Dinko Chakarov

An in vivo study of bone response to implants topographically modified by laser micromachining.

Dental implants topographically modified by laser ablation of periodic arrays of micron-sized craters, were studied in a two-part laboratory investigation. The patterned and control (turned) implants were inserted in rabbit femur and tibia. After 12 weeks the fixation in the bone was evaluated mechanically or by histomorphometry (all threads along the implant and the three best consecutive threads were analysed). In the pilot study no difference was found with respect to bone-to-implant contact and peak removal torque. Significantly more bone was found for the control implants when measuring the bone area inside the threads in the tibia. In the second part of the study, the pattern was improved and significantly more bone-to-implant contact was found for the laser-machined implants. The second part of the study also demonstrated significantly greater peak removal torque values in the tibia with the test implants than the control implants.

Graphene Oxide and Lipid Membranes: Interactions and Nanocomposite Structures

We have investigated the interaction between graphene oxide and lipid membranes, using both supported lipid membranes and supported liposomes. Also, the reverse situation, where a surface coated with graphene oxide was exposed to liposomes in solution, was studied. We discovered graphene oxide-induced rupture of preadsorbed liposomes and the formation of a nanocomposite, bio-nonbio multilayer structure, consisting of alternating graphene oxide monolayers and lipid membranes. The assembly process was monitored in real time by two complementary surface analytical techniques (the quartz crystal microbalance with dissipation monitoring technique (QCM-D) and dual polarization interferometry (DPI)), and the formed structures were imaged with atomic force microscopy (AFM). From a basic science point of view, the results point toward the importance of electrostatic interactions between graphene oxide and lipid headgroups. Implications from a more practical point of view concern structure-activity relationship for biological health/safety aspects of graphene oxide and the potential of the nanocomposite, multilayer structure as scaffolds for advanced biomolecular functions and sensing applications.

CO oxidation on Pt(111) promoted by coadsorbed H2O

It is well established that CO2 is produced at temperatures ∼300 K through the well known Langmuir–Hinshelwood mechanism, e.g. when CO and oxygen are coadsorbed on Pt(111) at temperatures 150–170 K and then heated. We demonstrate that the same coadsorbates after the addition of minute amounts (⩽0.1 ML) of H2O, causes CO2 production at 180–230 K. By analysis of temperature programmed reaction (TPR) spectra of desorbing H2O and CO2 for different O/CO/H2O coverage combinations, we suggest an autocatalytic reaction path where OH molecules, produced via the 2H2O+Oad→3OHad+Had reaction, induce low temperature CO oxidation. This result suggests a reinterpretation of earlier reported TPR spectra of low temperature CO2 production from CO+O coadsorbates. It also suggests that H2O may reduce the self poisoning by CO of supported Pt catalysts in e.g. vehicle emission cleaning.

Reusable hydroxyapatite nanocrystal sensors for protein adsorption

Abstract The repeatability of the adsorption and removal of fibrinogen and fetal bovine serum on hydroxyapatite (HAp) nanocrystal sensors was investigated by Fourier transform infrared (FTIR) spectroscopy and quartz crystal microbalance with dissipation (QCM-D) monitoring technique. The HAp nanocrystals were coated on a gold-coated quartz sensor by electrophoretic deposition. Proteins adsorbed on the HAp sensors were removed by (i) ammonia/hydrogen peroxide mixture (APM), (ii) ultraviolet light (UV), (iii) UV/APM, (iv) APM/UV and (v) sodium dodecyl sulfate (SDS) treatments. FTIR spectra of the reused surfaces revealed that the APM and SDS treatments left peptide fragments or the proteins adsorbed on the surfaces, whereas the other methods successfully removed the proteins. The QCM-D measurements indicated that in the removal treatments, fibrinogen was slowly adsorbed in the first cycle because of the change in surface wettability revealed by contact angle measurements. The SDS treatment was not effective in removing proteins. The APM or UV treatment decreased the frequency shifts for the reused HAp sensors. The UV/APM treatment did not induce the frequency shifts but decreased the dissipation shifts. Therefore, we conclude that the APM/UV treatment is the most useful method for reproducing protein adsorption behavior on HAp sensors.

