Photochemical modification and patterning of SU-8 using anthraquinone photolinkers

Bioactive protein patterns and microarrays achieved by selective localization of biomolecules find various applications in biosensors, bio-microelectromechanical systems (bio-MEMS), and in basic protein studies. In this paper we describe simple photochemical methods to fabricate two-dimensional patterns on a Novolac A derivative polymer (SU-8) and, subsequently, their functionalization with biomolecules. Anthraquinone (AQ) derivatives are used to chemically modify and pattern SU-8 surfaces. Features as small as 20 mum are obtained when using uncollimated light. The X-Y spatial resolution of micropatterned AQ molecules is improved to 1.5 mum when a collimated light source is used. This micropatterning process will be important for the functionalization of MEMS-based biosensors. The method saves several processing steps and can be integrated in cleanroom fabrication thus avoiding contamination of the sensor surfaces.     

Surface modification of polyurethane for enhanced blood compatibility

Surfaces of commercial polyurethanes (PUs) were modified by poly(ethylene oxide) (PEO) grafting and/or heparin immobilization or sulfonation to investigate the effect to antithrombogenicity. The hydrophilicity of the modified PUs surface was significantly increased. All the PEO-grafted PU surfaces displayed very little platelet adhesion and activation. The coupled heparin or sulfonate at the end of PEO exhibited anticoagulant activity to extend APTT. Lowering in vitro platelet adhesion of modified PUs led to a prolongation in the ex vivo occlusion time. In particular, the sulfonated PU-PEO surface showed the most enhanced blood compatibility due to the synergistic effects of PEO and SO₃ groups.     

Ultralow hysteresis superhydrophobic surfaces by excimer laser modification of SU-8

We present a new and simple method to produce superhydrophobic surfaces with ultralow hysteresis. The method involves surface modification of SU-8 using an excimer laser treatment. The modified surface is coated with a hydrophobic plasma-polymerized hexafluoropropene layer. The advancing and receding water contact angles were measured to be approximately 165 degrees . The achieved water contact angle hysteresis was below the measurement limit. This low hysteresis can be ascribed to nanoscale debris generated during the excimer laser process.     

Characterization of SU-8 for electrokinetic microfluidic applications

The characterization of SU-8 microchannels for electrokinetic microfluidic applications is reported. The electroosmotic (EO) mobility in SU-8 microchannels was determined with respect to pH and ionic strength by the current monitoring method. Extensive electroosmotic flow (EOF), equal to that for glass microchannels, was observed at pH > or =4. The highest EO mobility was detected at pH > or =7 and was of the order of 5.8 x 10(-4) cm(2) V(-1) s(-1) in 10 mM phosphate buffer. At pH < or =3 the electroosmotic flow was shown to reverse towards the anode and to reach a magnitude of 1.8 x 10(-4) cm(2) V(-1) s(-1) in 10 mM phosphate buffer (pH 2). Also the zeta-potential on the SU-8 surface was determined, employing lithographically defined SU-8 microparticles for which a similar pH dependence was observed. SU-8 microchannels were shown to perform repeateably from day to day and no aging effects were observed in long-term use.     

SU-8 flow field plates for a micro PEMFC

A SU-8 photoresist microfabrication process was developed for micro proton exchange membrane fuel cell flow structures for both anode and cathode flow field plates with a cross section of 5 cm² (22.5 mm×22.5 mm) and thickness (for a single cell) of about 750 µm. The new design for flow field plates would have SU-8 used as not only a photoresist but also as a microstructure material. A thickness of 30 nm Pt sputter loading deposited onto a Nafion 117 for membrane electrode assembly was made, with both scanning electron microscopy and atomic force microscopy characterization. Air flows were completed in hydrogen fuel cells with air breathing and forced air flows of low input pressure as well as low velocity. Performance tests of polarization curves and power density distribution as well as impendence measurements were conducted and discussed to examine the effects of orientation of the cathode surface with five hydrogen feeding rates as well as different airflow feeding modes.     

SU-8 as a structural material for labs-on-chips and microelectromechanical systems

Since its introduction in the nineties, the negative resist SU-8 has been increasingly used in micro- and nanotechnologies. SU-8 has made the fabrication of high-aspect ratio structures accessible to labs with no high-end facilities such as X-ray lithography systems or deep reactive ion etching systems. These low-cost techniques have been applied not only in the fabrication of metallic parts or molds, but also in numerous other micromachining processes. Its ease of use has made SU-8 to be used in many applications, even when high-aspect ratios are not required. Beyond these pattern transfer applications, SU-8 has been used directly as a structural material for microelectromechanical systems and microfluidics due to its properties such as its excellent chemical resistance or the low Young modulus. In contrast to conventional resists, which are used temporally, SU-8 has been used as a permanent building material to fabricate microcomponents such as cantilevers, membranes, and microchannels. SU-8-based techniques have led to new low-temperature processes suitable for the fabrication of a wide range of objects, from the single component to the complete lab-on-chip. First, this article aims to review the different techniques and provides guidelines to the use of SU-8 as a structural material. Second, practical examples from our respective labs are presented.     

