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Biomedical subjects

Edward J Kramer

Publications and source records attributed to Edward J Kramer.

16 recordsLinked to original sources
PubMed2006

Surfaces of fluorinated pyridinium block copolymers with enhanced antibacterial activity.

Polystyrene-b-poly(4-vinylpyridine) copolymers were quaternized with 1-bromohexane and 6-perfluorooctyl-1-bromohexane. Surfaces prepared from these polymers were characterized by contact angle measurements, near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy. The fluorinated pyridinium surfaces showed enhanced antibacterial activity compared to their nonfluorinated counterparts. Even a polymer with a relatively low molecular weight pyridinium block showed high antimicrobial activity. The bactericidal effect was found to be related to the molecular composition and organization in the top 2-3 nm of the surface and increased with increasing hydrophilicity and pyridinium concentration of the surface.

Anti-Bacterial Agents↗
PubMed2006

Semicrystalline thermoplastic elastomeric polyolefins: Advances through catalyst development and macromolecular design.

We report the design, synthesis, morphology, phase behavior, and mechanical properties of semicrystalline, polyolefin-based block copolymers. By using living, stereoselective insertion polymerization catalysts, syndiotactic polypropylene-block-poly(ethylene-co-propylene)-block-syndiotactic polypropylene and isotactic polypropylene-block-regioirregular polypropylene-block-isotactic polypropylene triblock copolymers were synthesized. The volume fraction and composition of the blocks, as well as the overall size of the macromolecules, were controlled by sequential synthesis of each block of the polymers. These triblock copolymers, with semicrystalline end-blocks and mid-segments with low glass-transition temperatures, show significant potential as thermoplastic elastomers. They have low Young's moduli, large strains at break, and better than 90% elastic recovery at strains of 100% or less. An isotactic polypropylene-block-regioirregular polypropylene-block-isotactic polypropylene-block-regioirregular polypropylene-block-isotactic polypropylene pentablock copolymer was synthesized that also shows exceptional elastomeric properties. Notably, microphase separation is not necessary in the semicrystalline isotactic polypropylenes to achieve good mechanical performance, unlike commercial styrenic thermoplastic elastomers.

Journal Article↗
PubMed2006

Hybrid particle-field simulations of polymer nanocomposites.

We present a theoretical framework and computer simulation methodology for investigating the equilibrium structure and properties of mesostructured polymeric fluids with embedded colloids or nanoparticles. The method is based on a field-theoretic description of the fluid in which particle coordinates and chemical potential field variables are simultaneously updated. The fluid model can contain polymers of arbitrary chemical and architectural complexity, along with particles of all shapes, sizes, and surface treatments. Simulation results are compared with experiments conducted on polystyrene (PS)-functionalized Au nanoparticles in a PS-P2VP diblock copolymer melt.

Journal Article↗
PubMed2006

The deformation and adhesion of randomly rough and patterned surfaces.

Using a surface forces apparatus (SFA) and an atomic force microscope (AFM) we have studied the effects of surface roughness (root-mean-square (RMS) roughness between 0.3 and 220 nm) on the "contact mechanics", which describes the deformations and loading and unloading adhesion forces, of various polymeric surfaces. For randomly rough, moderately stiff, elastomeric surfaces, the force-distance curves on approach and separation are nearly reversible and almost perfectly exponentially repulsive, with an adhesion on separation that decreases only slightly with increasing RMS. Additionally, the magnitude of the preload force is seen to play a large role in determining the measured adhesion. The exponential repulsion likely arises from the local compressions (fine-grained nano- or submicron-scale deformations) of the surface asperities. The resulting characteristic decay lengths of the repulsion scale with the RMS roughness and correlate very well with a simple finite element method (FEM) analysis based on actual AFM topographical images of the surfaces. For "patterned" surfaces, with a nonrandom terraced structure, no similar exponential repulsion is observed, suggesting that asperity height variability or random roughness is required for the exponential behavior. However, the adhesion force or energy between two "patterned" surfaces fell off dramatically and roughly exponentially as the RMS increased, likely owing to a significant decrease in the contact area which in turn determines their adhesion. For both types of rough surfaces, random and patterned, the coarse-grained (global, meso- or macroscopic) deformations of the initially curved surfaces appear to be Hertzian.

Journal Article↗
PubMed2006

Anti-biofouling properties of comblike block copolymers with amphiphilic side chains.

Surfaces of novel block copolymers with amphiphilic side chains were studied for their ability to influence the adhesion of marine organisms. The surface-active polymer, obtained by grafting fluorinated molecules with hydrophobic and hydrophilic blocks to a block copolymer precursor, showed interesting bioadhesion properties. Two different algal species, one of which adhered strongly to hydrophobic surfaces, and the other, to hydrophilic surfaces, showed notably weak adhesion to the amphiphilic surfaces. Both organisms are known to secrete adhesive macromolecules, with apparently different wetting characteristics, to attach to underwater surfaces. The ability of the amphiphilic surface to undergo an environment-dependent transformation in surface chemistry when in contact with the extracellular polymeric substances is a possible reason for its antifouling nature. Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) was used, in a new approach based on angle-resolved X-ray photoelectron spectroscopy (XPS), to determine the variation in chemical composition within the top few nanometers of the surface and also to study the surface segregation of the amphiphilic block. A mathematical model to extract depth-profile information from the normalized NEXAFS partial electron yield is developed.

