Electrical properties of diamond surfaces functionalized with molecular monolayers

Recent studies have shown that semiconductor surfaces such as silicon and diamond can be functionalized with organic monolayers, and that these monolayer films can be used to tether biomolecules such as DNA to the surfaces. Electrical measurements of these interfaces show a change in response to DNA hybridization and other biological binding processes, but the fundamental nature of the electrical signal transduction has remained unclear. We have explored the electrical impedance of polycrystalline and single-crystal diamond surfaces modified with an organic monolayer produced by photochemical reaction of diamond with 1-dodecene. Our results show that, by measuring the impedance as a function of frequency and potential, it is possible to dissect the complex interfacial structure into frequency ranges where the total impedance is controlled by the molecular monolayer, by the diamond space-charge region, and by the electrolyte. The results have implications for understanding the ability to use molecularly modified semiconductor surfaces for applications such as chemical and biological sensing.     

Structural and adhesion properties of surfaces functionalized with polyelectrolytes and polystyrene particles

Surfaces functionalized with polystyrene particles and polyelectrolytes were used to investigate the morphological and adhesion properties of composite substrates. Atomic force microscopy (AFM) studies showed that surfaces with non-homogeneous topography have non-homogeneous adhesion properties. In addition, the homogeneity of the adhesion properties is dependent upon the chemical species used to functionalize the surface. Force volume (FV) imaging was utilized to map the adhesion of the fabricated substrates with high-resolution. The FV studies revealed that the hydrophobicity of the surface is not uniform despite the fact that the surface was functionalized with the same polyelectrolyte. The analysis methodology we report here opens the possibility to design better surfaces for future tissue engineering applications.     

Optimizing biosensing properties on undecylenic Acid-functionalized diamond

The optimization of biosensing efficiency on a diamond platform depends on the successful coupling of biomolecules on the surface, and also on effective signal transduction in the biorecognition events. In terms of biofunctionalization of diamond surfaces, surface electrochemical studies of diamond modified with undecylenic acid (UA), with and without headgroup protection, were performed. The direct photochemical coupling method employing UA was found to impart a higher density of carboxylic acid groups on the diamond surface compared to that using trifluoroethyl undecenoate (TFEU) as the protecting group during the coupling process. Non-faradic impedimetric DNA sensing revealed that lightly doped diamond gives better signal transduction sensitivity compared to highly doped diamond.     

Cell adhesion on nanotextured slippery superhydrophobic substrates

In this work, the response of Saos2 cells to polymeric surfaces with different roughness/density of nanometric dots produced by a tailored plasma-etching process has been studied. Topographical features have been evaluated by atomic force microscopy, while wetting behavior, in terms of water-surface adhesion energy, has been evaluated by measurements of drop sliding angle. Saos2 cytocompatibility has been investigated by scanning electron microscopy, fluorescent microscopy, and optical microscopy. The similarity in outer chemical composition has allowed isolation of the impact of the topographical features on cellular behavior. The results indicate that Saos2 cells respond differently to surfaces with different nanoscale topographical features, clearly showing a certain inhibition in cell adhesion when the nanoscale is particularly small. This effect appears to be attenuated in surfaces with relatively bigger nanofeatures, though these express a more pronounced slippery/dry wetting character.     

Construction of a carbon nanotube/diamond hybrid functionalized electrode surface

Multiwalled carbon nanotubes were attached to the surface of boron-doped diamond by electropolymerization using a bridge of polyaniline. A carbon nanotube/diamond hybrid functionalized surface was obtained and testified by field emission scanning electron microscopy. The electrochemical impedance spectroscopy and cyclic voltammetry measurements revealed that this carbon hybrid surface possessed low electron-transfer resistance, large double-capacitance value, and high electrocatalytic ability. This indicated that this functionalized surface had a variety of potential sustainable technology applications such as in supercapacitors, biomolecule-sensing devices.     

