategies shown here, yielded nearly 100-fold faster infusion times than at ambient pressure.

Coils for large standoff relaxometry with unilateral magnets.

Maximizing standoff distance by direct placement of probe coils on magnet bodies, while maximizing signal-to-noise is critical to the successful application of unilateral NMR. Two types of radio frequency (rf) coils for linear array, unilateral magnets are described: "simple fringe" and "split fringe coils." These coils are designed to fully exploit the standoff distance of the unilateral magnet by placement directly on the magnet surface. Such placement fails for normal surface coils used for magnetic resonance due to eddy current induced shielding by the conductive magnet surface. The coil design strategy includes a rectangular cross section solenoid coil, either continuous or split in the center, mounted with the center axis of the coil parallel to the magnet surface. These geometries, when placed on a conducting surface, enhance the rf field produced in the sample region, outside of the solenoid coil. The spatial homogeneity of both rf coils are characterized using the ANSYS™ finite element modelling software. ANSYS™ modeled coil geometries led to homogeneous, surface displaced rf fields. These coils were then constructed and characterized with magnetic resonance imaging. Finally, two experiments that use these coils to perform large standoff relaxation measurements are described.

Noninvasive, Nondestructive Measurement of Tomato Concentrate Spoilage in Large-Volume Aseptic Packages.

Low frequency nuclear magnetic resonance (NMR) is used to noninvasively and nondestructively detect spoiled tomato concentrate stored in >200 L metal-lined containers. It is shown that longitudinal and transverse NMR relaxation times change as the tomato concentrate spoils. A rapid, viscosity-dependent spoilage detection method that takes advantage of the inherent inhomogeneity in single-sided NMR instruments is proposed. Here, the effective transverse magnetization decay rate is used as a parameter to determine tomato concentrate spoilage. Three different low frequency, single-sided NMR instruments are described and compared to determine the optimum sensor for spoiled tomato concentrate detection in large-format, metal-lined, aseptic containers. The most effective NMR sensor for this application is temperature stable and has large magnetic field gradients and a homogeneous magnetic field region offset >0.5 cm from the magnet surface. PRACTICAL APPLICATION: This manuscript describes a noninvasive and nondestructive tomato concentrate spoilage detector for application to large-format, sealed, commercial storage bins.

A low cost, portable NMR probe for high pressure, MR relaxometry.

A low cost, portable, high volume, stainless steel pressure reactor is modified to easily perform magnetic resonance relaxometry at industrially relevant pressures. Unlike existing pressurization strategies common to nuclear magnetic resonance (NMR) spectroscopy, this approach is amenable to realistic samples that feature heterogeneity and have traditionally escaped NMR study at pressure. This pressure reactor/NMR probe combination is easily accommodated by most single-sided and other low magnetic field permanent magnet assemblies. The performance of the probe is demonstrated by accomplishing NMR relaxometry on polydimethylsiloxane at different pressures with two types of unilateral magnets.

Direct-Write Optical Patterning of P3HT Films Beyond the Diffraction Limit.

Doping-induced solubility control is a patterning technique for semiconducting polymers, which utilizes the reduction in polymer solubility upon p-type doping to provide direct, optical control of film topography and doping level. In situ direct-write patterning and imaging are demonstrated, revealing sub-diffraction-limited topographic features. Photoinduced force microscopy shows that doping level can be optically modulated with similar resolution.

(2) H and (139) La†NMR Spectroscopy in Aqueous Solutions at Geochemical Pressures.

Nuclear spin relaxation rates of (2) H and (139) La in LaCl3 +(2) H2 O and La(ClO4 )3 +(2) H2 O solutions were determined as a function of pressure in order to demonstrate a new NMR probe designed for solution spectroscopy at geochemical pressures. The (2) H longitudinal relaxation rates (T1 ) vary linearly to 1.6 GPa, consistent with previous work at lower pressures. The (139) La T1 values vary both with solution chemistry and pressure, but converge with pressure, suggesting that the combined effects of increased viscosity and enhanced rates of ligand exchange control relaxation. This simple NMR probe design allows experiments on aqueous solutions to pressures corresponding roughly to those at the base of the Earth's continental crust.

Reversible optical control of conjugated polymer solubility with sub-micrometer resolution.

Organic electronics promise to provide flexible, large-area circuitry such as photovoltaics, displays, and light emitting diodes that can be fabricated inexpensively from solutions. A major obstacle to this vision is that most conjugated organic materials are miscible, making solution-based fabrication of multilayer or micro- to nanoscale patterned films problematic. Here we demonstrate that the solubility of prototypical conductive polymer poly(3-hexylthiophene) (P3HT) can be reversibly "switched off" using high electron affinity molecular dopants, then later recovered with light or a suitable dedoping solution. Using this technique, we are able to stack mutually soluble materials and laterally pattern polymer films by evaporation or with light, achieving sub-micrometer, optically limited feature sizes. After forming these structures, the films can be dedoped without disrupting the patterned features; dedoped films have identical optical characteristics, charge carrier mobilities, and NMR spectra as as-cast P3HT films. This method greatly simplifies solution-based device fabrication, is easily adaptable to current manufacturing workflows, and is potentially generalizable to other classes of materials.

Towards using NMR to screen for spoiled tomatoes stored in 1,000 L, aseptically sealed, metal-lined totes.

