Improved IRRAS Apparatus for Studies of Aqueous Monolayer Films: Determination of the Orientation of Each Chain in a Fatty-Acid Homogeneous Ceramide 2
| Autor: | Carol R. Flach, Zhi Xu, Joseph W. Brauner, Richard Mendelsohn, Xiaohong Bi |
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| Rok vydání: | 2001 |
| Předmět: |
Aqueous solution
Chemistry Bilayer 010401 analytical chemistry Analytical chemistry 01 natural sciences 0104 chemical sciences 010309 optics Light intensity Crystallography chemistry.chemical_compound Tilt (optics) Angle of incidence (optics) 0103 physical sciences Monolayer Molecule Instrumentation Spectroscopy Derivative (chemistry) |
| Zdroj: | Applied Spectroscopy. 55:1060-1066 |
| ISSN: | 1943-3530 0003-7028 |
| DOI: | 10.1366/0003702011952965 |
| Popis: | The performance of a new accessory for measuring IR reflection-absorption (IRRAS) spectra at various angles of incidence from monolayer films of lipids is demonstrated. The device is comprised of an external variable angle reflectance accessory and a self-contained computer-controlled unit for varying the angle of incidence, both units being coupled to a custom-designed Langmuir trough. This combination provides for excellent experimental precision and reduction of interference from H2O vapor in the 1500–1800 cm−1 spectral region. A set of ∼20 s- and p-polarized IRRAS spectra over a range of angles of incidence from 25° to 70° may be acquired from a single monolayer film in ∼3 h. The performance of the device is demonstrated for two lipids as follows. First, the instrument precision is demonstrated through determination of the orientation of each of the chains in a fatty acid homogeneous ceramide 2 derivative. Interestingly, the orientation (tilt angles from the bilayer normal) of the individual chains differ, as determined from an isotopically-labeled derivative where the fatty acid chain is perdeuterated. The fatty acid chain is tilted at 24° from the normal to the bilayer, while the base chain is tilted at 18°. As a control, the average tilt angle for both ceramide 2 acyl chains has been determined from a fully proteated derivative to be 20°. The precision of the derived tilt angle varies from ∼1–3°. Second, the reduction of interference from water vapor in the 1500–1800 cm−1 is demonstrated for sn-2–13C=O-1,2 distearoylphosphatidylcholine, where spectra from the individual C=O bonds in the molecule are readily detected with good signal/noise and signal/water vapor ratios. The device provides a major advance in the determination of chain orientation by IRRAS and will facilitate the determination of functional group orientation. |
| Databáze: | OpenAIRE |
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