Geologic Sediments↗
PubMed2006

Comparison of the fouling release properties of hydrophobic fluorinated and hydrophilic PEGylated block copolymer surfaces: attachment strength of the diatom Navicula and the green alga Ulva.

To understand the role of surface wettability in adhesion of cells, the attachment of two different marine algae was studied on hydrophobic and hydrophilic polymer surfaces. Adhesion of cells of the diatom Navicula and sporelings (young plants) of the green macroalga Ulva to an underwater surface is mainly by interactions between the surface and the adhesive exopolymers, which the cells secrete upon settlement and during subsequent colonization and growth. Two types of block copolymers, one with poly(ethylene glycol) side-chains and the other with liquid crystalline, fluorinated side-chains, were used to prepare the hydrophilic and hydrophobic surfaces, respectively. The formation of a liquid crystalline smectic phase in the latter inhibited molecular reorganization at the surface, which is generally an issue when a highly hydrophobic surface is in contact with water. The adhesion strength was assessed by the fraction of settled cells (Navicula) or biomass (Ulva) that detached from the surface in a water flow channel with a wall shear stress of 53 Pa. The two species exhibited opposite adhesion behavior on the same sets of surfaces. While Navicula cells released more easily from hydrophilic surfaces, Ulva sporelings showed higher removal from hydrophobic surfaces. This highlights the importance of differences in cell-surface interactions in determining the strength of adhesion of cells to substrates.

Biopolymers↗
PubMed2005

Control of nanoparticle location in block copolymers.

A simple procedure is described to incorporate gold nanoparticles and control their location within symmetric poly(styrene-b-2 vinyl pyridine) (PS-PVP) diblock copolymers. Gold nanoparticles coated with thiol-terminated PS and/or PVP homopolymer chains (Mn approximately 1300 and 1500 g/mol, respectively) are incorporated into alternating lamellar layers of PS and PVP (total Mn approximately 196 500 g/mol). The location of the particles is controlled by varying the composition of ligands on the particle surfaces. In particular, gold particles coated with 100% PS or PVP reside near the center of the respective polymer domains, while particles coated with a mixture of both homopolymers reside at the interfaces between the two blocks.

Journal Article↗
PubMed2005

Oligo(ethylene glycol) containing polymer brushes as bioselective surfaces.

The nitroxide-mediated polymerization of styrenic monomers containing oligo(ethylene glycol) (OEGn) moieties was chosen for the preparation of biocompatible polymer brushes tethered to silicon oxide surfaces due to the broad range of monomer structures available and the use of a nonmetallic initiator. These surfaces were characterized by near-edge X-ray absorption fine structure and water contact angle measurements. The biocompatibility of these grown polymer brushes was studied and compared with deposited assemblies of surface-bound OEGn-terminated silanes with selected chain lengths. Grown polymer brushes with short OEGn side chains suppressed protein adsorption significantly more than the deposited assemblies of short OEGn chains, and this was attributed to higher surface coverage by the brushes. Cell adhesion studies confirmed that OEGn-containing polymer brushes are particularly effective in preventing nonspecific adhesion. Studies of protein adsorption and cell localization carried out with specific ligands on surfaces patterned demonstrated the potential of these surface-tethered polymer brushes for the formation of micro- and nanoscale devices.

Adsorption↗
PubMed2005

Wetting morphologies at microstructured surfaces.

The wetting of microstructured surfaces is studied both experimentally and theoretically. Even relatively simple surface topographies such as grooves with rectangular cross section exhibit a large variety of different wetting morphologies as observed by atomic force microscopy. This polymorphism arises from liquid wedge formation along the groove corners and from contact line pinning along the groove edges. A global morphology diagram is derived that depends only on two system parameters: (i) the aspect ratio of the groove geometry and (ii) The contact angle of the underlying substrate material. For microfluidics, the most interesting shape regimes involve extended liquid filaments, which can grow and shrink in length while their cross section stays essentially constant. Thus, any method by which one can vary the contact angle can be used to switch the length of the filament, as is demonstrated in the context of electrowetting.

Humans↗
PubMed2004

Control of surface properties using fluorinated polymer brushes produced by surface-initiated controlled radical polymerization.

