Physisorbed surface coatings for poly(dimethylsiloxane) and quartz microfluidic devices

Surface modifications of microfluidic devices are of essential importance for successful bioanalytical applications. Here, we investigate three different coatings for quartz and poly(dimethylsiloxane) (PDMS) surfaces. We employed a triblock copolymer with trade name F₁₀₈, poly(l-lysine)-g-poly(ethylene glycol) (PLL-PEG), as well as the hybrid coating n-dodecyl-β-d-maltoside and methyl cellulose (DDM/MC). The impact of these coatings was characterized by measuring the electroosmotic flow (EOF), contact angle, and prevention of protein adsorption. Furthermore, we investigated the influence of static coatings, i.e., the incubation with the coating agent prior to measurements, and dynamic coatings, where the coating agent was present during the measurement. We found that all coatings on PDMS as well as quartz reduced EOF, increased reproducibility of EOF, reduced protein adsorption, and improved the wettability of the surfaces. Among the coating strategies tested, the dynamic coatings with DDM/MC and F₁₀₈ demonstrated maximal reduction of EOF and protein adsorption and simultaneously best long-term stability concerning EOF. For PLL-PEG, a reversal in the EOF direction was observed. Interestingly, the static surface coating strategy with F₁₀₈ proved to be as effective to prevent protein adsorption as dynamic coating with this block copolymer. These findings will allow optimized parameter choices for coating strategies on PDMS and quartz microfluidic devices in which control of EOF and reduced biofouling are indispensable.     

Stimuli‐Responsive Hybrid Coatings of Polyelectrolyte Multilayers and Nano‐Patterned Polymer Brushes

A new type of polymeric hybrid coating is created by layer‐by‐layer deposition of polyelectrolyte multilayers (PEM) onto nano‐patterned polymer brushes (NPB). The PEM is a hydrogen‐bonded multilayer consisting of poly(acrylic acid) and poly(acrylamide) and the NPB is derived from a surface reactive rod‐coil block copolymer, polystyrene‐block‐poly[3‐(triethoxysilyl)propylisocyanate]. The thickness of the PEM coating is optimized with respect to the height of the NPB mounds, to yield PEM/NPB hybrid coatings with unique nano‐embossed or nano‐porous structures that can be interchangeable by heating and moisture annealing. The hybrid coating is patternable by the micro‐contact printing method. The results demonstrate that the combination of surface‐bound, hydrophobic NPB layer with hydrophilic PEM films at the nanoscopic level offers a new organic hybrid coating with novel surface properties.

     

Bilayer nanocomposite molecular coatings from elastomeric/rigid polymers: fabrication,morphology, and micromechanical properties

We fabricated bilayered nanocomposite coatings composed of a hard polymer layer placed on top of an elastomeric layer. The primary layer of poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) was attached to the surface by grafting to a chemically reactive silicon surface functionalized with epoxy‐terminated SAM. The SEBS layer served as the compliant interlayer in the bilayered polymer coating. The topmost hard layer was a high performance polymer made of epoxy resin (EP) and an amino functionalized poly(paraphenylene) (PPP). We built the bilayered structure by spincoating the EP/PPP mixture on top of the grafted SEBS layer. The solidification of the topmost layer was initiated at low temperatures (40‐50°C) to avoid dewetting. The curing of the film was finished at 110°C (15 hours) and the EP/PPP layer was strongly attached to the SEBS layer. It was found that the EP/PPP layer did not penetrate inside the elastic primary layer during the solidification. The elastic response of the hard polymer layer was affected significantly by the underlying elastomeric layer. The SEBS layer served as a compliant interlayer capable of dissipating the interfacial stresses originating from dissimilarities in the physical properties between the polymer coating and the inorganic substrate.     

