"Big Dipper" Dynamic Contact Angle Curves for Pt-Cured Poly(dimethylsiloxane) on a Thermal Gradient: Inter-relationships of Hydrosilylation, Si-H Autoxidation, and Si-OH Condensation to a Secondary Network.

Platinum cure for poly(dimethylsiloxane) (PDMS) coatings on a thermal gradient (45-140 °C) was carried out to study the effect of temperature on surface chemistry and wetting behavior. The motivation is the interest in surfaces with continuous gradients in wettability for applications such as protein adsorption, controlling bacterial adhesion, directional movement of cells, and biosensors. The Wilhelmy plate method and the advancing/receding drop method were employed for determining the positional dependence of θA and θR. A strong dependence of receding contact angles (θR) on cure temperature was found for Sylgard 184 (S-PDMS) and a Pt-cured laboratory-prepared analogue (Pt-PDMS) of known composition. Cure on the thermal gradient gave rise to striking "Big Dipper" Wilhelmy plate dynamic contact angle curves. High contact angle hysteresis (60-80°) was found for 45 °C cure (CAH = Î¸Δ = θA - θR) but low CAH for 140 °C cure (10-20°). Drop addition/withdrawal using goniometry identified a similar trend. Attenuated total reflectance infrared spectroscopy showed absorptions for Si-OH (3500 cm-1) and Si-H (1250 cm-1) that were correlated with wetting behavior and near-surface chemistry. These studies revealed a complex relationship among hydrosilylation, Si-H autoxidation, and condensation of Si-OH. A model for advancing from a single network due to hydrosilylation to a double network for hydrosilylation plus Si-O-Si from condensation of Si-OH best explains evidence from spectroscopic and contact angle studies. These results are relevant to interactions of Pt-cured silicones at bio-interfaces, as receding contact angles determine work of adhesion, as well as applications that benefit from maximum hydrophobicity and minimizing water roll-off angles.

A Polycation Antimicrobial Peptide Mimic without Resistance Buildup against Propionibacterium Acnes.

A preliminary study is reported for a polycation antimicrobial peptide (AMP) mimic against Propionibacterium acnes, which is associated with acne vulgaris, a common skin condition. Antibiotics are commonly used against P. acnes but buildup of resistance is well-known. Worse, antibiotic regimens build up resistance for more sensitive bacteria such as Staphylococcus epidermidis. The polycation AMP mimic C12-50, 1, is chosen for the present study as it has been previously shown to have high antimicrobial effectiveness. This study reports that C12-50 is active against P. acnes (strain ATCC 6919) with a minimum inhibitory concentration (MIC) of 6.3 µg mL-1 . To monitor resistance build-up ten passages are conducted with C12-50 against P. acnes. The MIC remains constant with no resistance buildup. Parallel studies with erythromycin confirm previously reported resistance buildup. The results point to a promising pathway to applications for polycation AMP mimics against P. acnes.

Base Layer Influence on Protonated Aminosilane Gradient Wettability.

Protonated amine gradients have been prepared on silicon wafers via programmed controlled rate infusion (CRI) with varying degrees of hydrophobicity and characterized by X-ray photoelectron spectroscopy (XPS) and static and Wilhelmy plate dynamic contact angle measurements. Initially, base layers were spin coated from sols containing tetramethoxysilane (TMOS) and either phenyltrimethoxysilane (PTMOS), dimethyldimethoxysilane (DMDMOS), or octyltrimethoxysilane (OTMOS, C8). Amine gradients were then prepared from 3-aminopropyltriethoxysilane (APTEOS) via CRI. Gradients were exposed to concentrated HCl vapor for amine protonation. XPS showed that NH2 functional groups were distributed in a gradient fashion as a result of CRI controlling the time of exposure to APTEOS. Interestingly, the overall extent of N modification depended on the type of base layer used for gradient formation. The C8-derived base layer had about half the amount of nitrogen on the surface as compared to those prepared from TMOS, which was attributed to a reduction in the number and accessibility of surface silanol groups. The wettability and contact angle (CA) hysteresis were also dependent on the base layer and varied along the length of the gradient. The greatest CA change across the length of the gradient was observed on the gradient formed on the C8-derived base layer. Likewise, the CA hysteresis was approximately 2 times larger on the C8-modified surfaces, indicative of greater chemical inhomogeneity. In contrast to uniformly modified substrates, Wilhelmy plate CA analysis that involves the immersion of samples gave a unique S-shaped CA distance curve for the gradients. The three curve segments correspond to hydrophilic, hydrophobic, and a middle connecting region. Importantly, these curves give precise CAs along the gradient that reflect the surface chemistry and coverage defined by programmed CRI processing.

Sticky or Slippery Wetting: Network Formation Conditions Can Provide a One-Way Street for Water Flow on Platinum-cured Silicone.

