Three-Dimensional Soft Material Micropatterning via Grayscale Photolithography for Improved Hydrophobicity of Polydimethylsiloxane (PDMS)

In this present work, we aim to improve the hydrophobicity of a polydimethylsiloxane (PDMS) surface. Various heights of 3D PDMS micropillars were fabricated via grayscale photolithography, and improved wettability was investigated. Two approaches of PDMS replication were demonstrated, both using a single master mold to obtain the micropillar arrays. The different heights of fabricated PDMS micropillars were characterized by scanning electron microscopy (SEM) and a surface profiler. The surface hydrophobicity was characterized by measuring the water contact angles. The fabrication of PDMS micropillar arrays was shown to be effective in modifying the contact angles of pure water droplets with the highest 157.3-degree water contact angle achieved by implementing a single mask grayscale lithography technique.

HYDROGEL ANTIBACTERIAL COATING FOR SILICONE MEDICAL DEVICES

Effective antibacterial coatings are in demand in medicine, especially for urological medical devices such as catheters and stents. We propose the production method of an antibacterial hydrogel coating on polydimethylsiloxane (PDMS, silicone), a popular surface for medical materials. The coating process consists of the following steps: PDMS surface activation (introduction of hydroxyl groups), silanisation (introduction of amine groups) and application of chitosan/alginate hydrogel with the addition of lysozyme as an antibacterial agent using the layer-by-layer method. We investigated the effect of polyion concentration on the coating mass, swelling ratio and stability. We analysed the adsorption of Micrococcus luteus, Escherichia coli and Proteus rettgeri on a PDMS surface using confocal laser scanning microscopy. The chitosan/alginate hydrogel coating with immobilised lysozyme protected the PDMS surface against adhesion for all three tested bacterial strains.

Polysaccharide-Based Bilayer Coatings for Biofilm-Inhibiting Surfaces of Medical Devices

Chitosan (Chi) and 77KS, a lysine-derived surfactant, form polyelectrolyte complexes that reverse their charge from positive to negative at higher 77KS concentrations, forming aggregates that have been embedded with amoxicillin (AMOX). Dispersion of this complex was used to coat polydimethylsiloxane (PDMS) films, with an additional layer of anionic and hydrophilic hyaluronic acid (HA) as an outer adsorbate layer to enhance protein repulsion in addition to antimicrobial activity by forming a highly hydrated layer in combination with steric hindrance. The formed polysaccharide-based bilayer on PDMS was analyzed by water contact angle measurements, X-ray photoelectron spectroscopy (XPS), and surface zeta (ζ)-potential. All measurements show the existence and adhesion of the two layers on the PDMS surface. Part of this study was devoted to understanding the underlying protein adsorption phenomena and identifying the mechanisms associated with biofouling. Thus, the adsorption of a mixed-protein solution (bovine serum albumin, fibrinogen, γ-globulin) on PDMS surfaces was studied to test the antifouling properties. The adsorption experiments were performed using a quartz crystal microbalance with dissipation monitoring (QCM-D) and showed improved antifouling properties by these polysaccharide-based bilayer coatings compared to a reference or for only one layer, i.e., the complex. This proves the benefit of a second hyaluronic acid layer. Microbiological and biocompatibility tests were also performed on real samples, i.e., silicone discs, showing the perspective of the prepared bilayer coating for medical devices such as prostheses, catheters (balloon angioplasty, intravascular), delivery systems (sheaths, implants), and stents.

Fabrication of Ag/PDMS Substrate of High-Density Hot Spots and Its Application in in situ Detection

Through a replacement reaction approach, Ag nanostructure was easily prepared on economical digital video disc (DVD) and polydimethysiloxane (PDMS) with surface structure duplicating from the former. Distinct nanoscale morphology was observed, featuring intersecting Ag nanoplates with abundant hot spots on the DVD and spherical Ag nanoparticles on the PDMS. Surface-enhanced Raman scattering (SERS) spectra, using crystal violet as a probe, revealed a superior enhancement effect in Ag/DVD versus that in Ag/PDMS. Considering the desirable flexibility and transparency of PDMS for in situ detection, we further developed a protocol to introduce intersecting Ag nanoplates onto the PDMS surface. The resulting Ag/PDMS substrate was endowed with remarkable sensitivity, excellent uniformity and good stability under mechanical bending. Furthermore, effective in situ detection of malachite green on fish was demonstrated, highlighting the great potential of our approach for the in situ detection of target molecules on a curved surface.

Universal Plasma Jet for Droplet Manipulation on a PDMS Surface towards Wall-Less Scaffolds

Droplet manipulation is important in the fields of engineering, biology, chemistry, and medicine. Many techniques, such as electrowetting and magnetic actuation, have been developed for droplet manipulation. However, the fabrication of the manipulation platform often takes a long time and requires well-trained skills. Here we proposed a novel method that can directly generate and manipulate droplets on a polymeric surface using a universal plasma jet. One of its greatest advantages is that the jet can tremendously reduce the time for the platform fabrication while it can still perform stable droplet manipulation with controllable droplet size and motion. There are two steps for the proposed method. First, the universal plasma jet is set in plasma mode for modifying the manipulation path for droplets. Second, the jet is switched to air-jet mode for droplet generation and manipulation. The jetted air separates and pushes droplets along the plasma-treated path for droplet generation and manipulation. According to the experimental results, the size of the droplet can be controlled by the treatment time in the first step, i.e., a shorter treatment time of plasma results in a smaller size of the droplet, and vice versa. The largest and the smallest sizes of the generated droplets in the results are about 6 µL and 0.1 µL, respectively. Infrared spectra of absorption on the PDMS surfaces with and without the plasma treatment are investigated by Fourier-transform infrared spectroscopy. Tests of generating and mixing two droplets on a PDMS surface are successfully achieved. The aging effect of plasma treatment for the proposed method is also discussed. The proposed method provides a simple, fast, and low-cost way to generate and manipulate droplets on a polymeric surface. The method is expected to be applied to droplet-based cell culture by manipulating droplets encapsulating living cells and towards wall-less scaffolds on a polymeric surface.

