Portable microcoil NMR detection coupled to capillary electrophoresis.

High-efficiency separation techniques, such as capillary electrophoresis (CE), coupled to a nondestructive nuclear magnetic resonance (NMR) spectrometer offer the ability to separate, chemically identify, and provide structural information on analytes in small sample volumes. Previous CE-NMR coupled systems utilized laboratory-scale NMR magnets and spectrometers, which require very long separation capillaries. New technological developments in electronics have reduced the size of the NMR system, and small 1-2 T permanent magnets provide the possibilities of a truly portable NMR. The microcoils used in portable and laboratory-scale NMR may offer the advantage of improved mass sensitivity because the limit of detection (LOD) is proportional to the coil diameter. In this work, CE is coupled with a portable, briefcase-sized NMR system that incorporates a microcoil probe and a 1.8 T permanent magnet to measure (19)F NMR spectra. Separations of fluorinated molecules are demonstrated with stopped- and continuous-flow NMR detection. The results demonstrate that coupling CE to a portable NMR instrument is feasible and can provide a low-cost method to obtain structural information on microliter samples. An LOD of 31.8 nmol for perfluorotributylamine with a resolution of 4 ppm has been achieved with this system.

Metal-organic frameworks as templates for nanoscale NaAlH4.

Metal-organic frameworks (MOFs) offer an attractive alternative to traditional hard and soft templates for nanocluster synthesis because their ordered crystalline lattice provides a highly controlled and inherently understandable environment. We demonstrate that MOFs are stable hosts for metal hydrides proposed for hydrogen storage and their reactive precursors, providing platform to test recent theoretical predictions that some of these materials can be destabilized with respect to hydrogen desorption by reducing their critical dimension to the nanoscale. With the MOF HKUST-1 as template, we show that NaAlH(4) nanoclusters as small as eight formula units can be synthesized. The confinement of these clusters within the MOF pores dramatically accelerates the desorption kinetics, causing decomposition to occur at approximately 100 degrees C lower than bulk NaAlH(4). However, using simultaneous thermogravimetric modulated beam mass spectrometry, we also show that the thermal decomposition mechanism of NaAlH(4) is complex and may involve processes such as nucleation and growth in addition to the normally assumed two-step chemical decomposition reactions.

Magnetic resonance flow velocity and temperature mapping of a shape memory polymer foam device.

BACKGROUND: Interventional medical devices based on thermally responsive shape memory polymer (SMP) are under development to treat stroke victims. The goals of these catheter-delivered devices include re-establishing blood flow in occluded arteries and preventing aneurysm rupture. Because these devices alter the hemodynamics and dissipate thermal energy during the therapeutic procedure, a first step in the device development process is to investigate fluid velocity and temperature changes following device deployment. METHODS: A laser-heated SMP foam device was deployed in a simplified in vitro vascular model. Magnetic resonance imaging (MRI) techniques were used to assess the fluid dynamics and thermal changes associated with device deployment. RESULTS: Spatial maps of the steady-state fluid velocity and temperature change inside and outside the laser-heated SMP foam device were acquired. CONCLUSIONS: Though non-physiological conditions were used in this initial study, the utility of MRI in the development of a thermally-activated SMP foam device has been demonstrated.

Thermal degradation in a trimodal poly(dimethylsiloxane) network studied by (1)H multiple quantum NMR.

Thermal degradation of a filled, cross-linked siloxane material synthesized from poly(dimethylsiloxane) chains of three different average molecular weights and with two different cross-linking species has been studied by (1)H multiple quantum (MQ) NMR methods. Multiple domains of polymer chains were detected by MQ NMR exhibiting residual dipolar coupling () values of 200 and 600 Hz, corresponding to chains with high average molecular weight between cross-links and chains with low average molecular weight between cross-links or near the multifunctional cross-linking sites. Characterization of the values and changes in distributions present in the material were studied as a function of time at 250 degrees C and indicate significant time-dependent degradation. For the domains with low , a broadening in the distribution was observed with aging time. For the domain with high , increases in both the mean and the width in were observed with increasing aging time. Isothermal thermal gravimetric analysis reveals a 3% decrease in weight over 20 h of aging at 250 degrees C. Degraded samples also were analyzed by traditional solid-state (1)H NMR techniques, and off-gassing products were identified by solid-phase microextraction followed by gas chromatography-mass spectrometry. The results, which will be discussed here, suggest that thermal degradation proceeds by complex competition between oxidative chain scissioning and postcuring cross-linking that both contribute to embrittlement.

Portable, low-cost NMR with laser-lathe lithography produced microcoils.

