Polymer brush collapse under shear flow

Shear responsive surfaces offer potential advances in a number of applications. Surface functionalisation using polymer brushes is one route to such properties, particularly in the case of entangled polymers. We report on neutron reflectometry measurements of polymer brushes in entangled polymer solutions performed under controlled shear, as well as coarse-grained computer simulations corresponding to these interfaces. Here we show a reversible and reproducible collapse of the brushes, increasing with the shear rate. Using two brushes of greatly different chain lengths and grafting densities, we demonstrate that the dynamics responsible for the structural change of the brush are governed by the free chains in solution rather than the brush itself, within the range of parameters examined. The phenomenon of the brush collapse could find applications in the tailoring of nanosensors, and as a way to dynamically control surface friction and adhesion

Plasmonic Hepatitis B Biosensor for the Analysis of Clinical Saliva

A biosensor for the detection of hepatitis B antibodies in clinical saliva was developed. Compared to conventional analysis of blood serum, it offers the advantage of noninvasive collection of samples. Detection of biomarkers in saliva imposes two major challenges associated with the low analyte concentration and increased surface fouling. The detection of minute amounts of hepatitis B antibodies was performed by plasmonically amplified fluorescence sandwich immunoassay. To have access to specific detection, we prevented the nonspecific adsorption of biomolecules present in saliva by brushes of poly[(N-(2-hydroxypropyl) methacrylamide)-co-(carboxybetaine methacrylamide)] grafted from the gold sensor surface and post modified with hepatitis B surface antigen. Obtained results were validated against the response measured with ELISA at a certified laboratory using serum from the same patients. © 201

Plasmonic Hepatitis B Biosensor for the Analysis of Clinical Saliva

A biosensor for the detection of hepatitis B antibodies in clinical saliva was developed. Compared to conventional analysis of blood serum, it offers the advantage of noninvasive collection of samples. Detection of biomarkers in saliva imposes two major challenges associated with the low analyte concentration and increased surface fouling. The detection of minute amounts of hepatitis B antibodies was performed by plasmonically amplified fluorescence sandwich immunoassay. To have access to specific detection, we prevented the nonspecific adsorption of biomolecules present in saliva by brushes of poly[(N-(2-hydroxypropyl) methacrylamide)-co-(carboxybetaine methacrylamide)] grafted from the gold sensor surface and post modified with hepatitis B surface antigen. Obtained results were validated against the response measured with ELISA at a certified laboratory using serum from the same patients. © 201

Oriented immobilization of Pep19-2.5 on antifouling brushes suppresses the development of Staphylococcus aureus biofilms

Bacterial colonization of indwelling medical devices poses a danger to the patient and is a tremendous economic burden that costs billions of dollars to the healthcare system. Thus, it is essential to develop an effective mechanism that prevents the attachment of bacteria to the surface in combination with bactericidal strategies to kill them in direct contact. In this work, we combine the repellent/antifouling properties of polymer brushes with the antimicrobial activity of the synthetic peptide Pep19-2.5 and test its efficacy to inhibit Staphylococcus aureus biofilm formation. To tackle this, we utilized hierarchical polymer brushes, where the bottom block provides an effective barrier against adhesion while the top block provides functional groups for the immobilization of active molecules. Further, these polymer brushes were decorated with dibenzocyclooctine (DBCO)-functionalized Pep19-2.5 using strain-promoted alkyne-azide cycloaddition (SPAAC). This click chemistry proceeds very fast and does not require any catalyst, which is crucial for biomedical applications. The obtained coating was not only able to decrease the number of freely planktonic bacteria in the surrounding media (by 52.5%) but also inhibit the development of S. aureus biofilm by reducing the number of total, viable, and viable but non-culturable (VBNC) cells (up to 58%, 66%, and 70% respectively) and reduce the biovolume and thickness. Conversely, this coating does not exert any cytotoxic effect on Normal Human Dermal Fibroblasts (NHDF) cells. Thus, the combination of hierarchical polymer brushes with Pep19-2.5 is a promising approach to fight medical biofilms without affecting surrounding tissues

Controlled Surface Adhesion of Macrophages via Patterned Antifouling Polymer Brushes

