Effect of surface roughness on slip flows in hydrophobic and hydrophilic microchannels by molecular dynamics simulation

The influences of surface roughness on the boundary conditions for a simple fluid flowing over hydrophobic and hydrophilic surfaces are investigated by molecular dynamics (MD) simulation. The degree of slip is found to decrease with surface roughness for both the hydrophobic and hydrophilic surfaces. The flow rates measured in hydrophobic channels are larger than those in hydrophilic channels with the presence of slip velocity at the walls. The simulation results of flow rate are correlated with the theoretical predictions according to the assumption of no slip boundary condition. The slip boundary condition also strongly depends on the shear rate near the surface. For hydrophobic surfaces, apparent fluid slips are observed on smooth and rough surfaces. For simple fluids flowing over a hydrophobic surface, the slip length increases linearly with shear rate for both the smooth and rough surfaces. Alternately, the slip length has a power law dependence on the shear rate for the cases of hydrophilic surfaces. It is observed that there is a no-slip boundary condition only when shear rate is low, and partial slip occurs when it exceeds a critical level.     

Molecular dynamics simulation of O2 diffusion in polydimethylsiloxane (PDMS) and end-linked PDMS networks

Molecular dynamics simulations are used to compute diffusion coefficients for O₂ molecules in polydimethylsiloxane (PDMS) and end-linked PDMS networks. The PDMS chains and penetrants are modelled using a hybrid interatomic potential which treats the Si and O atoms along the chain backbone explicitly while coarse-graining the methyl side groups and penetrants. In PDMS models with different molecular weights, diffusivity of the O₂ penetrants is found to modestly decrease with an increase in chain length. To match typical experimental conditions, the end-linked PDMS networks are constructed with a PDMS to crosslinking (CL) molecule mass ratio of 5:1 or 10:1, demanding that the number of CL molecules exceeds the number of PDMS chains in each model. Despite end-linking, the presence of non-bonded CL molecules promotes increased O₂ diffusivity in comparison with uncrosslinked PDMS. Temperature dependence is captured using the Williams–Landel–Ferry equation.     

Interaction parameters between carbon nanotubes and water in Dissipative Particle Dynamics

Flow of water past an array of single-walled carbon nanotubes (SWNTs) is simulated in this work to determine the interaction parameters of carbon nanotubes (CNTs) and water using Dissipative Particle Dynamics (DPD). For this flow configuration, results from molecular dynamics simulations by Walther et al. are available and can be used for validation (Phys. Rev. E, 2004, 062201). The hydrodynamic properties for SWNT (32, 0) with diameter of 2.5 nm were determined in different Reynolds number flows. A set of appropriate DPD parameters was found so that the drag coefficients of the CNT agreed well with the Stokes–Oseen analytical solution and the fluid slip length on the CNT wall was comparable with the Walther et al. results. It was also found that it is feasible to apply these parameters in longer length and time scales by increasing the number of water molecules grouped into each DPD bead and still maintain the hydrodynamic properties of CNTs as well as their hydrophobic surface character.     

Thermoresponsive protein adsorption of poly(N-isopropylacrylamide)-modified streptavidin on polydimethylsiloxane microchannel surfaces

The control of protein adsorption on microchannel surfaces is important for biosensors. In this study, we demonstrated protein adsorption method that is controlled through temperature change, i.e., thermoresponsive protein adsorption, on polydimethylsiloxane (PDMS) microchannel surfaces using a thermoresponsive polymer, poly(N-isopropylacrylamide) (PNIPAAm). To provide general protein adsorption control method, we adopted biotin-streptavidin chemistry and synthesized streptavidin covalently modified with PNIPAAm (PNIPAAm-StAv). Modification of streptavidin, a hydrophilic protein, with PNIPAAm induced successful thermoresponsive adsorption on a PDMS microchannel surfaces: PNIPAAm-StAv adsorbed at 37 degrees C and desorbed at 10 degrees C on the surfaces. We also demonstrated the thermoresponsive adsorption of biotinylated immunoglobulin G (IgG-b) using PNIPAAm-StAv. Conjugation of IgG-b with PNIPAAm-StAv induced successful thermoresponsive IgG-b adsorption on PDMS. Modification of PDMS surfaces with PNIPAAm reduced physical adsorption of the partially hydrophobic IgG-b on the surface and contributed to the high-contrast thermoresponsive adsorption of IgG-b: less than 1% of the IgG-b adsorbed at 37 degrees C was detected after the PNIPAAm-PDMS surface was washed at 10 degrees C. The controllable adsorption of this system is expected to be applied to the regeneration of biosensor chips and to on-chip protein manipulation.     

