Biomedical subjects

Tadeusz Pakula

Publications and source records attributed to Tadeusz Pakula.

12 recordsLinked to original sources

PubMed2005

Structure of zone-cast HBC-C12H25 films.

The structure of a thin zone-cast film of the hexa-n-dodecyl-substituted hexa-peri-benzocoronene (HBC) has been investigated using grazing incidence X-ray diffraction. A model with an orthorhombic unit cell containing two molecules accounts well for the observations. The molecules are arranged in a "herringbone" structure resembling the packing observed for unsubstituted HBC. The molecular disk planes are oriented perpendicularly to the substrate, rotated by approximately 39 degrees about the film normal. The relatively long side chains of dodecyl were found to be in an ordered interdigitated state. The aliphatic side chains and the aromatic HBC-cores segregate to form regular vertical domains spanning the film thickness. For in-plane rocking scans a discrete orientation distribution is observed with peaks at regular angle intervals. We interpret this as a grain boundary effect induced by alkyl chain stacking faults.

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PubMed2005

Influence of alkyl substituents on the solution- and surface-organization of hexa-peri-hexabenzocoronenes.

Three hexa-peri-hexabenzocoronenes (HBCs) with branched, bulky alkyl substituents of different lengths in the periphery of the aromatic core have been synthesized to tune the self-association properties in solution. 1H NMR and photophysical measurements were used to probe the solution organization in comparison to the known hexa-dodecyl-substituted HBC in different solvent systems. Thermodynamic parameters for the self-association in solution, obtained by curve fitting of the concentration- and temperature-dependent NMR data using van't Hoff analysis, indicated that the self-association is an enthalpically driven process that is entropically disfavored. Photoluminescence and NMR results were both employed to determine the critical concentration where no self-association for different compounds occurred. The interactions between the molecules could be controlled by varying the nonsolvent content in the solvent mixtures, supporting the model of solvophobic effects. The spatial demand of the solubilizing side chains modulated the self-association in solution. This behavior was translated into the solution casting process, where the kinetic in addition to the thermodynamic parameters played an essential role for structure formation. The study illuminates the relationship between the solution association of HBCs and the morphology, when processed on a surface. These results are essential for the application of these materials in devices.

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PubMed2005

On the shape of bottle-brush macromolecules: systematic variation of architectural parameters.

We measured the form factor of bottle-brush macromolecules under good solvent conditions with small-angle neutron scattering and static light scattering. The systems under investigation are brushes, synthesized via the grafting-from route, built from a poly(alkyl methacrylate) backbone to which poly(n-butyl acrylate) side chains are densely grafted. The aim of our work is to study how the systematic variation of structural parameters such as the side chain length and backbone length change the conformation of the polymer brushes in solution. All spectra can be consistently described by a model, considering the bottle-brush polymers as flexible rods with internal density fluctuations. Parameters discussed are (1) the contour length per main chain monomer l(b), (2) the fractal dimension of the side chains Ds, as well as (3) the fractal dimension D, and (4) the Kuhn length lambdak of the overall brush. l(b)=0.253+/-0.008 nm is found to be independent of the side chain length and equal to the value found for the bare main chain, indicating a strongly stretched conformation for the backbone due to the presence of the side chains. The fractal dimension of the side chains is determined to be Ds=1.75+/-0.07 which is very close to the value of 10.588 approximately 1.70 expected for a three-dimensional self-avoiding random walk (3D-SAW) under good solvent conditions. On larger length scales the overall brush appears to be a 3D-SAW itself (D=1.64+/-0.08) with a Kuhn-step length of lambdak=70+/-4 nm. The value is independent of the side chain length and 46 times larger than the Kuhn length of the bare backbone (lambdak=1.8+/-0.2 nm). The ratio of Kuhn length to brush diameter lambda(k)d>or=20 determines whether lyotropic behavior can be expected or not. Since longer side chains do not lead to more persistent structures, lambda(k)d decreases from 8 to 4 with increasing side chain length and lyotropic behavior becomes unlikely.

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PubMed2005

Behavior of evaporating droplets at nonsoluble and soluble surfaces: Modeling with molecular resolution.

Liquid droplets in equilibrium with vapor are simulated at solidlike surfaces using the cooperative motion algorithm (CMA). These droplets behave like real droplets, i.e., the densities of the coexistent liquid and vapor phases obey empirical relations such as rho l - rho v proportional, variant (1 - T/Tc)(1/3). Droplet evaporation was studied under various interaction conditions, i.e., nonsoluble and soluble substrates. In the last case, substrate particles migrate toward the liquid-vapor interface to minimize the droplet surface energy. This leads to the formation of a microwell surrounded by a ringlike deposit on the substrate surface. It is shown that the ring formation in the first stages of evaporation results in pinning of the droplet contact area.

