Characterization of molecular motion in the solid state by carbon-13 spin-lattice relaxation times.

Relaxation calculations for rapidly spinning samples show that spin-lattice relaxation time (T(1Z)) anisotropy varies with the angle between the rotor spinning axis and the external field. When the rate of molecular motion is in the extreme narrowing limit, the measurement of T(1Z) anisotropies for two different values of the spinning angle allows the determination of two linear combinations of the three static spectral densities, J(0)(0), J(1)(0), and J(2)(0). These functions are sensitive to molecular geometry and the rate and trajectory of motion. The utility of these linear combinations in the investigation of molecular dynamics in solids has been demonstrated with natural abundance (13)C NMR experiments on ferrocene. In an isolated (13)C-(1,2)H group, the dipole-dipole interaction has the same orientational dependence as the quadrupole interaction. Thus, the spectral densities that are responsible for dipolar relaxation of (13)C are the same as those responsible for deuteron quadrupolar relaxation. For ferrocene-d(10), deuteron T(1Z) and T(1Q) anisotropies and the relaxation time of the (13)C magic angle spinning peak provide sufficient information to determine the orientation dependence of all three individual spectral densities.

Characterization of polyimides by 13C and 1H solid state nuclear magnetic resonance.

The polyimides LaRC-TPI, LaRC-IA and LaRC-SI and related model compounds were investigated using 13C and 1H nuclear magnetic resonance (NMR). Magic angle spinning was used to acquire 13C isotropic chemical shift spectra of these materials. The spectra were assigned as completely as possible. In addition, the principal components of some shielding tensors were measured using variable angle correlation spectroscopy (VACSY). Of those studied, LaRC-SI is the only polymer that is soluble. However, after it is heated past its glass transition temperature, LaRC-SI becomes insoluble. Experiments were performed in an attempt to identify causes of this behavior. When magnetization from nuclei in rigid regions of the polymer is suppressed, the 1H and 13C NMR spectra of soluble LaRC-SI are significantly different from those of insoluble LaRC-SI. Hydration studies of LaRC-SI show that absorbed water plasticizes the polymer.

The study of the influence of flow on vascular endothelial biology.

It is now recognized that the mechanical environment of a cell has an influence on its structure and function. For the vascular endothelial cell that resides at the interface of the flowing blood and the underlying vessel wall, there is mounting evidence of the importance of flow and the associated wall shear stress in the regulation of endothelial biology. Not only is it a sensitive regulator of endothelial structure and function, but different flow environments will influence endothelial cell biology differently. Furthermore, there may be an interaction between the chemical environment of a cell and its mechanical environment. This is illustrated by the inhibition by steady laminar shear stress of the cytokine induction of VCAM-1. Results also are presented in which flow studies have been conducted using a co-culture model of the vessel wall. These experiments provide evidence of a quiescent endothelium; however, much more needs to be done to engineer the cell culture environment to make it more physiologic.

Oscillatory shear stress stimulates adhesion molecule expression in cultured human endothelium.

Low and oscillatory shear stresses are major features of the hemodynamic environment of sites opposite arterial flow dividers that are predisposed to atherosclerosis. Atherosclerosis is a focal inflammatory disease characterized initially by the recruitment of mononuclear cells into the arterial wall. The specific characteristics of the hemodynamic environment that facilitate the generation of arterial inflammatory responses in the presence of, for example, hyperlipidemia are unknown. We show here that prolonged oscillatory shear stress induces expression of endothelial cell leukocyte adhesion molecules, which are centrally important in mediating leukocyte localization into the arterial wall. Vascular cell adhesion molecule-1 was upregulated an average 9-fold relative to endothelial monolayers in static culture. Intercellular adhesion molecule-1 and E-selectin exhibited 11-fold and 7.5-fold increases, respectively. Upregulation of these adhesion molecules was associated with enhanced monocyte adherence. Cytokine stimulation of surface vascular cell adhesion molecule-1 was maximally induced after 6 and 8 hours of cytokine incubation. Oscillatory shear stress for these time periods elicited respective vascular cell adhesion molecule-1 levels of 16% and 30% relative to those observed for cytokine stimulation. Surface intercellular adhesion molecule-1 induction by cytokine stimulation for 24 hours was found to be approximately five times the level detected after 24 hours of oscillatory shear stress. Experiments performed in the presence of the antioxidant N-acetylcysteine demonstrated that the expression of vascular cell adhesion molecule-1 could be almost totally abolished, whereas that of intercellular adhesion molecule-1 was typically reduced by approximately 70%. These results imply that oscillatory shear stress per se is sufficient to stimulate mononuclear leukocyte adhesion and, presumptively, migration into the arterial wall. These results further indicate that atherosclerotic lesion initiation is likely related, at least in part, to unique signals generated by oscillatory shear stress and that the mechanism of upregulation is, to some extent, redox sensitive.

