Crystallization on surfaces of well-defined topography

Single crystals of calcite with regular patterned surfaces comprising close-packed arrays of hemispherical cavities or domes were produced by crystallization on colloidal monolayers or PDMS replicas of these monolayers, respectively. Perfect replication of the substrate topography was achieved for all colloidal particles, irrespective of their size and surface chemistry when the substrate geometry permitted unrestricted ion flow to the growing crystal. This work demonstrates that crystallization within a mould provides a very general route to producing single crystals with curved surfaces and unusual morphologies and that such patterning can be applied from the micro- to the nanoscale.     

Tuning intermolecular attraction to create polar order and one-dimensional nanostructures on surfaces

This study utilizes atomic force microscopy and electrostatic force microscopy to investigate the orientation of overcrowded aromatics in films with submonolayer coverage. The results demonstrate that the side chains in the molecules can be used as a tool to control the molecular order and orientation in thin films. For molecules that do not self-associate well, the interaction with the substrate dominates, and the molecules orient with their aromatic planes parallel to the surface. These monolayers have measurable polar order. For molecules that self-associate well, the opposite orientation is observed. These films are comprised of isolated stacks of molecules parallel to the surface.     

Glyphosate and glufosinate detection at electrogenerated NiAl-LDH thin films

An amperometric sensor based on Ni_1−xAl_x(OH)₂NO_3x·nH₂O layered double hydroxide (LDH) has been developed for the electrochemical analysis in one step of two herbicides: glyphosate (N-(phosphonomethyl)glycine, Glyp) and glufosinate ((DL-homoalanine-4-yl)-methylphosphinic acid, Gluf). NiAl-LDH was prepared by coprecipitation or by electrodeposition at the Pt electrode surface. Inorganic films were fully characterized by X-ray diffraction, Raman spectroscopy and scanning electron microscopy. Adsorption isotherms of Glyp onto this inorganic lamellar material have been established. Electrocatalytic oxidation of Glyp and Gluf is possible at the Ni³⁺ centres of the structure. The electrochemical responses of the NiAl-LDH modified electrode were obtained by cyclic voltammetry and chronoamperometry at 0.49 V/SCE as a function of herbicide concentration in 0.1 M NaOH solution. The electrocatalytic response showed a linear dependence on the Glyp concentration ranging between 0.01 and 0.9 mM with a detection limit of 1 μM and sensitivity 287 mA/M cm². The sensitivity found for Gluf was lower (178 mA/M cm²).     

Biosensors based on immobilization of biomolecules by electrogenerated polymer films

The concept and potentialities of electrochemical procedures of biomolecule immobilization are described. The entrapment of biomolecules within electropolymerized films consists of the application of an appropriate potential to an electrode soaked in an aqueous solution containing monomer and biomolecules. This method of biosensor construction is compared with a two-step procedure based on the adsorption of an aqueous amphiphilic pyrrole monomer-biomolecule mixture on an electrode followed by the electropolymerization of the adsorbed monomers. Another approach is based on the electrogeneration of polymer films functionalized by specific groups allowing subsequently the attachment of biomolecules. The immobilization of biomolecules on these films by covalent binding or noncovalent interactions is described.     

Study of complement activation on well-defined surfaces using surface plasmon resonance

It has been accepted that covalent immobilization of C3b on artificial materials is the most important step to initiate the complement activation. However, there are few studies that have directly demonstrated covalent immobilization of C3b on artificial surfaces. In this study, model thin layers were prepared by the self-assembled monolayer method to produce a surface covered with hydroxyl or methyl groups using mercaptododecane (CH₃-SAM) and mercaptoundecanol (OH-SAM). Interactions of the complement system with the model surfaces were studied using a surface plasmon resonance instrument. The OH-SAM immobilized C3b, resulting in activating of the complement system through the alternative pathway in Veronal-buffered saline, but this surface did not activate the classical pathway. However, the OH-SAM could not activate the alternative pathway in Veronal-buffered saline containing 10 mM EGTA and 2 mM MgCl₂ that is believed not to interfere with the activation of the alternative pathway. The hydrophobic CH₃-SAM surface could not activate the classical pathway, but activated the alternative pathway, although the extent was small.     

Use of electrochemical deposition to create randomly rough surfaces and roughness gradients

A novel approach to reproducibly generating randomly rough surfaces over large areas and generating surface roughness gradients is presented. By tuning the electrochemical deposition potential for silver onto an electrode, the island nucleation density can be systematically varied resulting in thin films of different roughness. We find that the potential range that significantly influences the surface roughness also corresponds to a reaction/mixed-controlled deposition regime. The roughness can be replicated onto other moldable materials, thus enabling future studies involving the effect of surface roughness.     

