All-optical patterning of Au nanoparticles on surfaces using optical traps

The fabrication of nanoscale devices would be greatly enhanced by "nanomanipulators" that can position single and few objects rapidly with nanometer precision and without mechanical damage. Here, we demonstrate the feasibility and precision of an optical laser tweezer, or optical trap, approach to place single gold (Au) nanoparticles on surfaces with high precision (approximately 100 nm standard deviation). The error in the deposition process is rather small but is determined to be larger than the thermal fluctuations of single nanoparticles within the optical trap. Furthermore, areas of tens of square micrometers could be patterned in a matter of minutes. Since the method does not rely on lithography, scanning probes or a specialized surface, it is versatile and compatible with a variety of systems. We discuss active feedback methods to improve positioning accuracy and the potential for multiplexing and automation.     

Plasma induced patterning of polydimethylsiloxane surfaces

We report on a plasma-based method to fabricate chemical and physical patterns on polydimethylsiloxane (PDMS) surfaces. A copper TEM grid was placed on cured, planar (2D) and periodic (3D) PDMS surfaces, and the samples exposed to a low-pressure “air” plasma. The pattern of the grid was precisely replicated, forming hydrophilic channels only where the grid wires contacted the PDMS surface. Exposed regions of the surface between the mesh wires were not chemically modified and retained their hydrophobic character. This plasma-based procedure provides a simple, fast, and inexpensive method for creating patterned chemical functionalities on 2D and 3D PDMS surfaces for directed assembly and for the development of micro-scale sensors and bio-chip devices.     

A general method for patterning gradients of biomolecules on surfaces using microfluidic networks

This report outlines a general method for the fabrication of immobilized gradients of biomolecules on surfaces. This method utilizes a microfluidic network that generates a gradient of avidin in solution and immobilizes this protein on the surface of glass or poly(dimethylsiloxane) by physical adsorption. The immobilized gradient of avidin is then translated into gradients of biotinylated ligands (e.g., small molecules, oligomers of DNA, polysaccharides) using the specific interaction between biotin and avidin. This method can also generate immobilized gradients of certain proteins and artificial polymers by a direct transfer of gradients from solution onto the surface. The major advantage of this method is that almost any type of molecule can, in principle, be immobilized in a well-defined surface gradient of arbitrary shape with dimensions of a few micrometers to a few centimeters. It is possible to tailor the precise shapes of gradients on surfaces from gradients in solution, either kinetically or competitively. Kinetic methods rely on controlling the time that the surface is exposed to the gradient in solution: when a single protein adsorbs from solution, the amount that adsorbs depends both on its concentration in solution and on the time allowed for adsorption. Competitive methods rely on exposure of the surface to a complementary gradient of two proteins in solution (In these experiments, the sum of the concentrations of the proteins in solution is independent of positions although the concentration of each, individually, depends on the position. In this procedure, the relative amount of each protein, at saturation on the surface, depends only on its concentration.).     

Solvent-mediated repair and patterning of surfaces by AFM

A tip-based approach to shaping surfaces of soluble materials with nanometer-scale control is reported. The proposed method can be used, for example, to eliminate defects and inhomogeneities in surface shape, repair mechanical or laser induced damage to surfaces, or perform 3D lithography on the length scale of an AFM tip. The phenomenon that enables smoothing and repair of surfaces is based on the transport of material from regions of high to low curvature within the solution meniscus formed in a solvent-containing atmosphere between the surface in question and an AFM tip scanned over the surface. Using in situ AFM measurements of the kinetics of surface remodeling on KDP (KH(2)PO(4)) crystals in humid air, we show that redistribution of solute material during relaxation of grooves and mounds is driven by a reduction in surface free energy as described by the Gibbs-Thomson law. We find that the perturbation from a flat interface evolves according to the diffusion equation, where the effective diffusivity is determined by the product of the surface stiffness and the step kinetic coefficient. We also show that, surprisingly, if the tip is instead scanned over or kept stationary above an atomically flat area of the surface, a convex structure is formed, with a diameter that is controlled by the dimensions of the meniscus, indicating that the presence of the tip and meniscus reduces the substrate chemical potential beneath that of the free surface. This allows one to create nanometer-scale 3D structures of arbitrary shape without the removal of substrate material or the use of extrinsic masks or chemical compounds. Potential applications of these tip-based phenomena are discussed.     

Simultaneous observation of enzyme surface diffusion and surface reaction using microfluidic patterning of substrate surfaces

We present a study of the simultaneous observation of protease reaction and surface diffusion as the enzyme interacts with a model substrate surface. We use micro-fluidic patterning to decorate a bovine serum albumin substrate surface with stripes of adsorbed enzyme in the absence of physical barriers. Spreading of the enzyme from the initial striped region indicates surface diffusion, while removal of the substrate provides a measure of reactivity. Microfluidic patterning provides a means to determine the relative importance of enzyme adsorption, surface diffusion, and reaction on the rate of substrate removal.     