Nanomilling mechanism on Cu surfaces investigated using atomistic simulation

The nanoscale milling and scratching processes of copper workpieces are studied using molecular dynamics simulations based on the tight-binding and Morse potentials. The effects of the rotation velocity of the tool and the workpiece temperature are evaluated in terms of atomic trajectories, slip vectors, flow field of chips, cutting forces and groove characteristics. The simulation shows that a slip system in the ?110? direction on the workpiece surface occurs for milling with a tool rotation velocity of ω = 0°/fs. However, no apparent slip system appears for ω = 0.005°/fs or higher; instead, the number of amorphous areas increases. At ω = 0°/fs (nanoscratching), most of the removed atoms pile up in front of the tool and some gradually backfill when the tool rotates due to the effects of rotational friction and adhesion between the tool and the removed atoms. The largest number of removed atoms that piled up in front of the tool were obtained for milling with ω = 0°/fs; the number of removed atoms that piled up in front of the tool decreased with the increasing ω value. The component forces corresponding to the feed direction of the tool are the largest for the nanodrilling and nanomilling processes. High-precision grooves can be obtained at a low workpiece temperature (e.g. room temperature) with ω = 0°/fs.     

Micro-fabricated polydimethyl siloxane (PDMS) surfaces regulate the development of marine microbial biofilm communities

This study explored an antifouling (AF) concept based on deployment of microfabricated polydimethyl siloxane (PDMS) surfaces with 1–10?μm periodicity corrugated topographies in temperate marine waters. The effect of the surfaces on the development of microbial biofilms over 28?days and during different seasons, including both summer and winter, was examined using confocal laser scanning microscopy (CLSM) as well as terminal restriction fragment (T-RF) analysis for phylogenetic fingerprinting. The microscale topography significantly impacted biofilm development by altering the attachment pattern and reducing microcolony formation on the 1, 2 and 4?μm PDMS surfaces. Also, field deployments over 28?days showed a significant reduction in biovolume on the 4 and 10?μm PDMS surfaces despite altered environmental conditions. The microfabricated PDMS surfaces further significantly impacted on the community composition of the biofilms, as revealed by changes in T-RF profiles, at different stages of development. Moreover, altered biofilm resistance was demonstrated by exposing pre-established biofilms on 10?μm micro-fabricated surfaces to enhanced flagellate predation by a heterotrophic protist, Rhynchomonas nasuta. Pronounced changes in the overall marine microbial biofilm development as well as community composition warrant exploring substratum modification for marine AF applications.     

Anti-biofouling property studies on carboxyl-modified multi-walled carbon nanotubes filled PDMS nanocomposites

Polydimethylsiloxane (PDMS) with exceptional fouling-release properties is extremely susceptible to the microfouling resulted from the colonization of the pioneer microorganisms in the marine environment. In this study, six carboxyl-modified multi-walled carbon nanotubes (cMWNTs) nanoparticles were incorporated into the PDMS matrix, respectively, in order to produce the cMWNTs-filled PDMS nanocomposites (CPs) with improved antifouling (AF) properties. The AF properties of the six CPs were examined via the field assays conducted in Weihai, China. The effects of the anti-biofouling potential of the CPs (i.e. the P₃ surface) on the colonization of the pioneer prokaryotic and eukaryotic microbes were investigated using the single-stranded conformation polymorphism technique via the comparison of the diversity indices. Different CPs have displayed differential and better AF properties as compared to that of the unfilled PDMS (P₀). The P₃ surface has exhibited exceptional anti-biofouling capacity compared with the other CPs surfaces, which can effectively prevent biofouling for more than 14 weeks in the field. The SSCP analysis revealed that the P₃ surface may have significant modulating effect on the pioneer microbial communities. The pioneer eukaryotic microbes seemed more susceptible than the pioneer prokaryotic microbes to be subjected to the major perturbations exerted by the P₃ surface. The dramatically reduced eukaryotic-microbial diversity may contribute to the impeding and weakening of the development and growth of the biofilm. The P₃ surface has the potential to be used for future maritime applications.     

