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Biomedical subjects

Tomasz Kowalewski

Publications and source records attributed to Tomasz Kowalewski.

17 recordsLinked to original sources
PubMed2007

Synthesis and in situ atomic force microscopy characterization of temperature-responsive hydrogels based on poly(2-(dimethylamino)ethyl methacrylate) prepared by atom transfer radical polymerization.

Well-defined copolymers of 2-(dimethylamino)ethyl methacrylate (DMAEMA) and benzophenone methacrylate (BPMA) with different compositions were synthesized via atom transfer radical polymerization. The molecular weights of these copolymers were Mn approximately 30 000 g/mol, while the BPMA content varied from 2.5 to 10 mol %. The copolymers with a low content of BPMA (2.5 and 5 mol %) exhibited a sharp thermal transition at 33-36 degrees C in aqueous solution. A hydrogel was immobilized and patterned on a silicon wafer via UV treatment of the spin-coated polymer layer using a photomask technique. The thermoresponsive behavior of the patterned polymer gel was quantitatively investigated by variable temperature in situ contact mode atomic force microscopy, which revealed the presence of two lower critical solution temperature regions. One region was between 25 and 30 degrees C, corresponding to the topmost layer of the hydrogel film, and the other region, around 40 degrees C, corresponded to the bulk of the hydrogel. Concurrent lateral force microscopy measurements revealed that, just above the transition temperature, the bulk region exhibited enhanced friction.

Free Radicals↗
PubMed2006

Polymer-coated ferromagnetic colloids from well-defined macromolecular surfactants and assembly into nanoparticle chains.

A novel synthetic route to polymer-coated ferromagnetic colloids of metallic cobalt has been developed. Well-defined end-functional polystyrenes were synthesized using controlled radical polymerization and used as surfactants in the thermolysis of dicobaltoctacarbonyl to afford uniform ferromagnetic nanoparticles. The presence of the polymer shell enabled prolonged colloidal stability of dispersions in a wide range of organic solvents and formed glassy encapsulating coatings around ferromagnetic cores in the solid state. These polymer-coated colloids assembled into robust, micron-sized nanoparticle chains when cast onto supporting surfaces due to dipolar associations of magnetic cores. Hierarchical assemblies were also prepared by blending polystyrene-coated cobalt colloids with larger silica beads.

Journal Article↗
PubMed2006

Nanostructure dependence of field-effect mobility in regioregular poly(3-hexylthiophene) thin film field effect transistors.

Low polydispersity regioregular polythiophenes with number average molecular weights ranging from 2 to 13 kDa were cast under the same conditions from solution to form a series of field effect transistors (FETs). Tapping mode AFM and grazing incidence small-angle X-ray scattering revealed that in all cases the polymers formed regular nanofibrillar morphologies with the width of nanofibrils proportional to the weight average contour length of polymer chains, indicating that conjugated backbones were oriented perpendicular to the nanofibril axes. FET charge carrier mobilities exhibited exponential dependence on nanofibril width, pointing to the decisive role of extended conjugated pathways in charge transport.

Microscopy, Atomic Force↗
PubMed2006

Scanning probe acceleration microscopy (SPAM) in fluids: mapping mechanical properties of surfaces at the nanoscale.

One of the major thrusts in proximal probe techniques is combination of imaging capabilities with simultaneous measurements of physical properties. In tapping mode atomic force microscopy (TMAFM), the most straightforward way to accomplish this goal is to reconstruct the time-resolved force interaction between the tip and surface. These tip-sample forces can be used to detect interactions (e.g., binding sites) and map material properties with nanoscale spatial resolution. Here, we describe a previously unreported approach, which we refer to as scanning probe acceleration microscopy (SPAM), in which the TMAFM cantilever acts as an accelerometer to extract tip-sample forces during imaging. This method utilizes the second derivative of the deflection signal to recover the tip acceleration trajectory. The challenge in such an approach is that with real, noisy data, the second derivative of the signal is strongly dominated by the noise. This problem is solved by taking advantage of the fact that most of the information about the deflection trajectory is contained in the higher harmonics, making it possible to filter the signal by "comb" filtering, i.e., by taking its Fourier transform and inverting it while selectively retaining only the intensities at integer harmonic frequencies. Such a comb filtering method works particularly well in fluid TMAFM because of the highly distorted character of the deflection signal. Numerical simulations and in situ TMAFM experiments on supported lipid bilayer patches on mica are reported to demonstrate the validity of this approach.