Controlled modulation of laser beam and dynamic patterning of colloidal particles using optical tweezers

We present controlled generation of complex-structured beam profiles using diffractive optical element and demonstrate multiple dynamic trapping of colloidal particles. The phase element is programmed to generate various tailored optical fields having structures, similar to that of number three, spiral, and circle but in a tractable manner. Thus, the generated spatially tailored optical fields are confined to focal volume in optical tweezers. This enabled real-time trapping of multiple microscopic objects whereby its transverse organization was controlled in a dynamic manner from one structure to another with the help of spatial light modulator. Such a controlled beam shaping finds potential applications in biophotonics, super resolution imaging, and measurement of biophysical parameters, cell sorting, and micro-manipulation of colloidal particles.     

PECVD coatings for functionalization of point-of-care biosensor surfaces

In early stage disease diagnosis, an accurate and reliable measurement of low concentrations of specific biomarkers is a key need. The detection technique requires the reaction of an antibody, which is generally covalently bound to the biosensor platform, with its antigen. The application of Zeonor^®, a cyclo olefin copolymer (COP) with very low autofluorescence, good optical properties and high precision molding characteristics, as a biosensor platform has been demonstrated recently. Highly reproducible, industrial scale surface chemical modification of the COP plastic for covalent attachment of the biomolecules for specific recognition of the target, together with low non-specific binding of other proteins that may be present in the sample is a key challenge. In this work, the applicability of plasma enhanced chemical vapor deposition (PECVD) process has been demonstrated by depositing varying surface functionalities including amines, carboxylic, mercapto, epoxy and polyethylene glycol functionalities. The plasma functionalized coatings thus created possess both reactive and repellent sites on the biosensor chip, allowing the chip to be configured either for fluorescence or light scattering-based detection or for label-free surface plasmon resonance detection techniques. The versatility of the gas phase deposition process for building sequential chemistries on low cost and disposable plastic chips is presented in detail.     

Refractive-index patterning of tellurite glass surfaces by laser spot heating

A dot pattern of a refractive-index change was formed by spot heating with laser-beam irradiation on sodium tellurite glasses. The 15Na(2)O . 85TeO(2) (mol. %) glass doped with 2 mol. % of CoO was irradiated by a green light-beam spot (532 nm) ~800 mum in diameter from the second-harmonic generator of a Q-switched pulsed YAG laser. The map of the refractive index of the glass was determined with an He-Ne laser beam by a scanning ellipsometric technique at a resolution of 100 mum x 50 mum, indicating that the spots possessing a refractive index lower by ~0.05 were formed at the region irradiated by the laser beam.     

Modelling of surfaces. 2. Metallic alloy surfaces using the BFS method

Summary Using the semiempirical method for alloys developed by Bozzolo, Ferrante and Smith (BFS) [Bozzolo, G. et al., Phys. Rev., B45 (1992) 493] we study the surface structure of fcc-ordered binary alloys. We concentrate on the calculation of surface energies and surface relaxations for the L1₀- and L1₂ ordered structures. Different terminations of the low-index faces are studied. Also, we present results for the interlayer relaxations for planes close to the surface, revealing different relaxations for atoms of different species producing a rippled surface layer.     

Segregation of micrometer-dimension biosensor elements on a variety of substrate surfaces

With the rapid development of micro total analysis systems and sensitive biosensing technologies, it is often desirable to immobilize biomolecules to small areas of surfaces other than silicon. To this end, photolithographic techniques were used to derivatize micrometer-sized, spatially segregated biosensing elements on several different substrate surfaces. Both an interference pattern and a dynamic confocal patterning apparatus were used to control the dimensions and positions of immobilized regions. In both of these methods, a UV laser was used to initiate attachment of a photoactive biotin molecule to the substrate surfaces. Once biotin was attached to a substrate, biotin/avidin/biotin chemistry was used to attach fluorescently labeled or nonlabeled avidin and biotinylated sensing elements such as biotinylated antibodies. Dimensions of 2-10 microm were achievable with these methods. A wide variety of materials, including glassy carbon, quartz, acrylic, polystyrene, acetonitrile-butadiene-styrene, polycarbonate, and poly(dimethylsiloxane), were used as substrates. Nitrene- and carbene-generating photolinkers were investigated to achieve the most homogeneous films. These techniques were applied to create a prototype microfluidic sensor device that was used to separate fluorescently labeled secondary antibodies.     

On the fractal dimension of fracture surfaces of concrete elements

The problem of the relation between the fractal dimension of a fractured surface and the fracture toughness expressed by the stress intensity factor is investigated. The theoretical conditions for such assumptions are discussed. Collected experimental results and new tests performed onconcrete specimens subjected to Mode II fracture seem to confirm that relation within the scope of materials tested and with certain necessary restrictions.     

Hydroquinone-based derivatization reagents for the quantitation of amines using electrochemical detection.

