Local, environment structure

To summarize, solid-state NMR spectroscopy offer eight tensor parameters—Cq, rj, 1, k and (a, / , y)—that can be used to characterize the local environments (structure and bonding) of oxygen atoms. Therefore, an accurate determination of these parameters for individual oxygen atoms in the biomolecule under investigation is often the aim of many NMR experiments. 

Solid state NMR is a relatively recent spectroscopic technique that can be used to uniquely identify and quantitate crystalline phases in bulk materials and at surfaces and interfaces. While NMR resembles X-ray diffraction in this capacity, it has the additional advantage of being element-selective and inherently quantitative. Since the signal observed is a direct reflection of the local environment of the element under smdy, NMR can also provide structural insights on a molecularlevel. Thus, information about coordination numbers, local symmetry, and internuclear bond distances is readily available. This feature is particularly usefrd in the structural analysis of highly disordered, amorphous, and compositionally complex systems, where diffraction techniques and other spectroscopies (IR, Raman, EXAFS) often fail. 

ReflEXAES can be used for near-surface structural analysis of a wide variety of samples for which no other technique is appropriate. As with EXAES, ReflEXAES is particularly suited for studying the local atomic structure around particular atomic species in non-crystalline environments. It is, however, also widely used for the analysis of nanocrystalline materials and for studying the initial stages of crystallization at surfaces or interfaces. ReflEXAES was first proposed by Barchewitz [4.135], and after several papers in the early nineteen-eighties [4.136, 4.168-4.170] it became an established (although rather exotic) characterization technique. Most synchrotron radiation sources now have beam-lines dedicated to ReflEXAES experiments. 

Several different kinds of noncovalent interactions are of vital importance in protein structure. Hydrogen bonds, hydrophobic interactions, electrostatic bonds, and van der Waals forces are all noncovalent in nature, yet are extremely important influences on protein conformations. The stabilization free energies afforded by each of these interactions may be highly dependent on the local environment within the protein, but certain generalizations can still be made. 

One way in which to probe the structural surroundings of a protein is to monitor the pH behavior of specific carbon sites of the C probes. pH-titration studies, of given resonances, had previously been used for probing of the protein structure, because they are known to provide information concerning electrostatic (salt-bridging) interactions in the protein, neighboring group-ionizations, and local environments. ... 

The low Ti content (up to 3 wt % in Ti02) makes the extraction of vibrational, energetic, and geometric features specific to Ti04 moieties a difficult task as the experimental data are dominated by the features of the siliceous matrix. This is the reason why the structure of the local environment around Ti(IV) species inside TS-1 was only definitively assessed more than 10 years after the discovery of the material, when the atomic selectivity of X-ray absorption spectroscopies (both XANES and EXAFS) were used [58-60]. 

Local surface structure and coordination numbers of neighbouring atoms can be extracted from the analysis of extended X-ray absorption fine structures (EXAFS). The essential feature of the method22 is the excitation of a core-hole by monoenergetic photons modulation of the absorption cross-section with energy above the excitation threshold provides information on the distances between neighbouring atoms. A more surface-sensitive version (SEXAFS) monitors the photoemitted or Auger electrons, where the electron escape depth is small ( 1 nm) and discriminates in favour of surface atoms over those within the bulk solid. Model compounds, where bond distances and atomic environments are known, are required as standards. 

Table 8.53 shows the main features of XAS. The advantages of EXAFS over diffraction methods are that the technique does not depend on long-range order, hence it can always be used to study local environments in amorphous (and crystalline) solids and liquids it is atom specific and can be sensitive to low concentrations of the target atom (about 100 ppm). XAS provides information on interatomic distances, coordination numbers, atom types and structural disorder and oxidation state by inference. Accuracy is 1-2% for interatomic distances, and 10-25 % for coordination numbers. 

Rachofsky EL, Osman R, Ross JBA (2001) Probing structure and dynamics of DNA with 2-aminopurine effects of local environment on fluorescence. Biochem 40 946-956... 

IR spectroscopy is a powerful and readily available orientation characterization technique. It offers a high chemical selectivity since most functional groups absorb at distinct wavelengths (typically in the 2.5-25 pm range (4,000 00 cm-1 range)), which often depend on their local environment. IR spectroscopy thus provides qualitative and quantitative information about the chemical nature of a sample, its structure, interactions, etc. The potential of IR spectroscopy for orientation characterization stems from the fact that absorption only occurs if the electric field vector of the incident radiation, E, has a component parallel to the transition dipole moment, M, of the absorbing entity. The absorbance, A, is given... 

The nuclear transitions are very sensitive to the local environment of the atom, and Mossbauer spectroscopy is a sensitive probe of the different environments an atom occupies in a solid material. By analyzing the chemical shifts and quadrupole splitting in Mossbauer spectra of samples containing Mossbauer-ac-tive nuclei, information on the state of oxidation and the local structure can be obtained. Only a few nuclei can be used for this purpose, so this method has limited but powerful applications. 

By means of the radius ratio, we have already described the type of local environment around the ions in several types of simple crystals. For example, in the sodium chloride structure (not restricted to NaCl itself), there are six anions surrounding each cation. The sodium chloride crystal structure is shown in Figure 7.4. 

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