Journal Article↗
PubMed2006

Volatile organic compound detection using nanostructured copolymers.

Regioregular polythiophene-based conductive copolymers with highly crystalline nanostructures are shown to hold considerable promise as the active layer in volatile organic compound (VOC) chemresistor sensors. While the regioregular polythiophene polymer chain provides a charge conduction path, its chemical sensing selectivity and sensitivity can be altered either by incorporating a second polymer to form a block copolymer or by making a random copolymer of polythiophene with different alkyl side chains. The copolymers were exposed to a variety of VOC vapors, and the electrical conductivity of these copolymers increased or decreased depending upon the polymer composition and the specific analytes. Measurements were made at room temperature, and the responses were found to be fast and appeared to be completely reversible. Using various copolymers of polythiophene in a sensor array can provide much better discrimination to various analytes than existing solid state sensors. Our data strongly indicate that several sensing mechanisms are at play simultaneously, and we briefly discuss some of them.

Electrochemistry↗
PubMed2005

Self-assembly of pODMA-b-ptBA-b-pODMA triblock copolymers in bulk and on surfaces. A quantitative SAXS/AFM comparison.

The phase state of a series of poly(n-octadecyl methacrylate)-b-poly(tert-butyl acrylate)-b-poly(n-octadecyl methacrylate) (pODMA-b-ptBA-b-pODMA) triblock copolymers, synthesized through atom transfer radical polymerization, has been investigated in bulk and on surfaces using small-angle X-ray scattering and atomic force microscopy, respectively. The mean-field theory was employed to construct the bulk phase diagram. Excellent agreement was found between the bulk and surface morphologies as well as for the domain spacing (domain spacing scaled as d approximately equal to N(0.64)), suggesting that the strong polymer-polymer interactions in bulk are also the dominant interactions on surfaces.

Journal Article↗
PubMed2005

Synthesis of mesoporous carbons using ordered and disordered mesoporous silica templates and polyacrylonitrile as carbon precursor.

Mesoporous carbons were synthesized from polyacrylonitrile (PAN) using ordered and disordered mesoporous silica templates and were characterized using transmission electron microscopy (TEM), powder X-ray diffraction, nitrogen adsorption, and thermogravimetry. The pores of the silica templates were infiltrated with carbon precursor (PAN) via polymerization of acrylonitrile from initiation sites chemically bonded to the silica surface. This polymerization method is expected to allow for a uniform filling of the template with PAN and to minimize the introduction of nontemplated PAN, thus mitigating the formation of nontemplated carbon. PAN was stabilized by heating to 573 K under air and carbonized under N2 at 1073 K. The resulting carbons exhibited high total pore volumes (1.5-1.8 cm3 g(-1)), with a primary contribution of the mesopore volume and with relatively low microporosity. The carbons synthesized using mesoporous templates with a 2-dimensional hexagonal structure (SBA-15 silica) and a face-centered cubic structure (FDU-1 silica) exhibited narrow pore size distributions (PSDs), whereas the carbon synthesized using disordered silica gel template had broader PSD. TEM showed that the SBA-15-templated carbon was composed of arrays of long, straight, or curved nanorods aligned in 2-D hexagonal arrays. The carbon replica of FDU-1 silica appeared to be composed of ordered arrays of spheres. XRD provided evidence of some degree of ordering of graphene sheets in the carbon frameworks. Elemental analysis showed that the carbons contain an appreciable amount of nitrogen. The use of our novel infiltration method and PAN as a carbon precursor allowed us to obtain ordered mesoporous carbons (OMCs) with (i) very high mesopore volume, (ii) low microporosity, (iii) low secondary mesoporosity, (iv) large pore diameter (8-12 nm), and (v) semi-graphitic framework, which represent a desirable combination of features that has not been realized before for OMCs.