Fabrication of enclosed SU-8 tips for electrospray ionization-mass spectrometry

We describe a novel electrospray tip design for MS which is fabricated completely out of SU-8 photoepoxy. A three-layer SU-8 fabrication process provides fully enclosed channels and tips. The tip shape and alignment of all SU-8 layers is done lithographically and is therefore very accurate. Fabrication process enables easy integration of additional fluidic functions on the same chip. Separation channels can be made with exactly the same process. Fluidic inlets are made in SU-8 during the fabrication process and no drilling or other postprocessing is needed. Channels have been fabricated and tested in the size range of 10 microm x 10 microm-50 microm x 200 microm. Mass spectrometric performance of the tips has been demonstrated with both pressure-driven flow and EOF. SU-8 microtips have been shown to produce stable electrospray with EOF in a timescale of tens of minutes. With pressure driven flow stable spray is maintained for hours. Taylor cone was shown to be small in volume and well defined even with the largest channel cross section. The spray was also shown to be well directed with our tip design.     

Surface modification of praseodymium oxide/hematite doped into Polycaprolactone for enhanced wound management demands

Praseodymium oxide (Pr₆O₁₁), hematite (Fe₂O₃), graphene oxide (GO), and polycaprolactone (PCL) based polymeric nanocomposites (NCs) are fabricated, aiming their usage as bio-scaffold for medical purposes. Because of their distinctive light absorption and stability, Fe₂O₃ and Pr₆O₁₁ have been introduced as potential optical elements. The structure and size examination of NCs were executed by XRD, Raman, and FESEM. Pr₆O₁₁/Fe₂O₃/GO@PCL polymeric NC is exhibited Pr₆O₁₁, and Fe₂O₃ average size of 1.4, 0.4 µm, while average pores size 2.1 µm. As well, the Uv–Vis shows an absorption edge shifting along the x-axis that it begins with 3.1 eV for pure PCL, after that it declined to 1.7 eV for Pr₆O₁₁@PCL NC. Also, Pr₆O₁₁ @PCL, and Pr₆O₁₁/ Fe₂O₃@PCL NCs show the lowest similar contact angle with 38°. Regarding cell attachment evaluation test, the Pr₆O₁₁/Fe₂O₃/GO@PCL NC healing valuation is touched ∼ 80%. As a result, the structure enabled 3-dimensional the division of normal cells, so promoting wound healing.     

Surface modification of ZIF-90 with triptycene for enhanced interfacial interaction in mixed-matrix membranes for gas separation

Zeolite imidazole framework (ZIF-90) nanoparticles were chemically modified by grafting triptycene moieties. The modified nanoparticles were introduced into a triptycene-based polyimide as fillers to generate mixed matrix membranes (MMMs) for gas separation. The incorporation of “hook-like” triptycene moieties in both dispersed and continuous phases led to intimate contact between the two phases and thus defect-free interfacial morphology, due to the supramolecular interlocking and π–π stacking interaction between triptycene units presented in both phases. The filler/polymer solution showed shear thickening behavior due to such strong interfacial interaction. The separation performance of the prepared composite membranes was investigated as a function of filler loading and particle surface grafting density. Pure-gas permeation results showed that the gas permeabilities increased expectedly as the filler loading increased, with stable or improved selectivities. The reduced permeability relative to pristine polyimide film is likely due to the pore blockage of ZIF-90 upon grafting triptycene moieties on the particle surface. Reducing the grafting density of triptycene moieties led to improved permeability and selectivity suggesting good tunability of this series of new composite membranes. Overall, modification of nanofiller with hierarchical triptycene moieties offers a fundamentally new avenue for creation of composite membranes with unique properties in gas separations.     

Analytical characterization of microfabricated SU-8 emitters for electrospray ionization mass spectrometry

