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A versatile hybrid processing method that combines electrostatic deposition of microparticles and subsequent anisotropic plasma etching is described that can generate superhydrophobic engineering surfaces with tunable bimodal roughness and a thin hydrophobic fluorocarbon film. These surfaces exhibit contact angles with water of more than 160°.
A novel technique was developed to create superhydrophobic polytetrafluoroethylene (PTFE) surface using nanosecond pulse electron deposition (PED) technique. The PTFE or Teflon thin films deposited on silicon substrate showed superhydrophobicity evidenced by the contact angle of 166±2 degrees. The SEM micrographs reveal the clustered growth of the deposited film and two level sub-micron asperities which is corroborated by the AFM. FTIR and contact angle studies were conducted to study the chemical nature and the wetting properties of the films.
Leptothrix discophora SP-6, a type of manganese(Mn)-oxidizing bacteria, has been known to accumulate Mn oxides from the aqueous environment and thus play a key role in microbiologically influenced corrosion by increasing the electrochemical potential of steel and other metals. Similarly, this bacterium was found to modify the surface of glassy carbon in aqueous solution and increase its potential (i.e. ennoblement). In the latter case, biomineralized Mn oxides can be used as cathodic reactants for a new generation of microbial fuel cells featuring a bio-cathode. In this preliminary study, factors affecting the biofilm formation and biomineralization processes were examined. The inflow of air into the culture medium was found essential to sustain the ennoblement of substrate electrodes. The OCP and FESEM/EDS data indicated that a smoother initial substrate surface generally led to better ennoblement. Polarizing the carbon electrode at +500mVSCE for 15 minutes was found to facilitate the ennoblement on carbon electrodes, and so did the coating with a poly(L-lysine) layer. Independent of substrate material, initial surface roughness and pretreatment, there were three parameters in the EIS equivalent circuit that correlated well with the OCP indicating the level of ennoblement by L. discophora SP-6, i.e., electrolyte resistance, double-layer capacitance, and low-frequencies capacitance. These fascinating findings merit further investigation as they may shed light on the fundamental bacteria/substrate interactions and help advance the knowledge base needed for the engineering applications.
Mature tooth enamel does not remodel nor self-repairs after damage. Therefore, in vitro formation of a uniquely ordered composite similar to enamel is of particular interest. In this study we applied a newly developed electrolytic deposition (ELD) system to promote the amelogenin nano-chain self-assembly and simultaneous calcium phosphate crystallization. Composite coatings of amelogenin-calcium phosphate were prepared on a cathode substrate (Si wafer), from an initial pH of 4-5, and calcium and phosphorus containing solution at room temperature. The effects of a recombinant full-length amelogenin (rP172) and truncated protein without the C-terminal (rP148) on the growth and morphology of the calcium phosphate nano-composite were investigated. A potentiostat was used to control the electrochemical parameters.Following the application of electric current, the local pH around the cathode was increased and resulted in the self-assembly of amelogenin that occurred simultaneously with calcium phosphate mineralization. Transmission and scanning electron micrographs of assembled rp172 amelogenin collected from the 25mM sodium phosphate solution during electrodeposition showed uniform nanospheres and nano-chains structures, while the rP148 formed irregular aggregates. SEM observation of the surface of the nano-composite after electrodeposition, revealed organized nano-rod structures in the presence of rP172, while only nano-sized spherical aggregates were seen in the presence of rP148. ATR-IR confirmed that the mineral phases were mainly octacalcium phosphate, but apatite and amorphous calcium phosphate were also present. Nanoindentation was tested on rP172 and rP148 composite coating. The rP172 composite coating exhibited higher elastic modulus and hardness than rP148 composite. The fracture toughness of rP172 composite was comparable to mature enamel. We therefore conclude that the 24 amino acid hydrophilic C-terminal of amelogenin is essential for the self-assembly, and therefore, for calcium phosphate crystal organization. The new electro-deposition system is effective for fabrication of amelogenin/apatite composites with defined organized structures.
Pore channels of poly-carbonate membranes were recently used as biomimetic models to study the effect of confinement on silicate condensation, leading to the formation of silica tubes exhibiting a core-shell structure. In this work, we pre-immobilized lysozyme on the membrane pores, inducing the modification of the tube shell formation process, and variation in core particle size. These data strengthen previous assumptions on the role of interfacial interactions on the growth of the tube shell and indicate that such interactions also influence the core particle formation. Such approach therefore seems suitable to mimic the formation of silica/protein multilayers as found in several biomineralizing organisms
We demonstrate the polymerisation of PEGA hydrogel microparticles with a mean diameter of 16 µm (similar to that of biological cells), and we show that these particles are compatible with enzymes. Furthermore, we demonstrate that enzyme catalysed reactions occur faster with these microparticles than with commercially available macrobeads which are typically 200-400 µm in diameter.