Fabrication of carbon films with ∼500 nm holes for cryo-EM with a direct detector device

Single particle electron cryomicroscopy (cryo-EM) is often performed using EM grids coated with a perforated or holey layer of amorphous carbon. Regular arrays of holes enable efficient cryo-EM data collection and several methods for the production of micropatterned holey-carbon film coated grids have been described. However, a new generation of direct detector device (DDD) electron microscope cameras can benefit from hole diameters that are smaller than currently available. Here we extend a previously proposed method involving soft lithography with a poly(dimethylsiloxane) (PDMS) stamp for the production of holey-carbon film coated EM grids. By incorporating electron-beam (e-beam) lithography and modifying the procedure, we are able to produce low-cost high-quality holey-carbon film coated EM grids with ∼500 nm holes spaced 4 μm apart centre-to-centre. We demonstrate that these grids can be used for cryo-EM. Furthermore, we show that by applying image shifts to obtain movies of the carbon regions beside the holes after imaging the holes, the contrast transfer function (CTF) parameters needed for calculation of high-resolution cryo-EM maps with a DDD can be obtained efficiently.     

Chitosan-mediated synthesis of gold nanoparticles on patterned poly(dimethylsiloxane) surfaces

Synthesis of gold nanoparticles on surfaces has been accomplished by the incubation of poly(dimethylsiloxane) (PDMS) films in tetrachloroauric(III) acid and chitosan solution at room temperature and 4 degrees C. One important point in the present study is that the synthesis selectively occurred on the PDMS surface. These observations are substantially different from the reaction in solution, in which no particles can be formed at room temperature. Computation of surface plasmon bands (SPBs) based on Mie theory suggests that the particles are partially coated by chitosan molecules, and the experimental results confirm the theoretical calculations. The proposed mechanism is that chitosan molecules adsorbed or printed on the PDMS surfaces act as reducing/stabilizing agents. Furthermore, PDMS films patterned with chitosan could induce localized synthesis of gold nanoparticles in regions capped with chitosan only. In this way, colloidal patterns were fabricated on the surfaces with high spatial selectivity simultaneously with the synthesis of the particles. Surface-induced fluorescence quenching was observed in the regions capped with gold nanoparticles as well.     

Fluorine-free mixed amphiphilic polymers based on PDMS and PEG side chains for fouling release applications

Fluorine-free mixed amphiphilic block copolymers with mixtures of short side groups of polydimethyl siloxane (PDMS) and polyethylene glycol (PEG) were synthesized and studied for their ability to influence the surface properties and control the adhesion of marine organisms to coated surfaces. The settlement (attachment) and strength of adhesion of two different marine algae, the green seaweed Ulva and the diatom Navicula, were evaluated against the surfaces. It is known that hydrophobic coatings based on polydimethyl siloxane elastomers (PDMSe) are prone to protein adsorption and accumulation of strongly adherent diatom slimes, in contrast to PEG-based hydrophilic surfaces that inhibit protein adsorption and moderate only weak adhesion of diatoms. By incorporating both PDMS and PEG side chains into the polymers, the effect of incorporating both polar and non-polar groups on fouling-release could be studied. The dry surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). The ability of these mixed amphiphilic polymers to reconstruct in water was examined using underwater bubble contact angle and dynamic water contact angle experiments. To understand more about surface reconstruction behavior, protein adsorption experiments were carried out with fluorescein isothiocyanate-labeled bovine serum albumin (BSA-FITC) on both dry and pre-soaked surfaces.     