Nanoscale evaluation of lubricity on well-defined polymer brush surfaces using QCM-D and AFM

For preparing a “highly lubricated biointerface”, which has both excellent lubricity and biocompatibility, we investigated the factors responsible for resistance to friction during polymer grafting. We prepared poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), poly(2-hydroxyethyl methacrylate) (PHEMA), and poly(methyl methacrylate) (PMMA) brush layers with high graft density and well-controlled thickness using atom transfer radical polymerization (ATRP). We measured the water absorptivity in the polymer brush layers and the viscoelasticity of the polymer-hydrated layers using a quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. The PMPC brush layer had the highest water absorptivity, while the PMPC-hydrated layer had the highest fluidity. The friction properties of the polymer brush layers were determined in air, water, and toluene by atomic force microscopy (AFM). The friction on each polymer brush decreased only when a good solvent was chosen for each polymer. In conclusion, the brush layer possessing high water absorptivity and fluidity in water contributes to reduce friction. PMPC grafting is an effective and promising method for obtaining highly lubricated biointerfaces.     

Post-modification of poly(pentafluorostyrene): a versatile "click" method to create well-defined multifunctional graft copolymers

This communication reports a versatile post-modification reaction of poly(pentafluorostyrene) building blocks in order to design multifunctional graft copolymers by taking advantage of the selective replacement of the para-fluorine groups.     

Thin metal films on quasicrystalline surfaces

Thin metal films with a thickness of one or over one monolayer formed on quasicrystalline surfaces were studied using reflection high-energy electron diffraction, X-ray photoelectron spectroscopy, X-ray photoelectron diffraction and scanning tunneling microscopy. The substrates were the 10f surface of d-Al–Ni–Co and the 5f surface of i-Al–Pd–Mn. The metals deposited were Au, Pt, Ag and In. None of these metals forms any ordered layer by deposition onto clean quasicrystalline surfaces. However, if a submonolayer of In is present atop the 10f surface, an epitaxial layer of multiply-twinned AuAl₂ crystals is formed by Au deposition and subsequent annealing. This is also the case for Pt deposition, but not for Ag deposition. Although the surfactant effect of In is also observed in the case of Au deposition on the 5f surface of i-Al–Pd–Mn, the ordered layer formed is a film of Au–Al alloy with icosahedral symmetry. No ordered films are formed by Pt or Ag deposition onto the 5f surface, regardless of the presence of an In-precovered layer. A Sn film monolayer induced by surface diffusion was also studied.     

Block copolymer films on patterned surfaces

We present results from a numerical study of a coarse-grained model of diblock copolymer (BCP) thin films cast on a chemically patterned surface. The patterned surface contains chemical inhomogeneities with a repeat spacing length scale comparable to the linear size of the BCP molecules. We find that the orientation of the lamellae in the thin film and the overlap of the film morphology with the preassigned surface pattern is strongly influenced by the commensurability between the bulk unconstrained lamellar size λ^*, and the linear size of the surface inhomogeneities w. PACS Numbers: 64.60.Cn, 61.41.+e, 64.60.My, 64.75.+g. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3127–3136, 1998     

Wetting films on chemically patterned surfaces

The behavior of thin wetting films on chemically patterned surfaces was investigated. The patterning was performed by means of imprinting of micro-grid on methylated glass surface with UV-light (λ=184.8 nm). Thus imprinted image of the grid contained hydrophilic cells and hydrophobic bars on the glass surface. For this aim three different patterns of grids were utilized with small, medium and large size of cells. The experiment showed that the drainage of the wetting aqueous films was not affected by the type of surface patterning. However, after film rupturing in the cases of small and medium cells of the patterned grid the liquid from the wetting film underwent fast self-organization in form of regularly ordered droplets covering completely the cells of the grid. The droplets reduced significantly their size upon time due to evaporation. In the cases of the largest cell grid, a wet spot on the place of the imprinted grid was formed after film rupturing. This wet spot disassembled slowly in time. In addition, formation of a periodical zigzag three-phase contact line (TPCL) was observed. This is a first study from the planned series of studies on this topic.     

Differential receptors create patterns diagnostic for ATP and GTP

Herein we report the combination of a library of resin-bound sensors along with a multicomponent sensor array. This novel combinatorial array sensor system shows selectivity for nucleotide phosphates in solution. The design of the anchored receptor includes a 1,3,5-trisubstituted-2,4,6-triethylbenzene scaffold coupled with peptide libraries. Each chemosensor is placed into a micromachined cavity within a silicon wafer, and the optical changes observed by a charged-coupled device result in near-real-time digital analysis of solutions. A colorimetric displacement assay was performed, and time-dependent imaging studies of the selected sensing ensembles result in a differential responses upon addition of adenosine 5'-triphosphate (ATP), adenosine 5'-monophosphate (AMP), or guanosine 5'-triphosphate (GTP). An advantage to this approach is that it creates an array of sensors that gives a fingerprint response for each analyte. Principal component analysis indicates that the library of chemosensors can differentiate between ATP, GTP, and AMP. On the basis of factor loading values, individual sensors from the library were sequenced to elucidate their chemical composition.     

