Biomedical subjects

Paweł Krysiński

Publications and source records attributed to Paweł Krysiński.

7 recordsLinked to original sources

PubMed2005

Use of zirconium-phosphate-carbonate chemistry to immobilize polycyclic aromatic hydrocarbons on boron-doped diamond.

We report on the formation of monomolecular layers of perylene- and pyrene-alkanoic acids on boron-doped diamond (BDD) substrates. The carboxylic acid layers are bound by coordination to zirconium phosphate (ZP) functionalities on the BDD substrate surface. The resulting Zr-phosphate-carbonate (ZPC) linkages between the substrate and the adlayer are asymmetric, of the form -(OPO3(2-) Zr4+-O2C-R)+ X-. Pyrene and perylene are well-established optical probes of polarity and viscosity at interfaces. We have used electrochemical and steady-state fluorescence techniques to study the loading density and behavior of these monomolecular films, allowing comparison of BDD and indium-doped tin oxide (ITO) substrates. Electrochemical data suggest that the pyrene chromophores are positioned roughly at the same distance from the surface, regardless of the length of the anchoring alkanoic acid chain, a finding that can be explained by the pyrene lying on the substrate surface. Such a conformation is plausible given the surface coverage (5 x 10(-11) mol/cm2, ca. 0.1 monolayer) we measure for these systems.

Boron↗

PubMed2005

Probing interfacial organization in surface monolayers using tethered pyrene. 1. Structural mediation of electron and proton access to adsorbates.

We have synthesized and characterized a family of self-assembled monolayers containing pyrene derivatives on gold and indium-doped tin oxide (ITO) substrates. The covalently bound pyrene functionalities serve as either spectroscopic or electrochemical probes of their immediate environment, and we explore their electrochemical response in this paper. When these compounds are the only constituents bound to the interfaces, the molecules enjoy significant structural freedom. The addition of aliphatic adsorbates to the interfaces serves to place the pyrene derivatives in a more restricted environment. Cyclic voltammetry shows that the organization of a monolayer with pyrene derivatives, and the position of the terminal pyrene within such monolayer, depend sensitively on the length of the pyrene tether and the presence or absence of aliphatic interfacial species, as well as the identity of the substrate.

Journal Article↗

PubMed2005

Probing interfacial organization in surface monolayers using tethered pyrene. 2. Spectroscopy and motional freedom of the adsorbates.

We have studied the steady-state and time-resolved emission spectroscopy of the pyrene-containing monolayers reported in the previous article, where in this work we have bound the monolayers to SiO(x). We find that these monolayer structures are sensitive to the identity of the solvent overlayer, with the solvent playing a significant role in the organization of the surface-bound monolayers. We discuss our findings in the context of the known polarity dependence of the pyrene emission spectrum and find that the motional freedom of the chromophores varies with both the monolayer composition and the identity of the solvent overlayer. Our data point to the importance of neighbor-neighbor interactions within the monolayer structures in mediating the motional freedom of the tethered pyrene chromophores.

Journal Article↗

PubMed2005

Spectroscopic and electrochemical characterization of interfacial biomimetic assemblies on electrochemically generated gold oxide surfaces.

We report on the formation of a gold oxide layer and the reaction of this oxide with an acid chloride to form a stable, relatively complete monolayer bound through an ester-like bond to the gold oxide surface. We have used cyclic voltammetry, FTIR and optical ellipsometry to characterize this novel monolayer structure. The exposed functional groups of this monolayer can participate in subsequent surface reactions, opening the door to the use of oxide-based surface attachment chemistry on metallic substrates. This chemistry will allow for the formation of films tailored to contain both hydrophobic and hydrophilic regions, stacked at predetermined distances from the substrate that may serve as biomembrane mimetic assemblies.

Adipates↗

PubMed2004

Incorporation of Na(+),K(+)-ATP-ase into the thiolipid biomimetic assemblies via the fusion of proteoliposomes.

The black lipid membranes (BLMs) are artificial membrane systems that have been widely used in the study of different biological processes. In this paper the planar bilayer lipid membranes have been used to study the behavior of thiolipid molecules-dipalmitoyl-phosphatidyl-ethanolamine-mercaptopropionamide (DPPE-MPA) and cholesteryl 3-mercaptopropionate (Chs-MPA)-as compared to classical BLM made of natural lipids. We present our experiments on black thiolipid bilayer (BTM) formation from a thiolipid solution and basic results of pump currents generated by sodium-potassium pump-Na(+),K(+)-ATP-ase-introduced to such bilayer systems via proteoliposome adsorption with subsequent fusion. Our results imply that no substantial difference exists between BLMs formed from classical lipids and those made from thiolipids used in this study. The same thiolipid molecules were subsequently used for the formation of covalently bound, tethered bilayer lipid membranes (t-BLMs) on polycrystalline gold electrodes. Similarly, as in the case of BLMs, we took advantage of proteoliposome adsorption/fusion to obtain a t-BLM system with reconstituted enzyme. The vesicle fusion on hydrophobic or hydrophilic substrates is one of the main ways to obtain a bilayer system with incorporated biological species. In this paper we present also our preliminary results of electrochemical experiments using rapid solution exchange technique on such t-BLMs systems and their comparison with painted solid supported membranes (SSMs) and BLMs. We have also followed the process of vesicles fusion onto thiolipid monolayer by means of in situ atomic force microscopy in tapping mode (TM-AFM). On the basis of these experiments, we conclude that DPPE-MPA and Chs-MPA molecules used in our experiments preserve lipid properties, allowing for at least partial reconstitution of Na(+),K(+)-ATP-ase into such t-BLMs. On the other hand, the relatively compact organization on polycrystalline gold and the hydrophobic nature of the first monolayer of tethered thiolipids slows down the proteoliposome fusion onto such monolayers and consequently hinders the protein insertion. However, this effect can be overcome by mechanical stimulus that facilitates proteoliposome delamination onto the self-assembled monolayer.

Biomimetic Materials↗

PubMed2003

Covalent adlayer growth on a diamond thin film surface.

The surface of boron-doped diamond thin films can be modified by exposure to a strong oxidizing agent, resulting in the formation of -OH and =O terminated diamond. The -OH groups are reacted with an acid chloride to produce a covalently bound, modified diamond thin film surface. The demonstration of these reactions allows for the facile modification of diamond surfaces using techniques well established for oxide surfaces. Characterization of the covalently bound species shows submonolayer coverage, and time-resolved fluorescence measurements are reflective of the highly featured nature of the diamond film.

Journal Article↗

PubMed2002

Electrochemical studies of blocking properties of solid supported tethered lipid membranes on gold.

The insulating properties of self-assembled thiolipid monolayers and tethered lipid bilayers on polycrystalline gold electrodes were studied by means of cyclic voltammetry (CV). These films were formed by two-step self-assembly processes. Electrochemical measurements of the heterogeneous electron transfer rate constant of different redox couples such as potassium ferrocyanide (K(4)[Fe(CN)(6)]) and dopamine (DP) were used to examine the molecular integrity and structural defects and pinholes within the monolayers. We demonstrate by means of cyclic voltammetry that the bilayer lipid membranes tethered to the gold surface are blocking, stable, yet retaining their dynamic properties and can be used as a model of the cell membrane.

Electrochemistry↗