Molecular modelling of ionic liquids in the ordered mesoporous carbon CMK-5

We performed classical molecular dynamics simulations of the ionic liquids (ILs) [dmim⁺][Cl^?] and [emim⁺][NTf₂^?], confined in a model CMK-5 material, which consists of amorphous carbon nanopipes (ACNPs) arranged in a hexagonal array. We compare our findings against the behaviour of the same ILs inside an isolated ACNP (i.e. no IL adsorbed on the outer surface of the ACNP) and inside a model CMK-3 material (which is similar to CMK-5, but is formed by amorphous carbon nanorods). Our results indicate that the presence of IL adsorbed in the outer surface of an uncharged ACNP in CMK-5 affects the dynamics and the density of an IL adsorbed inside the ACNP and vice versa. ILs adsorbed outside the nanopipes in CMK-5 (i.e. with IL also adsorbed inside the nanopipes) have faster dynamics and remain closer to the carbon surfaces when compared to the same ILs adsorbed on CMK-3 materials. The trends are IL-specific: [dmim⁺][Cl^?] has slower dynamics when inside an isolated ACNP than when inside the ACNPs in CMK-5, but in contrast, [emim⁺][NTf₂^?] moves faster when it is inside an isolated ACNP than when it is inside the ACNPs in CMK-5 (i.e. with IL adsorbed outside the nanopipes).     

Double Emulsion Generation Using a Polydimethylsiloxane (PDMS) Co-axial Flow Focus Device

Double emulsions are useful in a number of biological and industrial applications in which it is important to have an aqueous carrier fluid. This paper presents a polydimethylsiloxane (PDMS) microfluidic device capable of generating water/oil/water double emulsions using a coaxial flow focusing geometry that can be fabricated entirely using soft lithography. Similar to emulsion devices using glass capillaries, double emulsions can be formed in channels with uniform wettability and with dimensions much smaller than the channel sizes. Three dimensional flow focusing geometry is achieved by casting a pair of PDMS slabs using two layer soft lithography, then mating the slabs together in a clamshell configuration. Complementary locking features molded into the PDMS slabs enable the accurate registration of features on each of the slab surfaces. Device testing demonstrates formation of double emulsions from 14 µm to 50 µm in diameter while using large channels that are robust against fouling and clogging.     

Stable immobilization of rat hepatocytes as hemispheroids onto collagen-conjugated poly-dimethylsiloxane (PDMS) surfaces: importance of direct oxygenation through PDMS for both formation and function

The highly oxygen-permeable material, poly-dimethylsiloxane (PDMS), has the potential to be applied to cell culture microdevices, but cell detachment from PDMS has been a major problem. In this study, we demonstrate that a combination of collagen covalently immobilized PDMS and an adequate oxygen supply enables the establishment of a stable, attached spheroid (hemispheroid) culture of rat hepatocytes. The bottom PDMS surfaces were first treated with oxygen plasma, then coupled with aminosilane followed by a photoreactive crosslinker, and they were finally reacted with a collagen solution. X-ray photoelectron spectroscopy (XPS) and contact angle measurements showed that the covalent immobilization of collagen on the surface occurred only where the crosslinker had been introduced. On the collagen-conjugated PDMS surface, rat hepatocytes organized themselves into hemispheroids and maintained the viability and a remarkably high albumin production at least for 2 weeks of culture. In contrast, hepatocytes on the other types of PDMS surfaces formed suspended spheroids that had low albumin production. In addition, we showed that blocking the oxygen supply through the bottom PDMS surface inhibited the formation of hemispheroids and the augmentation of hepatocellular function. These results show that appropriate surface modification of PDMS is a promising approach towards the development of liver tissue microdevices.     

