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As some proteins are known to interact with sulfated and phosphated biomolecules such as specific glycosaminoglycans, this study derives from the hypothesis that sulfonate and phosphonate groups on solid polymer surfaces might cause specific interfacial interactions. Such surfaces were prepared by plasma polymerization of heptylamine (HA) and subsequent grafting of sulfonate or phosphonate groups via Michael-type addition of vinylic compounds. Adsorption of the proteins fibrinogen, albumin (HSA) and lysozyme on these functionalised plasma polymer surfaces was studied by XPS and quartz crystal microbalance with dissipation (QCM-D). It was also studied whether pre-adsorption with HSA would lead to a passivated surface against further adsorption of other proteins. XPS confirmed grafting of vinyl sulfonate and vinyl phosphonate onto the amine surface and showed that the proteins adsorbed to saturation at between 1 and 2 h. QCM-D showed rapid and irreversible adsorption of albumin on all three surfaces, while lysozyme could be desorbed with PBS to substantial extents from the sulfonated and phosphonated surfaces but not from the amine surface. Fibrinogen showed rapid initial adsorption followed by slower additional mass gain over hours. Passivation with albumin led to small and largely reversible subsequent adsorption of lysozyme, whereas with fibrinogen partial displacement yielded a mixed layer, regardless of the surface chemistry. Thus, protein adsorption onto these sulfonated and phosphonated surfaces is complex, and not dominated by electrostatic charge effects. Refereed/Peer-reviewed

In this report, we demonstrate that continuous improvement in XPS instruments and the calibration standards as well as analysis with standard component-fitting procedures can be used to determine the binding energies of compounds containing phosphorus and sulfur of different oxidation states with higher confidence. Based on such improved XPS analyses, the binding energies (BEs) of S2p signals for sulfur of increasing oxidation state are determined to be 166-167.5 eV for S=O in dimethyl sulfoxide, 168.1 eV for S=O2 in polysulfone, 168.4 eV for SO3 in polystyrene sulfonate and 168.8 eV for SO4 in chondroitin sulfate. The BEs of P2p signals show the following values: 132.9 eV for PO3 in triisopropyl phosphite, 133.3 eV for PO4 in glycerol phosphate, 133.5 eV for PO4 in sodium tripolyphosphate and 134.0 eV for PO4 in sodium hexametaphosphate. These results showed that there are only small increases in the binding energy when additional oxygen atoms are added to the S-O chemical group. A similar result is obtained when the fourth oxygen or poly-phosphate environment is added to the phosphorus compound. These BE values are useful to researchers involved in identifying oxidation states of phosphorus and sulfur atoms commonly observed on modified surfaces and interfaces found in applications such as biomaterials, super-capacitors and catalysis Refereed/Peer-reviewed

In comparison with other chemistries, little has been reported on sulfur-containing plasma polymers; reasons include low volatility or high toxicity of monomers. Here, we report on plasma polymerization of dimethyl sulfoxide, by itself and its co-polymerization with 1,7-octadiene to generate S-containing plasma polymers. Results show dominance of S-S, S-H, and S-C with small percentages of SO and SO2. Upon storage in air there were no observable changes to the oxidation states of the S atoms in these plasma polymers, whereas the hydrocarbon component underwent oxidative changes. Methods were studied to oxidize the initial sulfur-containing surface groups, but approaches such as H2O2 treatment post-deposition and electrical biasing during deposition did not affect the oxidation states of the incorporated S. Refereed/Peer-reviewed

Polyphosphates are commonly used industrially to provide electrostatic stabilisation to mineral and material suspensions. Polyphosphate solutions however have shown instability under processing conditions such as high temperature and acidic pH which may lead to a reduction in dispersion properties when added to mineral or material suspensions. In this study the influence of pH, temperature and divalent cation concentration pre-treatment on polyphosphate dispersion properties is reported. Dispersion properties are determined using rheological suspension analysis. The suspensions investigated are material-based model systems of titania pigment and high purity boehmite. Infrared spectroscopy studies of polyphosphate solutions were undertaken to directly investigate the polyphosphate structure after pre-treatment. The rheological measurements show reduced polyphosphate dispersion properties with reduced pH, increased temperature and at high calcium concentrations which correlate with directly measured and reported changes in the polyphosphate structure. When pH, temperature and high divalent cation concentrations are combined, the synergistic effect on reduced polyphosphate dispersion performance is particularly prominent. Refereed/Peer-reviewed

