Native Polydimethylsiloxane Research Articles

In Vivo X-Ray Imaging of Phosphor-Doped PDMS and Phosphor-Doped Aerogel Biomaterials

Noninvasive rapid in vivo imaging and detection of biomedical implants is a critical part of the design and implementation of smart implants. Thermographic phosphors offer a precise and remotely accessible sensing method that has been utilized here. We present the first in vivo X-ray images of La2O2S:Eu-doped crosslinked silica aerogels and polydimethylsiloxane (PDMS) with increasing dopant concentrations. Results show that native PDMS and crosslinked silica aerogel do not show noticeable attenuation of X-rays while image analysis yields values of the absorption coefficient of 0.014 for the doped aerogel and a range of 0.015–0.017 for the doped PDMS.

Reducing wrinkles and cracks of metal films on PDMS substrate by hexane extraction and oxygen plasma etching

Metal films deposited on polydimethylsiloxane (PDMS) substrates frequently exhibit wrinkles and cracks, which is a problem in fabricating flexible electronics. Here, we present the result of a study investigating the influence of the PDMS surface roughness, surface free energy and wettability on the quality of metal films and explored methods to reduce those wrinkles and cracks. Initially, the low molecular weight chains (LMW) in PDMS substrate were extracted by hexane solution. After extraction, the PDMS was etched in an oxygen plasma and the metal was deposited. Both surface roughness measurements and microscopic photographs demonstrated that Cu film deposited on the pretreated PDMS substrate exhibited less wrinkles and cracks than on native PDMS substrate. Finally, to demonstrate the effectiveness of the wrinkle improvement, a flexible dry electrode with micro domes was fabricated and used for Electro Cardio Gram (ECG) recording. The results showed that the fabricated dry electrode with reduced wrinkles produced good ECG signals with distinct P, QRS, and T waves.

Enrichment of tumor-initiating breast cancer cells within a mammosphere-culture microdevice

We report for the first time a microdevice that enables the selective enrichment, culture, and identification of tumor-initiating cells on native polydimethylsiloxane (PDMS). For nearly a decade, researchers have identified tumor-initiating breast cancer cells within heterogeneous populations of breast cancer cells by utilizing low-attachment serum-free culture conditions, which lead to the formation of spheroidal colonies (mammospheres) that are enriched for tumor-initiating cells. However, the utility of this assay has been limited by difficulties in combining this culture-plate-based technique with other cellular and molecular analyses. Integrating the mammosphere technique into a microsystem can enable it to be combined directly with a number of functions, such as cell sorting, drug screens, and molecular assays. In this work, we demonstrate mammosphere culture within a PDMS microdevice. We first prove that a native hydrophobic PDMS surface is as effective as commercial low-attachment plates at selectively promoting the formation of mammospheres. We then experimentally assess the PDMS microdevice. Time-lapse images of mammosphere formation within the microdevice show that mammospheres form from single cells or small clusters of cells. Following formation of the mammospheres, it is desirable to evaluate the cells within the spheroids for enrichment of tumor initiating cells. To perform assays such as this (which require the loading and rinsing of reagents) without flushing the cells (which are in suspension) from the device, the culture chamber is separated from a reagent reservoir by a commercially available microporous membrane, and thus reagents are exchanged between the reservoir and the culture chamber by diffusion only. Using this capability, we verify that the mammospheres are enriched for tumor initiating cells by staining aldehyde dehydrogenase activity, a cancer stem cell marker. To the best of our knowledge, this is the first assay that enables the direct observation of tumor-initiating cells within a suspended mammosphere.

