PDMS is enjoying continued and ever increasing popularity as the material of choice for microfluidic devices due to its low cost, ease of fabrication, oxygen permeability and optical transparency. However, PDMS's hydrophobicity and fast hydrophobic recovery after surface hydrophilization, attributed to its low glass transition temperature of less than -120 degrees C, negatively impacts on the performance of PDMS-based microfluidic device components. This issue has spawned a flurry of research to devise longer lasting surface modifications of PDMS, with particular emphasis on microfluidic applications. This review will present recent research on surface modifications of PDMS using techniques ranging from metal layer coatings and layer-by-layer depositions to dynamic surfactant treatments and the adsorption of amphipathic proteins. We will also discuss significant advances that have been made with a broad palette of gas-phase processing methods including plasma processing, sol-gel coatings and chemical vapor deposition. Finally, we will present examples of applications and future prospects of modified PDMS surfaces in microfluidics, in areas such as molecular separations, cell culture in microchannels and biomolecular detection via immunoassays.
This review focuses on advances reported from April 2009 to May 2011 in PDMS surface modifications for the application in microfluidic devices. PDMS surface modification techniques presented here include improved plasma and graft polymer coating, dynamic surfactant treatment, hydrosilylation-based surface modification and surface modification with nanomaterials such as carbon nanotubes and metal nanoparticles. Recent efforts to generate topographical and chemical patterns on PDMS are also discussed. The described surface modifications not only increase PDMS wettability, inhibit or reduce non-specific adsorption of hydrophobic species onto the surfaces in the act, but also result in the display of desired functional groups useful for molecular separations, biomolecular detection via immunoassays, cell culture and emulsion formation.
In this work, the surface modification of poly(dimethylsiloxane) (PDMS) was carried out by using a 2-step plasma modification with Ar followed by acrylic acid (AAc). The optimal conditions were found to be 0.5 min with Ar at 0.7 mbar; and 5 min with AAc at 0.2 mbar. The water contact angle (WCA) of the native PDMS decreased from 110 degrees to 30 degrees after modification, then stabilized to values between 50 degrees to 60 degrees after 1 day exposure to air. The stability of the modified PDMS was further improved by Soxhlet-extracting the PDMS with hexane prior to plasma treatment. Atomic force microscopy (AFM) showed significant changes in surface morphology after the 2-step plasma modification. X-ray photoelectron (XPS) spectroscopy further confirmed the successful modification of the PDMS surface with PAAc, by exhibiting C1s peaks at 285.9 eV, 287.4 eV and 289.9 eV, originating from C-O, C=O and O-C=O moieties, respectively. Fourier transform infrared-attenuated total reflection (FTIR-ATR) spectroscopy of the poly(acrylic acid) (PAAc) modified PDMS surface showed a distinctive peak at 1715 cm(-1), attributed to the presence of COOH groups from the PAAc. The carboxyl peak on the spectra of the PAAc modified PDMS was quite stable even after storage at room temperature in phosphate buffer saline (PBS) and N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid (HEPES) buffer for 17 h. 5'-amino-terminated oligonucleotides were covalently attached to the PAAc modified PDMS surface via carbodiimide coupling. Subsequently, fluorescently tagged complementary oligonucleotides were successfully hybridized to this surface, as determined by fluorescence microscopy.
Here, we present a simple chemical modification of poly͑dimethylsiloxane͒ ͑PDMS͒ by curing a mixture of 2 wt% undecylenic acid ͑UDA͒ in PDMS prepolymer on a gold-coated glass slide. This gold slide had been previously pretreated with a self-assembled hydrophilic monolayer of 3-mercaptopropionic acid ͑MPA͒. During curing of the UDA/PDMS prepolymer, the hydrophilic UDA carboxyl moieties diffuses toward the hydrophilic MPA carboxyl moieties on the gold surface. This diffusion of the UDA within the PDMS prepolymer to the surface is a direct result of surface energy minimization. Once completely cured, the PDMS is peeled off the gold substrate, thereby exposing the interfacial carboxyl groups. These groups are then available for subsequent attachment of 5Ј-amino terminated DNA oligonucleotides via amide linkages. Our results show that the covalently tethered oligonucleotides can successfully capture fluorescein-labeled complementary oligonucleotides via hybridization, which are visualized using fluorescence microscopy.
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