Surfaces with Dual Functionality through Specific Coimmobilization of Self-Assembled Polymeric Nanostructures

Coimmobilization of functional, nanosized assemblies broadens the possibility to engineer dually functionalized active surfaces with a nanostructured texture. Surfaces decorated with different nanoassemblies, such as micelles, polymersomes, or nanoparticles are in high demand for various applications ranging from catalysis, biosensing up to antimicrobial surfaces. Here, we present a combination of bio-orthogonal and catalyst-free strain-promoted azide–alkyne click (SPAAC) and thiol–ene reactions to simultaneously coimmobilize various nanoassemblies; we selected polymersome–polymersome and polymersome–micelle assemblies. For the first time, the immobilization method using SPAAC reaction was studied in detail to attach soft, polymeric assemblies on a solid support. Together, the SPAAC and thiol–ene reactions successfully coimmobilized two unique self-assembled structures on the surfaces. Additionally, poly(dimethylsiloxane) (PDMS)-based polymersomes were used as “ink” for direct immobilization from a PDMS-based microstamp onto a surface creating locally defined patterns. Combining immobilization reactions has the advantage to attach any kind of nanoassembly pairs, resulting in surfaces with “desired” interfacial properties. Different nanoassemblies that encapsulate multiple active compounds coimmobilized on a surface will pave the way for the development of multifunctional surfaces with controlled properties and efficiency

Biomimetic Planar Polymer Membranes Decorated with Enzymes as Functional Surfaces

Functional surfaces were generated by a combination of enzymes with polymer membranes composed of an amphiphilic, asymmetric block copolymer poly(ethyleneglycol)-block-poly(γ-methyl-ε-caprolactone)-block-poly[(2-dimethylamino)ethylmethacrylate]. First, polymer films formed at the air–water interface were transferred in different sequences onto silica solid support using the Langmuir–Blodgett technique, generating homogeneous monolayers and bilayers. A detailed characterization of these films provided insight into their properties (film thickness, wettability, topography, and roughness). On the basis of these findings, the most promising membranes were selected for enzyme attachment. Functional surfaces were then generated by the adsorption of two model enzymes that can convert phenol and its derivatives (laccase and tyrosinase), well known as high-risk pollutants of drinking and natural water. Both enzymes preserved their activity upon immobilization with respect to their substrates. Depending on the properties of the polymer films, different degrees of enzymatic activity were observed: bilayers provided the best conditions in terms of both overall stability and enzymatic activity. The interaction between amphiphilic triblock copolymer films and enzymes is exploited to engineer “active surfaces” with specific functionalities and high efficacy resulting from the intrinsic activity of the biomolecules that is preserved by an appropriate synthetic environment

Functional Surfaces: Bio-Hybrid Membranes for Biosensing

Combining natural enzymes with synthetic membranes on solid support enables creation of functional surfaces able to serve for efficient biosensing. Enzymes (laccase and tyrosinase) integrated on soft copolymer mono- and bilayer membranes preserve their activity and specifically detect the presence of phenols. The straightforward approach to create these bio-hybrid membranes allows changing the enzyme type and thus producing functional surfaces for sensitive detection of desired molecules

Optimized reconstitution of membrane proteins into synthetic membranes

Light-driven proton pumps, such as proteorhodopsin, have been proposed as an energy source in the field of synthetic biology. Energy is required to power biochemical reactions within artificially created reaction compartments like proto-or nanocells, which are typically based on either lipid or polymer membranes. The insertion of membrane proteins into these membranes is delicate and quantitative studies comparing these two systems are needed. Here we present a detailed analysis of the formation of proteoliposomes and proteopolymersomes and the requirements for a successful reconstitution of the membrane protein proteorhodopsin. To this end, we apply design of experiments to provide a mathematical framework for the reconstitution process. Mathematical optimization identifies suitable reconstitution conditions for lipid and polymer membranes and the obtained data fits well to the predictions. Altogether, our approach provides experimental and modeling evidence for different reconstitution mechanisms depending on the membrane type which resulted in a surprisingly similar performance

Cooperative Adsorption of Lipoprotein Phospholipids, Triglycerides, and Cholesteryl Esters Are a Key Factor in Nonspecific Adsorption from Blood Plasma to Antifouling Polymer Surfaces

Nonspecific protein adsorption is a central challenge for the use of polymeric materials in biological media. While the quantity of adsorbed protein can be lowered, very few surfaces are protein resistant when exposed to undiluted serum or plasma. The underlying principles of this fouling and the adsorbing proteins remain to be identified. Here, we investigated adsorption from undiluted human blood plasma to three different polymer brushes. Our study showed that the polymer structure does not influence which proteins adsorb. Further, we identified 98 plasma proteins that still foul current “protein-resistant” polymer brushes. Detailed studies into the major adsorbing protein revealed the central role that lipoproteins and low density lipoprotein in particular play in fouling of plasma to polymeric biomaterials. However, although apolipoprotein B100 is found as a major fouling protein in our mass spectrometry screening, studies on individual components of lipoproteins show that it is not apoB100 but a mixture of phospholipids, triglycerides, and cholesteryl esters that plays a major role in lipoprotein adsorption

Expanding the potential of MRI contrast agents through multifunctional polymeric nanocarriers

MRI is a sought-after, noninvasive tool in medical diagnostics, yet the direct application of contrast agents to tissue suffers from several drawbacks. Hosting the contrast agents in polymeric nanocarriers can solve many of these issues while creating additional benefit through exploitation of the intrinsic characteristics of the polymeric carriers. In this report, the versatility is highlighted with recent examples of dendritic and hyperbranched polymers, polymer nanoparticles and micelles, and polymersomes as multifunctional bioresponsive nanocarriers for MRI contrast agents

Surfaces Decorated with Polymeric Nanocompartments for pH Reporting

Here we present a novel active surface that demonstrates pH responsiveness and can be used as a platform for designing smart labels`. To generate our active surfaces, we immobilized polymer nanocompartments onto glass surfaces using thiol-ene chemistry. Prior to surface attachment, a pH responsive model dye was encapsulated within nanocompartments at two different pH values. We confirmed the attachment and distribution of dye-loaded polymersomes and established the pH responsiveness of the active surface construct. The strategy presented here was carefully chosen to obtain small sized functional surfaces from commercially available materials that can be easily integrated into intelligent packaging systems. The ability to miniaturize such smart labels, while still being able to detect their response to the environment, is a crucial step towards developing active surfaces suitable for food packaging applications