Cellulose thin films: degree of cellulose ordering and its influence on adhesion

Adhesion measurements have been performed with thin cellulose films using continuum contact mechanics with application of the JKR theory. Three different cellulose surfaces were prepared, one crystalline and two surfaces with a lower degree of crystalline order. Adhesion between two cross-linked poly(dimethylsiloxane) (PDMS) caps, as well as the adhesion between PDMS and the various cellulose surfaces, was measured. The work of adhesion (from loading) was found to be similar for all three surfaces, and from contact angle measurement with methylene iodide it was concluded that dispersive interactions dominate. However, the adhesion hysteresis differed significantly, being larger for a less ordered cellulose surface and decreasing with increasing degree of crystalline order. This is suggested to be due to the surface groups' ability to orient themselves and participate in specific or nonspecific interactions, where a surface with a lower degree of crystalline order has a higher possibility for reorientation of the surface groups. The mobility of cellulose chains increases with water uptake, resulting in stronger adhesive joints. These films will hence allow for determination of the contributions of hydrogen bonding and inter-diffusion on the adhesion, determined from the unloading data, as the thermodynamic work of adhesion was found to be independent of the cellulose surface used.     

Fluorine-free mixed amphiphilic polymers based on PDMS and PEG side chains for fouling release applications

Fluorine-free mixed amphiphilic block copolymers with mixtures of short side groups of polydimethyl siloxane (PDMS) and polyethylene glycol (PEG) were synthesized and studied for their ability to influence the surface properties and control the adhesion of marine organisms to coated surfaces. The settlement (attachment) and strength of adhesion of two different marine algae, the green seaweed Ulva and the diatom Navicula, were evaluated against the surfaces. It is known that hydrophobic coatings based on polydimethyl siloxane elastomers (PDMSe) are prone to protein adsorption and accumulation of strongly adherent diatom slimes, in contrast to PEG-based hydrophilic surfaces that inhibit protein adsorption and moderate only weak adhesion of diatoms. By incorporating both PDMS and PEG side chains into the polymers, the effect of incorporating both polar and non-polar groups on fouling-release could be studied. The dry surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). The ability of these mixed amphiphilic polymers to reconstruct in water was examined using underwater bubble contact angle and dynamic water contact angle experiments. To understand more about surface reconstruction behavior, protein adsorption experiments were carried out with fluorescein isothiocyanate-labeled bovine serum albumin (BSA-FITC) on both dry and pre-soaked surfaces.     

Is cell culture stressful? Effects of degradable and nondegradable culture surfaces on U937 cell function

In vitro cell culture has become one of the most widely used techniques in biological and health sciences research, with the most common culture supports being either tissue culture grade polystyrene (TCPS) or polydimethylsiloxane (PDMS). It has previously been shown that monocyte-derived macrophages (MDMs) respond to material surface chemistry, synthesizing and releasing degradative activities that could produce products, which alter the cell's response. In this study, functional parameters of differentiated U937 macrophage-like cells were compared when cultured on nondegradable standard control surfaces versus models of biomaterials (polycarbonate-based polyurethanes) used in the manufacture of medical devices previously shown to degrade and/or elicit pathways of inflammation. Although the influence of PDMS and TCPS on cell function is often underappreciated by investigators, both surfaces elicited enzyme markers of inflammation. Cells on TCPS had the highest intracellular and released esterase activities and protein levels. Cells on PDMS had the most released acid phosphatase activity and protein (P < 0.001), as well as de novo 57- and 59-kDa released proteins. The criteria for defining an activated cell phenotype become critically important when materials such as PDMS and TCPS are used as standard control surfaces whether in experiments for research in elucidating metabolic pathways or in screening drugs and materials for therapeutic uses.     

Candida albicans biofilm formation on peptide functionalized polydimethylsiloxane

In order to prevent biofilm formation by Candida albicans, several cationic peptides were covalently bound to polydimethylsiloxane (PDMS). The salivary peptide histatin 5 and two synthetic variants (Dhvar 4 and Dhvar 5) were used to prepare peptide functionalized PDMS using 4-azido-2,3,5,6-tetrafluoro-benzoic acid (AFB) as an interlinkage molecule. In addition, polylysine-, polyarginine-, and polyhistidine-PDMS surfaces were prepared. Dhvar 4 functionalized PDMS yielded the highest reduction of the number of C. albicans biofilm cells in the Modified Robbins Device. Amino acid analysis demonstrated that the amount of peptide immobilized on the modified disks was in the nanomole range. Poly-d-lysine PDMS, in particular the homopeptides with low molecular weight (2500 and 9600) showed the highest activity against C. albicans biofilms, with reductions of 93% and 91%, respectively. The results indicate that the reductions are peptide dependent.     