Macrophages will play an important role in future diagnostics and immunotherapies of cancer. However, this demands to selectively capture and sort different subpopulations, which remains a challenge due to their innate ability to bind to a wide range of interfaces indiscriminately. The main obstacle here is the lack of interfaces combining sufficient antifouling properties with the display of specific binding sites allowing sorting and quantification. Herein, as a proof of principle means, it is introduced to pattern interfaces to locally and selective capture macrophages. The repellent coating is based on antifouling polymer brushes, which can be functionalized. Arrays of binding sites are constructed by microchannel cantilever spotting. Those structures are tested for the isolation of different macrophage subtypes, especially polarized anti‐inflammatory macrophages of the M2 type which can be found associated to tumors (“tumor associated macrophages”; TAMs). Using macrophages as a model system, it is demonstrated that the newly developed surfaces and patterns are efficient for specifically trapping targeted cells and can be useful for further development of therapeutic or diagnostic purposes in the future

Zwitterionic Dendrimersomes: A Closer Xenobiotic Mimic of Cell Membranes

Building functional mimics of cell membranes is an important task toward the development of synthetic cells. So far, lipid and amphiphilic block copolymers are the most widely used amphiphiles with the bilayers by the former lacking stability while membranes by the latter are typically characterized by very slow dynamics. Herein, a new type of Janus dendrimer containing a zwitterionic phosphocholine hydrophilic headgroup (JDPC) and a 3,5-substituted dihydrobenzoate-based hydrophobic dendron is introduced. JDPC self-assembles in water into zwitterionic dendrimersomes (z-DSs) that faithfully recapitulate the cell membrane in thickness, flexibility, and fluidity, while being resilient to harsh conditions and displaying faster pore closing dynamics in the event of membrane rupture. This enables the fabrication of hybrid DSs with components of natural membranes, including pore-forming peptides, structure-directing lipids, and glycans to create raft-like domains or onion vesicles. Moreover, z-DSs can be used to create active synthetic cells with life-like features that mimic vesicle fusion and motility as well as environmental sensing. Despite their fully synthetic nature, z-DSs are minimal cell mimics that can integrate and interact with living matter with the programmability to imitate life-like features and beyond

Zwitterionic Dendrimersomes: A Closer Xenobiotic Mimic of Cell Membranes

Building functional mimics of cell membranes is an important task toward the development of synthetic cells. So far, lipid and amphiphilic block copolymers are the most widely used amphiphiles with the bilayers by the former lacking stability while membranes by the latter are typically characterized by very slow dynamics. Herein, a new type of Janus dendrimer containing a zwitterionic phosphocholine hydrophilic headgroup (JDPC) and a 3,5-substituted dihydrobenzoate-based hydrophobic dendron is introduced. JDPC self-assembles in water into zwitterionic dendrimersomes (z-DSs) that faithfully recapitulate the cell membrane in thickness, flexibility, and fluidity, while being resilient to harsh conditions and displaying faster pore closing dynamics in the event of membrane rupture. This enables the fabrication of hybrid DSs with components of natural membranes, including pore-forming peptides, structure-directing lipids, and glycans to create raft-like domains or onion vesicles. Moreover, z-DSs can be used to create active synthetic cells with life-like features that mimic vesicle fusion and motility as well as environmental sensing. Despite their fully synthetic nature, z-DSs are minimal cell mimics that can integrate and interact with living matter with the programmability to imitate life-like features and beyond

Unraveling the Mechanism and Kinetics of Binding of an LCI-eGFP-Polymer for Antifouling Coatings

The ability of proteins to adsorb irreversibly onto surfaces opens new possibilities to functionalize biological interfaces. Herein, the mechanism and kinetics of adsorption of protein-polymer macromolecules with the ability to equip surfaces with antifouling properties are investigated. These macromolecules consist of the liquid chromatography peak I peptide from which antifouling polymer brushes are grafted using single electron transfer-living radical polymerization. Surface plasmon resonance spectroscopy reveals an adsorption mechanism that follows a Langmuir-type of binding with a strong binding affinity to gold. X-ray reflectivity supports this by proving that the binding occurs exclusively by the peptide. However, the lateral organization at the surface is directed by the cylindrical eGFP. The antifouling functionality of the unimolecular coatings is confirmed by contact with blood plasma. All coatings reduce the fouling from blood plasma by 8894% with only minor effect of the degree of polymerization for the studied range (DP between 101 and 932). The excellent antifouling properties, combined with the ease of polymerization and the straightforward coating procedure make this a very promising antifouling concept for a multiplicity of applications