Plasma polymers deposited from n-heptylamine onto silicon wafers have been found to form a porous microstructure when immersed in water and other solvents, with pores of dimensions and densities that vary considerably between coatings deposited under different plasma conditions. This solvent-induced pore formation was found to correlate with the observed percentage of extractable material. With low radio frequency (rf) power inputs, the resultant softer coatings possess considerably more extractable material than coatings deposited at higher applied power levels. The porosity is thus proposed to result from the formation of voids created by the extraction of soluble low-molecular-weight polymeric material, which produces shrinkage stress that the coating, firmly attached to the substrate, cannot relieve by macroscopic contraction. The microscopic contraction of plasma polymer volume creates voids that appear to span the entire film thickness. The effect of aging plasma polymers in air was also investigated. For films deposited at low power it led to reduced extraction of soluble material and different pore morphology, whereas for films deposited at higher rf power levels, the extracted amounts and pore formation were the same for aged coatings. It was also found that the density of surface amine groups was lower for films deposited under the two lowest power settings, in contrast to the commonly held belief that the use of minimal applied rf power aids retention of functional groups. These porous plasma polymer coatings with surface groups suitable for further interfacial chemical immobilization reactions may be useful for various membrane and biotechnology applications. Refereed/Peer-reviewed

This review surveys methods for the fabrication, by plasma surface treatments or plasma polymerization, of polymeric surfaces and thin plasma polymer coatings that contain reactive chemical groups useful for the subsequent covalent immobilization, by solution chemical reactions or vapor phase grafting, of molecules or polymers that can exert bio-specific interfacial responses. Surfaces containing amine, carboxy, hydroxy, and aldehyde groups are the subject of this review. Aminated surfaces have been fabricated using various plasma vapors or mixtures and have found wide use for bio-interface applications. However, in many cases the amine surfaces have a rather limited shelf life, with post-plasma oxidation reactions and surface adaptation leading to the disappearance of amine groups from the surface. Aging is a widespread phenomenon that often has not been recognized, particularly in some of the earlier studies on the use of plasma-fabricated surfaces for bio-interfacial applications, and can markedly alter the surface chemistry. Plasma-fabricated surfaces that contain carboxy groups have also been well documented. Fewer reports exist on hydroxy and aldehyde surfaces prepared by plasma methods. Hydroxy surfaces can be prepared by water plasma treatment or the plasma polymerization of alkyl alcohol vapors. Water plasma treatment on many polymer substrates suffers from aging, with surface adaptation leading to the movement of surface modification effects into the polymer. Both hydroxy and aldehyde surfaces have been used for the covalent immobilization of biologically active molecules. Aging effects are less well documented than for amine surfaces. This review also surveys studies using such surfaces for cell colonization assays. Generally, these surface chemistries show good ability to support cell colonization, though the effectiveness seems to depend on the process vapor and the plasma conditions. Carboxylate co-polymer surfaces have shown excellent ability to support the colonization of some human cell lines of clinical interest. Immobilization of proteins onto plasma-carboxylated surfaces is also well established.

Brominated furanones are promising antibacterial compounds, both in solution and immobilized on solid surfaces, and there is interest in their utilization as protective coatings on biomedical devices to combat device-centered infections. The rational design and optimization of antibacterial furanone coatings requires detailed spectroscopic surface characterization of the coatings produced and correlation of surface analysis data with antibacterial performance. However, as reported in this study, the extreme sensitivity of brominated furanones to radiation damage in the course of XPS analysis greatly complicates characterization. Our data show that rapid degradation occurs, as shown by the emergence of a signal assignable to Br− ion in the Br 3d spectrum. This Br− is water soluble as shown by washing experiments, whereas the CBr signal does not become reduced during washing, consistent with covalent interfacial immobilization of the furanone molecules. Furanone molecules were immobilized onto two different hydrogel interlayers (polyacrylic acid and polyethylene oxide (PEO)), and XPS analyses show that the interlayers did not suffer significant radiation degradation; the damage is limited to the furanone molecules. The results of this study may assist in XPS analyses of other brominated compounds on surfaces; the possibility of Br− ions deriving from XPS analysis–damage must be investigated before assigning their generation to side reactions in the coating or surface-modification procedure. Copyright © 2006 John Wiley & Sons, Ltd.

