Amphiphilic block copolymer/poly(dimethylsiloxane) (PDMS) blends and nanocomposites for improved fouling-release

Amphiphilic diblock copolymers, Sz6 and Sz12, consisting of a poly(dimethylsiloxane) block (average degree of polymerisation = 132) and a PEGylated-fluoroalkyl modified polystyrene block (Sz, average degree of polymerisation = 6, 12) were prepared by atom transfer radical polymerization (ATRP). Coatings were obtained from blends of either block copolymer (1–10 wt%) with a poly(dimethylsiloxane) (PDMS) matrix. The coating surface presented a simultaneous hydrophobic and lipophobic character, owing to the strong surface segregation of the lowest surface energy fluoroalkyl chains of the block copolymer. Surface chemical composition and wettability of the films were affected by exposure to water. Block copolymer Sz6 was also blended with PDMS and a 0.1 wt% amount of multiwall carbon nanotubes (CNT). The excellent fouling-release (FR) properties of these new coatings against the macroalga Ulva linza essentially resulted from the inclusion of the amphiphilic block copolymer, while the addition of CNT did not appear to improve the FR properties.     

Amphiphilic hydrolyzable polydimethylsiloxane-b-poly(ethyleneglycol methacrylate-co-trialkylsilyl methacrylate) block copolymers for marine coatings. II. Antifouling laboratory tests and field trials

Abstract

Poly(dimethylsiloxane) (PDMS) elastomer coatings containing an amphiphilic hydrolyzable diblock copolymer additive were prepared and their potential as marine antifouling and antiadhesion materials was tested. The block copolymer additive consisted of a PDMS first block and a random poly(trialkylsilyl methacrylate (TRSiMA, R?=?butyl, isopropyl)-co-poly(ethyleneglycol) methacrylate (PEGMA) copolymer second block. PDMS-b-TRSiMA block copolymer additives without PEGMA units were also used as additives. The amphiphilic character of the coating surface was assessed in water using the captive air bubble technique for measurements of static and dynamic contact angles. The attachment of macro- and microorganisms on the coatings was evaluated by field tests and by performing adhesion tests to the barnacle Amphibalanus amphitrite and the green alga Ulva rigida. All the additive-based PDMS coatings showed better antiadhesion properties to A. amphitrite larvae than to U. rigida spores. Field tests provided meaningful information on the antifouling and fouling release activity of coatings over an immersion period of 23?months.     

Impact of silicone-based block copolymer surfactants on the surface and bulk microscopic organization of a biodegradable polymer,poly(epsilon-caprolactone)

Two amphiphilic AB block copolymers, containing a highly compatible poly(epsilon-caprolactone) (PCL) block connected to a poly(dimethylsiloxane) (PDMS) block having a low surface energy, are synthesized and characterized in terms of their dispersion in a presynthesized PCL matrix. X-ray photoelectron spectroscopy, contact angle measurements, atomic force microscopy, and optical microscopy are used to describe the evolution of the surface chemical composition, as well as the surface and bulk morphology of the PCL/copolymer blends as a function of the nature and weight surface free energy and the dispersion of the copolymers in the blends, leading to important modifications of the bulk and the surface morphology. These differences are interpreted in terms of the impact of the block copolymers on the semicrystalline polymer structure and related properties in the prospect of using the surfactants to improve the synthesis of PCL in supercritical CO(2).     

A preliminary study on the properties and fouling-release performance of siloxane-polyurethane coatings prepared from poly(dimethylsiloxane) (PDMS) macromers

Siloxane-polyurethane fouling-release (FR) coatings based on aminopropyl terminated poly(dimethylsiloxane) (PDMS) macromers were prepared and characterized for FR performance via laboratory biological assays. These systems rely on self-stratification, resulting in a coating with a siloxane-rich surface and polyurethane bulk. Previously, these coating systems have used PDMS with multiple functional groups which react into the polyurethane bulk. Here, aminopropyl terminated PDMS macromers were prepared, where a single amine group anchors the PDMS in the coating. Coatings were prepared with four molecular weights (1000, 5000, 10,000, and 15,000 g mol?1) and two levels of PDMS (5% and 10%). High water contact angles and low surface energies were observed for the coatings before and after water immersion, along with low pseudobarnacle removal forces. Laboratory bioassays showed reduced biofilm retention of marine bacteria, good removal of diatoms from coatings with low molecular weight PDMS, high removal of algal sporelings (young plants), and low removal forces of live barnacles.     