Perfluorophenyl azide functionalization of electrospun poly(para‐dioxanone)

Strategies to surface‐functionalize scaffolds by covalent binding of biologically active compounds are of fundamental interest to control the interactions between scaffolds and biomolecules or cells. Poly(para‐dioxanone) (PPDO) is a clinically established polymer that has shown potential as temporary implant, eg, for the reconstruction of the inferior vena cava, as a nonwoven fiber mesh. However, PPDO lacks suitable chemical groups for covalent functionalization. Furthermore, PPDO is highly sensitive to hydrolysis, reflected by short in vivo half‐life times and degradation during storage. Establishing a method for covalent functionalization without degradation of this hydrolyzable polymer is therefore important to enable the surface tailoring for tissue engineering applications. It was hypothesized that treatment of PPDO with an N‐hydroxysuccinimide ester group bearing perfluorophenyl azide (PFPA) under UV irradiation would allow efficient surface functionalization of the scaffold. X‐ray photoelectron spectroscopy and attenuated total reflectance Fourier‐transformed infrared spectroscopy investigation revealed the successful binding, while a gel permeation chromatography study showed that degradation did not occur under these conditions. Coupling of a rhodamine dye to the N‐hydroxysuccinimide esters on the surface of a PFPA‐functionalized scaffold via its amine linker showed a homogenous staining of the PPDO in laser confocal microscopy. The PFPA method is therefore applicable even to the surface functionalization of hydrolytically labile polymers, and it was demonstrated that PFPA chemistry may serve as a versatile tool for the (bio‐)functionalization of PPDO scaffolds.     

High-temperature solvent stability of sol–gel germania triblock polymer coatings in capillary microextraction on-line coupled to high-performance liquid chromatography

Germania-based sol–gel organic–inorganic hybrid coatings were prepared for on-line coupling of capillary microextraction with high-performance liquid chromatography. For this, a germania-based sol–gel precursor, tetra-n-butoxygermane and a hydroxy-terminated triblock copolymer, poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) were used. These sol–gel germania triblock polymer coatings were chemically anchored to the inner walls of a fused silica capillary (0.25 mm I.D.) in course of its evolution from the sol solution. Scanning electron microscopy images of the sol–gel germania triblock polymer coating were obtained to estimate the coating thickness. For the first time, the analyte distribution constants between a sol–gel germania organic–inorganic hybrid coating and the samples (K_cs) were determined. For a variety of analytes from different chemical classes, including polycyclic aromatic hydrocarbons (PAHs), ketones, alcohols, phenols and amines, the K_cs values ranged from 8.1 × 10¹ to 5.6 × 10⁴. Also, for the first time, the stability of the sol–gel germania-based coating in high-temperature reversed-phase solvent environment was evaluated. The sol–gel germania triblock polymer coatings were capable of surviving exposure to high-temperature solvent conditions (200 °C) with little change in extraction capabilities. This demonstrates that sol–gel germania triblock polymer hybrid materials might be suitable for further applications in high-temperature HPLC. The reproducibility of the method for preparation of the sol–gel germania triblock polymer coatings was also evaluated, and the capillary-to-capillary RSD values ranged from 5.3 to 6.5%. The use of higher flow rates in extraction was found to significantly reduce the time required (from 30–40 to 10–15 min) to reach equilibrium between the sol–gel germania triblock polymer coating and the analytes in the sample solution.     

Cope elimination and complexation of poly(dimethylaminoethyl methacrylate N-oxide)