A novel open-tubular capillary electrochromatography using β-cyclodextrin functionalized graphene oxide-magnetic nanocomposites as tunable stationary phase

Chip-based enantioselective open-tubular capillary electrochromatography (OT-CEC) with β-cyclodextrin (β-CD) conjugated graphene oxide-magnetic nanocomposites (GO/Fe3O4 NCs) as stationary phase was developed. GO/Fe3O4 NCs with high magnetic responsivity, excellent solubility and high dispersibility in water were prepared through a facile and controllable in situ chemical deposition strategy. β-CD was then adsorbed onto the GO/Fe3O4 surface to form GO/Fe3O4/β-CD NCs which were localized to the pre-nominated position in polydimethylsiloxane (PDMS) microchannels with the help of magnets. The resultant GO/Fe3O4/β-CD NCs not only have the magnetism of Fe3O4 NPs that make them easily manipulated by an external magnetic field, but also have the larger surface which can incorporate much more chiral selector molecules. In addition, the successful β-CD decorations endowed GO/Fe3O4/β-CD NCs with excellent wettability and led to enhanced stability against high ionic strength. Compared with the native PDMS microchip, the modified surfaces exhibited more stable and suppressed electroosmotic mobility, and less nonspecific adsorption toward analytes. Successful baseline separation of tryptophan enantiomers was achieved in less than 50s with a resolution factor of 1.65 utilizing a separation length of 37mm coupled with in-column amperometric detection. Factors that influence the chiral separation resolution were examined. Under the optimized conditions, the proposed modified chip revealed adequate repeatability concerning run-to-run and day-to-day. These results show that the use of GO/Fe3O4/β-CD NCs within microfluidic channels hold great promise for a variety of analytical schemes.

A rapid, inexpensive surface treatment for enhanced functionality of polydimethylsiloxane microfluidic channels.

A rapid, inexpensive method using alkoxysilanes has been developed to selectively coat the interior of polydimethylsiloxane (PDMS) microfluidic channels with an integral silicaceous layer. This method combines the rapid prototyping capabilities of PDMS with the desirable wetting and electroosmotic properties of glass. The procedure can be carried out on the open faces of PDMS blocks prior to enclosure of the channels, or by flowing the reagents through the preformed channels. Therefore, this methodology allows for high-throughput processing of entire microfluidic devices or selective modification of specific areas of a device. Modification of PDMS with tetraethoxysilane generated a stable surface layer, with enhanced wettability and a more stable electroosmotic flow rate than native PDMS. Modification of PDMS with 3-aminopropyltriethoxysilane generated a surface layer bearing amine functionalities allowing for further chemical derivatization of the PDMS surface.

Surface texture and wetting stability of polydimethylsiloxane coated with aluminum oxide at low temperature by atomic layer deposition

The performance of polydimethylsiloxane (PDMS) elastomer in many of its applications, including surface molding and replication, microcontact lithography, and microfluidic device structures, is strongly influenced by its surface properties. While PDMS polymer is simple to use, the surface hydrophobicity and adsorptive properties of PDMS limit its functionality, for example, in aqueous microfluidic applications. Atomic layer deposition (ALD) is a low temperature vapor phase thin film coating technique that has recently been used to modify and encapsulate a wide range of polymer materials. In this work, the authors investigate reactions that proceed when PDMS polymer films are treated with cyclic gas exposure sequences commonly used to perform aluminum oxide ALD. Film growth is characterized by electron and infrared spectroscopy and by contact angle goniometry for a range of surface treatments and postdeposition air exposure times. The authors find that trimethylaluminum/water ALD can produce a smooth and uniform film coating on PDMS at 25–50 °C and that cracks become visible under optical microscopy for films >100 Å thick. At moderate temperatures, unique buckled surface textures appear in the deposited coating, which are ascribed to substrate thermal expansion effects. Aluminum oxide coatings on native PDMS, as well as on PDMS pretreated with UV ozone or oxygen plasma, show a hydrophilic surface condition immediately after deposition, but the surface becomes more hydrophobic after 24–48 h in ambient air or under inert gas storage, likely due to organic species out-diffusion through defects in the ALD coating. Infrared analysis is also used to identify consistent mechanisms associated with subsurface ALD nucleation on cast PDMS layers. These results provide valuable insight into a means to reliably modify the surface of PDMS using vapor phase precursor/surface reactions.