Novel polyethyleneimine–phosphonate–carboxylic copolymers with an increasing number of carboxyl-ate and phosphonate groups have been synthesised. The presence of positively charged amino groups andnegatively charged carboxylate and phosphonate groups influenced the adsorption of these copolymerson boehmite colloidal particles and their dispersant ability in solution at pH values below and abovethe isoelectric point (iep) of boehmite. It was found that the addition of negatively charged carboxylategroups to the polyethyleneimine polymer backbone had a positive effect on polymer adsorption densityand affinity for the boehmite surface while the phosphonate groups had a negative effect. The adsorptionof these copolymers on the boehmite surface is largely controlled by electrostatic attractions with thepositively and negatively charged aluminium sites below and above the iep of boehmite, respectively. Thechanges in yield stress of the boehmite particle suspension following copolymer adsorption are largelyexplained by electrical double layer interaction between the boehmite particles, but also by van der Waalsor steric interactions between the polymer-coated particles. Refereed/Peer-reviewed

Phosphate groups are part of biological molecules involved in bio-interfacial phenomena but monomers containing these groups are not volatile enough to be plasma polymerized(pp). Hence monomers with lower oxidation states of P are needed which then does not enable prediction of the oxidation state(s) of P in the pps, nor of possible aging effects. XPS and FTIR analyses of pps from triisopropyl phosphite (TIP) and diethyl phosphite (DEP) reveal the presence of phosphate and polyphosphate groups, while phosphonate and phosphate are found in pps of copolymerized1,7-octadiene and TIP. Post-plasma aging and electrical biasing have negligible effects on the oxidation state of P in TIP pps. Refereed/Peer-reviewed

Addition of ionized terminal groups to PEG graft layers may cause additional interfacial forces to modulate the net interfacial interactions between PEG graft layers and proteins. In this study we investigated the effect of terminal sulfonate groups, characterizing PEG-aldehyde (PEG-CHO) and sulfonated PEG (PEG-SO3) graft layers by XPS and colloid probe AFM interaction force measurements as a function of ionic strength, in order to determine surface forces relevant to protein resistance and models of bio-interfacial interaction of such graft coatings. On the PEG-CHO surface the measured interaction force does not alter with ionic strength, typical of a repulsive steric barrier coating. An analogous repulsive interaction force of steric origin was also observed on the PEG-SO3 graft coating; however, the net interaction force changed with ionic strength. Interaction forces were modelled by steric and electrical double layer interaction theories, with fitting to a scaling theory model enabling determination of the spacing and stretching of the grafted chains. Albumin, fibrinogen, and lysozyme did not adsorb on the PEG-CHO coating, whereas the PEG graft with terminal sulfonate groups showed substantial adsorption of albumin but not fibrinogen or lysozyme from 0.15 M salt solutions. Under lower ionic strength conditions albumin adsorption was again minimized as a result of the increased electrical double-layer interaction observed with the PEG-SO3 modified surface. This unique and unexpected adsorption behaviour of albumin provides an alternative explanation to the "negative cilia" model used by others to rationalize observed thromboresistance on PEG-sulfonate coatings. Refereed/Peer-reviewed

New siloxane coupling agents have been prepared by the platinum-catalyzed addition of CH 2 =CHSi(OR) 3 silanes (R=CH 3 or CH 2 CH 2 OCH 3 ) to four different siloxanes, poly[(methylhydrogen)siloxane-co-dimethylsiloxane], poly[(methylhydrogen)siloxane] (dp= 33), tetramethyldisiloxane, and tetramethylcyclotetrasiloxane. These new hydrophobic materials offer a distinct alternative to conventional silane coupling agents, prevalent in many industrial applications. The new preparations allow for control of molecular weight, the extent of coupling functionality, and the distribution of coupling groups on the siloxane backbone. The use of 2D NMR experiments, COSY, and HETCOR indicated two modes of addition to the Si-H groups had occurred, Markovnikov and anti-rnarkovnikov. GPC, FTIR, and 1 H and 13 C NMR were used to thoroughly characterize all the reaction products

Thesis (PhD)--University of South Australia, 2010 The aim of this research was to investigate the structural and chemical properties of dispersants and thereby identify a potential replacement for the phosphate dispersants in the titania pigment industry. Phosphonate copolymers which have improved thermal stability across a broad range of pH values have the potential to be used as dispersants in the titania pigment manufacturing process. The specific aims of this research were firstly to synthesize and characterise copolymers containing phosphonate and carboxylate functional groups with different phosphonate to carboxylate ratios, secondly to investigate their interaction with boehmite particles, used as model of the titania pigment surface, and thirdly to study their ability in dispersing boehmite suspensions as a function of pH and polymer concentration.