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PubMed2004

Equilibrium interaction of solid surfaces across a polymer melt.

Forces across polymer melts are poorly understood despite their importance for adhesion and fabricating composite materials. Using an atomic force microscope (AFM), this interaction was measured for poly(dimethyl siloxane) (PDMS). The structure of the polymer at the surface changed during the first approximately 10 h. Afterward, short-range attractive forces were observed with short-chain PDMS (M(w) = 4200 g/mol). Using PDMS with a molecular weight (M(w) = 18 000 g/mol) above the entanglement limit, we measured a monotonically decaying repulsive force, which indicates that a quasi-immobilized layer had formed at the solid surface. Due to the small radius of curvature of the tip, forces could be measured in equilibrium.

Dimethylpolysiloxanes↗

PubMed2004

Structure of star-burst dendrimers: a comparison between small angle x-ray scattering and computer simulation results.

We investigated the generation dependent shape and internal structure of star-burst dendrimers under good solvent conditions using small angle x-ray scattering and molecular modeling. Measurements have been performed on poly(amidoamine) dendrimers with generations ranging from g=0 up to g=8 at low concentrations in methanol. We described the static form factor P(q) by a model taking into account the compact, globular shape as well as the loose, polymeric character of dendrimers. Monomer distributions within dendrimers are of special interest for potential applications and have been characterized by the pair correlation function gamma(r), as well as by the monomer and end-group density profile, rho(r) and rho(e)(r), respectively. Monomer density profiles and gamma(r) can be derived from P(q) by modeling and via a model independent approach using the inverse Fourier transformation algorithm first introduced by Glatter. Experimental results are compared with computer simulations performed for single dendrimers of various generations using the cooperative motion algorithm. The simulation gives direct access to gamma(r) and rho(r), allows an independent determination of P(q), and yields in addition to the scattering experiment information about the distribution of the end groups. Excellent qualitative agreement between experiment and simulation has been found.

Journal Article↗

PubMed2004

Exceptionally long-range self-assembly of hexa-peri-hexabenzocoronene with dove-tailed alkyl substituents.

The substitution of a hexa-peri-hexabenzocoronene by bulky, space-demanding, 2-decyltetradecyl side chains proved to be an effective procedure to influence the thermal and self-aggregation behavior. The extremely large steric requirement of the introduced side chains modulated the aggregation and resulted in a dramatic lowering of the isotropization temperature and a higher solubility. As an additional consequence of the exceptional, long-range self-aggregation of the discotic molecule, spherulite formation was observed during crystallization by polarized light microscopy. Macroscopic self-assembly was induced by zone crystallization of the material, leading to aligned columnar superstructures as revealed by 2D-WAXS experiments. These extraordinary properties have not yet been reported for a discotic columnar material, making this compound very promising for application in electronic devices.

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PubMed2004

Homologous series of dendronized polymethacrylates with a methyleneoxycarbonyl spacer between the backbone and dendritic side chain: synthesis, characterization, and some bulk properties.

First through fourth generation (G1-G4) dendronized macromonomers, 3, 5, 7, and 9, with a methyleneoxycarbonyl spacer between the polymerizable group and dendritic side chain (dendron) were synthesized, and their polymerization behavior to the corresponding dendronized polymers PG1s, PG2s, PG3s, and PG4s, respectively, was investigated by heating the monomers to 55 degrees C without intentional addition of initiator. This self-induced polymerization is referred to as thermally induced radical polymerization (TRP). The molar masses of PG1s-PG4s were determined by gel permeation chromatography in DMF calibrated to a recently developed G1 dendronized polymer standard (PG1). A comparison of this homologous series' polymerization results with those of an already existing one, which differed only by the lack of this spacer (referred to as PG1-PG4), was made to contribute to the issue of whether short spacers have an effect on polymerization. Several representatives of both series were also used in the first systematic and generation-dependent investigation of these unusual comb polymers' bulk properties. Both structure and dynamics were investigated by DSC, X-ray diffraction, and dynamic mechanical measurements.

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PubMed2004

Simulation of polymer--polymer interdiffusion using the dynamic lattice liquid model.

