Spectroscopic near-field method

Table 15.1 Comparison of different near-field spectroscopic methods.

Precise kinetic electroanalytical data permit to describe quantitatively the kinetics of the whole process with a precision that has never been achieved before by patch-clamp techniques or spectroscopic near-field methods. This enables to investigate finely these events and to identify the exact physicochemical nature of all the individual physicochemical and biological factors which concur to produce vesicular release. 

More recently, the method of scanning near-field optical microscopy (SNOM) has been applied to LB films of phospholipids and has revealed submicron-domain structures [55-59]. The method involves scanning a fiber-optic tip over a surface in much the same way an AFM tip is scanned over a surface. In principle, other optical experiments could be combined with the SNOM, snch as resonance energy transfer, time-resolved flnorescence, and surface plasmon resonance. It is likely that spectroscopic investigation of snbmicron domains in LB films nsing these principles will be pnrsned extensively. 

In 1987 we reported26 that the three possible C3H2 isomers S-2, T-36, and S-37 can be transformed into each other under photochemical conditions. For several reasons propargylene (36) attracted our attention On the one hand the first C3H2 parent species, identified by direct spectroscopic methods, was triplet propargylene (T-36). Its ESR spectrum was published in 1965,63 and, based on the zero-field-splitting parameters, a linear or nearly linear structure was derived. On the other hand, the structural elucidation of 36 by comparison of the calculated and experimental IR spectra turned out to be rather difficult.64... 

One indication of the developing interest in PATs in the pharmaceutical area is the number of book chapters and review articles in this field that have appeared in the last few years. Several chapters in The Handbook of Vibrational Spectroscopy3 are related to the use of various optical spectroscopies in pharmaceutical development and manufacturing. Warman and Hammond also cover spectroscopic techniques extensively in their chapter titled Process Analysis in the Pharmaceutical Industry in the text Pharmaceutical Analysis.4 Pharmaceutical applications are included in an exhaustive review of near-infrared (NIR) and mid-infrared (mid-IR) by Workman,5 as well as the periodic applications reviews of Process Analytical Chemistry and Pharmaceutical Science in the journal Analytical Chemistry. The Encyclopedia of Pharmaceutical Technology has several chapters on spectroscopic methods of analysis, with the chapters on Diffuse Reflectance and Near-Infrared Spectrometry particularly highlighting on-line applications. There are an ever-expanding number of recent reviews on pharmaceutical applications, and a few examples are cited for Raman,7 8 NIR,9-11 and mid-IR.12... 

Spectroscopic methods are useful for characterization. The A H stretching frequency in the IR spectrum typically falls on hydrogen bond formation and the AH proton resonance also shifts to high field. Where A or B has a nuclear spin (e.g. F), the coupling constant between A or B and H can be used as long as exchange is not too rapid. For example, in the gas phase, HF has an H,F coupling constant near 600 Hz, but in amine H-F adducts, this value falls to about 450 Hz. ... 

Quality control, pharmaceutical product identity checks, and quantification are important fields in the broad application of the different spectroscopic methods. There are many spectroscopic aspects, e.g., concerning sample preparation, influences from different accessories, and possibly spectrometer effects, which certainly influences quantitative measurements. The latter problems could be solved using calibration transfer between different spectrometer types, for example, a scanning and an FT-near-IR spectrometer. 

Spectroscopic Imaging with Nanometer Resolution Using Near-Field Methods... 

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