Poly(dimethylaminoethyl methacrylate N-oxide) (poly(DMAEMNO)) was prepared by oxidation of poly(dimethylaminoethyl methacrylate) with hydrogen peroxide in methanol. From thermogravimetric and IR spectroscopic investigations Cope elimination of amine oxide group in poly(DMAENO) was found to occur at 120–150°C. The postpolymerization of partially pyrolyzed polymer carrying vinyl ester group as pendant was performed with azobisisobutyronitrile at 60°C in methanol to give cross-linked polymer that was found to form hydrogel. Poly(DMAEMNO) gave metal–polymer complexes with CuCl₂, ZnCl₂, and CoCl₂. Cobalt–polymer complex had a constitution of 1:2 of metal ion to amine oxide group, while copper– and zinc–polymer complexes seemed to have structures of 1:1 and 1:2 of metal ion to amine oxide group. Furthermore, polymer complexes of poly(DMAEMNO) with poly(methacrylic acid) and poly(acrylic acid) were found to be formed by mixing aqueous solutions of both polymers and also by radical polymerization of the acid monomers in the presence of poly(DMAEMNO). From elemental analysis, thermogravimetric investigation, and measurement of turbidity it was concluded that the resulting polymer–polymer complexes contained more than one acid monomer unit per one N-oxide unit.     

Experimental and theoretical studies on the corrosion properties of some conducting polymer coatings

In this study, the effects of poly(N-ethylaniline) (PNEA) monolayer coating and PPY/PNEA and PNEA/PPY bilayer coatings, which were formed on the low carbon steel (LCS) surface by electropolymerization in 0.1 M monomer + 0.3 M oxalic acid medium, on the corrosion of the LCS in 1 M H₂SO₄ medium have been investigated. LCS electrodes, which were coated with each of these conductive polymer layers, were held in 1 M H₂SO₄ medium for various time periods, in order to obtain current potential curves, and with the help of these curves, the corrosion parameters have been determined. Experimental findings show that the LCS coated with polymer layers prevent the corrosion of bare LCS in 1 M H₂SO₄ medium and bilayer PPY/PNEA and PNEA/PPY coatings are better than monolayer PNEA coating. In order to elucidate the interaction between the coatings and the metal, theoretical calculations have been done using AM1 semiempirical method. The calculated data have been found to support experimental findings.     

Preparation, characterization, and electrocatalytic properties of hybrid coatings of hexacyanometalate-doped-cationic films

Electrochemically active hybrid coatings based on cationic films, didodecyldimethylammonium bromide (DDAB), and poly(diallyldimethylammonium chloride) (PDDAC) are prepared on electrode surface by cycling the film-covered electrode repetitively in a pH 6.5 solution containing Fe(CN)₆ ³⁻ and Ru(CN)₆ ⁴⁻ anions. Modified electrodes exhibited stable and reversible voltammetric responses corresponding to characteristics of Fe(CN)₆ ^3−/4− and Ru(CN)₆ ^4−/3− redox couples. The cyclic voltammetric features of hybrid coatings resemble that of electron transfer process of surface-confined redox couple. Electrochemical quartz crystal microbalance results show that more amounts of electroactive anionic complexes partitioned into DDAB coating than those doped into PDDAC coating from the same doping solution. Peak potentials of hybrid film-bound redox couples showed a negative shift compared to those at bare electrode and this shift was more pronounced in the case of DDAB. Finally, the advantages of hybrid coatings in electrocatalysis are demonstrated with sulfur oxoanions.     

Nanomechanics of Poly(catecholamine) Coatings in Aqueous Solutions

Mussel‐inspired self‐polymerized catecholamine coatings have been widely utilized as a versatile coating strategy that can be applied to a variety of substrates. For the first time, nanomechanical measurements and an evaluation of the contribution of primary amine groups to poly(catecholamine) coatings have been conducted using a surface‐forces apparatus. The adhesive strength between the poly(catecholamine) layers is 30‐times higher than that of a poly(catechol) coating. The origin of the strong attraction between the poly(catecholamine) layers is probably due to surface salt displacement by the primary amine, π–π stacking (the quadrupole–quadrupole interaction of indolic crosslinks), and cation–π interactions (the monopole–quadrupole interaction between positively charged amine groups and the indolic crosslinks). The contribution of the primary amine group to the catecholamine coating is vital for the design and development of mussel‐inspired catechol‐based coating materials.     

