Marek Jasieniak

Reactive Epoxy-Functionalized Thin Films by a Pulsed Plasma Polymerization Process

A novel plasma functionalization process based on the pulsed plasma polymerization of allyl glycidyl ether is reported for the generation of robust and highly reactive epoxy-functionalized surfaces with well-defined chemical properties. Using a multitechnique approach including X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), infrared spectroscopy (FT-IR), atomic force microscopy (AFM) and ellipsometry, the effect of the plasma deposition parameters on the creation and retention of epoxy surface functionalities was characterized systematically. Under optimal plasma polymerization conditions (duty cycle: 1 ms/20 ms and 1 ms/200 ms), reactive uniform films with a high level of reproducibility were prepared and successfully used to covalently immobilize the model protein lysozyme. Surface derivatization was also carried out with ethanolamine to probe for epoxy groups. The ethanolamine blocked surface resisted nonspecific adsorption of lysozyme. Lysozyme immobilization was also done via microcontact printing. These results show that allyl glycidyl ether plasma polymer layers are an attractive strategy to produce a reactive epoxy functionalized surface on a wide range of substrate materials for biochip and other biotechnology applications.

Statistical comparison of surface species in flotation concentrates and tails from TOF-sims evidence

Abstract The coverage of potassium isobutyl xanthate (IBX) and sodium diisobutyl dithiophosphinate (DBPhos) adsorbed on the surface of galena has been investigated by Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS). Differences in surface concentrations and distributions between particles and across individual particle surfaces were sought comparing flotation concentrate and tail samples. This study has shown that a large difference is found in collector adsorption for both IBX and DBPhos between different faces of galena particles. The amount of collector adsorbed on galena particles of different sizes was statistically inseparable. However, a large variation in collector concentration on particles of the same size was observed. Statistical analysis of DBPhos on galena particles in the first concentrate and tail indicated that TOF-SIMS can be used to quantitatively investigate the flotation response of galena based on hydrophobic/hydrophilic ratios for each particle. Differences between collector distributions on concentrate and tail samples can be statistically separated. TOF-SIMS data also produced various hydrophilic and hydrophobic indices derived from the selected pairs of related spectral measures: Ca + /Pb + , Al + /Pb + , PbOH + /Pb + , SO 3 − /S 2 − , DBPhos − /SO 3 − . Linear regression and mean analyses were used to estimate these indices; the results correlated closely with the flotation response. Hydrophilic species concentrations such as calcium, aluminium and metal hydroxides were found to be statistically greater on tailings than on the concentrate particle surfaces. The method suggests that it will be possible to assess conditioning of sulphide surfaces for optimum selectivity.

SIMS studies of oxidation mechanisms and polysulfide formation in reacted sulfide surfaces

Abstract The surface oxidation of metal sulfides in air and aqueous solution is of central importance in mineral separation and environmental control of acid mine drainage. Mechanisms of oxidation, dissolution and surface restructuring have been extensively studied using XPS. High binding energy components in S 2p XPS spectra have been attributed to metal-deficiency, formation of polysulfide S n 2− , elemental sulfur and electronic defect structures (ie Cu(I)/ZnS). The assignment of these components in S 2p XPS spectra has, however, left significant uncertainties particularly in the formation of SS bonding in polysulfide species requiring confirmation from other surface analytical techniques. The use of static ToF-SIMS has provided a new avenue for identification of these species and their development in oxidation of the sulfide surfaces. For the iron sulfides, there is a systematic change in the FeS 2 /FeS fragment ratio from troilite (FeS) through pyrrhotite (Fe 1−x S) to pyrite (FeS 2 ) with ratios varying from 0.59, 1.2 to 32 respectively. Similarly, high ratios for FeS n /FeS are found for pyrite compared with pyrrhotite and troilite mirrored in the S n /S fragment ratios. Changes in surface oxidation, represented in atomic concentrations and S 2p XPS spectra, are seen in the ToF-SIMS signals for S n /SO n ratios in the same iron sulfide sequence. These mass markers, reflecting increased SS bonding, increase in surfaces after oxidation giving further confidence in XPS assignment to polysulfide species. Freshly cleaved galena PbS surfaces reacted in pH8 aqueous solution for increasing periods of time have also shown a systematic increase in S n /S ratios with increasing at.% of oxidised S n 2− species from XPS spectra. Statistical analysis of oxidised galena has shown that the ratios 206 PbO + / 206 Pb + and 208 PbOH + / 208 Pb + directly reflect the degree of oxidation of the surface lead species whilst the O − /S − , S − /total — ion yield and SO 3 − /S − are the best measures for following the oxidation of sulfur species. Results from these ratios suggest that initial air oxidation takes place predominantly on the S sites rather than Pb sites but, in solution at pH9, both sites are oxidised. The ToF-SIMS results appear to directly reflect the surface chemistry of the metal and sulfur species and are not consistent with recombination or fragmentation of secondary neutral or ionic species. The results strongly suggest increasing polymerisation of SS species with increasing oxidation in accord with the XPS assignment to polysulfide of increasing chain length.