Assembled monolayers of Mo3S4(4+) clusters on well-defined surfaces

A class of inorganic monolayers formed by assembling the molybdenum-sulfur cluster, Mo3S4(4+), onto a well-defined Au(111) surface is presented. The monolayers have been comprehensively characterized by electrochemistry, X-ray photoelectron spectroscopy (XPS), and in situ scanning tunneling microscopy (in situ STM). The voltammetric data show strong reductive and oxidative desorption signals from Au-S interactions, supported by the presence of both S and Mo signals in XPS. In situ STM shows many small pits in the dense adlayers uniformly spread over the surface, which is a typical feature of self-assembled monolayers (SAMs) of alkanethiols. The density of the pits is ca. 23 (+/-5)% and is significantly higher than for straight-chain alkanethiol SAMs with a single -SH group. The pit shapes are irregular, suggesting multiple Au-S interactions from Mo3S4(4+). High resolution images disclose bright round spots of ca. 8 A diameter representing individual molecules in the SAM. This is the first example of in situ monolayer formation by a metal-chalcogenide cluster directly anchored onto the gold surface through core ligands and offers a simple way to prepare a new class of functionalized inorganic monolayers.     

Microfluidic lithography of SAMs on gold to create dynamic surfaces for directed cell migration and contiguous cell cocultures

A straightforward, flexible, and inexpensive method to create patterned self-assembled monolayers (SAMs) on gold using microfluidics-microfluidic lithography-has been developed. Using a microfluidic cassette, alkanethiols were rapidly patterned on gold surfaces to generate monolayers and mixed monolayers. The patterning methodology is flexible and, by controlling the solvent conditions and thiol concentration, permeation of alkanethiols into the surrounding PDMS microfluidic cassette can be advantageously used to create different patterned feature sizes and to generate well-defined SAM surface gradients with a single microfluidic chip. To demonstrate the utility of microfluidic lithography, multiple cell experiments were conducted. By patterning cell adhesive regions in an inert background, a combination of selective masking of the surface and centrifugation achieved spatial and temporal control of patterned cells, enabling the design of both dynamic surfaces for directed cell migration and contiguous cocultures. Cellular division and motility resulted in directed, dynamic migration, while the centrifugation-aided seeding of a second cell line produced contiguous cocultures with multiple sites for heterogeneous cell-cell interactions.     

Optical and physical properties of cobalt oxide films electrogenerated in bicarbonate aqueous media

For the first time, cobalt oxide films that are highly protective against localized corrosion and depicting a wide variety of bright and uniform colors due to light interference, have been successfully electrogenerated on polycrystalline cobalt disk electrodes under potentiostatic polarization in a mild aqueous bicarbonate medium. Open circuit potential measurements have shown the formation of a film with a bilayered structure, organized as a thin Co3O4 outer layer and a thick CoO inner layer. The existence of Co3O4 as a thin outer layer, previously postulated from galvanostatic reduction experiments, has been confirmed from XPS analysis. Raman spectroscopy, performed using a very low laser intensity, has shown that the films are mainly composed of CoO. The broadness of the Raman bands observed is associated to the amorphous character of the film, a result that has been confirmed by spectroscopic ellipsometry and X-ray diffraction analysis. Overall film thicknesses, well controlled by the anodization duration, were determined and correlated using mechanical (atomic force microscopy and profilometry) and spectroscopic (specular UV-vis-NIR reflectance and ellipsometry) techniques. Spectroscopic ellipsometry, using a simple amorphous dispersion model, has proved efficient for measuring thicknesses of films ranging from 31 to 290 nm with very low standard deviations. The real part of the complex refractive indices of these films, ranging from 1.8 to 2.2 (at lambda = 632.8 nm) depending on the anodization duration, is in good agreement with values reported in the literature for CoO. The film with the highest refractive index, and consequently the more densely packed structure, was obtained following a 30-minute anodization period.     

Synthesis of well-defined hyperbranched polymers bio-based on multifunctional phenolic acids and their structure-thermal property relationships

A number of multifunctional ABx-type monomers exist in plant metabolites, and studies on the formation of hyperbranching polymers from ABx-type monomers are very significant in the development of bio-related polymeric materials. We established a method for the preparation of well-defined structures in bio-based, hyperbranched (HB) polyarylates by the copolycondensation of caffeic acid (DHCA) as an AB₂-monomer and p-coumaric acid (4HCA) as an AB-monomer, using the highly efficient catalyst Na₂HPO₄ to regulate the polymerization speed. ¹H NMR analysis revealed the time course of the formation of the hyperbranching structures. which strongly affected the glass transition and degradation temperatures, as well as the molecular weight and composition.