Electrochemical Study of the Interactions of DNA with Redox‐Active Molecules Based on the Immobilization of dsDNA on the Sol‐Gel Derived Nano Porous Hydroxyapatite‐Polyvinyl Alcohol Hybrid Material Coating

A novel type of sol‐gel inorganic‐organic hybrid material coated on glassy carbon electrode used for immobilization of double‐stranded DNA (dsDNA) and study of dsDNA with redox‐active molecules was developed. The hybrid material coating was produced by sol‐gel method with nano hydroxyapatite (HAp)‐polyvinyl alcohol (PVA). The optimum composition of the hybrid material was first examined, and the morphology of the nano HAp‐PVA coatings was investigated with the help of Scanning Electron Microscope (SEM). DsDNA was immobilized in/on the nano HAp‐PVA hybrid coatings by adsorption and the characteristics of the dsDNA/HAp‐PVA/GCE were studied by cyclic voltammetry (CV) using the probes of Co(phen) and Fe(CN) . The results indicate that the dsDNA can be immobilized on the nano porous HAp‐PVA coating effectively and its stability can satisfy the necessity of study on the interactions of dsDNA with redox‐active molecules on the electrode surface. Co(bpy) and Co(phen) were used as the model molecule to study the interactions of dsDNA with redox‐active molecules. Information such as ratio (K_Ox/K_Red) of the binding constant for the oxidized and reduced forms of a bound species, interaction mode, including change in the mode of interaction, and “limiting” ratio K /K at zero ionic strength (μ) can be obtained using dsDNA/HAp‐PVA/GCE with about 2 μg of DNA samples.     

Decontamination-Induced Modification of Bioactivity in Essential Oil-Based Plasma Polymer Coatings

Plasma polymer coatings fabricated from Melaleuca alternifolia essential oil and its derivatives have been previously shown to reduce the extent of microbial adhesion on titanium, polymers, and other implantable materials used in dentistry. Previous studies have shown these coatings to maintain their performance under standard operating conditions; however, when used in e.g., a dental implant, these coatings may inadvertently become subject to in situ cleaning treatments, such as those using an atmospheric pressure plasma jet, a promising tool for the effective in situ removal of biofilms from tissues and implant surfaces. Here, we investigated the effect of such an exposure on the antimicrobial performance of the Melaleuca alternifolia polymer coating. It was found that direct exposure of the polymer coating surface to the jet for periods less than 60 s was sufficient to induce changes in its surface chemistry and topography, affecting its ability to retard subsequent microbial attachment. The exact effect of the jet exposure depended on the chemistry of the polymer coating, the length of plasma treatment, cell type, and incubation conditions. The change in the antimicrobial activity for polymer coatings fabricated at powers of 20–30 W was not statistically significant due to their limited baseline bioactivity. Interestingly, the bioactivity of polymer coatings fabricated at 10 and 15 W against Staphylococcus aureus cells was temporarily improved after the treatment, which could be attributed to the generation of loosely attached bioactive fragments on the treated surface, resulting in an increase in the dose of the bioactive agents being eluted by the surface. Attachment and proliferation of Pseudomonas aeruginosa cells and mixed cultures were less affected by changes in the bioactivity profile of the surface. The sensitivity of the cells to the change imparted by the jet treatment was also found to be dependent on their origin culture, with mature biofilm-derived P. aeruginosa bacterial cells showing a greater ability to colonize the surface when compared to its planktonic broth-grown counterpart. The presence of plasma-generated reactive oxygen and nitrogen species in the culture media was also found to enhance the bioactivity of polymer coatings fabricated at power levels of 10 and 15 W, due to a synergistic effect arising from simultaneous exposure of cells to reactive oxygen and nitrogen species (RONS) and eluted bioactive fragments. These results suggest that it is important to consider the possible implications of inadvertent changes in the properties and performance of plasma polymer coatings as a result of exposure to in situ decontamination, to both prevent suboptimal performance and to exploit possible synergies that may arise for some polymer coating-surface treatment combinations.     