Polymer supported cobalt(II) catalysts for alkene epoxidation

Abstract A study of polyaniline (PANI), poly-o-toluidine (POT) and poly-o-anisidine (POA) cobalt supported catalysts has been presented. The catalysts were prepared by depositing cobalt species onto the polymers surfaces. Cobalt(II) acetate and N,N′-ethylene-bis(salicylideneimine) cobalt(II) (Co(II)Salen) were used in the syntheses. The catalysts performance was examined in epoxidation of trans-stilbene by molecular oxygen and they turned out to be very efficient under mild conditions. The relationship between the surface exposure of cobalt species and the activity of these polymeric catalysts has been established.

Grafting of poly(ethylene glycol) on click chemistry modified Si(100) surfaces.

Poly(ethylene glycol) (PEG) is one of the most extensively studied antifouling coatings due to its ability to reduce protein adsorption and improve biocompatibility. Although the use of PEG for antifouling coatings is well established, the stability and density of PEG layers are often inadequate to provide optimum antifouling properties. To improve on these shortcomings, we employed the stepwise construction of PEG layers onto a silicon surface. Acetylene-terminated alkyl monolayers were attached to nonoxidized crystalline silicon surfaces via a one-step hydrosilylation procedure with 1,8-nonadiyne. The acetylene-terminated surfaces were functionalized via a copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction of the surface-bound alkynes with an azide to produce an amine terminated layer. The amine terminated layer was then further conjugated with PEG to produce an antifouling surface. The antifouling surface properties were investigated by testing adsorption of human serum albumin (HSA) and lysozyme (Lys) onto PEG layers from phosphate buffer solutions. Detailed characterization of protein fouling was carried out with X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with principal component analysis (PCA). The results revealed no fouling of albumin onto PEG coatings whereas the smaller protein lysozyme adsorbed to a very low extent.

Comprehensive characterization of grafted expanded poly(tetrafluoroethylene) for medical applications

Successful implantation of any biomaterial depends on its mechanical, architectural, and surface properties. Materials with good bulk properties seldom possess the appropriate surface characteristics required for good biointegration. The present study investigates the results of surface modification of a highly porous, fully fluorinated polymeric substrate, expanded poly(tetrafluoroethylene) (ePTFE), with a view to improving the surface bioactivity and hence ultimately its biointegration. Modification involved gamma irradiation-induced graft copolymerization with the monomers monoacryloxyethyl phosphate (MAEP) and methacryloxyethyl phosphate (MOEP) in various solvent systems (water, methanol, methyl ethyl ketone, and mixtures thereof). In order to determine the penetration depth of the graft copolymer into the pores and/or the bulk of the ePTFE membranes, angle-dependent X-ray photoelectron spectroscopy (XPS) and magnetic resonance imaging (MRI) were used. It was found that the penetration depth was critically affected by the choice of monomer and solvent as well as by the technique used to remove dissolved oxygen from the grafting mixture: nitrogen degassing versus vacuum. Difficulties due to the porous nature of the membranes in establishing the lateral position of the graft copolymers were largely overcome by combining data from microattenuated total reflectance Fourier transfer infrared (μ-ATR-FTIR) mapping and time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging. Results show that the large variation in graft heterogeneity found between different samples is largely an effect of the underlying substrate and choice of monomer. The results from this study provide the necessary knowledge and experimental data to control both the graft copolymer lateral position and depth of penetration in these porous ePTFE membranes.

