Synthesis of hydroxyapatite on titanium coated with organic self-assembled monolayers

The work focuses the formation of hydroxyapatite (HA) layers from simulated body fluids (SBF) onto titanium coated with NH₂-, SH-, and SO₃H-SAMs, respectively, at room temperature and 37 °C as well as pH values of SBF of 7.4, 8, and 8.4. At an upside up arrangement of the samples in the SBF, the formation of sufficient thick HA layers with a pillow like structure onto all SAMs were observed, which is believed to be caused by combined homogeneous and heterogeneous precipitation of HA from the SBF. These layers do not show sufficient adhesive strength. An upside down arrangement of the samples result in the formation of up to 5–10 μm thick flat HA layers with a much higher adhesive strength, which is believed to be due to formation of HA from the SBF only by heterogeneous precipitation. Also HA layers were obtained onto all studied SAMs, SH-SAM appears to favour the formation of HA resulting in a layer with a thickness of about 10 μm and an almost stoichiometric Ca/P-ratio of the layer of 1.72. All other layers exhibit much lower ratios.     

Biomimetic synthesis of oriented hydroxyapatite mediated by nonionic surfactants

Highly oriented organization of hydroxyapatite (HAP) nanorods was achieved through a simple reflux method using mixtures of triblock copolymer pluronic P123 and tween-60 as the mediated agents. Raft-like organized complexes were prepared when the nanorods were only directed by the mixed surfactants. Bundles of nanorod-like HAP crystals were obtained when urea was used as the cosurfactant. These HAP nanorods with a large amount of uniform 4?nm worm-like mesopores were arranged in parallel to each other along the c axis of HAP. The raft-like complexes might be mediated by the reverse lamellar micelles. And the added urea transformed the reverse lamellar micelles into hexagonal ones due to its association with the surfactant molecules by hydrogen bonds, resulting in the formation of bundles of nanorod-like HAP crystals. The regulation of the oriented HAP complexes in morphology extends the understanding of biomineralization and permits controllable design of biomimetic materials. In addition, the c-axis oriented raft-like HAP complex has great potential in selective bio-absorption and separation.     

Biomimetic synthesis of hierarchical crystalline hydroxyapatite fibers in large-scale

Crystalline hierarchical hydroxyapatite [Ca₁₀(PO₄)₆(OH)₂, HAp)] fibers were successfully synthesized via a biomimetic route by using cotton cloth as a natural bio-template. The effects of pH value, aging time, ultrasonic cleaning time, and calcination temperature on the purity and morphology of the resulting hydroxyapatite (HAp) were monitored by scanning election microscope (SEM), X-ray diffraction (XRD), and infrared spectrophotometer (IR) to obtain an optimized reaction condition, namely, pH 9, ultrasonic cleaning for 1 min, aging for 24 h, and calcination at 600 °C for 4 h. We found that the natural cellulose could not only control the morphology of HAp but also lower its phase transformation temperature. The impact of this method lies in its low cost and successful production of large-scale patterning of three-dimensional hierarchical HAp fibers.     

Nanopatterned self-assembled monolayers

We report on the fabrication of chemically nanopatterned gold surfaces by combining electron-beam lithography with gas and liquid phase thiolization. The line-edge roughness of the patterns is ～4?nm, corresponding to a limiting feature size in the range of 15?nm. Indications for a lower packing density of the self-assembled monolayers grown in the nanofeatures are given, and evidences for the bleeding of thiols along the grain boundaries of the gold substrate are displayed. A comparison is provided between nanopatterned thiol and silane monolayers on gold and on silicon wafers, respectively. The line-edge roughnesses are shown to be close to each other for these two systems, indicating that the limiting step is currently the lithography step, suggesting possible improvement of the resolution. The advantages and drawbacks of thiol versus silane monolayers are finally discussed with respect to the formation of chemically nanopatterned surfaces.     

