More Like this

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

   https://doi.org/10.3390/membranes13040442  

   Bolmatov, Dima; Collier, C Patrick; Zav’yalov, Dmitry; Egami, Takeshi; Katsaras, John (April 2023, Membranes)

   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. 

   more » « less
2. Self-assembly of magnetic colloids with shifted dipoles

   https://doi.org/10.1039/c8sm02591f  

   Vega-Bellido, Gabriel I.; DeLaCruz-Araujo, Ronal A.; Kretzschmar, Ilona; Córdova-Figueroa, Ubaldo M. (May 2019, Soft Matter)

   The self-assembly of colloidal magnetic Janus particles with a laterally displaced (or shifted), permanent dipole in a quasi-two-dimensional system is studied using Brownian dynamics simulations. The rate of formation of clusters and their structures are quantified for several values of dipolar shift from the particle center, which is nondimensionalized using the particle's radius so that it takes values ranging from 0 to 1, and examined under different magnetic interaction strengths relative to Brownian motion. For dipolar shifts close to 0, chain-like structures are formed, which grow at long times following a power law, while particles of shift higher than 0.2 generally aggregate in ring-like clusters that experience limited growth. In the case of shifts between 0.4 and 0.5, the particles tend to aggregate in clusters of 3 to 6, while for all shifts higher than 0.6 clusters rarely contain more than 3 particles due to the antiparallel dipole orientations that are most stable at those shifts. The strength of the magnetic interactions hastens the rate at which clusters are formed; however, the effect it has on cluster size is lessened by increases in the shift of the dipoles. These results contribute to better understand the dynamics of magnetic Janus particles and can help the synthesis of functionalized materials for specific applications such as drug delivery. 

   more » « less
3. The stress in a dispersion of mutually polarizable spheres

   https://doi.org/10.1063/5.0052127  

   Reed, K_M; Swan, J_W (July 2021, The Journal of Chemical Physics)

   Dispersions of dielectric and paramagnetic nanoparticles polarize in response to an external electric or magnetic field and can form chains or other ordered structures depending on the strength of the applied field. The mechanical properties of these materials are of interest for a variety of applications; however, computational studies in this area have so far been limited. In this work, we derive expressions for two important properties for dispersions of polarizable spherical particles with dipoles induced by a uniform external field—the isothermal stress tensor and the pressure. Numerical calculations of these quantities, evaluated using a spectrally accurate Ewald summation method, are validated using thermodynamic integration. We also compare the stress obtained using the mutual dipole model, which accounts for the mutual polarization of particles, to the stress expected from calculations using a fixed dipole model, which neglects mutual polarization. We find that as the conductivity of the particles increases relative to the surrounding medium, the fixed dipole model does not accurately describe the dipolar contribution to the stress. The thermodynamic pressure, calculated from the trace of the stress tensor, is compared to the virial expression for the pressure, which is simpler to calculate but inexact. We find that the virial pressure and the thermodynamic pressure differ, especially in suspensions with a high volume fraction of particles. 

   more » « less
4. In-plane orientational motions of the functional groups of molecules at the air/water interface by time-resolved vibrational sum frequency generation

   https://doi.org/10.1063/5.0230223  

   Huang-Fu, Zhi-Chao; Zhang, Tong; Brown, Jesse B; Qian, Yuqin; Fisher, Haley; Rao, Yi (October 2024, The Journal of Chemical Physics)

   The movements of molecules at interfaces and surfaces are restricted by their asymmetric environments, leading to anisotropic orientational motions. In this work, in-plane orientational motions of the –C=O and –CF3 groups of coumarin 153 (C153) at the air/water interface were measured using time-resolved (TR) vibrational sum frequency generation (SFG). The in-plane orientational time constants of the –C=O and –CF3 groups of C153 are found to be 41.5 ± 8.2 and 36.0 ± 4.5 ps. These values are over five-times faster than that of 198 ± 15 ps for the permanent dipole of the whole C153 molecule at the interface, which may indicate that the two groups experience different interfacial friction in the plane. These differences could also be the result of the permanent dipole of C153 being almost five times those of the –C=O and –CF3 groups. The difference in orientational motions reveals the microscopic heterogeneous environment that molecules experience at the interface. While the interfacial dynamics of the two functional groups are similar, our TR-SFG experiments allowed the quantification of the in-plane dynamics of individual functional groups for the first time. Our experimental findings about the interfacial molecular motion have implications for molecular rotations, energy transfer, and charge transfer at material interfaces, photocatalysis interfaces, and biological cell/membrane aqueous interfaces. 

   more » « less
5. Progress toward a one-electron model for the non-valence correlation-bound anions of polycyclic aromatic hydrocarbons

   https://doi.org/10.1088/2516-1075/ac522a  

   Mulvey, Devin M; Jordan, Kenneth D (March 2022, Electronic Structure)

   Abstract A one-electron model Hamiltonian is used to characterize the non-valence correlation-bound (NVCB) anions of hexagonal polycyclic aromatic hydrocarbons (PAHs) C 6 n 2 H 6 n ( n = 3–7). The model incorporates atomic electrostatic moments up to the quadrupole, coupled inducible charges and dipoles, and atom-centered repulsive Gaussians to describe the interaction between the excess electron and PAH. These model components are parameterized on and validated against all-electron calculations. Good agreement is found between the static dipole polarizabilities obtained from the model and those from PBE0 density functional theory and second-order Møller–Plesset perturbation theory calculations. In the model, charge flow dominates the in-plane polarizability of PAHs larger than C 54 H 18 , yielding an approximately quadratic scaling of the mean polarizabilty with the number of carbon atoms. Inclusion of electrostatic interactions decreases the electron binding energies for the largest PAHs considered by about 20% and shift charge distribution from above and below the plane of the ring system toward the periphery. Analysis of the electrostatic and polarization interactions provides insight into qualitative trends in the electron binding energy and the charge distribution of the lowest energy NVCB anion. 

   more » « less