Activity of Antimicrobial Peptide Aggregates Decreases with Increased Cell Membrane Embedding Free Energy Cost

Antimicrobial peptides (AMPs) are a promising alternative to antibiotics for mitigating bacterial infections, in light of increasing bacterial resistance to antibiotics. However, predicting, understanding, and controlling the antibacterial activity of AMPs remain a significant challenge. While peptide intramolecular interactions are known to modulate AMP antimicrobial activity, peptide intermolecular interactions remain elusive in their impact on peptide bioactivity. Herein, we test the relationship between AMP intermolecular interactions and antibacterial efficacy by controlling AMP intermolecular hydrophobic and hydrogen bonding interactions. Molecular dynamics simulations and Gibbs free energy calculations in concert with experimental assays show that increasing intermolecular interactions via interpeptide aggregation increases the energy cost for the peptide to embed into the bacterial cell membrane, which in turn decreases the AMP antibacterial activity. Our findings provide a route for predicting and controlling the antibacterial activity of AMPs against Gram-negative bacteria via reductions of intermolecular AMP interactions

Competitive Binding in Mixed Surfactant Systems for Single-Walled Carbon Nanotube Separation

The separation of single-walled carbon nanotubes (SWNTs) by chirality is of great interest to enable the next generation of optical and optoelectronic devices. Many separation schemes employ the surfactant sodium dodecyl sulfate (SDS), with or without a bile salt surfactant such as sodium cholate (SC). In this study, we observe and explain the effect of these mixed surfactant systems on the hydrogel-based selective adsorption separation method. We find that sodium cholate outcompetes SDS more effectively on smaller diameter tubes and quantify this difference as the sodium cholate concentration is increased and (6,5) separation is diminished. These changes in separation efficiency with surfactant composition are understood using a theoretical model developed previously and predict that surfactant mixtures alter the charge per unit length of specific (<i>n</i>,<i>m</i>) SWNTs, altering the separation. This understanding of the chiral dependence of the surfactant binding will not only enable a greater understanding of surfactant coverage on the SWNT but also pave the path to further control the SWNT separation processes that depend on these surfactants

Lipid Exchange Envelope Penetration (LEEP) of Nanoparticles for Plant Engineering: A Universal Localization Mechanism

Nanoparticles offer clear advantages for both passive and active penetration into biologically important membranes. However, the uptake and localization mechanism of nanoparticles within living plants, plant cells, and organelles has yet to be elucidated. Here, we examine the subcellular uptake and kinetic trapping of a wide range of nanoparticles for the first time, using the plant chloroplast as a model system, but validated in vivo in living plants. Confocal visible and near-infrared fluorescent microscopy and single particle tracking of gold-cysteine-AF405 (GNP-Cys-AF405), streptavidin-quantum dot (SA-QD), dextran and poly­(acrylic acid) nanoceria, and various polymer-wrapped single-walled carbon nanotubes (SWCNTs), including lipid-PEG-SWCNT, chitosan-SWCNT and 30-base (dAdT) sequence of ssDNA (AT)₁₅ wrapped SWCNTs (hereafter referred to as ss­(AT)₁₅-SWCNT), are used to demonstrate that particle size and the magnitude, but not the sign, of the zeta potential are key in determining whether a particle is spontaneously and kinetically trapped within the organelle, despite the negative zeta potential of the envelope. We develop a mathematical model of this lipid exchange envelope and penetration (LEEP) mechanism, which agrees well with observations of this size and zeta potential dependence. The theory predicts a critical particle size below which the mechanism fails at all zeta potentials, explaining why nanoparticles are critical for this process. LEEP constitutes a powerful particulate transport and localization mechanism for nanoparticles within the plant system

A Nanobionic Light-Emitting Plant

The engineering of living plants for visible light emission and sustainable illumination is compelling because plants possess independent energy generation and storage mechanisms and autonomous self-repair. Herein, we demonstrate a plant nanobionic approach that enables exceptional luminosity and lifetime utilizing four chemically interacting nanoparticles, including firefly luciferase conjugated silica (SNP-Luc), d-luciferin releasing poly­(lactic-<i>co</i>-glycolic acid) (PLGA-LH₂), coenzyme A functionalized chitosan (CS-CoA) and semiconductor nanocrystal phosphors for longer wavelength modulation. An in vitro kinetic model incorporating the release rates of the nanoparticles is developed to maximize the chemiluminescent lifetimes to exceed 21.5 h. In watercress (<i>Nasturtium officinale)</i> and other species, the nanoparticles circumvent limitations such as luciferin toxicity above 400 μM and colocalization of enzymatic reactions near high adenosine triphosphate (ATP) production. Pressurized bath infusion of nanoparticles (PBIN) is introduced to deliver a mixture of nanoparticles to the entire living plant, well described using a nanofluidic mathematical model. We rationally design nanoparticle size and charge to control localization within distinct tissues compartments with 10 nm nanoparticles localizing within the leaf mesophyll and stomata guard cells, and those larger than 100 nm segregated in the leaf mesophyll. The results are mature watercress plants that emit greater than 1.44 × 10¹² photons/sec or 50% of 1 μW commercial luminescent diodes and modulate “off” and “on” states by chemical addition of dehydroluciferin and coenzyme A, respectively. We show that CdSe nanocrystals can shift the chemiluminescent emission to 760 nm enabling near-infrared (nIR) signaling. These results advance the viability of nanobionic plants as self-powered photonics, direct and indirect light sources