Adhesion Characteristics of a Novel Synthetic Polydimethylsiloxane for Bionic Adhesive Pads

Materials with appropriate adhesive properties are suitable for the fabrication of bionic adhesive pads. In this study, a novel polydimethylsiloxane （PDMS） material enhanced with two types of crosslinkers, carbon nanotubes and graphene sheets, was fabricated. The Contact Angle （CA） and cross-sectional morphology of the new material were investigated and observed using a CA meter and Scanning Electron Microscopy （SEM）, respectively. CA measurements indicate that the surface energy of the novel material is twice that of the common PDMS material. SEM observations show that carbon nanotubes and graphene sheets are well dispersed in the polymer, a feature that improves the mechanical properties of the new material. The adhesive performance of this novel composite was tested on an in-house fabricated friction machine. Results show that at a preload of only 50 mN, the adhesion of the novel PDMS material is up to -3.7 times that of common PDMS. The maximum macroscale shear strength and normal adhesion reach 4 N·cm^-2 and 1 N·cm^-2, respectively. The adhesive capability of the material is maintained even after hundreds of times of repeated use. This novel material exhibits excellent adhesion, sufficiently high elastic modulus and high repeatability at low preloads.     

Two-step cell patterning on planar and complex curved surfaces by precision spraying of polymers

Controlling adhesion of living animal cells plays a key role in biosensor fabrication, drug-testing technologies, basic biological research, and tissue engineering applications. Current techniques for cell patterning have two primary limitations: (1) they require photolithography, and (2) they are limited to patterning of planar surfaces. Here we demonstrate a simple, precision spraying method for both positive and negative patterning of planar and curved surfaces to achieve cell patterns rapidly and reproducibly. In this method, which we call precision spraying (PS), a polymer solution is aerosolized, focused with sheath airflow through an orifice, and deposited on the substrate using a deposition head to create approximately 25 microm sized features. In positive patterning, adhesive molecules, such as laminin or polyethylenimine (PEI) were patterned on polydimethylsiloxane (PDMS) substrates in a single spraying operation. A variety of animal cell types were found to adhere to the adhesive regions, and avoid the non-adhesive (bare PDMS) regions. In negative patterning, hydrophobic materials, such as polytetrafluoroethylene (PTFE) and PDMS, were patterned on glass substrates. Cells then formed patterns on the exposed glass regions and avoided the hydrophobic regions. Cellular patterns were maintained for up to 2 weeks in the presence of serum, which normally fouls non-adhesive regions. Additionally, we found that precision spraying enabled micropatterning of complex-curved surfaces. Our results show that precision spraying followed by cell plating enables rapid and flexible cellular micropatterning in two simple steps.     

Enhancing the efficacy of fouling-release coatings against fouling by Mytilus galloprovincialis using nanofillers

Fouling-release (FR) coatings minimise the adhesion strength of fouling organisms. This study describes improved technologies to control the settlement and adhesion of the important fouling organism Mytilus galloprovincialis by incorporating the nanofillers titanium dioxide (TiO₂) and carbon nanotubes (CNTs) in polydimethylsiloxane (PDMS) matrices. The incorporation of TiO₂ prevented larval settlement when photoactivated with UV light, even at the lowest concentration of the nanofiller (3.75 wt%). Notably, there was 100% mortality of pediveligers exposed to photoactivated TiO₂. However, plantigrades initially settled to photoactivated TiO₂, but their adhesion strength was significantly reduced on these surfaces in comparison to blank PDMS. In addition, plantigrades had high mortality after 6 h. In contrast to the enhanced antifouling and FR properties of PDMS incorporating TiO₂, the incorporation of CNTs had no effect on the settlement and adhesion of M. galloprovincialis.