We present a detailed optimization and characterization of the analytical performance of SU-8-based emitters for electrospray ionization mass spectrometry (ESI/MS). The improved SU-8 fabrication process presented here enhances patterning accuracy and reduces the time and cost of fabrication. All emitters are freestanding and enable sample delivery by both pressure-driven and spontaneous flows. The optimized emitter design incorporates a sharp, double-cantilevered tip implemented to the outlet of an SU-8 microchannel and provides highly sensitive ESI/MS detection. Moreover, the optimized design allows the use of relatively large microchannel dimensions (up to 200 x 50 microm(2), w x h) without sacrificing the detection sensitivity. This is advantageous with a view of preventing emitter clogging and enabling reproducible analysis. The measured limits of detection for the optimized emitter design were 1 nM for verapamil and 4 nM for Glu-fibrinopeptide B with good quantitative linearities between 1 nM and 10 microM (R(2) = 0.9998) for verapamil and between 4 nM and 3 microM (R(2) = 0.9992) for Glu-fibrinopeptide B. The measured tip-to-tip repeatability for signal intensity was 14% relative standard deviation (RSD) (n = 3; 5 microM verapamil) and run-to-run repeatability 4-11% RSD (n = 4; 5 microM verapamil) for all individual emitters tested. In addition, long-term stability of < 2% RSD was maintained for timescales of 30 min even under free flow conditions. SU-8 polymer was also shown to be chemically stable against most of the tested electrospray solvents.     

Electrochemical synthesis and one step modification of PMProDot nanotubes and their enhanced electrochemical properties

Poly (3,4-(2-methylene)propylenedioxythiophene) (PMProDot) nanotubes were synthesized within the pores of polycarbonate and were further modified with styrene and vinylcarbazole by a one step electrochemical method through the methylene functional group. The enhanced electrochemical and electrochromic properties of composite nanotubes were investigated using FTIR, UV/Vis absorbance spectroscopy, and AFM.     

Fabrication of SU-8 based microchip electrophoresis with integrated electrochemical detection for neurotransmitters

A new SU-8 based microchip capillary electrophoresis (MCE) device has been developed for the first time with integrated electrochemical detection. Embedded electrophoretic microchannels have been fabricated with a multilayer technology based on bonding and releasing steps of stacked SU-8 films. This technology has allowed the monolithic integration in the device of the electrochemical detection system based on platinum electrodes. The fabrication of the chips presented in this work is totally compatible with reel-to-reel techniques, which guarantee a low cost and high reliability production. The influence of relevant experimental variables, such as the separation voltage and detection potential, has been studied on the SU-8 microchip with an attractive analytical performance. Thus, the effective electrical isolation of the end-channel amperometric detector has been also demonstrated. The good performance of the SU-8 device has been proven for separation and detection of the neurotransmitters, dopamine (DA) and epinephrine (EP). High efficiency (30,000-80,000 N/m), excellent precision, good detection limit (450 nM) and resolution (0.90-1.30) has been achieved on the SU-8 microchip. These SU-8 devices have shown a better performance than commercial Topas (thermoplastic olefin polymer of amorphous structure) microchips. The low cost and versatile SU-8 microchip with integrated platinum film electrochemical detector holds great promise for high-volume production of disposable microfluidic analytical devices.     

SDS-CGE of proteins in microchannels made of SU-8 films

This work describes the SDS-CGE of proteins carried out in microchannels made of the negative photoresist EPON SU-8. Embedded electrophoretic microchannels have been fabricated with a multilayer technology based on bonding and releasing steps of stacked SU-8 films. This technology allows the monolithic integration of the electrodes in the device. A high wafer fabrication yield and mass production compatibility guarantees low costs and high reliability. A poly(methyl methacrylate) (PMMA) packaging allows an easy setup and replacement of the device for electrophoresis experiments. In addition, the wire-bonding step is avoided. The electrophoretic mobilities of four proteins have been measured in microchannels filled with polyacrylamide. Different pore sizes have been tested obtaining their Ferguson plots. Finally, a separation of two proteins (20 and 36 kDa) has been carried out confirming that this novel device is suitable for protein separation. A resolution of 2.75 is obtained. This is the first time that this SU-8 microfluidic technology has been validated for SDS-CGE of proteins. This technology offers better separation performance than glass channels, at lower costs and with an easy packaging procedure.     

Surface chemical modification of microfibrillated cellulose: improvement of barrier properties for packaging applications

Heterogeneous acetylation of microfibrillated cellulose (MFC) was carried out to modify its physical properties and at the same time to preserve the morphology of cellulose fibrils. The overall reaction success was assessed by FTIR together with the degree of substitution (DS) defined by titration and the degree of surface substitution (DSS) evaluated by means of XPS. Dynamic contact angle measurements confirmed the hydrophobicity improvement relative to non-modified samples. The increase of contact angle upon reaching a certain reaction time and some decrease following the further acetylation was confirmed. Mechanical properties of MFC films made from chemically modified material were evaluated using tensile strength tests which showed no significant reduction of tensile strength. According to SEM images, dimension analysis and tensile strength data, the acetylation seemed not to affect the morphology of cellulose fibrils.     