Development of Passive and Active Barrier Coatings on the Basis of Inorganic–Organic Polymers

Summary. With a new kind of barrier coating material, namely inorganic–organic polymers, it is possible to obtain excellent barrier properties against oxygen, water vapor, and flavor permeation. These hybrid polymers can be synthesized by the sol–gel technique. If extremely low permeation values are needed, the combination of hybrid polymer coatings with thin inorganic oxidic layers (SiO_x, AlO_x) is very effective and leads to permeation values for oxygen and water vapor below 10⁻³ cm³/m² · d · bar or g/m² · d. These passive barrier layers can be further improved by the combination with active oxygen barrier layers which have been developed for the food packaging industry. This approach makes these multilayer laminates promising candidates for special applications in the food packaging industry as well as for sophisticated applications in technical areas: the encapsulation of sensitive organic devices like solar cells, organic light emitting diodes, or polymer electronic systems.     

Function and performance of silicone copolymer (VI). Synthesis and novel solution behavior of water-soluble polysiloxanes with different hydrophiles

Silicone surfactants containing different pendant hydrophilic groups such as diethanol tertiary amine (SHE, nonionic), diethanol methyl quaternary amine (cationic) and triethyl quaternary amine (cationic) have been synthesized and characterized by ¹H and ¹³C NMR and gel permeation chromatography. The solution behavior of these novel surfactants has also been investigated by surface tension measurement and a fluorescence method. It has been observed that the surface tension of these surfactants decreases as a function of time at a very low polymer concentration (1 × 10⁻⁴ wt%). At higher concentration (0.1 wt%), the equilibrium surface tensions reached very low values compared to that of typical polymer surfactants, for example, poly(ethylene oxide–propylene oxide) block copolymer (EPE0.8). In addition, the low I ₁/I ₃ values of these silicone surfactants indicate the formation of polymer aggregates in aqueous solution, and an extremely low I ₁/I ₃ value of SHE (1.06) compared to other polymeric surfactants (EPE0.8) and conventional surfactants [poly(ethylene glycol n-nonyl phenyl ethers), cetyltrimethylammonium bromide, and sodium dodecyl sulfate] indicates its stronger hydrophobicity. Received: 15 May 2000 Accepted: 18 October 2000     

Synthesis and characterizations of anion exchange organic-inorganic hybrid materials based on poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)

A series of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based organic-inorganic hybrid materials for anion exchange were prepared through sol-gel process of polymer precursors PPO-Si(OCH₃)₃. PPO-Si(OCH₃)₃ were obtained from the reaction of bromomethylated PPO with 3-aminopropyl-trimethoxysilane (A1110). These polymer precursors then underwent hydrolysis and condensation with additional A1110 to generate hybrid materials. The reaction to produce polymer precursors was identified by FTIR; while FTIR, TGA, XRD, SEM, as well as conventional ion exchange capacity (IEC) measurements were conducted for the structures and properties of the prepared hybrids. TGA results show that this series of hybrid materials possess high thermal stability; XRD and SEM indicate that the prepared hybrid materials are amorphous and the inorganic and organic contents show good compatibility if the ratio between them is proper. The IEC values of the hybrid materials due to the amine groups range from 1.13 mmol/gBPPO (material i) to 4.80 mmol/gBPPO (material iv).     

Reversible addition–fragmentation chain transfer synthesis of amidine‐based,CO2‐responsive homo and AB diblock (Co)polymers comprised of histamine and their gas‐triggered self‐assembly in water