The preparation of thin film coatings with sulfonate and sulfate groups by plasma techniques is not straightforward due to limited volatility of suitable process vapours. We report a combination of plasma polymerisation and plasma treatment, treating heptylamine (HA-SO2) and 1, 7-octadiene (OD-SO2) plasma polymers with sulfur dioxide plasma. HA-SO 2 and OD-SO2 plasma polymer surfaces exhibited different compositions with the latter showing almost twice the amount of sulfur, as well as polysulfonate. Ageing of HA-SO2 plasma polymer surfaces in air or saline solution led to the disappearance of oligomers containing sulfonate and sulfate. Angle-dependent XPS analysis of HA-SO2 plasma polymers suggested that sulfur containing groups reptated into the plasma polymer upon storage after preparation. Refereed/Peer-reviewed

Porous silicon has received considerable interest in recent years in a range of biomedical applications, with its performance determined by surface chemistry. In this work, we investigate the PEGylation of porous silicon wafers using click chemistry. The porous silicon wafer surface chemistry was monitored at each stage of the reaction via photoacoustic Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, whereas sessile drop contact angle and model protein adsorption measurements were used to characterize the final PEGylated surface. This work highlights the simplicity of click-chemistry-based functionalization in tailoring the porous silicon surface chemistry and controlling protein−porous silicon interactions. Refereed/Peer-reviewed

Purpose. To examine the ability of contact lenses coated with fimbrolides, inhibitors of bacterial quorum sensing, to prevent microbial adhesion and their safety during short-term clinical assessment.Methods. A fimbrolide was covalently attached to commercially available high Dk contact lenses. Subsequently Pseudomonas aeruginosa, Staphylococcus aureus, Serratia marcescens, or Acanthamoeba sp. were added to the lenses and control uncoated contact lenses. Lenses plus microbes were incubated for 24 h, then washed thoroughly to removenon-adherent microbes. Lenses were macerated and resulting slurry plated onto agar plates. After appropriate incubation,the numbers of colony forming units of bacteria (or numbers of Acanthamoeba trophozoites measured using a hemocytometer)from fimbrolide-coated and uncoated lenses were examined. A Guinea Pig model of lens wear was used toassess the safety of lenses worn on a continuous basis for 1 month. In a separate study, 10 subjects wore fimbrolide-coatedlenses for 24 h. The responses of the Guinea Pigs and human volunteers to the lenses were assessed by slit lampexamination.Results. The fimbrolides-coated lenses reduced the adhesion of all bacterial strains tested, with reductions occurring of between 67 and 92%. For Acanthamoeba a reduction of 70% was seen. There were no significant differences in ocularresponses to fimbrolide-coated lenses compared with controls in either the 1 month animal model or overnight human trial.Conclusions. Fimbrolide-coated lenses show promise as an antibacterial and anti-acanthamoebal coating on contact lenses and appear to be safe when worn on the eye in an animal model. Refereed/Peer-reviewed

Chemical functionalisation of polymeric scaffolds with functional groups such as amine could provide optimal conditions for loading of signalling biomolecules over the entire volume of the porous scaffolds. Three-dimensional (both surface and bulk) functionlisation of large volume scaffolds is highly desirable, but preferably without any change to the basic morphological, structural and bulk chemical properties of the scaffolds. In this work, we have carried out and compared treatments of poly(lactide-co-glycolide) tissue engineering scaffolds by two methods, that is, a wet chemical method using ethylenediamine and a glow discharge plasma method using heptylamine as a precursor. The samples thus prepared were analysed by scanning electron microscopy and X-ray photoelectron spectroscopy. The plasma treatment generated amide and protonated amine (NH + ) groups which were present in the bulk and on the surface of the scaffold. Amination also occurred for the wet chemical treatments but the structural and chemical integrity were adversely affected.

Refereed/Peer-reviewed

Furanone compounds (fimbrolides) have attracted interest as antibacterial compounds for use in human health care, for instance, as an antibacterial coating for medical devices to combat device-centered infections. To ensure effectiveness for extended periods of time, they must be immobilized covalently onto a device surface; in this study, this was done via azide/nitrene chemistry and photochemical coupling. However, the detection and quantification of surface-immobilized small molecules such as furanones presents a considerable analytical challenge, yet is necessary for optimization of coatings and reliable interpretation of biological responses. We have utilized the surface sensitivity and chemical specificity of time-of-flight secondary ion mass spectrometry (TOF-SIMS) to characterize each step of the grafting sequence. On account of the complexity of the data, principal component analysis (PCA) was used to interpret and compare spectra. The results demonstrate the utility of TOF-SIMS with PCA for the detection of the surface-grafted small molecules azidoaniline and a brominated furanone; imaging of the bromine ion peaks also enabled assessment of grafting uniformity. Thus, successful multilayer coating and furanone grafting was observed, and substantial and uniform coverage of furanone molecules on the surface. Even multiple grafting steps involving, in the present case, two low molecular weight compounds can readily be disentangled by PCA. The utility of TOF-SIMS analysis with PCA is particularly well illustrated in the present case by the grafting of the furanone molecules, which did not yield a singular unique peak in the positive ion mass spectra, whereas the collective spectral changes elucidated by PCA provided unambiguous verification of successful grafting of this low molecular weight compound.