Katja Jankova

Surface-initiated atom transfer radical polymerization—a technique to develop biofunctional coatings

The initial formation of initiating sites for atom transfer radical polymerization (ATRP) on various polymer surfaces and numerous inorganic and metallic surfaces is elaborated. The subsequent ATRP grafting of a multitude of monomers from such surfaces to generate thin covalently linked polymer coatings is discussed briefly in order to provide a readily accessible survey. The potential for achieving a range of well-defined biofunctionalities, such as inhibition of non-specific fouling, immobilization of biomolecules, separation of proteins, adsorbents for proteins or cells, antibacterial activity, and encapsulation of drugs in particular provided by these surface-grafted polymers is described.

Synthesis of photoreactive α‐4‐azidobenzoyl‐ω‐methoxy‐poly(ethylene glycol)s and their end‐on photo‐grafting onto polysulfone ultrafiltration membranes

Covalent end-on grafting of poly(ethylene glycol) (PEG) onto a polysulfone (PSf) surface using α-4-azidobenzoyl-ω-methoxy-PEG (ABMPEG) is described. Photoreactive ABMPEG was synthesized by reacting monomethoxy-PEG (MPEG) with 4-azidobenzoyl chloride, yielding complete substitution of the hydroxyl groups. After adsorption from aqueous solutions, ABMPEG was photo-grafted under wet conditions onto PSf ultrafiltration (UF) membranes. Contact angle (CA) measurements showed the increased hydrophilicity of modified membranes and the irreversibility of the modification. Bovine serum albumin (BSA) adsorption decreased by 70% and the permeability decay after protein adsorption became less severe for the modified membranes compared to unmodified reference membranes.

Synthesis by ATRP of poly(ethylene‐co‐butylene)‐block‐polystyrene, poly(ethylene‐co‐butylene)‐block‐poly(4‐acetoxystyrene) and its hydrolysis product poly(ethylene‐co‐butylene)‐block‐poly(hydroxystyrene)

Diblock copolymers of poly(ethylene-co-butylene) and polystyrene or poly(4-acetoxystyrene) are synthesized by atom transfer radical polymerization (ATRP) using a 2-bromopropionic ester macroinitiator prepared from commercial monohydroxyl functional narrow dispersity hydrogenated polybutadiene (Kraton Liquid Polymer, L-1203). ATRP carried out in bulk and in xylene solution with cuprous bromide and two different complexing agents 2,2′-bipyridine (bipy) and 1,1,4,7,10,10-hexamethyltriethylenetetraamine (HMTETA) yielded well-defined diblock copolymers with polydispersities around 1,3. The diblock copolymer with poly(4-acetoxystyrene) was hydrolyzed to the corresponding poly(4-hydroxystyrene) sequence.

Adsorption and aqueous lubricating properties of charged and neutral amphiphilic diblock copolymers at a compliant, hydrophobic interface.

We have investigated the adsorption and lubricating properties of neutral and charged amphiphilic diblock copolymers at a hydrophobic polydimethylsiloxane (PDMS) interface in an aqueous environment. The diblock copolymers consist of a hydrophilic block of either neutral poly(ethylene glycol) (PEG) or negatively charged poly(acrylic acid) (PAA) and of a hydrophobic block of polystyrene (PS) or poly(2-methoxyethyl acrylate) (PMEA), thus generating PEG-b-X or PAA-b-X, where X block is either PS or PMEA. The molecular weight ratios were roughly 1:1 with each block ca. 5 kDa. Comparing the neutral PEG and charged PAA buoyant blocks with all other conditions identical, the former showed superior adsorption onto nonpolar, hydrophobic PDMS surfaces from a neutral aqueous solution. PEG-based copolymers showed substantial adsorption for both PS and PMEA as the anchoring block, whereas PAA-based copolymers showed effective adsorption only when PMEA was employed as the anchoring block. For PAA-b-PS, the poor adsorption properties are chiefly attributed to micellization due to the high interfacial tension between the PS core and water. The poor lubricating properties of PAA-b-PS diblock copolymer for a PDMS-PDMS sliding contact was well correlated with the poor adsorption properties. PAA-b-PMEA copolymers, despite their sizable amount of adsorbed mass, showed insignificant lubricating effects. When the charges of the PAA-b-PMEA diblock copolymers were screened by either adding NaCl to the aqueous solution or by lowering the pH, both the adsorption and lubricity improved. We ascribe the poor adsorption and inferior aqueous lubricating properties of the PAA-based diblock copolymers compared to their PEG-based counterparts mainly to the electrostatic repulsion between charged PAA blocks, hindering the facile formation of the lubricating layer under cyclic tribological stress at the sliding PDMS-PDMS interface.

Hydrophilization of poly(ether ether ketone) films by surface-initiated atom transfer radical polymerization

Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) has been exploited to hydrophilize PEEK. The ketone groups on the PEEK surface were reduced to hydroxyl groups which were converted to bromoisobutyrate initiating sites for SI-ATRP. The modification steps were followed by contact angle measurements and XPS. Moreover, ATR FTIR has been used to confirm the formation of initiating groups. Grafting of PEGMA from PEEK was performed in aqueous solution. The presence of the PPEGMA grafts on PEEK was revealed by the thermograms from TGA whereas investigations with AFM rejected changes in the surface topography. Two possible applications arose from the hydrophilization of PEEK, metal deposition and protein repellency. The performed modification allowed for successful electroless deposition and good adhesion of nickel as well as copper.