Aminosilane-based functionalization of two-photon polymerized 3D SU-8 microstructures

There is an increasing interest in functionalized complex 3D microstructures with sub-micrometer features for micro- and nanotechnology applications in biology. Depending primarily on the material of the structures various methods exist to create functional layers of simple chemical groups, biological macromolecules or metal nanoparticles. Here an effective coating method is demonstrated and evaluated on SU-8 based 3D microstructures made by two-photon polymerization. Protein streptavidin and gold nanoparticles (NP) were bound to the microstructures utilizing acid treatment-mediated silane chemistry. The protein surface density, quantified with single molecule fluorescence microscopy revealed that the protein forms a third of a monolayer on the two-photon polymerized structures. The surface coverage of the gold NPs on the microstructures was simply controlled with a single parameter. The possible degrading effect of the acid treatment on the sub-micrometer features of the TPP microstructures was analyzed. Our results show that the silane chemistry-based method, used earlier for the functionalization of large-area surfaces can effectively be adapted to coat two-photon polymerized SU-8 microstructures with sub-micrometer features.     

Dual-functional ROMP-based betaines: effect of hydrophilicity and backbone structure on nonfouling properties

Foundational materials for nonfouling coatings were designed and synthesized from a series of novel dual-functional zwitterionic polymers, Poly[NRZI], which were easily obtained via ring-opening metathesis polymerization (ROMP) followed by a single step transformation of the cationic precursor, Poly[NR(+)], to the zwitterion, Poly[NRZI]. The resulting unique dual-functional structure contained the anion and the cation within the same repeat unit but on separate side chains, enabling the hydrophilicity of the system to be tuned at the repeat unit level. These dual-functional zwitterionic polymers were specifically designed to investigate the impact of structural changes, including the backbone, hydrophilicity, and charge, on the overall nonfouling properties. To evaluate the importance of backbone structure, and as a direct comparison to previously studied methacrylate-based betaines, norbornene-based carbo- and sulfobetaines (Poly[NCarboZI] and Poly[NSulfoZI]) as well as a methacrylate-based sulfobetaine (Poly[MASulfoZI]) were synthesized. These structures contain the anion-cation pairs on the same side chain. Nonfouling coatings were prepared from copolymers, composed of the zwitterionic/cationic precursor monomer and an ethoxysilane-containing monomer. The coatings were evaluated by using protein adsorption studies, which clearly indicated that the overall hydrophilicity has a major influence on the nonfouling character of the materials. The most hydrophilic coating, from the oligoethylene glycol (OEG)-containing dual-functional betaine, Poly[NOEGZI-co-NSi], showed the best resistance to nonspecific protein adsorption (Γ(FIB) = 0.039 ng/mm(2)). Both norbornene-based polymers systems, Poly[NSulfoZI] and Poly[NCarboZI], were more hydrophilic and thus more resistant to protein adsorption than the methacrylate-based Poly[MASulfoZI]. Comparing the protein resistance of the dual-functional zwitterionic coatings, Poly[NRZI-co-NSi], to that of their cationic counterparts, Poly[NR(+)-co-NSi], revealed the importance of screening electrostatic interactions. The adsorption of negatively charged proteins on zwitterionic coatings was significantly less, despite the fact that both coatings had similar wetting properties. These results demonstrate that the unique, tunable dual-functional zwitterionic polymers reported here can be used to make coatings that are highly efficient at resisting protein adsorption.     

Direct immobilization of cholesteryl-TEG-modified oligonucleotides onto hydrophobic SU-8 surfaces

We introduce a rapid, simple one-step procedure for the high-yield immobilization of cholesteryl-tetraethyleneglycol-modified oligonucleotides (chol-DNA) at hydrophobic sites made of SU-8 photoresist. Topographic structures of SU-8 were microfabricated on microscope glass coverslips sputtered with a Ti/Au layer. Upon application, chol-DNA adsorbed to the SU-8 structures from solution, leaving the surrounding gold surface free of chol-DNA. chol-DNA immobilization is complete within 15 min and yields a surface coverage in the range of 20-95 pmol/cm(2), which corresponds to a film density of 10(12)-10(13) molecules/cm(2). chol-DNA immobilization is stable and can be sustained despite rinsing, drying, dry storage for several hours, and rehydration of chips. Furthermore, complementary DNA in solution hybridizes efficiently to immobilized chol-DNA.     

Surface modification for PDMS-based microfluidic devices

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.     

Surface enhanced optical spectroscopies for bioanalysis

Surface enhancement can provide improved detection sensitivity in a range of optical spectroscopies. When applied to bioanalysis these enhanced techniques allow for the detection of disease biomarkers at lower levels, which has a clear patient benefit. However, to achieve widespread clinical use of surface enhanced techniques there remain several "grand challenges". In this review we consider the substrates employed to achieve enhancement before reviewing each enhanced optical technique in detail; surface plasmon resonance, localised surface plasmon resonance, surface enhanced fluorescence, surface enhanced infrared absorption spectroscopy and surface enhanced (resonance) Raman spectroscopy. Finally we set out the "grand challenges" currently facing the field.