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Biomedical subjects

Igor Luzinov

Publications and source records attributed to Igor Luzinov.

6 recordsLinked to original sources

To patterned binary polymer brushes via capillary force lithography and surface-initiated polymerization.

An effective approach is described for the synthesis of binary patterned polymer brushes using a combination of capillary force lithography and surface-initiated polymerization. First, the approach calls for an ultrathin polystyrene (PS) mask to be deposited, in a pattern, over a surface to which a layer of polymerization initiator has already been anchored. Next, surface-initiated atom transfer radical polymerization (ATRP) is performed. This can graft the initial polymer brush onto those areas of the surface unprotected by the PS mask. After grafting is complete, the PS mask is removed and a second brush is synthesized on the newly exposed areas.

Acrylamides↗

Synthesis of high-density grafted polymer layers with thickness and grafting density gradients.

A novel approach was developed for the synthesis of tethered polymer layers with thickness and grafting density gradients. Poly(glycidyl methacrylate) (PGMA) was employed as a primary anchoring layer to attach the polymer chains to the surface of a silicon wafer. A linear temperature gradient heated stage was used for the generation of a gradual variation in the thickness of the anchoring PGMA film along the substrate. The obtained gradient was translated into the polymerization initiator gradient via the reaction between the epoxy groups of PGMA and the carboxyl functionality of 2-bromo-2-methylpropionic acid (BPA). The attachment of BPA to the surface modified with the monolayer of PGMA was confirmed by X-ray photoelectron spectroscopy experiments. To complete the experimental procedures, surface-initiated atom transfer radical polymerization was performed to synthesize the grafted polymer layers with thickness and surface densities that were varied along the substrate. The grafting density of the samples created in this three-step process ranged from 0.75 +/- 0.05 to 1.5 +/- 0.25 chains/nm(2). It was estimated, from a comparison of the surface densities of the initiator and the attached polymer, that the efficiency of the initiation from the surface was on the order of 5-10% and was dependent upon the surface concentration of the initiator and the time of polymerization.

Journal Article↗

Inverse and reversible switching gradient surfaces from mixed polyelectrolyte brushes.

We report on a thin polyelectrolyte film (mixed polyelectrolyte brush) with a gradual change of the composition (ratio between two different oppositely charged surface-grafted weak polyelectrolytes) across the sample. The gradient of surface composition creates a gradient in surface charge density and, consequently, a gradient of the wetting behavior. The gradient film is sensitive to a pH signal and can be reversibly switched via pH change.

Journal Article↗

Effect of molecular weight on synthesis and surface morphology of high-density poly(ethylene glycol) grafted layers.

This work describes studying the permanent grafting of carboxylic acid end-functionalized poly(ethylene glycol) methyl ether (PEG) chains of different molecular weights from the melt onto a surface employing poly(glycidyl methacrylate) ultrathin film as an anchoring layer. The grafting led to the synthesis of the complete PEG brushes possessing exceptionally high grafting density. The maximum thickness of the attached PEG films was strongly dependent on the length of the polymer chains being grafted. The maximum grafting efficiency was close to the critical entanglement molecular weight region for PEG. All grafted PEG layers were in the "brush regime", since the distance between grafting sites for the layers was lower than the end-to-end distance for the anchored macromolecules. Scanning probe microscopy revealed that the grafting process led to complete PEG layers with surface smoothness on a nanometric scale. Practically all samples were partly or fully covered with crystalline domains that disappeared when samples were scanned under water. Due to the PEG hydrophilic nature, the surface with the grafted layer exhibited a low (up to 21 degrees ) water contact angle.

Membranes, Artificial↗

Polymer grafting via ATRP initiated from macroinitiator synthesized on surface.

Macromolecular anchoring layer approach was used for preparation of an effective macroinitiator for the synthesis of grafted polymer layers by atom transfer radical polymerization (ATRP) initiated from the surface. For the initial surface modification, a thin layer of poly(glycidyl methacrylate) (PGMA) was deposited on the surface of a silicon wafer. The ATRP macroinitiator was synthesized on the substrate surface by the reaction between epoxy groups of PGMA and carboxy functionality of bromoacetic acid (BAA). Variation of the time and temperature of the BAA deposition as well as PGMA layer thickness allowed control over the amount of BAA attached to the surface. The PGMA anchoring layer allowed the achievement of initiator surface density significantly higher than that reported for a self-assembled monolayer of ATRP initiators. Polymer brushes were synthesized on the PGMA/BAA-modified substrates by ATRP. Different surface concentrations of BAA were used in our grafting experiments to acquire knowledge about the relationship between the amount of initiator anchored to the surface through PGMA and the rate of the grafted layer formation. The increase in the surface density of the initiating moieties led to the increase in the grafting rate. However, a cutoff initiator concentration beyond which no increase of the thickness of the grafted layer was observed. From comparison between the surface densities of the initiator and the attached polymer it was determined that the efficiency of the initiation from the surface was on the level of 5-15%.

Journal Article↗

Mixed polymer brushes by sequential polymer addition: anchoring layer effect.

Smart surfaces can be described as surfaces that have the ability to respond in a controllable fashion to specific environmental stimuli. A heterogeneous (mixed) polymer brush (HPB) can provide a synthetic route to designing smart polymer surfaces. In this research we study HPB comprised of end-grafted polystyrene (PS) and poly(2-vinyl pyridine) (P2VP). The synthesis of the HPB involves the use of an "intermolecular glue" acting as a binding/anchoring interlayer between the polymer brush and the substrate, a silicon wafer. We compare anchoring layers of epoxysilane (GPS), which forms a self-assembled monolayer with epoxy functionality, to poly(glycidyl methacrylate) (PGMA), which forms a macromolecular monolayer with epoxy functionality. The PS and P2VP were deposited onto the wafers in a sequential fashion to chemically graft PS in a first step and subsequently graft P2VP. Rinsing the HPB in selective solvents and observing the change in water contact angle as a function of the HPB composition studied the switching nature of the HPB. Scanning probe microscopy was used to probe the topography and phase imagery of the HPB. The nature of the anchoring layer significantly affected the wettability and morphology of the mixed brushes.

Journal Article↗