Cell adhesion on nanofibrous polytetrafluoroethylene (nPTFE)

Here, we described the in vitro biocompatibility of a novel nanostructured surface composed of PTFE as a potential polymer for the prevention of adverse host reactions to implanted devices. The foreign body response is characterized at the tissue-material interface by several layers of macrophages and large multinucleated cells known as foreign body giant cells (FBGC), and a fibrous capsule. The nanofibers of nanofibrous PTFE (nPTFE) range in size from 20 to 30 nm in width and 3-4 mm in length. Glass surfaces coated with nPTFE (produced by jet-blowing of PTFE 601A) were tested under in vitro conditions to characterize the amount of protein adsorption, cell adhesion, and cell viability. We have shown that nPTFE adsorbs 495 +/- 100 ng of bovine serum albumin (BSA) per cm2. This level was considerably higher than planar PTFE, most likely due to the increase in hydrophobicity and available surface area, both a result of the nanoarchitecture. Endothelial cells and macrophages were used to determine the degree of cell adsorption on the surface of the nanostructured polymer. Both cell types were significantly more round and occupied less area on nPTFE as compared to tissue culture polystyrene (TCPS). Furthermore, a larger majority of the cells on the nPTFE were dead compared to TCPS, at dead-to-live ratios of 778 +/- 271 to 1 and 23 +/- 5.6 to 1, respectively. Since there was a high amount of cell death (due to either apoptosis or necrosis), and the foreign body response is a form of chronic inflammation, an 18 cytokine Luminex panel was performed on the supernatant from macrophages adherent on nPTFE and TCPS. As a positive control for inflammation, lipopolysaccharide (LPS) was added to macrophages on TCPS to estimate the maximum inflammation response of the macrophages. From the data presented with respect to IL-1, TNF-alpha, IFN-gamma, and IL-5, we concluded that nPTFE is nonimmunogenic and should not yield a huge inflammatory response in vivo, and cell death observed on the surface of nPTFE was likely due to apoptosis resulting from the inability of cells to spread on these surface. On the basis of the production of IL-1, IL-6, IL-4, and GM-CSF, we concluded that FBGC formation on nPTFE may be decreased as compared to materials known to elicit FBGC formation in vivo.     

Cell adhesion and locomotion on microwell-structured glass substrates

The purpose of this study was to investigate the effect of microstructured material surface on cell adhesion and locomotion in real-time. ArF excimer laser direct-writing ablation was used to fabricate microwell patterns with precise control of size and spacing on glass. The influence of the ablation process parameters (laser fluence, pulse number and repetition rate) on the micromachining quality (depth, width, aspect ratio and edge effects) of the microwells was established. Human fibroblast cells, as an example of anchorage-dependent cells, were seeded onto the microstructured glass substrate and time-lapse microscopy was used to study cell adhesion and locomotion. The interaction with microstructured materials resulted in fibroblast cell repulsion and the cells exhibited a higher locomotion speed (75.77±3.36 μm/h) on the structures in comparison with plane glass control (54.01±15.53 μm/h). Further studies are needed to firmly establish the potential of microstructuring, for example, in elongating the life spans of implantable devices.     

Bacterial adhesion inhibition of the quaternary ammonium functionalized silica nanoparticles

Quaternary ammonium compounds have been considered as excellent antibacterial agents due to their effective biocidal activity, long term durability and environmentally friendly performance. In this work, 3-(trimethoxysilyl)-propyldimethyloctadecylammonium chloride as a quaternary ammonium silane was applied for the surface modification of silica nanoparticles. The quaternary ammonium silane provided silica surface with hydrophobicity and antibacterial properties. In addition, the glass surface which was coated with the surface modified silica nanoparticles presented bacterial growth inhibition activity. For comparison of bacterial growth resistance, hydrophobic silane (alkyl functionalized silane) modified silica nanoparticles and pristine silica nanoparticles were prepared. As a result of bacterial adhesion test, the quaternary ammonium functionalized silica nanoparticles exhibited the enhanced inhibition performance against growth of Gram-negative Escherichia coli (96.6%), Gram-positive Staphylococcus aureus (98.5%) and Deinococcus geothermalis (99.6%) compared to pristine silica nanoparticles. These bacteria resistances also were stronger than that of hydrophobically modified silica nanoparticles. It could be explained that the improved bacteria inhibition performance originated from the synergistic effect of hydrophobicity and antibacterial property of quaternary ammonium silane. Additionally, the antimicrobial efficacy of the fabricated nanoparticles increased with decreasing size of the nanoparticles.     