Acrylic Resins↗
PubMed2005

Long-range ordered thin films of block copolymers prepared by zone-casting and their thermal conversion into ordered nanostructured carbon.

Large-scale alignment of lamellae in thin films of diblock copolymers containing polyacrylonitrile and poly(n-butyl acrylate) was achieved by casting copolymer solution on a silicon substrate moved away at a constant speed from the casting nozzle (zone-casting). Grazing incidence small-angle X-ray scattering revealed that the lamellae, which were perpendicular to the substrate, were also aligned over macroscopic scale in the direction perpendicular to the casting direction. Such long-range ordered block copolymer films were then converted by pyrolysis into nanostructured carbons, with excellent preservation of lamellar morphology and orientation.

Acrylates↗
PubMed2005

Monitoring surface thermal transitions of ABA triblock copolymers with crystalline segments using phase contrast tapping mode atomic force microscopy.

Variable-temperature tapping mode atomic force microscopy was used to follow thermal transitions in nanoscale phase separated triblock copolymers containing partially crystalline poly(octadecyl methacrylate) or poly(docosyl methacrylate) and glassy (poly(tert-butyl acrylate)) segments. Melting/crystallization and devitrification/vitrification transitions in phase separated domains were followed with the aid of "phase shift thermograms" constructed from cantilever phase shift maps acquired at different temperatures. This type of analysis turned out to be particularly useful in following melting/crystallization and devitrification/vitrification transitions occurring in the same temperature range and thus difficult or impossible to resolve using differential scanning calorimetry.

Letter↗
PubMed2004

In situ AFM studies of astrocyte-secreted apolipoprotein E- and J-containing lipoproteins.

The three-dimensional shapes and sizes of plasma lipoproteins and astrocyte-secreted lipoproteins (ASLPs) were characterized with the aid of in situ atomic force microscopy (AFM), which has the unique ability to study three-dimensional nanostructures under physiological conditions. Apolipoprotein E (apoE) and apolipoprotein J (apoJ) are the two most abundant apolipoproteins produced in the central nervous system (CNS). This study revealed that ASLPs containing apoE3, apoE4, or apoJ significantly differ from high density lipoprotein particles, thought to be their closest analogs in plasma, in aggregation properties, size, and shape. ASLPs were found to be significantly flatter and smaller than their plasma counterparts. Plasma lipoproteins were able to form ordered arrays on a mica surface at high concentration, but ASLPs did not. Rather, they formed amorphous aggregates at similar concentrations. Comprehensive quantitative characterization of particle size and shape was facilitated by two advances in AFM image analysis: (1) automated analysis through image-recognition algorithms, and (2) correction for the finite size of the AFM probe based on geometric modeling. This study and the developed AFM methodologies open the way to further in situ AFM studies of the lipoproteins in general and more specifically of CNS lipoproteins.

Animals↗
PubMed2004

ABCA1 is required for normal central nervous system ApoE levels and for lipidation of astrocyte-secreted apoE.

ABCA1 is an ATP-binding cassette protein that transports cellular cholesterol and phospholipids onto high density lipoproteins (HDL) in plasma. Lack of ABCA1 in humans and mice causes abnormal lipidation and increased catabolism of HDL, resulting in very low plasma apoA-I, apoA-II, and HDL. Herein, we have used Abca1-/- mice to ask whether ABCA1 is involved in lipidation of HDL in the central nervous system (CNS). ApoE is the most abundant CNS apolipoprotein and is present in HDL-like lipoproteins in CSF. We found that Abca1-/- mice have greatly decreased apoE levels in both the cortex (80% reduction) and the CSF (98% reduction). CSF from Abca1-/- mice had significantly reduced cholesterol as well as small apoE-containing lipoproteins, suggesting abnormal lipidation of apoE. Astrocytes, the primary producer of CNS apoE, were cultured from Abca1+/+, +/-, and -/- mice, and nascent lipoprotein particles were collected. Abca1-/- astrocytes secreted lipoprotein particles that had markedly decreased cholesterol and apoE and had smaller apoE-containing particles than particles from Abca1+/+ astrocytes. These findings demonstrate that ABCA1 plays a critical role in CNS apoE metabolism. Since apoE isoforms and levels strongly influence Alzheimer's disease pathology and risk, these data suggest that ABCA1 may be a novel therapeutic target.