Surface Coating with Hyaluronic Acid-Gelatin-Crosslinked Hydrogel on Gelatin-Conjugated Poly(dimethylsiloxane) for Implantable Medical Device-Induced Fibrosis

Polydimethylsiloxane (PDMS) is a biocompatible polymer that has been applied in many fields. However, the surface hydrophobicity of PDMS can limit successful implementation, and this must be reduced by surface modification to improve biocompatibility. In this study, we modified the PDMS surface with a hydrogel and investigated the effect of this on hydrophilicity, bacterial adhesion, cell viability, immune response, and biocompatibility of PDMS. Hydrogels were created from hyaluronic acid and gelatin using a Schiff-base reaction. The PDMS surface and hydrogel were characterized using nuclear magnetic resonance, X-ray photoelectron spectroscopy, attenuated total reflection Fourier-transform infrared spectroscopy, and scanning electron microscopy. The hydrophilicity of the surface was confirmed via a decrease in the water contact angle. Bacterial anti-adhesion was demonstrated for Pseudomonas aeruginosa, Ralstonia pickettii, and Staphylococcus epidermidis, and viability and improved distribution of human-derived adipose stem cells were also confirmed. Decreased capsular tissue responses were observed in vivo with looser collagen distribution and reduced cytokine expression on the hydrogel-coated surface. Hydrogel coating on treated PDMS is a promising method to improve the surface hydrophilicity and biocompatibility for surface modification of biomedical applications.

Impact of Plasma Pre-Treatment on the Tribological Properties of DLC Coatings on PDMS Substrates

The processes of the deposition of carbon coatings on PDMS (polydimethylsiloxane) substrates using plasma techniques are widely used in a large number of studies, in applications ranging from electronic to biological. That is why the potential improvement of their functional properties, including tribological properties, seems very interesting. This paper presents an analysis of the impact of plasma pre-treatment on the properties of the produced diamond-like carbon (DLC) coatings, including changes in the coefficients of friction and wear rates. The initial modification processes were performed using two different techniques based on low-pressure plasma (RF PACVD, radio-frequency plasma-assisted chemical vapour deposition) and dielectric barrier discharge (DBD) plasma. The effects of the above-mentioned treatments on the geometric structure of the PDMS surface and its water contact angles and stability over time were determined. The basic properties of the DLC coatings produced on unmodified substrates were compared to those of the coatings subjected to plasma pre-treatment. The most interesting effects in terms of tribological properties were achieved after the DBD process and production of DLC coatings, achieving a decrease in wear rates to 2.45 × 10−8 mm3/Nm. The tests demonstrate that the cross-linking of the polymer substrate occurs during plasma pre-treatment.

Surface Modification Techniques for Endothelial Cell Seeding in PDMS Microfluidic Devices

Microfluidic lab-on-a-chip cell culture techniques have been gaining popularity by offering the possibility of reducing the amount of samples and reagents and greater control over cellular microenvironment. Polydimethylsiloxane (PDMS) is the commonly used polymer for microfluidic cell culture devices because of the cheap and easy fabrication techniques, non-toxicity, biocompatibility, high gas permeability, and optical transparency. However, the intrinsic hydrophobic nature of PDMS makes cell seeding challenging when applied on PDMS surface. The hydrophobicity of the PDMS surface also allows the non-specific absorption/adsorption of small molecules and biomolecules that might affect the cellular behaviour and functions. Hydrophilic modification of PDMS surface is indispensable for successful cell seeding. This review collates different techniques with their advantages and disadvantages that have been used to improve PDMS hydrophilicity to facilitate endothelial cells seeding in PDMS devices.

Fabrication of Tapered 3D Microstructure Arrays Using Dual-Exposure Lithography (DEL)

Three-dimensional (3D) microstructure arrays (MSAs) have been widely used in material science and biomedical applications by providing superhydrophobic surfaces, cell-interactive topography, and optical diffraction. These properties are tunable through the engineering of microstructure shapes, dimensions, tapering, and aspect ratios. However, the current fabrication methods are often too complex, expensive, or low-throughput. Here, we present a cost-effective approach to fabricating tapered 3D MSAs using dual-exposure lithography (DEL) and soft lithography. DEL used a strip-patterned film mask to expose the SU-8 photoresist twice. The mask was re-oriented between exposures (90° or 45°), forming an array of dual-exposed areas. The intensity distribution from both exposures overlapped and created an array of 3D overcut micro-pockets in the unexposed regions. These micro-pockets were replicated to DEL-MSAs in polydimethylsiloxane (PDMS). The shape and dimension of DEL-MSAs were tuned by varying the DEL parameters (e.g., exposure energy, inter-exposure wait time, and the photomask re-orientation angle). Further, we characterized various properties of our DEL-MSAs and studied the impact of their shape and dimension. All DEL-MSAs showed optical diffraction capability and increased hydrophobicity compared to plain PDMS surface. The hydrophobicity and diffraction angles were tunable based on the MSA shape and aspect ratio. Among the five MSAs fabricated, the two tallest DEL-MSAs demonstrated superhydrophobicity (contact angles >150°). Further, these tallest structures also demonstrated patterning proteins (with ~6–7 μm resolution), and mammalian cells, through microcontact printing and direct culturing, respectively. Our DEL method is simple, scalable, and cost-effective to fabricate structure-tunable microstructures for anti-wetting, optical-, and bio-applications.