Phospholipid bilayers can be described as capacitors whose capacitance per unit area (specific capacitance, Cm) is determined by their thickness and dielectric constant–independent of applied voltage. It is also widely assumed that the Cm of membranes can be treated as a “biological constant”. Recently, using droplet interface bilayers (DIBs), it was shown that zwitterionic phosphatidylcholine (PC) lipid bilayers can act as voltage-dependent, nonlinear memory capacitors, or memcapacitors. When exposed to an electrical “training” stimulation protocol, capacitive energy storage in lipid membranes was enhanced in the form of long-term potentiation (LTP), which enables biological learning and long-term memory. LTP was the result of membrane restructuring and the progressive asymmetric distribution of ions across the lipid bilayer during training, which is analogous, for example, to exponential capacitive energy harvesting from self-powered nanogenerators. Here, we describe how LTP could be produced from a membrane that is continuously pumped into a nonequilibrium steady state, altering its dielectric properties. During this time, the membrane undergoes static and dynamic changes that are fed back to the system’s potential energy, ultimately resulting in a membrane whose modified molecular structure supports long-term memory storage and LTP. Here, we also show that LTP is very sensitive to different salts (KCl, NaCl, LiCl, and TmCl3), with LiCl and TmCl3 having the most profound effect in depressing LTP, relative to KCl. This effect is related to how the different cations interact with the bilayer zwitterionic PC lipid headgroups primarily through electric-field-induced changes to the statistically averaged orientations of water dipoles at the bilayer headgroup interface.
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Real Space and Time Imaging of Collective Headgroup Dipole Motions in Zwitterionic Lipid Bilayers
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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- Award ID(s):
- 2219289
- PAR ID:
- 10526487
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Membranes
- Volume:
- 13
- Issue:
- 4
- ISSN:
- 2077-0375
- Page Range / eLocation ID:
- 442
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Phosphatidic acid (PA) is a signaling lipid that is produced enzymatically from phosphatidylcholine (PC), lysophosphatidic acid, or diacylglycerol. Compared to PC, PA lacks a choline moiety on the headgroup, making the headgroup smaller than that of PC and PA, and PA has a net negative charge. Unlike the cylindrical geometry of PC, PA, with its small headgroup relative to the two fatty acid tails, is proposed to support negatively curved membranes. Thus, PA is thought to play a role in a variety of biological processes that involve bending membranes, such as the formation of intraluminal vesicles in multivesicular bodies and membrane fusion. Using supported tubulated lipid bilayers (STuBs), the extent to which PA localizes to curved membranes was determined. STuBs were created via liposome deposition with varying concentrations of NaCl (500 mM to 1 M) on glass to form supported bilayers with connected tubules. The location of fluorescently labeled lipids relative to tubules was determined by imaging with total internal reflection or confocal fluorescence microscopy. The accumulation of various forms of PA (with acyl chains of 16:0-6:0, 16:0-12:0, 18:1-12:0) were compared to PC and the headgroup labeled phosphatidylethanolamine (PE), a lipid that has been shown to accumulate at regions of curvature. PA and PE accumulated more at tubules and led to the formation of more tubules than PC. Using large unilamellar liposomes in a dye-quenching assay, the location of the headgroup labeled PE was determined to be mostly on the outer, positively curved leaflet, whereas the tail labeled PA was located more on the inner, negatively curved leaflet. This study demonstrates that PA localizes to regions of negative curvature in liposomes and supports the formation of curved, tubulated membranes. This is one way that PA could be involved with curvature formation during a variety of cell processes.
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Biological and technological processes that involve liquids under negative pressure are vulnerable to the formation of cavities. Maximal negative pressures found in plants are around −100 bar, even though cavitation in pure bulk water only occurs at much more negative pressures on the relevant time scales. Here, we investigate the influence of small solutes and lipid bilayers, both constituents of all biological liquids, on the formation of cavities under negative pressures. By combining molecular dynamics simulations with kinetic modeling, we quantify cavitation rates on biologically relevant length and time scales. We find that lipid bilayers, in contrast to small solutes, increase the rate of cavitation, which remains unproblematically low at the pressures found in most plants. Only when the negative pressures approach −100 bar does cavitation occur on biologically relevant time scales. Our results suggest that bilayerbased cavitation is what generally limits the magnitude of negative pressures in liquids that contain lipid bilayers.more » « less
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Abstract After the preparation of 2D electronic flat band (EFB) in van der Waals (vdW) superlattices, recent measurements suggest the existence of 1D electronic flat bands (1D‐EFBs) in twisted vdW bilayers. However, the realization of 1D‐EFBs is experimentally elusive in untwisted 2D layers, which is desired considering their fabrication and scalability. Herein, the discovery of 1D‐EFBs is reported in an untwisted in situ‐grown two atomic‐layer Bi(110) superlattice self‐aligned on an SnSe(001) substrate using scanning probe microscopy measurements and density functional theory calculations. While the Bi–Bi dimers of Bi zigzag (
ZZ ) chains are buckled, the epitaxial lattice mismatch between the Bi and SnSe layers induces two 1D buckling reversal regions (BRRs) extending along theZZ direction in each Bi(110)‐11 × 11 supercell. A series of 1D‐EFBs arises spatially following BRRs that isolate electronic states along the armchair (AC ) direction and localize electrons in 1D extended states alongZZ due to quantum interference at a topological node. This work provides a generalized strategy for engineering 1D‐EFBs in utilizing lattice mismatch between untwisted rectangular vdW layers. -
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Artificial polariton bandgaps at infrared frequencies are investigated by exploiting the strong coupling of electromagnetic waves with induced electric dipoles in two‐dimensional (2D) indium tin oxide nanorod arrays (ITO‐NRAs). The electric dipoles originate from the collective oscillations of free electrons within the individual ITO nanorods undergoing plasmonic resonance. Controlling the near‐field interactions among the neighboring electric dipoles allows for manipulation of the collective polariton modes that are manifested as a polariton bandgap. A theoretical model is developed to understand the coupled phenomena underlying the unique characteristics of plasmon–polariton bandgaps. With high‐degree geometric control of the ITO‐NRAs, it is experimentally demonstrated that reducing the spacing between ITO nanorods in a square array strengthens the near‐field interactions and thus results in a redshift as well as broadening of the polariton bandgap. Furthermore, arranging ITO‐NRAs in a rectangular lattice breaks the symmetry with respect to the principle axis, which leads to a splitting of the collective polariton modes owing to the competition between the quasi‐longitudinally and quasi‐transversely coupled plasmon–polariton modes. The work highlights the use of a classical dipole coupling method for scaling polariton bandgaps to the infrared in artificial plasmonic lattices, thereby offering a new design dimension for infrared sensing, absorbers, and optical communications.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/membranes13040442
