Abstract
Infrared (IR) spectroscopy offers unique advantages for the study of phospholipid acyl chain structures and interactions. As is well known, the technique monitors molecular vibrations that produce dipole moment oscillations at infrared frequencies. The observed frequencies, intensities, and band shapes are dependent on molecular conformation, configuration, and chain packing. The method does not depend on probe molecules, is effective in sampling all relevant phases adopted by phospholipids (crystal, gel, liquid crystal, inverted hexagonal, cubic, etc.), and provides structural information not directly accessible to many other methods, e.g., the membranes of intact cells in normal and pathological states (Mantsch et al, 1988; Moore and Mendelsohn, 1994; Moore et al, 1995; Moore et al, 1993), and monolayer films (Dluhy, 1986; Flach et al, 1994; Ger-icke and Hühnerfuss, 1993; Mitchell and Dluhy, 1988). A major advantage for the study of phospholipids lies in the extensive IR spectra-structure correlations derived from alkanes. Assignments of the observed frequencies to specific normal modes, and the sensitivities of these modes to conformational change are in large part understood.
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References
Cameron DG, Gudgin EF, Mantsch HH (1981): Dependence of acyl chain packing of phospholipids on the head group and acyl chain length. Biochemistry 20:4496–4500
Cameron DG, Casal HL, Mantsch HH (1980): Characterization of the pretransition in 1,2-dipalmitoyl-sn-glycero-3-phosphocholine by Fourier transform infrared spectroscopy. Biochemistry 19:3665–3672
Casal HL, McElhaney RN (1990): Quantitative determination of hydrocarbon chain conformational order in bilayers of saturated phosphatidylcholines of various chain lengths by Fourier transform infrared spectroscopy. Biochemistry 29:5423–5427
Cates DA, Strauss HL, Snyder RG (1994): Vibrational modes of liquid n-alkanes. J Phys Chem 98:4482–4488
Cevc G, Marsh D (1987): Phospholipid Bilayers: Physical Principles and Models New York: Wiley Interscience
Chia N-C, Mendelsohn R (1992): CH2 wagging modes of unsaturated acyl chains as IR probes of conformational order in methyl alkenoates and phospholipid bilayers. J Phys Chem 96:10543–10547
Davies MA, Brauner, JW, Schuster HF, Mendelsohn R (1990a): A quantitative infrared determination of acyl chain conformation in gramicidin/dipalmitoylphosphatidylcholine mixtures. Biochem Biophys Res Comm 168:85–90
Davies MA, Schuster HF, Brauner JW, Mendelsohn R (1990b): Effects of cholesterol on conformational disorder in dipalmitoylphosphatidylcholine bilayers. A quantitative IR study of the depth dependence. Biochemistry 29:4368–4373
Dluhy RA (1986): Quantitative external reflection infrared spectroscopic analysis of insoluble monolayers spread at the air-water interface. J Phys Chem 90:1373–1379
Doebler RW, Steggles AW, Holloway, PW (1995): FTIR analysis of acyl chain conformation and its role in the free energy of binding of native and mutant cytochrome B5 to lipid vesicles. Biophys J 68:A429
Flach CR, Brauner JW, Taylor JW, Baldwin RC, Mendelsohn R (1994): External reflection FTIR of peptide monolayer films in situ at the air/water interface: Experimental design, spectra-structure correlations, and effects of hydrogen-deuterium exchange. Biophys 7 67:402–41
Flory PJ (1989): Statistical Mechanics of Chain Molecules. Hanser, Munich
Gericke A, Hühnerfuss H (1993): In situ investigation of saturated long-chain fatty acids at the air/water interface by external infrared reflection-absorption spectroscopy. J Phys Chem 97:12899–12908
Griffiths PR, de Haseth JA (1986): Fourier transform infrared spectrometry. In: Chemical Analysis: A Series of Monographs on Analytical Chemistry and Its Applications, Vol 83, Elving PJ, Winefordner JD, eds.New York: Wiley Interscience
Mantsch HH, McElhaney RN (1991): Phospholipid phase transitions in model and biological membranes as studied by infrared spectroscopy. Chem Phys Lipids 57:213–226
Mantsch HH, Yang PW, Martin A, Cameron DG (1988): Infrared spectroscopic studies of Acholeplasma laidlawii B membranes. Comparison of the gel to liquid-crystal phase transition in intact cells and isolated membranes. Eur J Biochem 178:335–341
Maroncelli M, Strauss HL, Snyder RG (1985a): On the CD2 probe infrared method for determining polymethylene chain conformation. J Phys Chem 89:4390–4395
Maroncelli M, Strauss HL, Snyder RG (1985b): The distribution of conformational disorder in the high-temperature phases of the crystalline n-alkanes. J Chem Phys 82:2811–2824