Theoretical study of the surface properties of poly(dimethylsiloxane) and poly(tetrafluoroethylene)

Molecular dynamics (MD) simulations of poly(dimethylsiloxane) (PDMS) and poly(tetrafluoroethylene) (PTFE) were carried out to determine their surface properties and energies. This study helps to gain better insight into the molecular modeling of PDMS and PTFE, in particular how different approaches affect calculations of surface energy. Current experimental and theoretical data were used to further understand the surface properties of PDMS and PTFE as well as to validate and verify results obtained from the combination of density functional theory (DFT) calculations (including periodic boundary conditions) and MD simulations. Detailed analysis of the structure and electronic properties (by calculation of the projected density of states) of the bulk and surface models of PDMS and PTFE was performed. The sensitivity of the surface energy calculation of these two polymers to the chemistry and model preparation was indicated. The balance between the molecular density, weight (which also reflects bond orientation in the surface region), bond flexibility, and intramolecular interactions including bond stretching was revealed to govern the results obtained. In modeling, the structural organization of polymer near a given surface (types and number of end groups and broken bonds due to application of different cut offs of the periodic structure) also significantly affects the final results. Besides the structural differences, certain simulation parameters, such the DFT functionals and simulation boxes utilized, play an important role in determining surface energy. The models used here were shown to be sufficient due to their good agreement with experimental and other theoretical data related to surface properties and surface energies.     

In situ oligonucleotide synthesis on poly(dimethylsiloxane): a flexible substrate for microarray fabrication

In this paper, we demonstrate in situ synthesis of oligonucleotide probes on poly(dimethylsiloxane) (PDMS) microchannels through use of conventional phosphoramidite chemistry. PDMS polymer was moulded into a series of microchannels using standard soft lithography (micro-moulding), with dimensions <100 μm. The surface of the PDMS was derivatized by exposure to ultraviolet/ozone followed by vapour phase deposition of glycidoxypropyltrimethoxysilane and reaction with poly(ethylene glycol) spacer, resulting in a reactive surface for oligonucleotide coupling. High, reproducible yields were achieved for both 6mer and 21mer probes as assessed by hybridization to fluorescent oligonucleotides. Oligonucleotide surface density was comparable with that obtained on glass substrates. These results suggest PDMS as a stable and flexible alternative to glass as a suitable substrate in the fabrication and synthesis of DNA microarrays.     

Poly(dimethyl siloxane) (PDMS) network blends of amphiphilic acrylic copolymers with poly(ethylene glycol)-fluoroalkyl side chains for fouling-release coatings. II. Laboratory assays and field immersion trials

Amphiphilic copolymers containing different amounts of poly(ethylene glycol)-fluoroalkyl acrylate and polysiloxane methacrylate units were blended with a poly(dimethyl siloxane) (PDMS) matrix in different proportions to investigate the effect of both copolymer composition and loading on the biological performance of the coatings. Laboratory bioassays revealed optimal compositions for the release of sporelings of Ulva linza, and the settlement of cypris larvae of Balanus amphitrite. The best-performing coatings were subjected to field immersion tests. Experimental coatings containing copolymer showed significantly reduced levels of hard fouling compared to the control coatings (PDMS without copolymer), their performance being equivalent to a coating based on Intersleek 700?. XPS analysis showed that only small amounts of fluorine at the coating surface were sufficient for good antifouling/fouling-release properties. AFM analyses of coatings under immersion showed that the presence of a regular surface structure with nanosized domains correlated with biological performance.     

A preliminary study on the properties and fouling-release performance of siloxane–polyurethane coatings prepared from poly(dimethylsiloxane) (PDMS) macromers

Siloxane–polyurethane fouling-release (FR) coatings based on aminopropyl terminated poly(dimethylsiloxane) (PDMS) macromers were prepared and characterized for FR performance via laboratory biological assays. These systems rely on self-stratification, resulting in a coating with a siloxane-rich surface and polyurethane bulk. Previously, these coating systems have used PDMS with multiple functional groups which react into the polyurethane bulk. Here, aminopropyl terminated PDMS macromers were prepared, where a single amine group anchors the PDMS in the coating. Coatings were prepared with four molecular weights (1000, 5000, 10,000, and 15,000 g mol^?1) and two levels of PDMS (5% and 10%). High water contact angles and low surface energies were observed for the coatings before and after water immersion, along with low pseudobarnacle removal forces. Laboratory bioassays showed reduced biofilm retention of marine bacteria, good removal of diatoms from coatings with low molecular weight PDMS, high removal of algal sporelings (young plants), and low removal forces of live barnacles.     

