Sample Preparation Solid Materials

Ultramicrotomy is sometimes also used to produce thin samples of solid materials, such as metals [13] which are, however, preferentially prepared by chemical- or ion-etching (see [1]) and focused ion beam (FIB) teclmiques [14]. 

Sample preparation requirements in solid state NMR are strikingly simple because the measurement is carried out at ambient temperature and pressure. Wide-line NMR experiments can be carried out on solid samples in any form, as far as the sample dimensions fit those of the coil in the NMR probe. MAS experiments require the material to be uniformly distributed within the rotor. 

Comparative method. Sometimes, as in the analysis of a mineral, it may be impossible to prepare solid synthetic samples of the desired composition. It is then necessary to resort to standard samples of the material in question (mineral, ore, alloy, etc.) in which the content of the constituent sought has been determined by one or more supposedly accurate methods of analysis. This comparative method, involving secondary standards, is obviously not altogether satisfactory from the theoretical standpoint, but is nevertheless very useful in applied analysis. Standard samples can be obtained from various sources (see Section 4.5). 

Margarine is an example of a solid sample where the materials of interest are soluble in one solvent (in this case methanol) whereas the matrix materials, largely triglycerides, are not. As a consequence, the sample preparation procedure is relatively simple. The chromatographic separation is achieved by using the dispersive interactions between the hydrocarbon chains of the fatty acids and the hydrocarbon chains of a reversed phase. 

The analysis of a pharmaceutical tablet (6) requires sample preparation that is little more complex as most tablets contain excipients (a solid diluent) that may be starch, chalk, silica gel, cellulose or some other physiologically inert material. This sample preparation procedure depends on the insolubility of the excipient in methanol. As the components of interest are both acidic and neutral, the separation was achieved by exploiting both the ionic interactions between the organic acids and the adsorbed ion exchanger and the dispersive interactions with the remaining exposed reverse phase. 

A 20 g sample, prepared and stored in a dry box for several months, developed a thin crust of oxidation/hydrolysis products. When the crust was disturbed, a violent explosion occurred, later estimated as equivalent to 230 g TNT. A weaker explosion was observed with potassium tetrahydroaluminate. The effect was attributed to superoxidation of traces of metallic potassium, and subsequent interaction of the hexahydroaluminate and superoxide after frictional initiation. Precautions advised include use of freshly prepared material, minimal storage in a dry diluent under an inert atmosphere and destruction of solid residues. Potassium hydrides and caesium hexahydroaluminate may behave similarly, as caesium also superoxidises in air. 

Removal of all possible contaminants is not the only reason for sample preparation, since each clean and purified material has then to be converted into the chemical form suitable for the accelerator ion source. In most cases (as explained in the previous section), samples are put into the caesium sputtering source as graphite, solid elemental carbon, and for this reason samples are first burnt and then chemically reduced to graphite. 

Thanks to the pioneering works of many research groups, solid-state NMR is now a well established spectroscopy for the study of biological solids, particularly for those with inherent structural disorder such as amyloid fibrils. We have provided an overview of a rather complete set of NMR techniques which have developed for samples prepared by chemical synthesis or protein expression. There are many different ways to present the materials discussed in this review. We hope that the way we have chosen can give a snapshot of some facets of the very exciting discipline of biological solid-state NMR spectroscopy. In spite of the success of solid-state NMR as a tool in biological study, it is not yet a mature technique and there is much room for further development. Below we will speculate on a few possibilities from our own perspective. 

When working with metal electrodes, the energy of the electrons in the metal is lower than the vacuum level by the work function of the metal, which tends to be 3-5 eV. Work functions of some materials relevant to LED devices are collected in Table 10.2 [11]. The work function can vary depending upon the crystal facet from which emission is measured (or if the metal is amorphous), and sample preparation details. The photoelectric (PE) effect is exploited in XPS (ESCA) or UPS to measure the work function. It is very critical to realize that, in these experiments, what is measured is the energy required to remove an electron to a point just outside the surface of the solid, not to infinity. At this range, the dipolar forces at the surface are still active, and one can learn about surface dipoles in the material. 

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