Intermolecular Hydrogen-Bond Interactions in DPPE and DMPC Phospholipid Membranes Revealed by Far-Infrared Spectroscopy

Nibali, Valeria Conti; Branca, C.; Wanderlingh, U.; D’Angelo, Giovanna

doi:10.3390/app112110038

Cited by 7 publications

(3 citation statements)

References 17 publications

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“…The presence of a cyclopropane ring structure increases the spacing between hydrocarbon chains by reducing their ability to pack tightly due to the weakening of the Lifshitz-van der Waals forces that stabilize chain-chain interactions. Moreover, electrically neutral PE can form hydrogen bonds with amino acids in the LL-37 structure due to the presence of −NH + 3 and −OPO − 3 − [28], promoting peptide embedding inside the monolayer. The longer distances between molecules limit the creation of PE-PE hydrogen bonds in favor of LL-37.…”

Section: Discussionmentioning

confidence: 99%

Susceptibility of Legionella gormanii Membrane-Derived Phospholipids to the Peptide Action of Antimicrobial LL-37—Langmuir Monolayer Studies

Pastuszak,

Jurak,

Kowalczyk

et al. 2024

Molecules

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LL-37 is the only member of the cathelicidin-type host defense peptide family in humans. It exhibits broad-spectrum bactericidal activity, which represents a distinctive advantage for future therapeutic targets. The presence of choline in the growth medium for bacteria changes the composition and physicochemical properties of their membranes, which affects LL-37’s activity as an antimicrobial agent. In this study, the effect of the LL-37 peptide on the phospholipid monolayers at the liquid–air interface imitating the membranes of Legionella gormanii bacteria was determined. The Langmuir monolayer technique was employed to prepare model membranes composed of individual classes of phospholipids—phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylglycerol (PG), cardiolipin (CL)—isolated from L. gormanii bacteria supplemented or non-supplemented with exogenous choline. Compression isotherms were obtained for the monolayers with or without the addition of the peptide to the subphase. Then, penetration tests were carried out for the phospholipid monolayers compressed to a surface pressure of 30 mN/m, followed by the insertion of the peptide into the subphase. Changes in the mean molecular area were observed over time. Our findings demonstrate the diversified effect of LL-37 on the phospholipid monolayers, depending on the bacteria growth conditions. The substantial changes in membrane properties due to its interactions with LL-37 enable us to propose a feasible mechanism of peptide action at a molecular level. This can be associated with the stable incorporation of the peptide inside the monolayer or with the disruption of the membrane leading to the removal (desorption) of molecules into the subphase. Understanding the role of antimicrobial peptides is crucial for the design and development of new strategies and routes for combating resistance to conventional antibiotics.

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Section: Discussionmentioning

confidence: 99%

Susceptibility of Legionella gormanii Membrane-Derived Phospholipids to the Peptide Action of Antimicrobial LL-37—Langmuir Monolayer Studies

Pastuszak,

Jurak,

Kowalczyk

et al. 2024

Molecules

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“…[5][6][7] Vibration spectroscopy is the most effective method for studying the structure of hydration clusters and formation of hydrogen bonding. 8,9 Infrared spectra of matrix isolated formic acid have identified the CQO stretching vibration frequencies of monomers, as well as the splitting doublet frequencies of dimers (cyclic and open chain), 10,11 which laid the foundation for the spectral identification of complex dynamic processes. Formic acid (FA) is the simplest carboxylic acid and one of the simplest rotational isomers, which is of great significance for studying molecular structure and kinetic properties.…”

Section: Introductionmentioning

confidence: 99%

Study on depolymerization kinetics of formic acid dimers in binary mixture

Han¹,

Wang²,

Qiao³

et al. 2023

Phys. Chem. Chem. Phys.

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“…From left to right: POPC (16:0/18:1 PC), DPPC (16:0/16:0 PC), and a hydrated PC bilayer.Dashed ellipses around the POPC and DPPC phospholipid headgroups highlighting their positive charged choline (blue) and negative charged phosphate (orange) groups. The lipid bilayer is fully hydrated with the hydrophilic PC headgroups interacting with polar water molecules, which continuously experience the formation and breakup of hydrogen bonds at picosecond time scales[35][36][37].…”

mentioning

confidence: 99%

Real Space and Time Imaging of Collective Headgroup Dipole Motions in Zwitterionic Lipid Bilayers

et al. 2023

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Lipid bilayers are supramolecular structures responsible for a range of processes, such as transmembrane transport of ions and solutes, and sorting and replication of genetic materials, to name just a few. Some of these processes are transient and currently, cannot be visualized in real space and time. Here, we developed an approach using 1D, 2D, and 3D Van Hove correlation functions to image collective headgroup dipole motions in zwitterionic phospholipid bilayers. We show that both 2D and 3D spatiotemporal images of headgroup dipoles are consistent with commonly understood dynamic features of fluids. However, analysis of the 1D Van Hove function reveals lateral transient and re-emergent collective dynamics of the headgroup dipoles—occurring at picosecond time scales—that transmit and dissipate heat at longer times, due to relaxation processes. At the same time, the headgroup dipoles also generate membrane surface undulations due a collective tilting of the headgroup dipoles. A continuous intensity band of headgroup dipole spatiotemporal correlations—at nanometer length and nanosecond time scales—indicates that dipoles undergo stretching and squeezing elastic deformations. Importantly, the above mentioned intrinsic headgroup dipole motions can be externally stimulated at GHz-frequency scale, enhancing their flexoelectric and piezoelectric capabilities (i.e., increased conversion efficiency of mechanical energy into electric energy). In conclusion, we discuss how lipid membranes can provide molecular-level insights about biological learning and memory, and as platforms for the development of the next generation of neuromorphic computers.

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Intermolecular Hydrogen-Bond Interactions in DPPE and DMPC Phospholipid Membranes Revealed by Far-Infrared Spectroscopy

Cited by 7 publications

References 17 publications

Susceptibility of Legionella gormanii Membrane-Derived Phospholipids to the Peptide Action of Antimicrobial LL-37—Langmuir Monolayer Studies

Susceptibility of Legionella gormanii Membrane-Derived Phospholipids to the Peptide Action of Antimicrobial LL-37—Langmuir Monolayer Studies

Study on depolymerization kinetics of formic acid dimers in binary mixture

Real Space and Time Imaging of Collective Headgroup Dipole Motions in Zwitterionic Lipid Bilayers

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