Biomimetic synthesis of hydroxyapatite/bacterial cellulose nanocomposites for biomedical applications

Hydroxyapatite (HAp) and bacterial cellulose (BC) are both excellent materials for use in biomaterial areas. The former has outstanding osteoconductivity and bioactivity and the latter is a high-strength nano-fibrous and extensively used biomaterial. In this work, the HAp/BC nanocomposites with a 3-dimensional (3-D) network were synthesized via a biological route by soaking both phosphorylated and unphosphorylated BCs in 1.5 simulated body fluid (SBF). Scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), and transmission electron microscopy (TEM) were employed to characterize the HAp/BC nanocomposites. SEM observations demonstrated that HAp crystals were uniformly formed on the phosphorylated BC fibers after soaking in 1.5 SBF whereas little HAp was observed on individual unphosphorylated BC fibers. Our experimental results suggested that the unphosphorylated BC did not induce HAp growth and that phosphorylation effectively triggered HAp formation on BC. Mechanisms were proposed for the explanation of the experimental observations. XRD and FTIR results revealed that the HAp crystals formed on the phosphorylated BC fibers were carbonate-containing with nano-sized crystallites and crystallinities less than 1%. These structural features were close to those of biological apatites.     

Biomimetic synthesis of micrometer spherical hydroxyapatite with β-cyclodextrin as template

Spherical hydroxyapatite (HA) crystals were prepared successfully with β-cyclodextrin (β-CD) as template by biomimetic method. Their properties were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscope (FTIR), thermogravimetric analyzer (TG), and scanning electron microscope (SEM). The results show that the concentration of β-CD have a significant effect on the morphology of HA crystals. Spherical HA crystals with the diameter of 1.0–3.0 μm can be obtained in the presence of 1.5% β-CD. The obtained crystals are the composites of HA/β-CD. This is a result of the interaction between HA and β-CD.     

Photo-deprotection patterning of self-assembled monolayers

Photo-deprotectable self-assembled monolayers (SAMs) provide a versatile platform for creating functional patterned surfaces. In this study, we present nanoscale photo-patterning, multi-component patterning, and a method for producing molecular gradients using photo-deprotectable SAMs. Nanoscale patterning of photo-deprotectable SAMs was achieved by coupling a UV laser (365 nm) through a scanning near field probe to produce nanoscale lines of ～40 nm, i.e. λ/9. Multi-component patterning was achieved by a two-stage method combining both microcontact printing and soft-UV photo-patterning. The example demonstrated in this study produced a three-component patterned surface with regions of CF₃, CH₃ and COOH/CF₃ functionality. The versatility of these photocleavable SAMs is further demonstrated by creating linear molecular gradients of two functionalities along a distance of ～25 mm. The use of ‘soft’ UV gives several advantages including the ability to pattern SAMs with micron-scale features over large areas quickly, with greater control over the photochemical reactions, and compatibility with existing lithographic facilities thus offering an effective alternative to other patterning methods such microcontact-printing or deep UV patterning.     

Modeling organic surfaces with self-assembled monolayers

The interfacial properties of organic materials are of critical importance in many applications, especially the control of wettability, adhesion, tribology, and corrosion. The relationships between the microscopic structure of an organic surface and its macroscopic physical properties are, however, only poorly understood. This short review presents a model system that has the ease of preparation and the structural definition required to provide a firm understanding of interfacial phenomena. Long-chain thiols, HS(CH₂)_nX, adsorb from solution onto gold and form densely packed, oriented monolayers. By varying the terminal functional group, X, of the thiol, organic surfaces can be created having a wide range of structures and properties. More, complex systems can be constructed by coadsorbing two or more thiols with different terminal functional groups or with different chain lengths onto a common gold substrate. By these techniques, controlled degrees of disorder can be introduced into model surfaces. We have used these systems to explore the relationships between the microscopic structure of the monolayers on a molecular and supramolecular scale and their macroscopic properties. Wettability is a macroscopic interfacial property that has proven of particular interest.     

The adhesive properties of pyridine-terminated self-assembled monolayers

The atomic force microscopy (AFM) adhesion force behaviour and contact angle titration behaviour of self-assembled monolayers (SAMs) presenting surface pyridine and substituted pyridine moieties has been investigated as a function of pH and electrolyte concentration. The pK_as of the pyridine moieties were modified through the incorporation of fluorine, chlorine and bromine substituents in the pyridyl ring. Contact angle titration and AFM adhesion force measurements were performed using aqueous phosphate buffered saline solutions over the pH range 3-9, and at concentrations of 150 mM and 0.1 mM. AFM adhesion force measurements were performed using a clean Si₃N₄ pyramidal-tipped AFM cantilever.     