Two new reagents, NDTE (2,5-dihydroxyphenylacetic acid, 2,5-bis-tetrahydropyranyl ether p-nitrophenyl ester) and HLTE (homogentisic gamma-lactone tetrahydropyranyl ether), are described for the chemical derivatization of primary and/or secondary amines to form an electrochemically active product. These reagents undergo reaction with the aforementioned analytes to form a product possessing the hydroquinone moiety, thus allowing for reversible electrochemical detection at mild oxidation potentials. The reactivity of each reagent was demonstrated by using N-ethylbenzylamine (EBzA) and the dipeptide isoleucine leucine methyl ester as model analytes. The investigation included the isolation and identification of the intermediates and final products from derivatization of EBzA. These isolated standards were subsequently characterized with respect to electrochemical properties by means of cyclic voltammetry. In LC-EC experiments, the concentration limit of detection (CLOD) of the purified EBzA product was determined to be 5 nM (100 fmol) at a detection potential of +200 mV vs Ag/AgCl ([Cl-] = 3 M). The CLOD values obtained by LC-EC after derivatization of aqueous solutions of EBzA and Ile-Leu-OMe with NDTE were 25 nM (250 fmol) and 250 nM (2.5 pmol), respectively.     

Nanoscale patterning of colloidal quantum dots on transparent and metallic planar surfaces

The patterning of colloidal quantum dots with nanometer resolution is essential for their application in photonics and plasmonics. Several patterning approaches, such as the use of polymer composites, molecular lock-and-key methods, inkjet printing and microcontact printing of quantum dots have been recently developed. Herein, we present a simple method of patterning colloidal quantum dots for photonic nanostructures such as straight lines, rings and dot patterns either on transparent or metallic substrates. Sub-10?nm width of the patterned line could be achieved with a well-defined sidewall profile. Using this method, we demonstrate a surface plasmon launcher from a quantum dot cluster in the visible spectrum.     

Application of nanotechnology to control bacterial adhesion and patterning on material surfaces

Bacterial adhesion and biofilm formation on surfaces raises health hazard issues in the medical environment. Previous studies of bacteria adhesion have focused on observations in their natural/native environments. Recently, surface science has contributed in advancing the understanding of bacterial adhesion by providing ideal platforms that attempt to mimic the bacteria's natural environments, whilst also enabling concurrent control, selectivity and spatial control of bacterial adhesion. In this review, we will look at techniques of how nanotechnology is used to control cell adhesion on a planar scale, in addition to describing the use of nanotools for cell micropatterning. Additionally, it will provide a general background of common methods for nanoscale modification enabling biologist unfamiliar with nanotechnology to enter the field.     

Methodological approaches for histamine quantification using derivatization by chloroethylnitrosourea and ELISA measurement. Part II: Optimisation of the derivatization step

In a previous paper (part I), new strategy was used for raising antibodies against hapten (< 300 Da) and the quantification of these hapten by ELISA using derivatization by chloroethyl nitrosourea (CENU). After raising antibodies against histamine, they were characterized and used for ELISA measurements. Optimal detection conditions were determined for the histamine quantification by ELISA method. The present study investigates the derivatization step of the histamine by chloroethylnitrosourea (CENU). Five factors (2 qualitative: nature of the solvent and nature of the antibodies and 3 quantitative: pH, % of solvent and time of derivatization) have been considered. Optimal reaction conditions were established by calculation of a validated model.     

An electrochemical redox couple activitated by microelectrodes for confined chemical patterning of surfaces

Microelectrodes, printed as an array on the surface of a silicon chip, generate chemically active species in a solution of electrolyte held between the electrode array and a glass plate. The active species induce chemical change in molecules coupled to the surface of the glass plate, which is separated from the electrode array by a gap of several micrometers. This paper explores the nature and pattern of the induced chemical change. The patterning is discussed with respect to the electrolyte composition and the magnitude and duration of current applied to the microelectrodes. We show that under suitable conditions the active species is confined to micrometer-sized features and diffusion does not obscure the surface pattern produced.     

Refractive index patterning of tellurite glass surfaces by ultra short pulse laser spot heating

Dot patterns of refractive indices were formed by the laser pulse irradiation on the tellurite glasses. The ternary tellurite glasses of TeO₂-Na₂O-Al₂O₃, TeO₂-Na₂O-GeO₂ and TeO₂-Na₂O-TiO₂ doped with 2 mol% of CoO were irradiated by a femtosecond pulse laser beam (800 nm) or by a green light beam (532 nm) from a second harmonic generator of a Q switch pulse YAG laser. The refractive index map of the glass was composed with an He-Ne laser beam by an scanning ellipsometric technique at a resolution of 100 m × 50 m, indicating that the spots possessing refractive index lower by about 0.05–0.38 than the surroundings were formed at the region irradiated by the laser beam. The irradiation of the femtosecond laser beam generated the dot patterns roughly equivalent to the beam size. The change of refractive index could be tunable by adjusting laser power, suggesting that the process could be applied to optical recording.