Poly(dimethyl siloxane) (PDMS) network blends of amphiphilic acrylic copolymers with poly(ethylene glycol)-fluoroalkyl side chains for fouling-release coatings. II. Laboratory assays and field immersion trials

Amphiphilic copolymers containing different amounts of poly(ethylene glycol)-fluoroalkyl acrylate and polysiloxane methacrylate units were blended with a poly(dimethyl siloxane) (PDMS) matrix in different proportions to investigate the effect of both copolymer composition and loading on the biological performance of the coatings. Laboratory bioassays revealed optimal compositions for the release of sporelings of Ulva linza, and the settlement of cypris larvae of Balanus amphitrite. The best-performing coatings were subjected to field immersion tests. Experimental coatings containing copolymer showed significantly reduced levels of hard fouling compared to the control coatings (PDMS without copolymer), their performance being equivalent to a coating based on Intersleek 700?. XPS analysis showed that only small amounts of fluorine at the coating surface were sufficient for good antifouling/fouling-release properties. AFM analyses of coatings under immersion showed that the presence of a regular surface structure with nanosized domains correlated with biological performance.     

Poly(vinyl alcohol) functionalized poly(dimethylsiloxane) solid surface for immunoassay

In this communication, we describe a simple and robust method for the covalent bonding of poly(vinyl alcohol) (PVA) on a silanized poly(dimethylsiloxane) (PDMS) surface. Nonspecific adsorption of proteins via hydrophobic-hydrophobic interactions of the PVA-coated surface is greatly reduced, and biomolecules can be rapidly anchored on the PVA-coated surface with high loading and uniformity. On the basis of a sandwich immunoassay with the anti-rabbit IgG and IgG pair as a model, the detection limit for IgG is down to 1 pg/mL with linearity up to 11 microg the levels often encountered in biological, forensic, and environmental samples.     

Oxygen-independent poly(dimethylsiloxane)-based carbon-paste glucose biosensors

Several silicone oils have been assessed and compared as an internal source of oxygen in connection to their use as binders for carbon-paste glucose biosensors. All four poly(dimethylsiloxane) (PDMS) oils tested a dramatic increase in the oxygen capacity of carbon-paste enzyme electrodes to allow convenient biosensing under severe oxygen-deficit conditions. The resulting oxygen independence is better than that exerted by perfluorocarbon binders or that displayed by mediator-based bioelectrodes. The resistance to oxygen effects is indicated from the identical response (observed in the presence and absence of oxygen) up to 2 x 10(-2) M glucose and the slight (12%) sensitivity loss at 4 x 10(-2) M. The influence of the viscosity of the PDMS binder upon the internal oxygen supply is examined. The PDMS carbon-paste enzyme electrode displays a stable glucose response over prolonged (15 h) operation in an oxygen-free solution. On-line continuous testing indicates favorable dynamic properties with no carry-over effects over the physiological and pathophysiological range (3-12 mM glucose).     

Silicone fouling-release coatings: effects of the molecular weight of poly(dimethylsiloxane) and tetraethyl orthosilicate on the magnitude of pseudobarnacle adhesion strength

A series of poly(dimethyl siloxane) (PDMS)/silica nanocomposites were synthesized utilizing a sol gel method. The samples were evaluated using pseudobarnacle adhesion and tensile strength tests. The effects of the molecular weight of the PDMS and the size and structure of the silica domains on biofouling release and the mechanical behavior of the PDMS/silica materials were investigated. Three different molecular weights (18,000, 49,000 and 79,000 g mol(-1)) of hydroxyl-terminated PDMS (HT-PDMS) were used to prepare the nanocomposites with three different weight ratios (1:1, 3:1 and 5:1) of HT-PDMS to tetraethyl orthosilicate (TEOS). TEOS served as a crosslinker to form PDMS networks and as a precursor to form silica domains. Two different variants of TEOS with regard to its degree of polymerization (n) (monomeric type: n ≈= 1 and oligomeric type: n ≈= 5) were used for in situ formation of silica particles via the sol-gel process. The mechanical properties of the composites were characterized using stress-strain isotherms. All the mechanical properties evaluated (Young's modulus, tensile strength, energy required for rupture, elongation at break) improved with increases in the molecular weight of the HT-PDMS and the silica content. The pseudobarnacle adhesion test was used to examine the fouling- release (FR) properties of coatings applied on aluminum plates. The rupture energy and tensile strength increased substantially when oligomeric TEOS was employed in the PDMS/silica composites. Scanning electron microscopy (SEM) was used to investigate the structure of the silica domains. It was found that the use of oligomeric TEOS in higher molecular weight PDMS samples with higher PDMS/TEOS weight ratios led to low pseudobarnacle adhesion strengths of ≈ 0.3 MPa, which is in the range of commercial FR coatings.     