ATP Binding Cassette Transporter 1↗
PubMed2004

Effect of different anti-Abeta antibodies on Abeta fibrillogenesis as assessed by atomic force microscopy.

Extensive data suggest that the conversion of the amyloid-beta (Abeta) peptide from soluble to insoluble forms is a key factor in the pathogenesis of Alzheimer's disease (AD). In recent years, atomic force microscopy (AFM) has provided useful insights into the physicochemical processes involving Abeta morphology, and it can now be used to explore factors that either inhibit or promote fibrillogenesis. We used ex situ AFM to explore the impact of anti-Abeta antibodies directed against different domains of Abeta on fibril formation. For the AFM studies, two monoclonal antibodies (m3D6 and m266.2) were incubated in solution with Abeta(1-42) with a molar ratio of 1:10 (antibody to Abeta) over several days. Fibril formation was analyzed quantitatively by determining the number of fibrils per microm(2) and by aggregate size analysis. m3D6, which is directed against an N-terminal domain of Abeta (amino acid residues 1-5) slowed down fibril formation. However, m266.2, which is directed against the central domain of Abeta (amino acid residues 13-28) appeared to completely prevent the formation of fibrils over the course of the experiment. Inhibition of fibril formation by both antibodies was also confirmed by thioflavin-T (ThT) fluorescence experiments carried out with Abeta(1-40) incubated for five days. However, unlike AFM results, ThT did not differentiate between the samples incubated with m3D6 versus m266.2. These results indicate that AFM can be not only reliably used to study the effect of different molecules on Abeta aggregation, but that it can provide additional information such as the role of epitope specificity of antibodies as potential inhibitors of fibril formation.

Alzheimer Disease↗
PubMed2002

Nanostructured carbon arrays from block copolymers of polyacrylonitrile.

Arrays of graphitic carbon nanoclusters were obtained by pyrolysis of nanoscale phase-separated block copolymers of polyacrylonitrile and poly(n-butyl acrylate). Upon heating in an inert atmosphere to temperatures ranging from approximately 400 to 1200 degrees C, polyacrylonitrile domains were converted into carbon nanoclusters, maintaining the overall shape and spacing, whereas the poly(n-butyl acrylate) phase was sacrificed. Preservation of the original nanoscale morphology of a block copolymer was possible only if pyrolysis was preceded by oxidation at temperatures of approximately 230 degrees C, in analogy with thermal stabilization of polyacrylonitrile precursor in the process used in the manufacturing of carbon fibers. Preorganization of the carbon precursor through self-assembly in block copolymers of polyacrylonitrile appears to be an attractive and robust strategy for templated synthesis of well-defined nanostructured carbon materials.

Journal Article↗
PubMed2002

Chemically induced supramolecular reorganization of triblock copolymer assemblies: trapping of intermediate states via a shell-crosslinking methodology.

The mechanism of morphological phase transitions was studied for rod-shaped supramolecular assemblies comprised of a poly(acrylic acid)-block-poly(methyl acrylate)-block-polystyrene (PAA(90)-b-PMA(80)-b-PS(100)) triblock copolymer in 33% tetrahydrofuran/water after perturbation by reaction with a positively charged water-soluble carbodiimide. Tetrahydrofuran solvation of the hydrophobic core domain provided the dynamic nature required for the rod-to-sphere phase transition to be complete within 30 min. The intermediate morphologies such as fragmenting rods and pearl-necklace structures were trapped kinetically by the subsequent addition of a diamino crosslinking agent, which underwent covalent crosslinking of the shell layer. Alternatively, shell-crosslinked rod-shaped nanostructures with preserved morphology were obtained by the addition of the crosslinking agent before the addition of the carbodiimide, which allowed for the shell crosslinking to be performed at a faster rate than the morphological reorganization. The formation of robust shell-crosslinked nanostructures provides a methodology by which the morphological evolution processes can be observed, and it allows access to otherwise thermodynamically unstable nanostructures.

Carbodiimides↗