Photopolymerization-Induced Polymersome Rupture.

Poly(butadiene)- b-poly(ethylene oxide) (PBut2.5- b-PEO1.3) giant polymersomes were prepared using an emulsion-centrifugation method. The impact of a fast decrease of the osmotic pressure inside the lumen of giant PBut- b-PEO vesicles was studied by confocal microscopy. This osmotic imbalance was created by performing the photoinduced polymerization of acrylamide inside these giant polymersomes, mimicking cell-like confinement. Experimental conditions (irradiation time, relative concentration of monomer, and photoinitiator) were optimized to induce the fastest and highest osmotic pressure difference in bulk solution. When confined inside polymersomes with a low permeability membrane made of PBut- b-PEO copolymers, this hyper-osmotic shock induced a fast disruption of the membrane and polymersome burst. These findings, complementary to hypotonic shock approaches previously reported, are demonstrating the versatility and relevance of controlling and modulating osmotic pressure imbalance in self-assembled artificial cell systems and protocells.

Photo-triggered polymer nanomedicines: From molecular mechanisms to therapeutic applications.

The use of nanotechnology to improve treatment efficacy and reduce side effects is central to nanomedicine. In this context, stimuli-responsive drug delivery systems (DDS) such as chemical/physical gels or nanoparticles such as polymersomes, micelles or nanogels are particularly promising and are the focus of this review. Several stimuli have been considered but light as an exogenous trigger presents many advantages that are pertinent for clinical applications such as high spatial and temporal control and low cost. Underlying mechanisms required for the release of therapeutic agents in vitro and in vivo range from the molecular scale, namely photoisomerization, hydrophobicity photoswitching, photocleavage or heat generation via nanoheaters, through to the macromolecular scale. As well as these approaches, DDS destabilization, DDS permeation pore unblocking and formation are discussed.

Synthetic water soluble di-/tritopic molecular receptors exhibiting Ca2+/Mg2+ exchange.

Structural integration of two synthetic water soluble receptors for Ca2+ and Mg2+, namely 1,2-bis(2-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid (BAPTA) and o-aminophenol-N,N,O-triacetic acid (APTRA), respectively, gave novel di- and tritopic ionophores (1 and 2). As Mg2+ and Ca2+ cannot be simultaneously complexed by the receptors, allosteric control of complexation results. Potentiometric measurements established stepwise protonation constants and showed high affinity for Ca2+ (log K = 6.08 and 8.70 for 1 and 2, respectively) and an excellent selectivity over Mg2+ (log K = 3.70 and 5.60 for 1 and 2, respectively), which is compatible with magnesium-calcium ion exchange. While ion-exchange of a single Mg2+ for a single Ca2+ is possible in both 1 and 2, the simultaneous binding of two Mg2+ by 2 appears prohibitive for replacement of these two ions by a single Ca2+. Ion-binding and exchange was further rationalized by DFT calculations.

Polymersome Popping by Light-Induced Osmotic Shock under Temporal, Spatial, and Spectral Control.

The light-triggered, programmable rupture of cell-sized vesicles is described, with particular emphasis on self-assembled polymersome capsules. The mechanism involves a hypotonic osmotic imbalance created by the accumulation of photogenerated species inside the lumen, which cannot be compensated owing to the low water permeability of the membrane. This simple and versatile mechanism can be adapted to a wealth of hydrosoluble molecules, which are either able to generate reactive oxygen species or undergo photocleavage. Ultimately, in a multi-compartmentalized and cell-like system, the possibility to selectively burst polymersomes with high specificity and temporal precision and to consequently deliver small encapsulated vesicles (both polymersomes and liposomes) is demonstrated.