Cell adhesion and surface properties of polystyrene surfaces grafted with poly(N-isopropylacrylamide)

Cell adhesion plays a key role in various aspects of biological and medical sciences. In this study, poly(Nisopropylacrylamide) (PNIPAM) was grafted on polystyrene surfaces using different solvents under UV radiation. Moreover, the relation between surface roughness and cell adhesion were evaluated by gravimetric, SEM, AFM, contact angle measurement and cellular analyses. The gravimetric analysis clearly indicated an increase in the grafting by adding 10% methanol to water. The study of surface topography by AFM images showed an increase in the surface roughness and as a result of which, a decrease in wettablity was observed. At 37 °C, epithelial cells were well attached and proliferated on the grafted surfaces, while these cells were spontaneously detached below 32 °C in the absence of any enzymes. Moreover, MTT assay and SEM images indicated good cell viability and an increase in cell adhesion caused by the roughness increase. The results of this study reveal the great potential of PNIPAM-grafted polystyrene for being used in the biomedical fields such as drug delivery systems, tissue engineering and cell separation.     

Synthesis and properties of functionalized alkylalkoxysilanes

A method of chloroalkylalkoxysilanes synthesis scalable to pilot production has been proposed. Morpholinotrialkoxysilanes have been prepared and studied as vulcanizing agents for low-molecular silicone rubbers. The reaction of N-morpholinomethyltrialkoxysilanes with triethanolamine has afforded N-[(silatranyl)-methyl]morpholine; it has been studied by X-ray analysis.     

Electronic properties of metal-arene functionalized graphene

We have employed first-principles density-functional calculations to study the electronic characteristics of covalently functionalized graphene by metal-bis-arene chemistry. It is shown that functionalization with M-bis-arene (M = Ti, V, Cr, Mn, Fe) molecules leads to an opening in the bandgap of graphene (up to 0.81 eV for the Cr derivative), and as a result, transforms it from a semimetal to a semiconductor. The bandgap induced by attachment of a metal atom topped by a benzene ring is attributed to modification of π-conjugation and depends on the concentration of functionalizing molecules. This approach offers a means of tailoring the band structure of graphene and potentially its applications for future electronic devices.     

Geometric properties of covalently bonded DNA on single-crystalline diamond

Diamond is a promising candidate for bioapplications. Properties of hybridized DNA arrays on single-crystalline diamond are studied on a microscopic level by atomic force microscopy (AFM) in buffer solutions. Compact DNA layers in a thickness of 76 A are resolved by optimizing phase and height contrast in AFM. The height shows some long-range (30 nm) undulations of +/-5 A due to tip and DNA interactions. The axis of double helix DNA is oriented at about 36 degrees with respect to the diamond surface. DNA molecules can be removed by contact-mode AFM with forces >45 nN, indicating stronger DNA bonding than on gold substrates.     

Semiconductor properties of nanocrystalline diamond electrodes

The semiconductor properties of nitrogenated nanocrystalline diamond electrodes and their corrosion transformations caused by electrochemical experiment in indifferent electrolyte (1 M K₂SO₄) were studied by the electrochemical impedance spectroscopy method. It was shown that after electrochemical measurements a narrow diamond peak at 1335.7 cm^?1 appears in the Raman spectrum; formerly the peak was hidden at a background of the intense signal inherent to graphite-like carbon. It was suggested that the corrosion damage caused by the exposure to electrochemical experiment resulted in a decrease of relative amount of nondiamond (graphite-like) carbon in the subsurface layer in the nanocrystalline diamond. By using Mott-Schottky plots, the nanocrystalline diamond was shown having n-type conductance. Within the bounds of the “effective medium” approach, the nanocrystalline diamond’s flat-band potential in aqueous solution and the noncompensated donor apparent concentration were estimated.     

Highly sensitive detection of platelet-derived growth factor on a functionalized diamond surface using aptamer sandwich design

Aptamer-based fluorescence detection of platelet-derived growth factor (PDGF) on a functionalized diamond surface was demonstrated. In this work, a sandwich design based on the ability of PDGF to bind with aptamers at its two available binding sites was employed. It was found that this sandwich design approach significantly increases the fluorescence signal intensity, and thereby a very low detection limit of 4 pM was achieved. The effect of the ionic strength of MgCl(2) buffer solution was also investigated, and the most favourable binding for PDGF-BB occurred at a Mg(2+) concentration of 5.5 mM. Since the aptamers bind to the target PDGF with high affinity, fluorescence detection exhibited high selectivity towards different biomolecules. The high reproducibility of detection was confirmed by performing three cycles of measurements over a period of three days.     