Nuclear magnetic resonance (NMR) spectroscopy is used to track factory relevant tomato paste spoilage. It was found that spoilage in tomato paste test samples leads to longer spin lattice relaxation times T1 using a conventional low magnetic field NMR system. The increase in T1 value for contaminated samples over a five day room temperature exposure period prompted the work to be extended to the study of industry standard, 1,000 L, non-ferrous, metal-lined totes. NMR signals and T1 values were recovered from a large format container with a single-sided NMR sensor. The results of this work suggest that a handheld NMR device can be used to study tomato paste spoilage in factory process environments.

General implementation of the ERETIC method for pulsed field gradient probe heads.

A capacitive coupling between a secondary radiofrequency (rf) channel and the gradient coil of a standard commercially available high resolution NMR spectrometer and probe head is described and used to introduce a low level exponentially damped rf signal near the frequency of the primary rf channel to serve as an external concentration standard, in analogy to the so-called ERETIC method. The stability of this inexpensive and simple to implement method, here referred to as the Pulse Into the Gradient (PIG) approach, is superb over a 14-h period and both gradient tailored water suppression and one-dimensional imaging applications are provided. Since the low level signal is introduced via the pulsed field gradient coil, the coupling is identical to that for a free induction signal and thus the method proves to be immune (within 5%) to sample ionic strength effects up to the 2M NaCl solutions explored here.

Convergent syntheses of [Sn7{C6H3-2,6-(C6H3-2,6-iPr2)2}21: a cluster with a rare pentagonal bipyramidal motif.

Two complementary synthetic routes to a pentagonal bipyramidal Sn7 cluster, Sn7Aryl2 (Aryl = terphenyl ligand), are reported.

Solid-state 119Sn NMR and Mössbauer spectroscopy of "distannynes": evidence for large structural differences in the crystalline phase.

The "distannynes" Ar'SnSnAr' (Ar' = C6H3-2,6(C6H3-2,6-Pr(i)2)2) and ArSnSnAr (Ar = C6H3-2,6(C6H2-2,4,6-Pr(i)3)2) were examined by solid-state (119)Sn NMR and Mössbauer spectroscopy. The two compounds display substantially different spectroscopic parameters, while differing only in the absence (Ar'SnSnAr') or presence (ArSnSnAr) of a para-Pr(i) group in the flanking aryl rings of their terphenyl substituents. The spectroscopic differences can be interpreted in terms of a more trans-bent geometry and a longer Sn-Sn bond for ArSnSnAr in comparison to the wider Sn-Sn-C angle (125.24(7) degrees ) and shorter Sn-Sn bond length (2.6675(4)A) determined from the crystal structure of Ar'SnSnAr'. The differences are consistent with previously published calculations by Nagase and Takagi for ArSnSnAr.

Towards rapid throughput NMR studies of full wine bottles.

A rapid throughput method for the quantitation of the oxidation level of intact full bottles of wine based on the 1331 water suppression pulse sequence is described. The ideal pulse sequence suppresses water in the (1)H nuclear magnetic resonance spectrum while uniformly and phase coherently exciting the resonances pertaining to ethyl alcohol at 1.1 ppm and oxidation products at 2.1 ppm. The anticipated results of the pulse sequence based on simulations are tested in small sample and full bottle standards and an application to the detection of wine spoilage in more than century old wine is provided.

Energy-transfer dynamics of high-pressure rovibrationally excited molecular H2.

The energy-transfer dynamics of high-pressure molecular H(2) gas initially prepared in the |X (1)Sigma(g) (+),v = 1,J = 1 state using stimulated Raman pumping are probed with rotational Raman scattering. A computer simulation that incorporates the effects of collision-induced vibrational energy transfer is described and used to fit the experimental Raman scattering results obtained as a function of the pump/probe delay time. The 4.78 x 10(-14) +/- 3.85 x 10(-16) cm(3) s(-1) molecule(-1) vibrational energy-transfer rate for decay from the |X (1)Sigma(g) (+),v = 1,J = 1 >state compares well with other lower-pressure studies.

Capture and manipulation of magnetically aligned Pf1 with an aqueous polymer gel.

The magnetic alignment of the Pseudomonas bacteriophage Pf1 is captured indefinitely in a gel of the aqueous triblock copolymer Pluronic F-127. In addition to preserving high-resolution liquids NMR spectra for dissolved solutes, the gel prevents the reorientation of the phage allowing mechanical manipulation of the angle between the axis of the phage alignment and the static magnetic field. The residual 2H quadrupolar couplings for several solutes dissolved in this material as a function of the angle Theta between the non-spinning sample tube and the static magnetic field are consistent with the value of P(2)(cosTheta)=(3cos(2)Theta-1)/2. The variable-angle correlation spectrum for these solutes is shown to separate residual quadrupolar effects from isotropic chemical shifts. Finally, the compatibility of Pluronic F-127 with NMR studies of aqueous biological macromolecules is demonstrated in a measurement of residual dipolar couplings in an 15N-labeled nucleic acid.

Solution reduction synthesis of surface stabilized silicon nanoparticles.

This paper describes the preparation of air and moisture stable octanol derivatized crystalline silicon nanoparticles by room temperature sodium naphthalenide reduction of silicon halides.