In this paper, we present computer simulation results concerning interdiffusion of fully compatible components in symmetric binary (AB) polymer mixtures in solutions. The simulation is performed in two dimensions using the algorithm based on the dynamic lattice liquid model. The solvent molecules are taken into account explicitly. The evolution of the concentration profiles in time at an interface is studied for chain lengths N=2,4,8,16 for three polymer concentrations phi=0.1,0.5,0.9. The tracer diffusion coefficients for polymer chains and for the solvent are obtained by monitoring the mean square displacements of their center of mass. The relationships between coefficients of interdiffusion and self-diffusion are tested.

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PubMed2004

Self-assembly of electron donor-acceptor dyads into ordered architectures in two and three dimensions: surface patterning and columnar "double cables".

We report the synthesis and characterization of covalent dyads and multiads of electron acceptors (A) and donors (D), with the purpose of exploiting their nanophase separation behavior toward (a) two-dimensional (2D) surface patterning with well-defined integrated arrays of dissimilar molecular electronic features and (b) bulk self-assembly to noncovalent columnar versions of the so-called "double cable" systems, the likes of which could eventually provide side-by-side percolation pathways for electrons and holes in solar cells. Soluble, alkylated hexa-peri-hexabenzocoronenes (HBCs) bearing tethered anthraquinones (AQs) are shown by scanning tunneling microscopy (STM) to self-assemble at the solution-graphite interface into either defect-rich polycrystalline monolayers or extended 2D crystalline domains, depending on the number of tethered AQs. In the bulk, the thermal stability of the room-temperature HBC columnar phase is increased, which is attributed to the desired nanotriphase separation of HBC columns, insulating alkyl sheaths, and AQ units. Homeotropic alignment (columns normal to surfaces), predicted to be ideal for potential exploitation of such "double cables" in photovoltaic devices, is demonstrated.

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PubMed2003

Uniaxial alignment of the columnar super-structure of a hexa (alkyl) hexa-peri-hexabenzocoronene on untreated glass by simple solution processing.

Uniaxially aligned, thin films of a discotic columnar thermotropic liquid crystalline material can be prepared by a simple solution zone-casting method, without the need for modified surfaces or traditional alignment techniques. Atomic force microscopy together with X-ray diffraction reveals single-crystalline-like order over several square centimeters, far exceeding the requirements for application of such films in organic molecular electronic devices such as field-effect transistors.

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PubMedDate not supplied

Material properties of various intraocular lenses in an experimental study.

INTRODUCTION: With the recent introduction of small-incision cataract surgery, requirements for intraocular lens (IOL) flexibility, strength and hydrophilicity have rapidly evolved. The IOL surface, however, remains a critical factor influencing uveal biocompatibility. PURPOSE: To objectively quantify factors of material properties of various IOLs using contact angle measurements, differential scanning calorimetry, dynamic-mechanical measurements and scanning electron microscopy. MATERIAL AND METHODS: In our study, 17 currently available IOLs were investigated using contact angle measurements to assess hydrophilicity and biocompatibility, as well as differential scanning calorimetry for the estimation of glass transition temperature. Mechanical capacity and flexibility were investigated using dynamic-mechanical measurements. Additional analysis of the IOL surface was performed using scanning electron microscopy. RESULTS: The contact angle measurements of the studied IOLs revealed similar values within each group. The silicone IOLs had values between 106 and 119 degrees. The PMMA IOLs were found to have a narrower range of values, between 73.2 and 75.5 degrees. Lenses made of hydrogel had values between 59.2 and 69.1 degrees. The heparin-modified surface showed the lowest contact angle of 56.5 degrees. The glass transition temperature was determined by dynamic differential scanning calorimetry. The resulting values were between 118.8 and 113.5 degrees C for PMMA IOLs, 15.5 and 14.0 degrees C for acrylic IOLs, and -91.7 and -119.6 degrees C for silicone IOLs. The dynamic-mechanical measurements revealed that PMMA lenses manifested characteristics similar to glass, whereas silicone lenses had characteristics similar to rubber. Acrylic lenses were between rubber and glass. Scanning electron microscopy revealed smooth dispersion of fibrin on hydrophobic IOLs and a relative lack of fibrin adhesion on hydrophilic materials. CONCLUSION: These results demonstrate that material properties of various IOL materials are consistent within classes of IOL materials. This suggests that the intraoperative and postoperative behavior of an IOL is predictable and related to its composition, thus allowing surgeons to choose IOLs more appropriate for different surgical situations and individual patient characteristics.

Acrylates↗