Desorption atmospheric pressure photoionization with polydimethylsiloxane as extraction phase and sample plate material

Desorption atmospheric pressure photoionization (DAPPI) is an ambient ionization technique for mass spectrometry (MS) that can be used to ionize polar as well as neutral and completely non-polar analytes. In this study polydimethylsiloxane (PDMS) was used as a solid phase extraction sorbent for DAPPI-MS analysis. Pieces of PDMS polymer were soaked in an aqueous sample, where the analytes were sorbed from the sample solution to PDMS. After this, the extracted analytes were desorbed directly from the polymer by the hot DAPPI spray solvent plume, without an elution step. Swelling and extracting the PDMS with a cleaning solvent prior to extraction diminished the high background in the DAPPI mass spectrum caused by PDMS oligomers. Acetone, hexane, pentane, toluene, diisopropylamine and triethylamine were tested for this purpose. The amines were most efficient in reducing the PDMS background, but they also suppressed the signals of low proton affinity analytes. Toluene was chosen as the optimum cleaning solvent, since it reduced the PDMS background efficiently and gave intensive signals of most of the studied analytes. The effects of DAPPI spray solvents toluene, acetone and anisole on the PDMS background and the ionization of analytes were also compared and extraction conditions were optimized. Anisole gave a low background for native PDMS, but toluene ionized the widest range of analytes. Analysis of verapamil, testosterone and anthracene from purified, spiked wastewater was performed to demonstrate that the method is suited for in-situ analysis of water streams. In addition, urine spiked with several analytes was analyzed by the PDMS method and compared to the conventional DAPPI procedure, where sample droplets are applied on PMMA surface. With the PDMS method the background ion signals caused by the urine matrix were lower, the S/N ratios of analytes were 2–10 times higher, and testosterone, anthracene and benzo[a]pyrene that were not detected from PMMA in urine, were observed in the MS spectrum.

Functional Fluorinated Modifications on a Polyelectrolyte Coated Polydimethylsiloxane Substrate for Fabricating Antibody Microarrays

Fluorinated compounds exhibit hydrophobic, nonstick, and self-cleaning properties, making them attractive for use as the coating material for biochips. In this study, we copolymerized the fluorinated compound 1H,1H,2H-perfluoro-1-decene (FD) with acrylic acid (AA) and bonded the resulting copolymer with protein G on the surface of polyelectrolyte coated polydimethylsiloxane (PDMS) to form a functional surface that captures antibodies. We demonstrated that the modified PDMS surface remained hydrophobic while becoming resistant to nonspecific protein binding. Thus, aqueous sample solutions formed the droplets (4 μL) on the surface without spreading and drying during the sample printing. Contact angle measurements showed that this functionalized surface was as hydrophobic as the native PDMS with a virtually constant contact angle over seven days of the study under dried condition at 4 °C. Spectroscopic measurements revealed that FD/AA copolymerization formed a homogeneous and highly dense multilayer (50 mg/mm(2)) with a fluorine coverage of 35.4%. Moreover, protein G was shown to covalently bind to AA molecules on the surface at a binding density of 0.24 μg/mm(2). We demonstrated that the fluorinated coating withstood nonspecific binding with extremely low background emission, leading to bioassays that, without the need of blocking agents, exhibited six times more sensitivity than PEG coatings. The fluorinated PDMS antibody microarrays were further applied to accurately determine the absolute concentration of ERα in MCF-7 cells. In conclusion, the unique properties of fluorinated compounds, such as withstanding wetting, nonspecific binding and contamination, make them an excellent coating material for use in sensitive and simple on-chip assays.

Cassie-State Wetting Investigated by Means of a Hole-to-Pillar Density Gradient

The superhydrophobicity of rough surfaces owes its existence to heterogeneous wetting. To investigate this phenomenon, density gradients of randomly placed holes and pillars have been fabricated by means of photolithography. On such surfaces, drops can be observed in the Cassie state over the full range of f(1) (fraction of the drop's footprint area in contact with the solid). The gradient was produced with four different surface chemistries: native PDMS (polydimethylsiloxane), perfluorosilanized PDMS, epoxy, and CH(3)-terminated thiols on gold. It was found that f(1) is the key parameter influencing the static water contact angle. Advancing and receding contact angles at any given position on the gradient are sensitive to the type of surface feature--hole or pillar--that is prevalent. In addition, roll-off angles have been measured and found to be influenced not only by the drop weight but also by suction events, edge pinning, and f(1).