Determination of benzene in polypropylene food-packaging materials and food-contact paraffin waxes.

An analytical procedure was developed for determination of benzene in polypropylene food packaging and was adapted for determination of benzene in commercial paraffin waxes intended for food-contact use. The polymer was dissolved in hexadecane at 150 degrees C. The wax was melted in an 80 degrees C oven. A simple helium-sparging apparatus was used to remove the volatile chemical from the polymer or wax. The contaminant was collected in methanol, distilled water was added, and the resulting solution was analyzed by headspace gas chromatography. The instrument was equipped with a 30 m fused silica open tubular capillary column and a photoionization detector. Average recoveries of benzene from polymer and paraffin wax at low parts-per-billion concentrations were 63 and 70%, respectively. Limits of detection and quantitation for analysis of polypropylene were 8 and 17 ppb, respectively; the limit of quantitation for analysis of paraffin wax was 2 ppb. In several commercial polypropylene products examined, benzene levels ranged from none detected to 426 ppb. In 3 commercial waxes examined, concentrations of 16-73 ppb benzene were determined. The presence of benzene was confirmed by gas chromatography/mass spectrometry.

Electron impact mass spectrometry of BHT and its alteration products.

The electron impact (EI) mass spectra of 2,6-di-tert-butyl-4-methylphenol (BHT) and certain of its alteration products are described in detail. Accurate mass measurements confirm the elemental compositions of important fragment ions in the EI spectra. Collisionally activated mass spectra are also used to study fragmentation and suggest common ion structures. The reference spectra provide the basis for identifying various alteration products of BHT by capillary gas chromatography/mass spectrometry (GC/MS) without the necessity of isolating individual components. Application of GC/MS is made to three studies: (i) pyrolysis of hydroperoxy-BHT as a potential pathway to alteration products in food; (ii) GC/MS pyrolysis of hydroperoxy-BHT as a model study; and (iii) alteration of BHT in ethanol/water as a food-simulating solvent.

Determination of styrene migration from food-contact polymers into margarine, using azeotropic distillation and headspace gas chromatography.

Migration studies were conducted to determine the quantity of styrene that migrates from polymers into fatty foods, specifically margarine. Azeotropic distillation was used to isolate styrene from the margarine. Headspace gas chromatography with a Chromosorb 104 column and a flame ionization detector was used for quantitation. The quantitation limit for the method was about 25 ppb (wt/wt) styrene in margarine. On the average, greater than 90% of the styrene was recovered. Several commercial margarines were examined. The method and results of the migration studies are presented. There was no detectable migration of styrene into margarine.

Headspace sampling and gas chromatographic determination of styrene migration from food-contact polystyrene cups into beverages and food simulants.

Migration studies using coffee, tea, water, and 8% ethanol were conducted with various types of food-contact polystyrene cups. Study conditions simulated filing and storage at room temperature and hot-filling or pasteurization above 150 degrees F (65.6 degrees C). The quantity of styrene migrating was determined by headspace sampling and gas chromatography (GC). The GC column was 6% Carbowax 20M on Chromosorb 101 with quantitation via a flame ionization detector. Detection limits ranged from 3 to 10 ppb in various liquids. The method and results of the migration studies are presented.