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Graphical abstract Highlights • SO 3 and PO 3 groups produced by Michael addition on heptylamine plasma polymer. • XPS analysis shows that protein adsorption saturated between 1 and 2 h. • QCM-D shows that passivation with HSA leads to reversible adsorption of lysozyme. • For fibrinogen, partial displacement occurs, regardless of surface chemistry. • Protein adsorption onto SO 3 or PO 3 surfaces is not dominated by electrostatics. Abstract 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Novel polyethyleneimine–phosphonate–carboxylic copolymers with an increasing number of carboxylate and phosphonate groups have been synthesised. The presence of positively charged amino groups and negatively charged carboxylate and phosphonate groups influenced the adsorption of these copolymers on boehmite colloidal particles and their dispersant ability in solution at pH values below and above the isoelectric point (iep) of boehmite. It was found that the addition of negatively charged carboxylate groups to the polyethyleneimine polymer backbone had a positive effect on polymer adsorption density and affinity for the boehmite surface while the phosphonate groups had a negative effect. The adsorption of these copolymers on the boehmite surface is largely controlled by electrostatic attractions with the positively and negatively charged aluminium sites below and above the iep of boehmite, respectively. The changes in yield stress of the boehmite particle suspension following copolymer adsorption are largely explained by electrical double layer interaction between the boehmite particles, but also by van der Waals or steric interactions between the polymer-coated particles. [ABSTRACT FROM AUTHOR]

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 co-polymerized 1,7-octadiene and TIP. Post-plasma aging and electrical biasing have negligible effects on the oxidation state of P in TIP pps. [ABSTRACT FROM AUTHOR]

Abstract: 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 0.15M 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. [Copyright &y& Elsevier]

Abstract: 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. [Copyright &y& Elsevier]

Abstract: Brominated furanones have attracted recent interest as antibacterial compounds. To utilize them as protective coatings in biomedical device applications, they must be covalently immobilized onto solid surfaces; however, interfacial coupling protocols developed for other biomolecules are not applicable to furanones. An azide reaction scheme has enabled covalent immobilization onto fluorinated ethylene propylene copolymer but its chemistry is less predictable, requiring detailed characterization by XPS and tapping mode AFM after each step of the immobilization sequence. XPS curve fitting resolved components in the C1s, N1s and Br3d regions. Angle dependent XPS was used to assess the depth distributions and layer thicknesses. The results indicated successful covalent immobilization of furanones; however, side reactions occurred. In addition to the expected Ctribution from bromine ion (Br−) was detected, indicating that photo-degradation of furanones took place during UV illumination, and this reaction was found to increase with illumination time. The Br− was removed by washing with water, whereas the C from immobilized furanone remained. Spectroscopic characterization will assist in elucidating the structure of furanone coatings, understanding their mode of action when covalently immobilized on surfaces, and rationally designing and optimizing an effective antibacterial coating for biomedical applications. [Copyright &y& Elsevier]

The interaction of sodium stearate with titania pigment particles from aqueous suspension has been investigated using thermal analysis and infrared spectroscopy combined with electrochemical studies. Thermogravimetric analysis (TGA) was used both to determine the adsorption isotherm and to investigate the interaction behavior. Monolayer coverage is determined to be 0.95 mg/m2; however, unlike the case with organic solvents, multilayer adsorption occurs. Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, combined with TGA, revealed that the surface monolayer is chemically bound. DRIFT spectroscopic data also indicated that the stearate bridged across two aluminum atoms. Subsequent stearate layers were physisorbed to the stearate monolayer and were readily removed with acetone washing. [Copyright &y& Elsevier]

Ensuring discrete dispersion of pigment particles is crucial to maintain their separation during processing and storage, and to achieve the desired properties in coatings. To facilitate dispersion and prevent aggregation, the stability of the dispersant along with the chemical interaction between pigment particles and dispersants is critical. This study was conducted to investigate the interaction between robust dispersants containing thermally stable carboxylate and phosphonate functional groups and the titania pigment surface at pH values experienced in pigment manufacturing as well as in application. The study found that the interaction depends on the type of group, the distribution density of the group, and the solution pH. Dispersant adsorption can occur under both alkaline and acidic solution conditions, with the adsorption density increasing when the pH is reduced or the carboxylate group density is increased. At pH 9.5, dispersant adsorption affinity and density is low, and hydrogen bonding occurs in addition to phosphate group chemisorption. At pH 5.5, both the adsorption affinity and density significantly increase due to electrostatic interactions between carboxylate and/or phosphonate groups and the pigment surface, combined with phosphate group driven chemisorption. Linear carboxylate-phosphonate copolymers and carboxylate dispersants present at the pigment surface provide electrostatic stabilisation while branched copolymers provide both electrostatic and steric stabilisation. The synergistic physical and chemical interaction combined with dispersion stability may lead to improved titania pigment suspensions using branched copolymer dispersants. [Display omitted] • Dispersant architectural framework drives the pigment stabilisation mechanism • Chemical functionality of a dispersant dictates its pigment surface interactions • Branched dispersants can synergistically interact and improve dispersion stability [ABSTRACT FROM AUTHOR]

Abstract: 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. [Copyright &y& Elsevier]

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. [ABSTRACT FROM AUTHOR]