Phospholipid morphologies on photochemically patterned silane monolayers

We have studied the spreading of phospholipid vesicles on photochemically patterned n-octadecylsiloxane monolayers using epifluorescence and imaging ellipsometry measurements. Self-assembled monolayers of n-octadecylsiloxanes were patterned using short-wavelength ultraviolet radiation and a photomask to produce periodic arrays of patterned hydrophilic domains separated from hydrophobic surroundings. Exposing these patterned surfaces to a solution of small unilamellar vesicles of phospholipids and their mixtures resulted in a complex lipid layer morphology epitaxially reflecting the underlying pattern of hydrophilicity. The hydrophilic square regions of the photopatterned OTS monolayer reflected lipid bilayer formation, and the hydrophobic OTS residues supported lipid monolayers. We further observed the existence of a boundary region composed of a nonfluid lipid phase and a lipid-free moat at the interface between the lipid monolayer and bilayer morphologies spontaneously corralling the fluid bilayers. The outer-edge of the boundary region was found to be accessible for subsequent adsorption by proteins (e.g., streptavidin and BSA), but the inner-edge closer to the bilayer remained resistant to adsorption by protein or vesicles. Mechanistic implications of our results in terms of the effects of substrate topochemical character are discussed. Furthermore, our results provide a basis for the construction of complex biomembrane models, which exhibit fluidity barriers and differentiate membrane properties based on correspondence between lipid leaflets. We also envisage the use of this construct where two-dimensionally fluid, low-defect lipid layers serve as sacrificial resists for the deposition of protein and other material patterns.     

Theoretical perspective on properties of DNA‐functionalized surfaces

The molecular recognition properties of DNA gave rise to many novel materials and applications such as DNA biosensors, DNA‐functionalized colloidal materials, DNA origami and DNA‐based directed surface assembly. The DNA‐functionalized surfaces are used in biosensors and for programmed self‐assembly of biological, organic and inorganic moieties into novel materials. However, surface density, length, and linker design of the surface functionalized DNAs significantly influence the properties of DNA‐driven assemblies and materials. This perspective discusses the understanding of structure and dynamics of DNA immobilized on the surfaces from the theoretical point of view including recent progress in analytical theories, atomistic simulations, and coarse‐grained models. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1563–1568, 2011     

Sorption properties of functionalized liquid crystalline networks

Functionalized polydomain chiral elastomers were obtained by cross-linking side-chain liquid crystalline polysiloxanes bearing acid functions. Sorption experiments were performed by the use of an electronic microbalance, in the presence of one enantiomer of a chiral amine molecule, able to interact with the acid groups. The results showed that Fick's diffusion law is not valid anymore as soon as an interaction between the material and the molecule is present. Moreover, it was demonstrated that the grafting of interacting groups on a chiral elastomer enhanced both the capacity and selectivity toward one enantiomer.     

Biosensing properties of diamond and carbon nanotubes

The biochemical properties of boron-doped diamond (BDD), carbon nanofiber, fullerene, and multiwalled carbon nanotube (MWCNT) electrodes have been investigated comparatively. Physiochemical factors which affect the biosensing properties such as surface hydrophobicities, effective surface area, and intrinsic material properties are studied. Voltammetric responses of the as-grown thin film electrode and surface-modified electrode to biomolecules such as L-ascorbic acid (L-AA), dopamine (DA), and uric acid are examined. As-grown MWCNT electrodes exhibit selective voltammetric responses to the different biomolecules and faster electron-transfer kinetics compared to BDD. The selective response is due to the considerably lower anodic potential of L-AA on MWCNT (-48 mVvs Ag/AgCl compared to 575 mV on BDD). This electrocatalytic response can be replicated on a nonselective carbon nanofiber electrode by coating it with gold nanoparticles. BDD has no intrinsic selective response to L-AA, and surface modification by anodic polarization is necessary for resolving L-AA and DA.