Lipid sponge droplets as programmable synthetic organelles.

Living cells segregate molecules and reactions in various subcellular compartments known as organelles. Spatial organization is likely essential for expanding the biochemical functions of synthetic reaction systems, including artificial cells. Many studies have attempted to mimic organelle functions using lamellar membrane-bound vesicles. However, vesicles typically suffer from highly limited transport across the membranes and an inability to mimic the dense membrane networks typically found in organelles such as the endoplasmic reticulum. Here, we describe programmable synthetic organelles based on highly stable nonlamellar sponge phase droplets that spontaneously assemble from a single-chain galactolipid and nonionic detergents. Due to their nanoporous structure, lipid sponge droplets readily exchange materials with the surrounding environment. In addition, the sponge phase contains a dense network of lipid bilayers and nanometric aqueous channels, which allows different classes of molecules to partition based on their size, polarity, and specific binding motifs. The sequestration of biologically relevant macromolecules can be programmed by the addition of suitably functionalized amphiphiles to the droplets. We demonstrate that droplets can harbor functional soluble and transmembrane proteins, allowing for the colocalization and concentration of enzymes and substrates to enhance reaction rates. Droplets protect bound proteins from proteases, and these interactions can be engineered to be reversible and optically controlled. Our results show that lipid sponge droplets permit the facile integration of membrane-rich environments and self-assembling spatial organization with biochemical reaction systems.

Single-Chain ß-d-Glycopyranosylamides of Unsaturated Fatty Acids: Self-Assembly Properties and Applications to Artificial Cell Development.

Amphiphilic molecules undergo self-assembly in aqueous medium to yield various supramolecular structures depending on their chemical structure and molecular geometry. Among these, lamellar membrane-bound vesicles are of special interest due to their resemblance to cellular membranes. Here we describe the self-assembly of single-chain amide-linked amphiphiles derived from ß-d-galactopyranosylamine and various unsaturated fatty acids into vesicles. In contrast, the analogous amphiphiles derived from ß-d-glucopyranosylamine self-assemble into nanotubes. Fluorescence spectroscopy, X-ray diffraction, and differential scanning calorimetry are used to determine various physical parameters pertinent to the self-assembly process. The vesicular architecture is characterized using optical microscopy and transmission electron microscopy. Moreover, we show that the vesicles derived from these amphiphiles can encapsulate molecules of various sizes and host model biochemical reactions. Our work demonstrates that single-chain glycolipid-based amphiphiles could serve as robust building blocks for artificial cells and have potential applications in drug delivery and microreactor design.

One-Dimensional Anomalous Diffusion of Gold Nanoparticles in a Polymer Melt.

We investigated the dynamics of polymer-grafted gold nanoparticles loaded into polymer melts using x-ray photon correlation spectroscopy. For low molecular weight host matrix polymer chains, normal isotropic diffusion of the gold nanoparticles is observed. For larger molecular weights, anomalous diffusion of the nanoparticles is observed that can be described by ballistic motion and generalized Lévy walks, similar to those often used to discuss the dynamics of jammed systems. Under certain annealing conditions, the diffusion is one-dimensional and related to the direction of heat flow during annealing and is associated with an dynamic alignment of the host polymer chains. Molecular dynamics simulations of a single gold nanoparticle diffusing in a partially aligned polymer network semiquantitatively reproduce the experimental results to a remarkable degree. The results help to showcase how nanoparticles can under certain circumstances move rapidly in polymer networks.

Highly Stable Artificial Cells from Galactopyranose-Derived Single-Chain Amphiphiles.

Single-chain amphiphiles (SCAs) that self-assemble into large vesicular structures are attractive components of synthetic cells because of the simplicity of bilayer formation and increased membrane permeability. However, SCAs commonly used for vesicle formation suffer from restricted working pH ranges, instability to divalent cations, and the inhibition of biocatalysts. Construction of more robust biocompatible membranes from SCAs would have significant benefits. We describe the formation of highly stable vesicles from alkyl galactopyranose thioesters. The compatibility of these uncharged SCAs with biomolecules makes possible the encapsulation of functional enzymes and nucleic acids during the vesicle generation process, enabling membrane protein reconstitution and compartmentalized nucleic acid amplification, even when charged precursors are supplied externally.

Interplay of electrostatics and lipid packing determines the binding of charged polymer coated nanoparticles to model membranes.

Understanding of nanoparticle-membrane interactions is useful for various applications of nanoparticles like drug delivery and imaging. Here we report on the studies of interaction between hydrophilic charged polymer coated semiconductor quantum dot nanoparticles with model lipid membranes. Atomic force microscopy and X-ray reflectivity measurements suggest that cationic nanoparticles bind and penetrate bilayers of zwitterionic lipids. Penetration and binding depend on the extent of lipid packing and result in the disruption of the lipid bilayer accompanied by enhanced lipid diffusion. On the other hand, anionic nanoparticles show minimal membrane binding although, curiously, their interaction leads to reduction in lipid diffusivity. It is suggested that the enhanced binding of cationic QDs at higher lipid packing can be understood in terms of the effective surface potential of the bilayers which is tunable through membrane lipid packing. Our results bring forth the subtle interplay of membrane lipid packing and electrostatics which determine nanoparticle binding and penetration of model membranes with further implications for real cell membranes.

Measurements of the electric field of zero-point optical phonons in GaAs quantum wells support the Urbach rule for zero-temperature lifetime broadening.

We study a specific type of lifetime broadening resulting in the well-known exponential "Urbach tail" density of states within the energy gap of an insulator. After establishing the frequency and temperature dependence of the Urbach edge in GaAs quantum wells, we show that the broadening due to the zero-point optical phonons is the fundamental limit to the Urbach slope in high-quality samples. In rough analogy with Welton's heuristic interpretation of the Lamb shift, the zero-temperature contribution to the Urbach slope can be thought of as arising from the electric field of the zero-point longitudinal-optical phonons. The value of this electric field is experimentally measured to be 3 kV cm-1, in excellent agreement with the theoretical estimate.