We describe the combination of soft-lithographic patterning and biomolecule-induced deposition to create microscale patterns of silica on a diverse array of substrates. A soft lithographic technique was used to create a sacrificial layer of the polymer poly(n-propyl methacrylate) (PPMA) on the desired substrate. Subsequently, poly-L-lysine was deposited on the substrate, after which removal of the PPMA yielded a pattern of PLL on the substrate. Exposure of the PLL template to a silicic acid solution resulted in silica deposition in the pattern spatially and geometrically controlled by the PLL. With this procedure, we have created both continuous and discontinuous silica patterns on metallic, ceramic, and polymer substrates. While morphology of the deposited silica varied between substrates, the ability to pattern silica through this templated growth was demonstrated on all investigated substrates. EDS, optical micrography, and SEM analysis verified the controlled deposition of silica on the PLL template patterns. This PLL template-mediated induction of silica formation may facilitate the incorporation of silica in new microdevices and serve as a prototype process for controlled deposition with other biomolecule-material systems.
The synthesis of nano-functionalized drug particles or drug particles with nanoscale biodegradable polymeric coatings has wider ranging applications in sustained release drug delivery systems. An important area of application includes delivery of drugs, such as proteins, peptides, and glucocorticoids via the inhalation process. The advantages of this method include, rapid absorption by the body and lack of metabolic degradation effects which is typically by some drugs during oral delivery. Here we discuss the novel pulsed laser and pulsed electron method to synthesize nanoscale biodegradable coatings of poly lactic acid (PLA) onto antiasthmatic drugs. In pulsed laser method a pulsed excimer laser ablates a thin layer of polymer which is deposited onto 1 -5 micron drug particles which are fluidized in the gas chamber. The control of the thickness, conformation and the chemistry of the nanoscale coating process will be discussed in detail. Applications of this methodology to delivery of anti asthamtic drugs and insulin will be discussed. The effect of polymer coating chemistry, molecular weight, hydrophobicity, and thickness on the sustained release characteristics will be discussed. A unique method for depositing the PLA films, pulsed electron beam deposition (PED) was used to deposit the films. This technique was tried done to overcome the difficulties like low absorption co-efficient of UV-laser. Method proved to be promising for producing smooth films and offers a better thickness control of the deposition. The RMS roughness and other morphological characteristics of PED deposited films were superior over the conventional laser ablated films.
In this paper, the suitability of DNA- and RNA-bases, nucleosides and nucleotides, and DNA itself as structure-directing agents for the mineralization of ZnO-based materials is discussed. Those bioorganic molecules are able to trigger the morphology of mineralization products ranging from smooth, homogenous thin films to sponge-like, sheet-like and fibrous products. Besides the investigation of morphological features by scanning electron microscopy, the structural characterization of these materials by X-ray diffraction, vibrational spectroscopy, photoluminescence spectroscopy and photoelectron spectroscopy is discussed.
Hydroxyapatite coatings have been widely recognized for their biocompatibility and utility in promoting biointegration of implants in both osseous and soft tissue. Conventional sputtering techniques have shown some advantages over the commercially available plasma spraying method; however, the as-sputtered coatings are usually non-stoichiometric and amorphous which can cause some serious problems such as poor adhesion and excessive coating dissolution rate. A versatile right-angle radio frequency magnetron sputtering (RAMS) approach has been developed to deposit HA coatings on various substrates at low power levels. Using this alternative magnetron geometry, as-sputtered HA coatings are nearly stoichiometric, highly crystalline, and strongly bound to the substrate, as evidenced by analyses using x-ray diffraction (XRD), atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). In particular, coatings deposited on oriented substrates show a polycrystalline XRD pattern but with some strongly preferred orientations, indicating that HA crystallization is sensitive to the nature of the substrate. Post deposition heat treatment under high temperature does not result in a marked improvement in the degree of crystallinity of the coatings. To study the biocompatibility of these coatings, murine osteoblast cells were seeded onto various substrates. Cell density counts using fluorescence microscopy show that the best osteoblast proliferation is achieved on an HA RAMS-coated titanium substrate. These experiments demonstrate that RAMS is a promising coating technique for biomedical applications.
Materials based on ureidopyrimidinone (UPY) dimers and Adenine (A) / Thymine (T) derivatives were synthesized and characterized by advanced solid state NMR (Nuclear Magnetic Resonance) techniques. Silylated UPY molecules were used as model compounds, leading to structured organic-inorganic materials after hydrolysis and condensation processes (sol-gel reactions). High resolution 1H solid state NMR has been extensively used for the in-depth description of the H-bond networks, including very fast MAS (Magic Angle Spinning) experiments at very high field and DQ (double quantum) recoupling experiments. The chemical nature of the organic-inorganic interface has been illuminated by such techniques. In, particular, it has been demonstrated that H-bond networks were preserved during sol-gel reactions and were comparable to those observed in the UPY crystalline precursors.
In a search for new drug delivery matrix, the synthesis of a novel collagen material based on tiopronin protected gold clusters (MPC) as a crosslinking agent is proposed. The structure of collagen matrix modified with MPC is studied using transmission electron microscope. The thermal properties are examined with differential scanning calorimetry. To assess the biocompatibility of the matrix, the cytotoxicity assays are conducted.