Crystal fingerprints

Powder diffraction patterns have three main features that can be measured t5 -spacings, peak intensities, and peak shapes. Because these patterns ate a characteristic fingerprint for each crystalline phase, a computer can quickly compare the measured pattern with a standard pattern from its database and recommend the best match. Whereas the measurement of t5 -spacings is quite straightforward, the determination of peak intensities can be influenced by sample preparation. Any preferred orientation, or presence of several larger crystals in the sample, makes the interpretation of the intensity data difficult. 

In view of the magnitude of crystal-field effects it is not surprising that the spectra of actinide ions are sensitive to the latter s environment and, in contrast to the lanthanides, may change drastically from one compound to another. Unfortunately, because of the complexity of the spectra and the low symmetry of many of the complexes, spectra are not easily used as a means of deducing stereochemistry except when used as fingerprints for comparison with spectra of previously characterized compounds. However, the dependence on ligand concentration of the positions and intensities, especially of the charge-transfer bands, can profitably be used to estimate stability constants. 

The series of deviation from a strictly octahedral crystal field follows the sequence ammonium tungstate > tungstic acid > WO3 [14]. The s->d transition becomes allowed as distortion of the octahedral environment increases. Viewed as a fingerprint technique. Figure 6 shows that the bulk of W present in both WZ (calcined) and PtWZ(acac, reduced) behaves as WO3, as also shown by our XRD data [10], sugesting that only a small extent of W reduction is expected to have taken place during catalyst conditioning prior to reaction. 

Detection powders and fingerprint development kits commonly contain cream- or yellow-colored ninhydrin crystals or a solution of dissolved ninhydrin. Ninhydrin (also known as 1,2,3-indantrione, monohydrate 2,2-dihydroxy-1,3-indandione triketohydrindene, monohydrate and triketohydrinden hydrate) has the structure presented in Fig. 13.3.1. Ninhydrin will react with a free a-amino group, -NH2. This group is contained in all amino acids, and analysis with ninhydrin is often performed to verify the presence of amino acids. When a-amino acids (i.e., amino acids with the structure NH2-CHR-COOH) react with ninhydrin, a characteris-... 

Silver halide fibres (AgClxBri x) have the widest spectral range in the mid-IR, well into the fingerprint range. Due to their crystalline nature, they have a superior flexibility. Problematic is their tendency to decompose upon contact with UV radiation or base metals. Also sulphides will chemically destroy the fibre material. Other points against are the high intrinsic attenuation due to absorption by impurities or scattering at inclusions or micro-crystals and the non-availability of (applicable) core-clad fibres. 

Cruciani et al. [92] have developed the program Metasite for the prediction of the site of oxidative metabolism by CYP450 enzymes. Metasite uses GRID molecular interaction fields to fingerprint both structures of CYP450s (from homology models or crystal structures) and test substrates and then matches the fields. Zhou et al. [93] showed that Metasite was able to correctly predict the site(s) of metabolism 78% of the time for 227 CYP3A4 substrates. Caron et al. [94] used Metasite to predict the oxidative metabolism of seven statins. 

Any crystal modification is practically fingerprinted by its X-ray diffraction spectrum. Another factor determined by the same instrumentation is isomorphism in chemically different pigments, which is associated with almost equal diffraction angles and X-ray intensities in both experiments. It is also important to ensure that the intensity of the incident beam is approximately the same for both measurements. 

More examples of forensic applications of Raman spectroscopy have been published recently. It has been used to identify individual crystals of drugs and excipients on paper currency [110], multilayer paint chips, inks, plastics [111], and fibers [112], A study demonstrated the feasibility of quantifying acetaminophen in the presence of many excipient types [113], Other studies seek to identify particulates, such as illicit or abused drugs, in fingerprints lifted at a crime scene [114,115]. 

Osmium (VIII) tetraoxide (Os + 40 —> OsO ) is a yellow crystal and probably the most important compound used as an oxidizing agent, as a biological stain in microscopy, and to detect fingerprints. 

A basic, yet crucially important, application of powder XRD is in the identification ( fingerprinting ) of crystalline phases, based on the fact that different crystal structures give rise to distinct powder XRD patterns. Qualitative characterization of materials in this manner finds applications in many scientific disciplines (both academic and industrial), including quality control, polymorph screening, and the characterization of products from rapid throughput crystallization experiments [97, 98]. 

A note of caution is necessary when deahng with these materials. It is not trivial to distinguish between CuInS(Se)2 and some phases of Cu—S(Se). Diffraction and optical properties may be similar. Elemental analysis is particularly important to verify inclusion of indium in the films and in the correct ratio. A fingerprint of the chalcopyrite XRD is the presence of a weak peak at 26 = 17-18°, corresponding to the (101) chalcopyrite reflection. This is often not seen, although this could be either because the deposit is not chalcopyrite or because weak peaks are usually not seen in nanocrystaUine materials with particularly small crystal size. 

The OJ ion is a 19-electron radical and is isoelectronic with AB2-type radicals such as SOJ and NO2- which have been observed on surfaces. In these ions, the energy levels are well separated (Fig. 21) and because they are not significantly perturbed by the surface crystal field, the g tensor can be used to fingerprint the species (96). Comparison between the g tensor... 

Is there any relevance of this new potential, work function, to electrochemistry The main idea is that because of its nature, the work function can be considered fingerprints of individual metals. If the electrode studied is a metal, then the work function is expected to be a relevant physical property in electrochemistry. It is involved in all electrochemical processes and accounts for effects observed on metals with different surface orientations. An example of these effects is given in Fig. 6.46. Obviously, different metals would have different chemical potentials, and that would account for the different values of d> in Fig. 6.46. But what about the differences observed, for example, for two of the crystalline faces of silver (Ag) For both crystals He is clearly the same thus the work function difference arises from different dipole layers at surfaces with different surface geometry. Another important involvement of in electrochemistry is in the determination of the absolute electrode potential, as will be explained in the next section. 

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