Time-of-Flight-Secondary Ion Mass Spectrometry Study of the Temperature Dependence of Protein Adsorption onto Poly(N-isopropylacrylamide) Graft Coatings

Stimuli-responsive materials show considerable promise for applications that require control over biomolecule interactions at solid material interfaces. Graft coatings of poly(N-isopropylacrylamide) (pNIPAM) are of interest for biomedical and biotechnological applications due to their temperature-dependent switching of surface properties between adhesive and nonadhesive states for cells and proteins. The characterization of protein adsorption to these switchable coatings is a formidable task since switching not only influences the affinity for proteins but at the same time induces a significant change in the coating. Here, the highly sensitive analytical technique of time-of-flight-secondary ion mass spectrometry (TOF-SIMS) combined with principal component analysis (PCA) was used for the characterization of protein adsorption onto pNIPAM coatings prepared by free radical polymerization onto surface-bound polymerizable groups. Adsorption of bovine serum albumin and lysozyme onto pNIPAM coatings from phosphate buffered solutions was investigated at temperatures above and below the polymers lower critical solution temperature (LCST). Below the LCST, no adsorbed proteins could be detected even with this ultrasensitive method. Whereas above the LCST, adsorbed protein was detected in amounts corresponding at less than the monolayer. PCA loadings plots showed that adventitious contaminants, which might lead to confounding or misleading spectral changes upon protein exposure, were not observed.

Surface coatings with covalently attached caspofungin are effective in eliminating fungal pathogens

In this work we have prepared surface coatings formulated with the antifungal drug caspofungin, an approved pharmaceutical lipopeptide compound of the echinocandin drug class. Our hypothesis was to test whether an antifungal drug with a known cell-wall disrupting effect could be irreversibly tethered to surface coatings and kill (on contact) biofilm-forming fungal human pathogens from Candida spp. The first aim of the study was to use surface analysis to prove that the chemical binding to the surface polymer interlayer was through specific and irreversible bonds (covalent) and not due to non-specific adsorption through weak forces that could be later reversed (physisorption). Secondly, we quantified the antifungal nature of these coatings in a biological assay showing excellent killing against C. albicans and C. tropicalis and moderate killing against C. glabrata and C. parapsilosis. We concluded that caspofungin retains antifungal activity even when it is irreversibly immobilized on a surface, providing a new insight into its mechanism of action. Thus, surface coatings that have echinocandins permanently bound will be useful in preventing the establishment of fungal biofilms on materials.

Photo-doping of plasma-deposited polyaniline (PAni)

Although polyaniline (PAni) has been studied extensively in the past, little work has been done on producing films of this material via plasma deposition. We have synthesized and analysed the photoresponse behavior of plasma-deposited polyaniline films and proceeded to dope the films using light and with various metal ions. Upon illumination, the photocurrent responses of the thin plasma films increased over time, and the response was dependent on the film thickness. On doping the film with metal ions, the photocurrent densities were enhanced from nano- to micro-amperes per square centimeters. Doping seemed, however, to cause the films to become unstable. Despite this setback, which requires further research, the drastic increase in current shows great promise for the development of plasma-deposited polyaniline films for application in the area of organic electronics and photovoltaics.

Comparison of Plasma Polymerization under Collisional and Collision-Less Pressure Regimes

While plasma polymerization is used extensively to fabricate functionalized surfaces, the processes leading to plasma polymer growth are not yet completely understood. Thus, reproducing processes in different reactors has remained problematic, which hinders industrial uptake and research progress. Here we examine the crucial role pressure plays in the physical and chemical processes in the plasma phase, in interactions at surfaces in contact with the plasma phase, and how this affects the chemistry of the resulting plasma polymer films using ethanol as the gas precursor. Visual inspection of the plasma reveals a change from intense homogeneous plasma at low pressure to lower intensity bulk plasma at high pressure, but with increased intensity near the walls of the chamber. It is demonstrated that this occurs at the transition from a collision-less to a collisional plasma sheath, which in turn increases ion and energy flux to surfaces at constant RF power. Surface analysis of the resulting plasma polymer films show that increasing the pressure results in increased incorporation of oxygen and lower cross-linking, parameters which are critical to film performance. These results and insights help to explain the considerable differences in plasma polymer properties observed by different research groups using nominally similar processes.