In the course of studies on Sylgard 184 (S-PDMS), we discovered strong effects on receding contact angles (CAs), θrec, while cure conditions have little effect on advancing CAs. Network formation at high temperatures resulted in high θadv of 115-120° and high θrec ≥ 80°. After network formation at low temperatures (≤25 °C), θadv was still high but θrec was 30-50°. Uncertainty about compositional effects on wetting behavior resulted in similar experiments with a model D(V)D(H) silicone elastomer (Pt-PDMS) composed of a vinyl-terminated poly(dimethylsiloxane) (PDMS) base and a polymeric hydromethylsilane cross-linker. Again, network formation at high temperature (∼100 °C) resulted in high CAs, while low-temperature curing retained high advancing CAs but gave low receding CAs (θrec 30-50°). These changes in receding CAs translate to strong effects on water adhesion, wp, which is the actual work required to separate a liquid (water) from a surface: wp ∝ (1 + θrec). When the values θrec 84° for high-temperature and θrec 50° for low-temperature network formation are used, wp is ∼1.5 times higher for curing at low temperature. The origin of low receding contact angles was investigated by attenuated total reflectance IR spectroscopy. Absorptions for Si-OH hydrogen-bonded to water (3350 cm(-1)) were stronger for low- versus high-temperature curing. This result is attributed to faster hydrosilylation during curing at higher temperatures that consumes Si-H before autoxidation to Si-OH. Sharp bands at 3750 and 3690 cm(-1) due to isolated -Si-OH are more prominent for Pt-PDMS than those for S-PDMS, which may be due to an effect of functionalized nanofiller. To explore the impact of wp on water droplet flow, gradient coatings of S-PDMS and Pt-PDMS elastomers were prepared by coating a slide, maintaining opposite ends at high and low temperatures and thus forming a thermal gradient. When the slide was tilted, a droplet moved easily on the high-temperature end (slippery surface) but became pinned at the low-temperature end (sticky surface) and did not move when the slide was rotated 180°. The surface was therefore a "one-way street" for water droplet flow. Theory provides fundamental understanding for slippery/sticky behavior for gradient S-PDMS and Pt-PDMS coatings. A model for network formation is based on hydrosilylation at high temperature and condensation curing of Si-OH from autoxidation of Si-H at low temperatures. In summary, network formation conditions strongly affect receding contact angles and water adhesion for Sylgard 184 and the filler-free mimic Pt-PDMS. These findings suggest careful control of curing conditions is important to silicones used in microfluidic devices or as biomedical materials. Network-forming conditions also impact bulk mechanical properties for Sylgard 184, but the range that can be obtained has not been critically examined for specific applications.

Real-Time Observation of Antimicrobial Polycation Effects on Escherichia coli: Adapting the Carpet Model for Membrane Disruption to Quaternary Copolyoxetanes.

Real-time atomic force microscopy (AFM) was used for analyzing effects of the antimicrobial polycation copolyoxetane P[(C12)-(ME2Ox)-50/50], C12-50 on the membrane of a model bacterium, Escherichia coli (ATCC# 35218). AFM imaging showed cell membrane changes with increasing C12-50 concentration and time including nanopore formation and bulges associated with outer bacterial membrane disruption. A macroscale bactericidal concentration study for C12-50 showed a 4 log kill at 15 µg/mL with conditions paralleling imaging (1 h, 1x PBS, physiological pH, 25 °C). The dramatic changes from the control image to 1 h after introducing 15 µg/mL C12-50 are therefore reasonably attributed to cell death. At the highest concentration (60 µg/mL) further cell membrane disruption results in leakage of cytoplasm driven by detergent-like action. The sequence of processes for initial membrane disruption by the synthetic polycation C12-50 follows the carpet model posited for antimicrobial peptides (AMPs). However, the nanoscale details are distinctly different as C12-50 is a synthetic, water-soluble copolycation that is best modeled as a random coil. In a complementary AFM study, chemical force microscopy shows that incubating cells with C12-50 decreased the hydrophobicity across the entire cell surface at an early stage. This finding provides additional evidence indicating that C12-50 polycations initially bind with the cell membrane in a carpet-like fashion. Taken together, real time AFM imaging elucidates the mechanism of antimicrobial action for copolyoxetane C12-50 at the single cell level. In future work this approach will provide important insights into structure-property relationships and improved antimicrobial effectiveness for synthetic amphiphilic polycations.

Integrated compositional and nanomechanical analysis of a polyurethane surface modified with a fluorous oxetane siliceous-network hybrid.

Investigating the surface characteristics of heterogeneous polymer systems is important for understanding how to better tailor surfaces and engineering specific reactions and desirable properties. Here we report on the surface properties for a blend consisting of a major component, a linear polyurethane or thermoplastic elastomer (TPU), and a minor component that is a hybrid network. The hybrid network consists of a fluorous polyoxetane soft block and a hydrolysis/condensation inorganic (HyCoin) network. Phase separation during coating formation results in surface concentration of the minor fluorous hybrid domain. The TPU is H12MDI/BD(50)-PTMO-1000 derived from bis(cyclohexylmethylene)-diisocyanate and butane diol (50 wt %) and poly(tetramethylene oxide). Surface modification results from a novel network-forming hybrid composed of poly(trifluoroethoxymethyl-methyl oxetane) diol) (3F) as the fluorous moiety end-capped with 3-isocyanatopropylriethoxysilane and bis(triethoxysilyl)ethane (BTESE) as a siliceous stabilizer. We use an integrated approach that combines elemental analysis of the near surface via X-ray photoelectron microscopy with surface mapping using atomic force microscopy that presents topographical and phase imaging along with nanomechanical properties. Overall, this versatile, high-resolution approach enabled unique insight into surface composition and morphology that led to a model of heterogeneous surfaces containing a range of constituents and properties.