Well‐defined homopolymers of pentafluorophenyl acrylate (PFPA) and AB diblock copolymers of N,N‐dimethylacrylamide (DMA) and poly(ethylene glycol) methyl ether acrylate (PEGA) with PFPA were prepared by reversible addition–fragmentation chain transfer (RAFT) radical polymerization. Three PFPA homopolymers of different molecular weights were reacted with the commercially available amidine and guanidine species histamine (HIS) dihydrochloride and L ‐arginine methyl ester (ARG) dihydrochloride in the presence of S‐methyl methanethiosulfonate to yield, quantitatively, the corresponding amidine and guanidine‐based acrylamido homopolymers. Both the HIS and ARG homopolymers are known to reversibly bind CO₂ with, in the case of the former, CO₂ fixation being accompanied with a switch from a hydrophobic to hydrophilic state. The RAFT synthesis of PFPA‐DMA and PEGA‐PFPA diblock copolymers yielded well‐defined materials with a range of molar compositions. These precursor materials were converted to the corresponding HIS and ARG block copolymers whose structure was confirmed using ¹H NMR spectroscopy. Employing a combination of dynamic light scattering and transmission electron microscopy, we demonstrate that the DMA‐HIS and PEGA‐HIS diblock copolymers are able to undergo reversible and cyclable self‐directed assembly in aqueous media using CO₂ and N₂ as the triggers between fully hydrophilic and amphiphilic (assembled) states. For example, in the case of the 54:46 DMA‐HIS diblock, aggregates with hydrodynamic diameters of about 40.0 nm are readily formed from the molecularly dissolved state. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Efficient and robust coatings using poly(2-methyl-2-oxazoline) and its copolymers for marine and bacterial fouling prevention

Molecular design, fabrication, and properties of thin-film coatings based on poly(2-methyl-2-oxazoline) (PMOX) and its copolymers were investigated to tackle problem of marine and bacterial fouling prevention. The ultraviolet crosslinkable macromonomer poly(2-methyl-2-oxazoline) dimethylacrylate was synthesized by cationic ring-opening polymerization in a microwave reactor initiated by 1,4-dibromobutane. In order to study the charge effect of the PMOX coatings on the adhesion of fouling organisms, PMOX surfaces with negative, neutral, and positive ζ-potential values were prepared by copolymerization with the positively charged monomer [2-(methacryloyloxy)-ethyl]trimethylammonium chloride. The coatings were stable in sea water for at least 1 month without significant reduction in the film thickness. The marine antifouling activity was evaluated against barnacle cyprids Amphibalanus amphitrite and algae Amphora coffeaeformis. Results showed that PMOX coatings provide effective reduction of the settlement regardless of the molar mass and surface charge of the polymer. Bacterial adhesion test showed that PMOX coatings effectively reduce Staphylococcus aureus and Escherichia coli adhesion. Owing to its good stability and antifouling activity PMOX has a great potential as antifouling coating for marine antifouling applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 275–283     

Influence of polyelectrolyte capillary coating conditions on protein analysis in CE

CE of biomolecules is limited by analyte adsorption on the capillary wall. To prevent this, monolayer or successive multiple ionic‐polymer layers (SMILs) of highly charged polyelectrolytes can be physically adsorbed on the inner capillary surface. Although these coatings have become commonly used in CE, no systematic investigation of their performance under different coating conditions has been carried out so far. In a previous study (Nehmé, R., Perrin, C., Cottet, H., Blanchin, M. D., Fabre, H., Electrophoresis 2008, 29, 3013–3023), we investigated the influence of different experimental parameters on coating stability, repeatability and peptide peak efficiency. Optimal coating conditions for monolayer and multilayer (SMILs) poly(diallyldimethylammonium) chloride/ poly(sodium 4‐styrenesulfonate) coated capillaries were determined. In this study, the influence of polyelectrolyte concentration and ionic strength of the coating solutions, and the number of coating layers on coating stability and performance in limiting protein adsorption was carried out. EOF magnitude and repeatability were used to monitor coating stability. Coating ability to limit protein adsorption was investigated by monitoring variations of migration times, time‐corrected peak areas and separation efficiency of test proteins. The separation performance of polyelectrolyte coatings were compared with those obtained with bare silica capillaries.     