Mendelsohn R, Mantsch HH (1986): Fourier transform infrared studies of lipid-protein interaction. In: Progress in Protein-Lipid Interactions 2 Watts A, De Pont JJHHM, eds. Amsterdam: Elsevier-North Holland
Mendelsohn R, Brauner JW, Gericke A (1995a): External infrared reflection absorption spectrometry of monolayer films at the air/water interface. Ann Rev Phys Chem 46:305–334
Mendelsohn R, Davies MA, Schuster HF, Xu Z, Bittman R (1991): CD2 rocking modes as quantitative infrared probes of one-, two-, and three-bond conformational disorder in dipalmitoylphosphatidylcholine and dipalmitoylphosphatidylcholine/cholesterol mixtures. Biochemistry 30:8558–8563
Mendelsohn R, Davies MA, Brauner JW, Schuster HF, Dluhy RA (1989): Quantitative determination of conformational disorder in the acyl chains of phospholipid bilayers by infrared spectroscopy. Biochemistry 28:8934–8939
Mendelsohn R, Liang GL, Strauss HL, Snyder RG (1995b): IR spectroscopic determination of gel state miscibility in long-chain phosphatidylcholines mixtures. Biophys J: submitted
Mitchell ML, Dluhy RA (1988): In situ FT-IR investigation of phospholipid monolayer phase transitions at the air-water interface. J Am Chem Soc 110:712–718
Moore DJ, Mendelsohn R (1994): Adaptation to altered growth temperatures in Acholeplasma laidlawii B: Fourier transform infrared studies of acyl chain conformational order in live cells. Biochemistry 33:4080–4085
Moore DJ, Sills RH, Mendelsohn R (1995) Peroxidation of erythrocytes: FTIR spectroscopy studies of extracted lipids, isolated membranes, and intact cells. Biospectro-scopy: in press
Moore DJ, Wyrwa M, Reboulleau CP, Mendelsohn R (1993): Quantitative IR studies of acyl chain conformational order in fatty acid homogeneous membranes of live cells of Acholeplasma laidlawii B. Biochemistry 32:6281–6287
Schachtschneider JM, Snyder RG (1963): Vibrational analysis of the n-paraffms-II. Normal co-ordinate calculations. Spectrochim Acta 19:117–168
Senak L, Davies MA, Mendelsohn R (1991): A quantitative IR study of hydrocarbon chain conformation in alkanes and phospholipids. CH2 wagging modes in disordered bilayer and HII phases. J Phys Chem 95:2565–2571
Senak L, Moore D, Mendelsohn R (1992): CH2 wagging progressions as IR probes of slightly disordered phospholipid acyl chain states. J Phys Chem 96:2749–2754
Shannon VL, Strauss HL, Snyder RG, Elliger CA, Mattice WL (1989): Conformation of the cycloalkanes C4H28, C16H32, and C22H44 in the liquid and high-temperature crystalline phases by vibrational spectroscopy. J Am Chem Soc 111:1947–1958
Snyder RG (1967): Vibrational study of the chain conformation of the liquid n-paraffms and molten polyethylene. J Chem Phys 47:1316–1360
Snyder RG (1965): Group moment interpretation of the infrared intensities of crystalline n-paraffins. J Chem Phys 42:1744–1763
Snyder RG (1961): Vibrational spectra of crystalline n-paraffins. Part II. Intermolecular effects. J Mol Spec 7:116–144
Snyder RG (1960): Vibrational spectra of crystalline n-paraffins Part I. methylene rocking and wagging modes. J Mol Spec 4:411–434
Snyder RG, Poore MW (1973): Conformational structure of polyethylene chains from the infrared spectrum of the partially deuterated polymer. Macromolecules 6:708–712
Snyder RG, Conti G, Strauss HL, Dorset DL (1993): Thermally-induced mixing in partially microphase segregated binary n-alkane crystals. J Phys Chem 97:7342–7350
Snyder RG, Goh MC, Srivatsavoy VJP, Strauss HL, White JW, Dorset DL (1992): Measurement of the growth kinetics of microdomains in binary n-alkane solid solutions by infrared spectroscopy. J Phys Chem 96:10008–10019
Snyder RG, Srivatsavoy VJP, Cates DA, Strauss HL, Dorset DL (1994): Hydrogen/deuterium isotope effects on microphase separation in unstable crystalline mixtures of binary n-alkanes. J Phys Chem 98:674–684
Snyder RG, Strauss HL, Cates DA (1995): Detection and measurement of microaggre-gation in binary mixtures of esters and of phospholipid dispersions. J Phys Chem: in press
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© 1996 Birkhäuser Boston
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Mendelsohn, R., Snyder, R.G. (1996). Infrared Spectroscopic Determination of Conformational Disorder and Microphase Separation in Phospholipid Acyl Chains. In: Merz, K.M., Roux, B. (eds) Biological Membranes. Birkhäuser Boston. https://doi.org/10.1007/978-1-4684-8580-6_6
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DOI: https://doi.org/10.1007/978-1-4684-8580-6_6
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