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

Flach, Carol R.; Brauner, Joseph W.; Taylor, John W.; Baldwin, Robertl .; Mendelsohn, R.

doi:10.1016/s0006-3495(94)80495-3

Cited by 124 publications

(67 citation statements)

References 39 publications

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“…The purification of the final compounds proved to be very difficult and could finally only be accomplished using a Sephadex LH-20 column. 6 Differential scanning calorimetry of LUVET 100 revealed that the main transition temperature is increasing linearly with the length of the hydrocarbon chain C 12 < 273 K; C 14 ≈ 294 K; C 16 ≈ 308 K; C 18 ≈ 325 K.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Monolayer Properties of 1,3-Diamidophospholipids

2013

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While nature provides an endless variety of phospholipids presenting hydrolyzable ester linkages for the 1,2-positioned hydrocarbon tails, we designed and synthesized 1,3-diamidophospholipids which contain stable fatty acid amides. These new phospholipids form faceted unilamellar vesicles with mechanosensitive properties. Aiming to understand the mechanism responsible for this behavior at a molecular level, we investigated the 1,3-diamidophospholipid family in monolayers, a simplified model membrane system. Langmuir isotherms combined with in situ grazing incidence X-ray diffraction (GIXD), specular X-ray reflectivity (XR), and infrared reflection−absorption spectroscopy (IRRAS) allowed the characterization of the monolayers from a structural and thermodynamical point of view. The existence of strong headgroup interactions due to the formation of a hydrogen-bonding network was clearly revealed by IRRAS and by the high rigidity of the monolayers. GIXD showed that only the longer chain compounds of the series (Pad-PC-Pad (1,3-dipalmitamidopropan-2-phosphocholine) and Sad-PC-Sad (1,3-distearamidopropan-2-phosphocholine) were able to form ordered monolayers. The chains are strongly tilted in a rigid lattice formed due to these hydrogenbonding interactions between the headgroups. The thermodynamical analysis leads to a critical temperature of the monolayer which is clearly different from the main phase transition temperature in bulk, indicating that there must be a different structural arrangement of the 1,3-diamidophospholipids in monolayers and in bilayers.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Monolayer Properties of 1,3-Diamidophospholipids

2013

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“…To overcome this problem, two approaches have been developed. The Rutgers group developed [23] a sample shuttle technique in which a reference IRRAS spectrum is acquired from a film-free surface. The intensity of light reflected from the film-covered surface is then ratioed to the reference spectrum.…”

Section: A Backgroundmentioning

confidence: 99%

Infrared reflection–absorption spectroscopy: Principles and applications to lipid–protein interaction in Langmuir films

Mendelsohn

Mao

Flach

2010

Biochimica et Biophysica Acta (BBA) - Biomembranes

213

155

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Infrared reflection-absorption spectroscopy (IRRAS) of lipid/protein monolayer films in situ at the air/water interface provides unique molecular structure and orientation information from the film constituents. The technique is thus well suited for studies of lipid/protein interaction in a physiologically relevant environment. Initially, the nature of the IRRAS experiment is described and the molecular structure information that may be obtained is recapitulated. Subsequently, several types of applications, including the determination of lipid chain conformation and tilt as well as elucidation of protein secondary structure are reviewed. The current article attempts to provide the reader with an understanding of the current capabilities of IRRAS instrumentation and the type of results that have been achieved to date from IRRAS studies of lipids, proteins and lipid/protein films of progressively increasing complexity. Finally, possible extensions of the technology are briefly considered.

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“…[17][18][19] For instance, leucine-lysine dipeptide units were studied by using polarization-modulated (PM) IRRAS. [20] These linear (KL) m K peptides (4 m 7) form intermolecular antiparallel b-sheets in pure peptide and mixed peptide/DMPC films at the air/water interface.…”

Section: Introductionmentioning

confidence: 99%

Interactions of KLA Amphipathic Model Peptides with Lipid Monolayers

Erbe¹,

Kerth²,

Dathe³

et al. 2009

ChemBioChem

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Interactions of the cationic amphipathic peptide KLALKLALKALKAALKLA-NH(2) (KLAL) and its double D-amino acid replacement analogues l(11)k(12)-KLAL and k(9)a(10)-KLAL with lipid monolayers of anionic POPG, zwitterionic POPC and mixtures thereof at the air/water interface were investigated by infrared reflection- absorption spectroscopy (IRRAS). At high surface pressure (>30 mN m(-1)) all peptides incorporated into lipid monolayers containing at least 25 % anionic POPG, and adopted an alpha-helical conformation. Creation of free surface by expansion of the monolayers resulted in an additional adsorption of peptides from the subphase, but now in a beta-sheet conformation; this led to the coexistence of peptides in two distinctly different conformations within the lipid monolayer. The beta-sheets bound to the free surface could be squeezed out of the film by compressing the film to low surface areas, whereas the alpha-helices remained bound to the lipids until the film collapsed. When bound to the lipid monolayer, the helical axis of the peptides is oriented almost parallel to the surface of the monolayer.

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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

Cited by 124 publications

References 39 publications

Monolayer Properties of 1,3-Diamidophospholipids

Monolayer Properties of 1,3-Diamidophospholipids

Infrared reflection–absorption spectroscopy: Principles and applications to lipid–protein interaction in Langmuir films

Interactions of KLA Amphipathic Model Peptides with Lipid Monolayers

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