Combinatorial and high-throughput screening of the effect of siloxane composition on the surface properties of crosslinked siloxane-polyurethane coatings

Libraries of siloxane-polyurethane coatings were designed, formulated, and screened using high-throughput experimentation. Four independent variables that were analyzed were the molecular weight of poly(dimethylsiloxane) (PDMS), presence or absence of poly(epsilon-caprolactone) (PCL) blocks attached to the PDMS backbone, the length of the PCL blocks, and the siloxane polymer level in the coating formulations. In addition to the siloxane libraries (3-aminopropyl-terminated PDMS and poly(epsilon-caprolactone)-poly(dimethylsiloxane)-poly(epsilon-caprolactone) (PCL-PDMS-PCL) triblock copolymers), the coating formulation included a trifunctional isocyanate crosslinker, trifunctional poly(epsilon-caprolactone) polyol, 2,4-pentanedione (pot-life extender), dibutyltin diacetate (catalyst), and a blend of solvents. The resulting coatings were analyzed for their surface energy and pseudobarnacle adhesion both before and after aging the coatings for 30 days in water. The water and methylene iodide contact angle averages increase with increasing molecular weight of PDMS. Coatings prepared from PCL-PDMS-PCL triblock copolymers have lower surface energies than coatings prepared from 3-aminopropyl-terminated PDMS; however, lower pseudobarnacle adhesion results were obtained for the coatings prepared from 3-aminopropyl-terminated PDMS than coatings prepared from PCL-PDMS-PCL triblock copolymers. The siloxane polymer level in the coating formulations does not have a significant effect on the surface energy of the coatings, but it resulted in higher pseudobarnacle adhesion.     

Stabilization of two-phase octanol/water flows inside poly(dimethylsiloxane) microchannels using polymer coatings

In this paper we present our first results on the realization of stable water/octanol, two-phase flows inside poly(dimethylsiloxane) (PDMS) microchannels. Native PDMS microchannels were coated with high molecular weight polymers to change the surface properties of the microchannels and thus stabilize the laminar flow profile. The polymers poly(2-hydroxyethyl methacrylate), poly(vinyl pyrrolidone), poly(ethylene oxide), poly(ethylene glycol), and poly(vinyl alcohol) were assessed for their quality as stabilization coatings after deposition from flowing and stationary solutions. Additionally, the influence of coating the microchannels homogeneously with a single kind of polymer or heterogeneously with two different polymers was investigated. From the experimental observations, it can be concluded that homogeneous polymer coatings with poly(2-hydroxyethyl methacrylate) and poly(vinyl pyrrolidone) led to the effective stabilization of laminar water/octanol flows. Furthermore, heterogeneous coatings led to two-phase flows which had a better-defined and more stable interface over long distances (i.e., 40-mm-long microchannels). Finally, the partitioning of fuchsin dye in the coated microchannels was demonstrated, establishing the feasibility of the use of the polymer-coated PDMS microchannels for determination of logP values in laminar octanol/water flows.     

Bioactive and Protective Sol-Gel Coatings on Metals for Orthopaedic Prostheses

The aim of this work has been the preparation and evaluation of sol-gel coatings for clinical applications. Research was focussed in the development of highly corrosion resistant and/or bioactive sol-gel coatings onto AISI 316L stainless steel. Hybrid SiO₂ sol-gel coatings inhibited corrosion and Fe diffusion, although no signal of bioactivity was detected. The inclusion of Ca- and P-alcoxides in the sol composition did not promote bioactivity. Bioactive coatings were obtained from suspensions prepared by adding glass (CaO·SiO₂·P₂O₅) particles to an hybrid organic-inorganic SiO₂ sol. The dissolution of glass particles promoted in vitro induction of apatite along with a slight reduction in the corrosion resistance of coated pieces. By combining an inner SiO₂ hybrid film acting as barrier against corrosion with an outer coating containing bioactive glass particles, a significant improvement in the electrochemical behaviour was observed. This double-layered coating showed in vitro signals of bioactivity, and preliminary in vivo tests gave promising results.