Poly(Dimethylsiloxane) (PDMS) Affects Gene Expression in PC12 Cells Differentiating into Neuronal-Like Cells

Introduction

Microfluidics systems usually consist of materials like PMMA - poly(methyl methacrylate) and PDMS - poly(dimethylsiloxane) and not polystyrene (PS), which is usually used for cell culture. Cellular and molecular responses in cells grown on PS are well characterized due to decades of accumulated research. In contrast, the experience base is limited for materials used in microfludics chip fabrication.

Methods

The effect of different materials (PS, PMMA and perforated PMMA with a piece of PDMS underneath) on the growth and differentiation of PC12 (adrenal phaeochromocytoma) cells into neuronal-like cells was investigated using cell viability, cell cycle distribution, morphology, and gene expression analysis.

Results/Conclusions

After differentiation, the morphology, viability and cell cycle distribution of PC12 cells grown on PS, PMMA with and without PDMS underneath was the same. By contrast, 41 genes showed different expression for PC12 cells differentiating on PMMA as compared to on PS. In contrast, 677 genes showed different expression on PMMA with PDMS underneath as compared with PC12 cells on PS. The differentially expressed genes are involved in neuronal cell development and function. However, there were also many markers for neuronal cell development and functions that were expressed similarly in cells differentiating on PS, PMMA and PMMA with PDMS underneath. In conclusion, it was shown that PMMA has a minor impact and PDMS a major impact on gene expression in PC12 cells.     

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.     

Electrochemical detection of cardiac troponin I using a microchip with the surface-functionalized poly(dimethylsiloxane) channel

A sensitive and rapid electrochemical microchip fabricated by assembling a surface-functionalized poly(dimethylsiloxane) (PDMS) microchannel with an interdigitated array (IDA) gold electrode was developed for the detection of human cardiac troponin I (cTnI) in the early diagnosis of acute myocardial infarction. Anti-cTnI was immobilized onto the internal surface of the PDMS channel on which protein G layer had been generated by silanization. To reduce electrode fouling, a PDMS channel was assembled with an IDA chip after surface treatment. The detection experiments were performed with successive injection of cTnI, alkaline phosphatase (AP)-labeled anti-cTnI, and p-aminophenylphosphate. Then, cyclic voltammograms were obtained by the oxidation peak current proportionally to the concentration of enzymatic product, p-aminophenol. The optimal packing density of anti-cTnI on the surface of the PDMS channel was determined at the anti-cTnI concentration of 30 microg/ml for the highest electrochemical signal. These demonstrate that the proper orientation and best packing density of antibody as well as no electrode fouling contributed to the low detection limit (148 pg/ml) of cTnI within 8 min.     

On-line monitoring of antifouling and fouling-release surfaces using bioluminescence and fluorescence measurements during laminar flow

A laminar flow biofilm-monitoring system was used to determine the efficacies of three antifouling (AF) coatings and five fouling-release (FR) coatings againstVibrio harveyi attachment. On-line measurements of tryptophan fluorescence and bioluminescence from each coating, normalized to an upstream stainless steel coupon, were used to determine the effects of AF and FR surfaces on biofilm formation. The AF coatings consisted of 5, 10, and 35 wt% Sea Nine 211 (C9211) incorporated into a vinyl copolymer. Both the 10 and 35 wt% coatings significantly inhibited biofilm biomass development measured by tryptophan fluorescence compared to the stainless steel control.V. harveyi bioluminescence was significantly greater than tryptophan fluorescence in cells attached to these coatings, suggesting that bioluminescence expression may be a marker for cellular stress or toxicity in biofilms. Five different polydimethylsiloxane (PDMS) FR coatings did not inhibit biofilm formation under low flow conditions. However, four PDMS coatings demonstrated decreased biomass levels compared to stainless steel after exposure to a shear stress of 330 dynes cm^–2. There was no toxic additive in these coatings; bioluminescence and tryptophan fluorescence were proportional.     

