The permeability and solute transport characteristics of amphiphilic triblock-polymer vesicles containing the bacterial water-channel protein Aquaporin Z (AqpZ) were investigated. The vesicles were made of a block copolymer with symmetric poly-(2-methyloxazoline)-poly-(dimethylsiloxane)-poly-(2-methyloxazoline) (PMOXA 15-PDMS110-PMOXA 15) repeat units. Light-scattering measurements on pure polymer vesicles subject to an outwardly directed salt gradient in a stopped-flow apparatus indicated that the polymer vesicles were highly impermeable. However, a large enhancement in water productivity (permeability per unit driving force) of up to Ϸ800 times that of pure polymer was observed when AqpZ was incorporated. The activation energy (E a) of water transport for the protein-polymer vesicles (3.4 kcal/mol) corresponded to that reported for water-channel-mediated water transport in lipid membranes. The solute reflection coefficients of glucose, glycerol, salt, and urea were also calculated, and indicated that these solutes are completely rejected. The productivity of AqpZ-incorporated polymer membranes was at least an order of magnitude larger than values for existing salt-rejecting polymeric membranes. The approach followed here may lead to more productive and sustainable water treatment membranes, whereas the variable levels of permeability obtained with different concentrations of AqpZ may provide a key property for drug delivery applications.permeability ͉ triblock copolymer ͉ water treatment B iological membranes have excellent water transport characteristics, with certain membranes able to regulate permeability over a wide range. The permeability of membranes such as those present in the proximal tubules of the human kidney (1) can be increased by insertion of specific water-channel membrane proteins known as Aquaporins (AQPs). Other biological membranes, such as those in mammalian optic lenses (2), erythrocytes (3), and many other cell membranes (4) are constitutively AQP-rich. The permeabilities of AQP-rich membranes are orders of magnitude higher than those observed for unmodified phospholipid membranes (5). Additionally, some members of the AQP family have excellent solute retention capabilities for small solutes such as urea, glycerol, and glucose, even at high water transport rates (5, 6). These properties result from the unique structure of the water-selective AQPs. These AQPs have six membrane-spanning domains and a unique hourglass structure (7) with conserved charged residues that form a pore that allows both selective water transport and solute rejection. The AQP used in this study was a bacterial aquaporin from Escherichia coli, Aquaporin Z (AqpZ). AqpZ was selected because it can enhance the permeability of lipid vesicles by an order of magnitude while retaining small uncharged solutes (5). Additionally, AqpZ can be expressed in relatively large quantities in E. coli and has been reported to be quite stable under different reducing conditions and at temperatures of 4°C (5)-properties that make it att...

Biological membranes play an essential role in living organisms by providing stable and functional compartments, preserving cell architecture, whilst supporting signalling and selective transport that are mediated by a variety of proteins embedded in the membrane. However, mimicking cell membranes - to be applied in artificial systems - is very challenging because of the vast complexity of biological structures. In this respect a highly promising strategy to designing multifunctional hybrid materials/systems is to combine biological molecules with polymer membranes or to design membranes with intrinsic stimuli-responsive properties. Here we present supramolecular polymer assemblies resulting from self-assembly of mostly amphiphilic copolymers either as 3D compartments (polymersomes, PICsomes, peptosomes), or as planar membranes (free-standing films, solid-supported membranes, membrane-mimetic brushes). In a bioinspired strategy, such synthetic assemblies decorated with biomolecules by insertion/encapsulation/attachment, serve for development of multifunctional systems. In addition, when the assemblies are stimuli-responsive, their architecture and properties change in the presence of stimuli, and release a cargo or allow "on demand" a specific in situ reaction. Relevant examples are included for an overview of bioinspired polymer compartments with nanometre sizes and membranes as candidates in applications ranging from drug delivery systems, up to artificial organelles, or active surfaces. Both the advantages of using polymer supramolecular assemblies and their present limitations are included to serve as a basis for future improvements.

The synthesis and the characterization of a poly(2-methyloxazoline)-block-poly(dimethylsiloxane)-blockpoly(2-methyloxazoline) (PMOXA-PDMS-PMOXA) triblock copolymer carrying polymerizable groups at both chain ends are described. This copolymer forms vesicular structures in dilute aqueous solution, the size of which can be controlled in the range from 50 nm up to about 500 nm. The methacrylate end groups of the triblock copolymer can be polymerized in the vesicular aggregates using an UV-induced free radical polymerization. Static and dynamic light scattering, scanning electron microscopy, and transmission electron microscopy on both the resulting nanocapsules and their nonpolymerized precursors clearly show that the cross-linking polymerization does not lead to morphological changes in the underlying vesicles. Moreover, due to their cross-linked structure, the nanocapsules are shape persistent, thus maintaining their integrity even after their isolation from the aqueous solution.

No abstract

Hollow polymer particles with dimensions in the submicrometer region possess great potential for encapsulation of large quantities of and large sized guest molecules into their empty core domains. Conventional molecular chemistry requires costly synthetic procedures and only in special cases allows such particles to be prepared with exact control over their size and morphology. Therefore various selfassembly and templating approaches have been developed which will be briefly introduced in this article.

Polymeric formulations (micelles, vesicles etc.) have emerged as versatile drug carriers due to their increased stability, site specificity, blood circulation resistance and thus overall potential therapeutic effects compared to liposomes. Furthermore, stimuli‐responsive systems have been developed whose properties change after applying certain external triggers. Polymersomes are mainly composed of amphiphilic block copolymers that are held together in water due to strong physical interactions between the insoluble hydrophobic blocks, thus forming a bilayer morphology or, in the case of triblock copolymers, a bilayer‐like morphology. Formation and destabilization of these assemblies is a consequence of external stimuli (temperature, pH, oxidation/reduction conditions etc.). This review focuses on recent developments concerning stimuli‐ responsive polymersomes made of amphiphilic block copolymers and their potential applications within the biomedical field.magnified image

Giant unilamellar vesicles or GUVs are systems of choice as biomimetic models of cellular membranes. Although a variety of procedures exist for making single walled vesicles of tens of microns in size, the range of lipid compositions that can be used to grow GUVs by the conventional methods is quite limited, and many of the available methods involve energy input that can damage the lipids or other molecules present in the growing solution for embedment in the membrane or in the vesicle interior. Here, we show that a wide variety of lipids or lipid mixtures can grow into GUVs by swelling lipid precursor films on top of a dried polyvinyl alcohol gel surface in a swelling buffer that can contain diverse biorelevant molecules. Moreover, we show that the encapsulation potential of this method can be enhanced by combining polyvinyl alcohol-mediated growth with inverse-phase methods, which allow (bio)molecule complexation with the lipids.

A new kind of nanoreactor has been prepared by the incorporation of a channel protein into the shell of (polymerized) vesicles formed from an amphiphilic ABA-triblock copolymer.