Teflon films for chemically-inert microfluidic valves and pumps

We present a simple method for fabricating chemically-inert Teflon microfluidic valves and pumps in glass microfluidic devices. These structures are modeled after monolithic membrane valves and pumps that utilize a featureless polydimethylsiloxane (PDMS) membrane bonded between two etched glass wafers. The limited chemical compatibility of PDMS has necessitated research into alternative materials for microfluidic devices. Previous work has shown that spin-coated amorphous fluoropolymers and Teflon-fluoropolymer laminates can be fabricated and substituted for PDMS in monolithic membrane valves and pumps for space flight applications. However, the complex process for fabricating these spin-coated Teflon films and laminates may preclude their use in many research and manufacturing contexts. As an alternative, we show that commercially-available fluorinated ethylene-propylene (FEP) Teflon films can be used to fabricate chemically-inert monolithic membrane valves and pumps in glass microfluidic devices. The FEP Teflon valves and pumps presented here are simple to fabricate, function similarly to their PDMS counterparts, maintain their performance over extended use, and are resistant to virtually all chemicals. These structures should facilitate lab-on-a-chip research involving a vast array of chemistries that are incompatible with native PDMS microfluidic devices.

Microfluidic devices for culturing primary mammalian neurons at low densities

Microfluidic devices have been used to study high-density cultures of many cell types. Because cell-to-cell signaling is local, however, there exists a need to develop culture systems that sustain small numbers of neurons and enable analyses of the microenvironments. Such cultures are hard to maintain in stable form, and it is difficult to prevent cell death when using primary mammalian neurons. We demonstrate that postnatal primary hippocampal neurons from rat can be cultured at low densities within nanoliter-volume microdevices fabricated using polydimethylsiloxane (PDMS). Doing so requires an additional fabrication step, serial extractions/washes of PDMS with several solvents, which removes uncrosslinked oligomers, solvent and residues of the platinum catalyst used to cure the polymer. We found this step improves the biocompatibility of the PDMS devices significantly. Whereas neurons survive for > or = 7 days in open channel microdevices, the ability to culture neurons in closed-channel devices made of untreated, native PDMS is limited to < or = 2 days. When the closed-channel PDMS devices are extracted, biocompatibility improves allowing for reliable neuron cultures at low densities for > or = 7 days. Comparisons made to autoclaved PDMS and native, untreated PDMS reveal that the solvent-treated polymer is superior in sustaining low densities of primary neurons in culture. When neuronal affinity for local substrates is observed directly, we find that axons localize to channel corners and prefer PDMS surfaces to glass in hybrid devices. When perfusing the channels with media by gravity flow, cultured hippocampal neurons survive for > or = 11 days. Extracting PDMS improves biocompatibility of microfluidic devices and thus enables the study of differentiation of identifiable neurons and the characterization of local extracellular signals.

Surface characterization using chemical force microscopy and the flow performance of modified polydimethylsiloxane for microfluidic device applications.

The widespread interest in micro total analysis systems has resulted in efforts to develop devices in cheaper polymer materials such as polydimethylsiloxane (PDMS) as an alternative to expensive glass and silicon devices. We describe the oxidation of the PDMS surface to form ionizable groups using a discharge from a Tesla coil and subsequent chemical modification to augment electroosmotic flow (EOF) within the microfluidic devices. The flow performance of oxidized, amine-modified and unmodified PDMS materials has been determined and directly compared to conventional glass devices. Exact PDMS replicas of glass substrates were prepared using a novel two step micromolding protocol. Chemical force microscopy has been utilized to monitor and measure the efficacy of surface modification yielding information about the acid/base properties of the modified and unmodified surfaces. Results with different substrate materials correlates well with expected flow modifications as a result of surface modification. Oxidized PDMS devices were found to support faster EOF (twice that of native PDMS) similar to glass while those derivatized with 3-aminopropyl triethoxysilane (APTES) showed slower flow rates compared to native PDMS substrates as a result of masking surface charge. Results demonstrate that the surface of PDMS microdevices can be manipulated to control EOF characteristics using a facile surface derivatization methodology allowing surfaces to be tailored for specific microfluidic applications and characterized with chemical force microscopy.