Nanostructures for Enhanced Light Absorption in Solar Energy Devices

The fascinating optical properties of nanostructured materials find important applications in a number of solar energy utilization schemes and devices. Nanotechnology provides methods for fabrication and use of structures and systems with size corresponding to the wavelength of visible light. This opens a wealth of possibilities to explore the new, often of resonance character, phenomena observed when the object size and the electromagnetic field periodicity (light wavelength lambda) match. Here we briefly review the effects and concepts of enhanced light absorption in nanostructures and illustrate them with specific examples from recent literature and from our studies. These include enhanced optical absorption of composite photocatalytically active TiO(2)/graphitic carbon films, systems with enhanced surface plasmon resonance, field-enhanced absorption in nanofabricated carbon structures with geometrical optical resonances and excitation of waveguiding modes in supported nanoparticle assembles. The case of Ag particles plasmon-mediated chemistry of NO on graphite surface is highlighted to illustrate the principle of plasmon-electron coupling in adsorbate systems.

Photo ejection of water molecules from amorphous ice films.

Water molecules are photo-ejected upon laser irradiation from the surface of ice films grown on graphite (0001) and Pt(111). The films are deposited at temperatures between 40 and 140 K and irradiated with nanosecond laser pulses. The process is investigated in the wavelength range between 275 and 670 nm. The wavelength and photon flux dependence suggest a multi-photon process with energy threshold of around 9 eV. The photo-detachment is less effective or negligible from films annealed at temperatures above the amorphous-crystalline transition temperature of ice films. Coverage dependence of the phenomena relates the photo yield to surface roughness. Electronic excitation mechanism related to the defects in ice is proposed to explain the observations.

Two-dimensional hydration shells of alkali metal ions at a hydrophobic surface

We study the hydration shell formation of alkali metal ions at a graphite surface. Two-dimensional shell structures are found in the initial stage of hydration, in contrast to the three-dimensional structures in bulk water and clusters. Comparison of vibrational spectra with experiments identifies the shell structures and the thermally induced transition from the first to the second shell. We also found intriguing competition between hydration and ion-surface interaction, leading to different solvation dynamics between K and Na. Implications of these results in ionic processes at interfaces are elaborated.

Protein Adsorption on Hydroxyapatite Nano-Crystals with Quartz Crystal Microbalance Technique

Real time adsorption behaviors of six proteins with different isoelectric points on hydroxyapatite (HAp) nanocrystal surfaces have been investigated by using HAp sensors for quartz crystal microbalance with dissipation technique (QCM-D). The dissipation (D)–frequency (f) plots clearly showed that the different types of protein adsorption behaviors; the D-f plots of acidic proteins lie on one straight line with a constant slope under all initial protein concentrations, while those of neutral and basic proteins lie on two straight lines with different slopes. The acidic proteins formed a monolayer, while the neutral and basic proteins could cause conformational changes with the adsorbed amount of proteins. The QCM-D technique with novel HAp nanocrystal sensor is useful for the liquid phase changes of proteins on the surface.

Adsorption of Proteins Derived from Fetal Bovine Serum onto Hydroxyapatite Nanocrystals with Quartz Crystal Microbalance Technique

The adsorption of multiple proteins derived from fetal bovine serum (FBS) in phosphate buffer saline (PBS) and alpha minimum essential (aMEM) was in situ analyzed with a quartz crystal microbalance with dissipation technique on gold, titanium and HAp sensors. The adsorption behaviors of FBS proteins were varied depending on the sensors. The DD/Df value of the HAp sensor were clearly different in PBS and aMEM, and others were not changed. The viscoelastic properties of the protein films adsorbed on the HAp sensor in PBS were flexible in comparison with those on the gold and titanium sensors. The D-f plots incidated that the proteins adsorbed on HAp in PBS would lead to competitive adsorption and conformational change and those in aMEM could form a monolayer. The adsorption behavior on the HAp in carbonate buffer saline was found to be similar to that in aMEM. These differential adsorption behaviors on the HAp surface were attributed to the pre-adsorptive ion, such PO43- or CO32- in the solvent.

The Surface Property of Hydroxyapatite: Sensing with Quartz Crystal Microbalance

Hydroxyapatite (HAp) sensor, available for quartz crystal microbalance with dissipation (QCM-D) technique, has been fabricated by an electrophoretic deposition method. The method of re-usability of the sensor after adsorption of fibrinogen and the biological apatite (BAp) growth on the sensor with and without the adsorption of feral bovine serum (FBS) from 1.5 simulated body fluid were investigated. The re-usability of the sensor, cleaning with the combination of ammonia and hydrogen peroxide mixture and UV/ozone treatment, achieved ten times reuses. BAp was grown on the HAp surface but not on the gold surface at 37.5 oC for 40 hours. The viscoelastic property (DD/Df value) of the BAp layer on the HAp sensor showed harder than that of the protein adsorption films from FBS. The amount of the BAp grown on the HAp sensor adsorbed FBS is lower than that on the HAp sensor. The adsorption of FBS proteins on the HAp surface strongly inhibited the BAp growth.