Nuclear Magnetic Resonance (NMR) is unsurpassed in its ability to non-destructively probe chemical identity. Portable, low-cost NMR sensors would enable on-site identification of potentially hazardous substances, as well as the study of samples in a variety of industrial applications. Recent developments in RF microcoil construction (i.e. coils much smaller than the standard 5mm NMR RF coils), have dramatically increased NMR sensitivity and decreased the limits-of-detection (LOD). We are using advances in laser pantographic microfabrication techniques, unique to LLNL, to produce RF microcoils for field deployable, high sensitivity NMR-based detectors. This same fabrication technique can be used to produce imaging coils for MRI as well as for standard hardware shimming or "ex-situ" shimming of field inhomogeneities typically associated with inexpensive magnets. This paper describes a portable NMR system based on the use of a 2 kg hand-held permanent magnet, laser-fabricated microcoils, and a compact spectrometer. The main limitations for such a system are the low resolution and sensitivity associated with the low field values and quality of small permanent magnets, as well as the lack of large amounts of sample of interest in most cases. The focus of the paper is on the setting up of this system, initial results, sensitivity measurements, discussion of the limitations and future plans. The results, even though preliminary, are promising and provide the foundation for developing a portable, inexpensive NMR system for chemical analysis. Such a system will be ideal for chemical identification of trace substances on site.

Electronic characterization of lithographically patterned microcoils for high sensitivity NMR detection.

Nuclear magnetic resonance (NMR) offers a non-destructive, powerful, structure-specific analytical method for the identification of chemical and biological systems. The use of radio frequency (RF) microcoils has been shown to increase the sensitivity in mass-limited samples. Recent advances in micro-receiver technology have further demonstrated a substantial increase in mass sensitivity [D.L. Olson, T.L. Peck, A.G. Webb, R.L. Magin, J.V. Sweedler, High-resolution microcoil H-1-NMR for mass-limited, nanoliter-volume samples, Science 270 (5244) (1995) 1967-1970]. Lithographic methods for producing solenoid microcoils possess a level of flexibility and reproducibility that exceeds previous production methods, such as hand winding microcoils. This paper presents electrical characterizations of RF microcoils produced by a unique laser lithography system that can pattern three dimensional surfaces and compares calculated and experimental results to those for wire wound RF microcoils. We show that existing optimization conditions for RF coil design still hold true for RF microcoils produced by lithography. Current lithographic microcoils show somewhat inferior performance to wire wound RF microcoils due to limitations in the existing electroplating technique. In principle, however, when the pitch of the RF microcoil is less than 100mum lithographic coils should show comparable performance to wire wound coils. In the cases of larger pitch, wire cross sections can be significantly larger and resistances lower than microfabricated conductors.

Identification of endohedral water in single-walled carbon nanotubes by (1)H NMR.

Water confinement within single-walled carbon nanotubes (SWCNTs) has been a topic of current interest, due in part to their potential nanofiltration applications. Experiments have recently validated molecular dynamics predictions of flow enhancement within these channels, although few studies have probed the detailed structure and dynamics of water in these systems. Proton nuclear magnetic resonance ( (1)H NMR) is a technique capable of providing some of these details, although care must be exercised in separating the confined water of interest from exterior water. By using controlled experiments with both sealed and opened SWCNTs and by providing a quantitative measure of water content through desorption experiments, a signature for confined water in SWCNTs has been positively identified. This endohedral or interior water is characterized by a relatively broad feature located at 0.0 ppm, shifted upfield relative to bulk water. With the identification of a signature for water inside SWCNTs, further studies aimed at probing water dynamics will be enabled.

NMR metabolomics of planktonic and biofilm modes of growth in Pseudomonas aeruginosa.

Bacteria often reside in communities where the cells have secreted sticky, polymeric compounds that allow them to attach to surfaces. This sessile lifestyle, referred to as a biofilm, affords the cells within these communities a tolerance of antibiotics and antimicrobial treatments. Biofilms of the bacterium Pseudomonas aeruginosa have been implicated in cystic fibrosis and are capable of colonizing medical implant devices, such as heart valves and catheters, where treatment of the infection often requires the removal of the infected device. This mode of growth is in stark contrast to planktonic, free floating cells, which are more easily eradicated with antibiotics. The mechanisms contributing to a biofilm's tenacity and a planktonic cell's susceptibility are just beginning to be explored. In this study, we have used a metabolomic approach employing nuclear magnetic resonance (NMR) techniques to study the metabolic distinctions between these two modes of growth in P. aeruginosa. One-dimensional 1H NMR spectra of fresh growth medium were compared with spent medium supernatants from batch and chemostat planktonic and biofilms generated in continual flow system culture. In addition, 1H high-resolution magic angle spinning NMR techniques were employed to collect 1H NMR spectra of the corresponding cells. Principal component analysis and spectral comparisons revealed that the overall metabolism of planktonic and biofilm modes of growth appeared similar for the spent media, while the planktonic and biofilm cells displayed marked differences. To determine the robustness of this technique, we prepared cell samples under slightly different preparation methods. Both techniques showed similar results. These feasibility studies show that there exist chemical differences between planktonic and biofilm cells; however, in order to identify these metabolomic differences, more extensive studies would have to be performed, including 1H-1H total correlated spectroscopy.