Biomimetic synthesis of the composites of hydroxyapatite and chitosan–phosphorylated chitosan polyelectrolyte complex

A polyelectrolyte complex (PEC) composed of chitosan (CS) and phosphorylated chitosan (PCS) was used to encapsulate a calcium phosphate by a biomimetic method. An acidic CS (polycation) solution containing calcium and phosphate ions (Ca²⁺: 6 mM, Ca/P = 1.67) was added into a PCS (polyanion) solution leading to the formation of a polyelectrolyte complex (PEC) with nanoscopic carbonate-containing, low-crystallinity hydroxyapatite (HA) distributed evenly in the fibrils of the PEC by controlled crystal growth. The resulting composite material, PEC–HA, has a complicated porous structure that is expected to have high biocompatibility and that may be of use as materials for bone replacement and a carrier for controlled-release therapeutic agents.     

Surface mass spectrometry of biotinylated self-assembled monolayers

Biotin and biotinylated self-assembled monolayers (SAMs) on gold have been investigated using time-of-flight secondary ion mass spectrometry, direct laser desorption, laser desorption with 193 nm photoionization of ion- and laser-desorbed species, and laser desorption with vacuum ultraviolet (VUV, 118 nm) photoionization. Our results indicate that direct laser desorption and laser desorption combined with 193 nm multiphoton ionization can detect a chromophoric molecule like biotin that is covalently bound to a SAM. However, secondary ion mass spectra were dominated by fragmentation, and ion desorption/193 nm photoionization detected no species related to biotin. The dominant features of the laser desorption/VUV mass spectra were neat and Au-complexed dimers of intact and fragmented biotinylated SAM molecules. Multiphoton and single-photon ionization of laser-desorbed neutrals from biotinylated SAMs both led to the production of ions useful for chemical analysis of the monolayer. Multiphoton ionization with ultraviolet radiation was experimentally less challenging but required a chromophore for ionization and resulted in significant fragmentation of the adsorbate. Single-photon ionization with VUV radiation was experimentally more challenging but did not require a chromophore and led to less fragmentation. X-ray photoelectron spectra indicated that the biotinylated SAM formed a disordered, 40-60 ? thick monolayer on Au. Additionally, projection photolithography with a Schwarzschild microscope was used to pattern the biotinylated SAM surface and laser desorption/photoionization was used to detect biotinylated adsorbates from the ～10 μm sized pattern.     

Immobilization of methylene blue on self-assembled iodine monolayers on gold

The immobilization of methylene blue (MB) on iodine-covered Au(111) is studied by electrochemical techniques, scanning tunneling microscopy (STM), Auger Electron Spectroscopy (AES), and Raman spectroscopy. Results show that MB species are efficiently adsorbed on the square root of 3 x square root of 3 R30 degrees I lattice on Au(111). The electrochemical behavior of the adsorbed MB molecules is reversible, indicating a relatively fast electron transfer from the Au(111) surface to the immobilized MB species through the iodine layer. STM images with molecular resolution are consistent with adsorption of MB dimers on a square root of 3 x square root of 3 R30 degrees I lattice placed atop of the Au(111) substrate. Results are compared to those obtained for MB immobilized on Au(111) covered by S(n) (n = 3-8) surface structures.     

Antibody arrays prepared by cutinase-mediated immobilization on self-assembled monolayers

Antibody arrays hold considerable potential in a variety of applications including proteomics research, drug discovery, and diagnostics. Many of the schemes used to fabricate the arrays fail to immobilize the antibodies at a uniform density or in a single orientation; consequently, the immobilized antibodies recognize their antigens with variable efficiency. This paper describes a strategy to immobilize antibodies in a single orientation, with a controlled density, using the covalent interaction between cutinase and its suicide substrate. Protein fusions between cutinase and five antibodies of three different types (scFv, V(HH), and FN3) were prepared and immobilized upon self-assembled monolayers (SAMs) presenting a phosphonate capture ligand. The immobilized antibodies exhibit high affinity and selectivity for their target antigens, as monitored by surface plasmon resonance and fluorescence scanning. Furthermore, by changing the density of capture ligand on the SAM the density of the immobilized antibody could be controlled. The monolayers, which also present a tri(ethylene glycol) group, are inert to nonspecific adsorption of proteins and allow the detection of a specific antigen in a complex mixture. The demonstration of cutinase-directed antibody immobilization with insert SAMs provides a straightforward and robust method for preparing antibody chips.     