Surface-grafted styrene-based homopolymer and diblock copolymer brushes bearing semifluorinated alkyl side groups were synthesized by nitroxide-mediated controlled radical polymerization on planar silicon oxide surfaces. The polymer brushes were characterized by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and time-dependent water contact angle measurements. Angle-resolved XPS studies and water contact angle measurements showed that, in the case of the diblock copolymer brushes, the second block to be added was always exposed at the polymer-air interface regardless of its surface energy. Values of z*/Rg were estimated based on the radius of gyration, Rg, of the grafted homopolymer or block copolymer chains for the grafted brushes and thickness of the brush, z*. The fact that z*/Rg > 1 suggests that all these brushes are stretched. These results support the idea that after grafting the first block onto the surface the nitroxide-end capped polymer chains were able to polymerize the second block in a "living" fashion and the stretched brush so formed was dense enough that the outermost block in all cases completely covers the surface. NEXAFS analysis showed a relationship between the surface orientation of the fluorinated side chains and brush thickness with thicker brushes having more oriented side chains. Time-dependent water contact angle measurements revealed that the orientation of the side chains of the brush improved the surface stability toward reconstruction upon prolonged exposure to water.

Absorption↗
PubMed2004

Synthesis of block copolymer segments containing different ratios of ethylene and 5-norbornen-2-yl acetate.

Block copolymerization of ethylene with 5-norbornen-2-yl acetate (1) by the nickel catalyst system [N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamide]Ni(eta1-CH2Ph)(PMe3) (2) and Ni(COD)2 (bis(1,4-cyclooctadiene)nickel) (3) produces a variety of block copolymer structures that demonstrate microphase separation. Typical block copolymerizations were carried out in an autoclave charged with a solution of the catalyst mixture and 1 (0.15 M) in toluene. The autoclave was sealed and exposed to PC2H4 = 50 psi for a period of time (T1). A pressure jump to PC2H4 = 1100 psi was then applied and the reaction allowed to proceed for another predetermined interval (T2). Independent experiments were performed to isolate and examine the molecular weight and comonomer composition of the first block. Narrow molecular weight distributions and the increase of polymer molecular weight with increases in T1 or T2 are consistent with a product in which an initial block is formed at low ethylene pressures and quantitatively converted to a block copolymer by the jump to high pressure. Transmission electron microscopy confirms that the materials are microphase separated.

Journal Article↗
PubMed2004

Thin films of bicontinuous cubic mesostructured silica templated by a nonionic surfactant.

Thin films ofbicontinuous cubic mesostructured silica were formed using the nonionic poly(oxyethylene)-alkyl ether surfactant Brij-56 as a structure-directing agent. The synthesis conditions were chosen such that the estimated volume fraction of surfactant in the silica/surfactant films corresponded approximately to the composition at which the bicontinuous cubic phase occurs in the water/surfactant phase diagram. Small-angle X-ray scattering and transmission electron microscopy measurements reveal that the cubic phase corresponds to the Ia3(-)d double-gyroid structure, with some distortion due to anisotropic film shrinkage. The cubic structure grows as faceted domains that are well-oriented with respect to the substrate and often occur in coexistence with a lamellar phase. By adjusting the temperature at which the films are aged, it is possible to create films with 2D hexagonal, cubic, or lamellar structures at a single composition.

Journal Article↗
PubMed2003

Edge effects on the order and freezing of a 2D array of block copolymer spheres.

The order in a single layer of spherical domains of a block copolymer melt is investigated as a function of distance from the edges of the 15 microm wide, 30 nm deep wells that confine it along a substrate. At 255 degrees C the edge induces the formation of a hexatic phase whose orientational and translational order decreases slowly away from the edge until in the center of the well the block copolymer spheres have liquidlike order.

Journal Article↗
PubMed2003

Templating organic semiconductors via self-assembly of polymer colloids.

A route for producing semiconducting polymer blends is demonstrated in which a doped pi-conjugated polymer is forced into a three-dimensionally continuous minor phase by the self-assembly of colloidal particles and block copolymers. The resulting cellular morphology can be viewed as a high-internal phase polymeric emulsion. Compared with traditional blending procedures, this process reduces the percolation threshold for electrical conductivity by a factor of 10, increases the conductivity by several orders of magnitude, and simultaneously improves thermal stability. Following this route, new applications can be envisaged for semiconducting polymer blends that require only minimal concentrations of doped pi-conjugated polymer.

Journal Article↗
PubMed2003

Coatings based on side-chain ether-linked poly(ethylene glycol) and fluorocarbon polymers for the control of marine biofouling.

The preparation of side group modified polystyrene-based surface-active block copolymers (SABC) for use as marine fouling resistance/release applications is described. Modifying moieties such as poly(ethylene glycol) (PEG) and semifluorinated segments were used. A novel bilayer methodology has been employed that provides both suitable mechanical properties through the use of an elastomeric primer layer of styrene-ethylene/butylene-styrene (SEBS) and control of surface-chemistry through use of the SABCs. This approach has potential as a cost-effective technology for environmentally benign coatings that resist and release marine biofouling. Initial testing of these materials included determination of captive bubble contact angles and protein adsorption. Testing against marine fouling organisms was performed using settlement and adhesion bioassays with zoospores of the green alga Enteromorpha. The results showed that all surfaces had markedly reduced levels of zoospore settlement compared with glass controls and that adhesion strength was strongly affected by the semifluorinated SABC. The results are discussed in terms of surface properties.

Adhesiveness↗