Synthesis of chitosan networks: Swelling, drug release, and magnetically assisted BSA separation using Fe(3)O(4) nanoparticles

Chitosan (CS) nanohydrogel networks were prepared by reaction with glyceroldiglycidylether (GDE) and poly(dimethylsiloxane) (PDMS), as crosslinking agents in an emulsion system. The nanogel content increased with increasing the amount of crosslinkers and reached to a maximum of 90% with GDE. The nanogels structure was characterized by FT-IR, AFM, DSC, and TGA. The average size for CS-GDE and CS-PDMS particles were 59nm and 180nm, respectively. The swelling behavior of nanohydrogels was observed to be dependent on pH, temperature, degree of crosslinking, and on the chemical structure of crosslinker. The equilibrium water content of CS-GDE nanohydrogels reached to a maximum of 600% at neutral pH, and decreased at high and low pH and low temperature. These nanohydrogels were tested for sodium diclofenac (SDF) loading and releasing efficiency. The covalent conjugation of bovine serum albumin (BSA) and magnetic Fe(3)O(4) nanoparticles on the hydrogels were found to hold a potential application in magnetically assisted bioseparation.     

On-chip cell culture on a microarray of extracellular matrix with surface modification of poly(dimethylsiloxane)

Microfluidic cell culture chips allow to perform assays of small-volume samples rapidly and reproducibly. Most of these chips are made of poly(dimethylsiloxane) (PDMS), which is a flexible, durable, transparent and inexpensive polymer that can be easily applied to fabrication of microstructures by photolithography and replica molding. However, not many cells are able to grow on unmodified PDMS because the cells need appropriate scaffolds on the surface. Here we report surface modification of a PDMS substrate with a microarray of extracellular matrix (ECM) for on-chip cell culture. The ECM proteins collagen and fibronectin were covalently immobilized on an 8 x 8 microarray format by micropatterned UV-induced graft polymerization through a photomask and dehydration-condensation reaction through a microfabricated stencil. Identical spots of ECMs were successfully formed and the geometry of the spots accurately corresponded to the micropattern of the photomask and stencil. We demonstrate the culture of CHO-K1 cells on the ECM microarray chip. Cells proliferated on the fibronectin spots during the 2-day culture.     

Artificial carrier for oxygen supply in biological systems

Several poly (dimethylsiloxanes) (PDMS) copolymers of dimethylsiloxane (DMS) with ethylene or propylene oxide were tested as artificial carriers for the delivery of oxygen to biological systems. Copolymers with a DMS content of 33% or lower enhanced glucose oxidation by 200% in contrast to the 25% increase produced by the same concentration of perfluorodecalin. When 0.05% of the copolymer with 18% DMS was included in the growth media of Bacillus thuriginensis, the biomass (growth rate) increased 1.5-fold. With 0.1% of this copolymer, actinorhodin production by Streptomyces coelicolor A3 (2) occurred in half the normal time and with an increased yield. In conclusion, these PDMS copolymers are a good alternative to perfluorodecalin as oxygen carriers in biotechnological processes.     

Laboratory screening of coating libraries for algal adhesion

Coatings libraries achieved through a combinatorial chemistry approach, which may generate tens to hundreds of formulations, can be deposited in an array of 12 patches, each approximately 9 cm(2), on 10 x 20 cm primed aluminum panels. However, existing methods to quantify algal biomass on coatings are unsuitable for this type of array format. This paper describes an algorithm modelled on a probability distribution that quantifies the area of surface covered by a green alga from digital images. The method allows coatings with potential fouling-release properties to be down-selected for further evaluation. The use of the algorithm is illustrated by a set of eight siloxane-polyurethane coatings made using organofunctional poly(dimethylsiloxane) (PDMS) and poly(epsilon-caprolactone)-PDMS-poly(epsilon-caprolactone) (PCL-PDMS-PCL) triblock copolymers along with four PDMS standards which were deposited on one panel. Six replicate panels were seeded with Ulva zoospores which grew into sporelings (small plants) that completely covered the surface. The ease of removal of the Ulva sporeling biofilms was determined by automated water jetting at six different impact pressures. The coverage of the biofilm on the twelve individual formulations after jet washing was quantified from the green colour of digital images. The data are discussed in relation to the composition of the coatings.