Biomimetic patterning of polymer hydrogels with hydroxyapatite nanoparticles

We report here an in situ process to produce nano-composite polymer hydrogels having surfaces patterned with hydroxyapatite (HA) nanoparticles (100 nm). Poly (vinyl alcohol) (PVA) has been used as a hydrogel forming medium. A three step process, comprising precipitation of HA nanoparticles in presence of PVA molecules and freeze thawing of obtained PVA-HA emulsion, followed by critical point drying, has been devised to produce three dimensional nanocomposite hydrogels. Interaction of Ca²⁺ with oxygen atoms of PVA and the hydrogen bonding characteristic of the polymer have been exploited to have controlled size distribution of HA in a continuous and macroporous network of PVA. A systematic variation in the polymer concentration could be correlated with microstructural features of the hydrogel.     

Immobilisation of cobaltferritin onto gold electrode based on self-assembled monolayers

The iron storage protein, ferritin, has a cavity of ～7?nm in diameter in which iron is oxidised and stored as a hydrated oxide core. Electron transfer is known to be an important step in the sequestering of iron by cellular ferritin. The cavity was used as a nanocontainer to grow cobalt nanoparticles. The immobilisation of ferritin on the electrode surface is essential for various bioelectronic applications. A cobaltferritin-immobilised electrode based on self-assembled monolayer (SAM)-modified gold electrode was developed. The cobaltferritin-immobilised SAM-modified electrode was characterised by electrochemical and atomic force microscopy (AFM) techniques. The results indicated that cobaltferritin was selectively immobilised onto succinimidyl alkanedisulfide-modified Au electrode by the covalent interaction between cobaltferritin and the terminal functional groups of the SAMs. The cobaltferritin immobilised modified electrode showed a direct electron transfer reaction between cobaltferritin and the electrode. The electrochemically regulated uptake and release of cobalts for cobaltferritin immobilised on the SAMs were demonstrated. The results obtained in this study indicate that cobaltferritin has potential for a biomaterial in nanoscale synthesis for potential magnetic, catalytic and biomedical-sensing applications.     

Molecular dynamics studies of microscopic wetting phenomena on self-assembled monolayers

Molecular dynamics calculations have been used to investigate the behavior of overlayers of water or n-alkane fluids on solid surfaces formed from “self-assembled” monolayers of long-chain hydrocarbons. A microscopic analog of the wetting contact angle is used to measure the surface wetting characteristics. On a nonpolar surface, formed by close packed chains having -CH₃ tailgroups, the water molecules aggregate to form a compact droplet. The calculated contact angle of the droplet is similar to experimental values for macroscopic water droplets. Contrary to intuition, the overlayers of hexadecane or decane form droplets with smaller contact angles on the same surface. However, the calculated contact angles are again in reasonable accord with experimental values.     

Temperature-dependent surface potentials of fluorinated alkanethiolate self-assembled monolayers

Self-assembled monolayers (SAMs) consisting of twenty-two carbon, methyl-terminated alkanethiolates adsorbed on vapor-deposited gold have been fluorinated in vacuum using an effusive F atom source. The reactive uptake of fluorine as a function of F atom exposure was calibrated using X-ray photoelectron spectroscopy. The surface potentials (V_s) of SAMs that were fluorinated to different degrees were measured as a function of temperature using a high-sensitivity vibrating probe electrostatic voltmeter. The surface potential grew increasingly negative with increasing fluorine uptake, reflecting the charge asymmetry that is induced in the alkanethiolate chains as a result of the substitution of fluorine for hydrogen. The V_s of the most highly fluorinated SAMs displayed a negative temperature dependence. This observation may be indicative of a pyroelectric effect in these monolayers although a definitive conclusion awaits further measurements.