Protein repellent hydrophilic grafts prepared by surface-initiated atom transfer radical polymerization from polypropylene

Grafting of poly(ethylene glycol)methacrylate (PEGMA) and N,N-dimethylacrylamide (DMAAm) from UV-initiator modified polypropylene (PP) was performed by Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP). The modification and hydrophilization of the PP substrates were confirmed with Attenuated Total Reflectance (ATR) Fourier Transform Infrared (FTIR) spectroscopy and Water Contact Angle (WCA) measurements. Confocal fluorescence microscopy of modified and unmodified substrates immersed in labelled insulin aspart showed superior repulsion of this protein for the poly(PEGMA) grafts, due to the achieved architecture.

Hydrolysis of 4-acetoxystyrene polymers prepared by atom transfer radical polymerization

Hydrolysis of 4-acetoxystyrene polymers prepared by atom transfer radical polymerization was carried out under various reaction conditions. It was found that hydrazinolysis of 4-acetoxystyrene homopolymers, random and block copolymers with styrene in 1,4-dioxane, afforded the corresponding narrow dispersed materials with phenolic groups which were substantially free from crosslinkages. Gel permeation chromatographic (GPC) analysis of these polymers revealed different extents of molecular weight distribution (MWD) broadening for the hydrolysis products for the different structures. On the other hand, by NaOH catalyzed deprotection, the 4-acetoxystyrene polymers including triblock copolymer poly(4-acetoxystyrene-b-isobutylene-b-4-ace-toxystyrene) suffered from some degrees of coupling or even gelation, except for poly-(styrene-b-4-acetoxystyrene-b-styrene) which also by this method could be conveniently converted to its phenolic product.

Neutral, anionic, cationic, and zwitterionic diblock copolymers featuring poly(2-methoxyethyl acrylate) “hydrophobic” segments

Amphiphilic diblock copolymers incorporating “hydrophobic” poly(2-methoxyethyl acrylate) (PMEA) and hydrophilic neutral poly(ethylene glycol) monomethyl ether (mPEG), anionic poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA), cationic poly(2-dimethylaminoethyl methacrylate) (PDMAEMA), and zwitterionic poly(3-(N-(2-methacryloyloxyethyl)-N,N-dimethylammonio)propane sulfonate) (PDMAPS) blocks are constructed. mPEG, poly(tert-butyl acrylate) (PtBA), and poly(tert-butyl methacrylate) (PtBMA) macroinitiators are chain extended with 2-methoxyethyl acrylate (MEA) employing copper-mediated atom transfer radical polymerization (ATRP) garnishing well-defined diblock copolymers with narrow polydispersities (1.11–1.30). Selective cleavage of the tert-butyl esters affords PAA-b-PMEA and PMAA-b-PMEA. ATRP of 2-dimethylaminoethyl methacrylate (DMAEMA) from the PMEA macroinitiator results in PMEA-b-PDMAEMA while the betainisation of the latter provides zwitterionic diblock amphiphile PMEA-b-PDMAPS. Inspection of these macromolecular architectures by NMR spectroscopy and size exclusion chromatography (SEC) confirms a fairly high degree of control over the reactions emphasizing flexibility and precision of the approach.

Enhancing the phase segregation and connectivity of hydrophilic channels by blending highly sulfonated graft copolymers with fluorous homopolymers

The influence of tuning the ionic content of membranes by blending, as opposed to varying the degree of sulfonation, is evaluated. Membranes of fully sulfonated poly(vinylidene fluoride-co-chlorotrifluoroethylene)-g-poly(styrene sulfonic acid) blended with PVDF were prepared and investigated for morphology, water sorption, and proton transport properties. The blend membranes exhibit conductivities superior to pure graft copolymers under fully humidified conditions despite their lower water uptake. Transmission electron microscopy images of the blends reveal that the membranes comprise a combination of macro-phase segregated regions of ion-rich and PVDF-rich domains, and, at higher PVDF contents, ion-rich nano-scale domains within fluorine-rich domains.

Tetrazole substituted polymers for high temperature polymer electrolyte fuel cells

While tetrazole (TZ) has much lower basicity than imidazole and may not be fully protonated in the presence of phosphoric acid (PA), DFT calculations suggest that the basicity of TZ groups can be increased by the introduction of a 2,6-dioxy-phenyl-group in position 5 of TZ. This structure allows hydrogen bonds between TZ protons and ether oxygen atoms, and thereby establishes a resonance stabilised, co-planar structure for tetrazolium ions. Molecular electrostatic potential (MEP) calculations also indicate that tetrazolium ions possess two sites for proton hopping. This makes such materials interesting for use in a high temperature fuel cell (HT PEMFC). Based on these findings, two polymers incorporating the proposed TZ groups were synthesised, formed into membranes, doped with PA and tested for fuel cell relevant properties. At room temperature, TZ-PEEN and commercial meta-PBI showed an equilibrium uptake of 0.5 and 4.7 mol PA per mol heterocycle, respectively, indicating that PBI has higher affinity for PA than TZ-PEEN. The highest achieved PA uptake was ca. 110 wt%, resulting in a proton conductivity of 25 mS cm−1 at 160 °C with a low activation energy of about 35 kJ mol−1. In a first HT PEMFC test at 160 °C, a peak power density of 287 mW cm−2 was achieved.