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  • 1.
    Aldred, Nick
    et al.
    Newcastle University, England .
    Gohad, Neeraj V.
    Clemson University, SC USA .
    Petrone, Luigi
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Orihuela, Beatriz
    Duke University, NC USA .
    Liedberg, Bo
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Ederth, Thomas
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Mount, Andrew
    Clemson University, SC USA .
    Rittschof, Dan
    Duke University, NC USA .
    Clare, Anthony S.
    Newcastle University, England .
    Confocal microscopy-based goniometry of barnacle cyprid permanent adhesive2013In: Journal of Experimental Biology, ISSN 0022-0949, E-ISSN 1477-9145, Vol. 216, no 11, p. 1969-1972Article in journal (Refereed)
    Abstract [en]

    Biological adhesives are materials of particular interest in the fields of bio-inspired technology and antifouling research. The adhesive of adult barnacles has received much attention over the years; however, the permanent adhesive of the cyprid - the colonisation stage of barnacles - is a material about which very little is presently known. We applied confocal laser-scanning microscopy to the measurement of contact angles between the permanent adhesive of barnacle cyprid larvae and self-assembled monolayers of OH- and CH3-terminated thiols. Measurement of contact angles between actual bioadhesives and surfaces has never previously been achieved and the data may provide insight into the physicochemical properties and mechanism of action of these functional materials. The adhesive is a dual-phase system post-secretion, with the behaviour of the components governed separately by the surface chemistry. The findings imply that the cyprid permanent adhesion process is more complex than previously thought, necessitating broad re-evaluation of the system. Improved understanding will have significant implications for the production of barnacle-resistant coatings as well as development of bio-inspired glues for niche applications.

  • 2.
    Di Fino, A.
    et al.
    Newcastle University, England .
    Petrone, Luigi
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Aldred, N.
    Newcastle University, England .
    Ederth, Thomas
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Liedberg, Bo
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Clare, A. S.
    Newcastle University, England .
    Correlation between surface chemistry and settlement behaviour in barnacle cyprids (Balanus improvisus)2014In: Biofouling (Print), ISSN 0892-7014, E-ISSN 1029-2454, Vol. 30, no 2, p. 143-152Article in journal (Refereed)
    Abstract [en]

    In laboratory-based biofouling assays, the influence of physico-chemical surface characteristics on barnacle settlement has been tested most frequently using the model organism Balanus amphitrite (= Amphibalanus amphitrite). Very few studies have addressed the settlement preferences of other barnacle species, such as Balanus improvisus (= Amphibalanus improvisus). This study aimed to unravel the effects of surface physico-chemical cues, in particular surface-free energy (SFE) and surface charge, on the settlement of cyprids of B. improvisus. The use of well-defined surfaces under controlled conditions further facilitates comparison of the results with recent similar data for B. amphitrite. Zero-day-old cyprids of B. improvisus were exposed to a series of model surfaces, namely self-assembled monolayers (SAMs) of alkanethiols with varying end-groups, homogenously applied to gold-coated polystyrene (PS) Petri dishes. As with B. amphitrite, settlement of cyprids of B. improvisus was influenced by both SFE and charge, with higher settlement on low-energy (hydrophobic) surfaces and negatively charged SAMs. Positively charged SAMs resulted in low settlement, with intermediate settlement on neutral SAMs of similar SFE. In conclusion, it is demonstrated that despite previous suggestions to the contrary, these two species of barnacle show similar preferences in response to SFE; they also respond similarly to charge. These findings have positive implications for the development of novel antifouling (AF) coatings and support the importance of consistency in substratum choice for assays designed to compare surface preferences of fouling organisms.

  • 3.
    Petrone, Luigi
    Linköping University, Department of Physics, Chemistry and Biology, Sensor Science and Molecular Physics. Linköping University, The Institute of Technology.
    Molecular surface chemistry in marine bioadhesion2013In: Advances in Colloid and Interface Science, ISSN 0001-8686, E-ISSN 1873-3727, Vol. 195-196, p. 1-18Article in journal (Refereed)
    Abstract [en]

    This review covers the in situ molecular physicochemical characterisation of bioadhesives at solid/liquid interfaces, with the aim of elucidating the adhesion strategies that lie at the root of marine biofouling. It focuses on three major foulers: mussels, algae and barnacles. The dispersal of these organisms, their colonisation of surfaces, and ultimately their survival rely critically on the ability of the organisms larvae or spores to locate a favourable settlement site and undergo metamorphosis, thus initiating their sessile existence. Differences in the composition of adhesive secretions and the strategies employed for their temporary or permanent implementation exists between the larval and adult life stages. To date, only a few adhesive secretions from marine fouling organisms have been adequately described in terms of their chemical composition, and a survey revealed the presence of certain recurrent functional groups, specifically catechol, carboxylate, monoester-sulphate and -phosphate. This review will describe the binding modes of such functionalities to wet mineral/metal oxides surfaces. Such functionalities will be ranked based on their ability to bind to hydrophilic surfaces replacing surface-bound water (Langmuir adsorption constant) as well as other adsorbates (competitive adsorption). A plausible explanation for the propensity of the reviewed adhesive functionalities to bind to hydrous metal oxide surfaces will be given on the basis of the Hard and Soft Acids and Bases principle, Hofmeister effects and entropic considerations. From the in situ analysis of marine organism bioadhesives and adsorption studies of functionalities relevant to the bioadhesion process, insights can be gleaned for a knowledge-based innovation of antifouling strategies and the synthesis of strong, durable adhesive materials, which are suitable for implementation in wet environments.

  • 4.
    Petrone, Luigi
    et al.
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Aldred, Nick
    Newcastle University, England.
    Emami, Kaveh
    Newcastle University, England.
    Enander, Karin
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, The Institute of Technology.
    Ederth, Thomas
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, The Institute of Technology.
    Clare, Anthony S.
    Newcastle University, England.
    Chemistry-specific surface adsorption of the barnacle settlement-inducing protein complex2015In: Interface Focus, ISSN 2042-8898, E-ISSN 2042-8901, Vol. 5, no 1, p. 20140047-Article in journal (Refereed)
    Abstract [en]

    Gregarious settlement in barnacle larvae (cyprids) is induced by a contact pheromone, the settlement-inducing protein complex (SIPC). The SIPC has been identified both in the cuticle of adult barnacles and in the temporary adhesive secretion (footprint) of cyprids. Besides acting as a settlement inducer, the presence of the SIPC in footprints points to its additional involvement in the adhesion process. SIPC adsorption behaviour was therefore investigated on a series of self-assembled monolayers (SAMs) by surface plasmon resonance at the pH of seawater (8.3). Fibrinogen and alpha(2)-macroglobulin (A2M) (blood complement protease inhibitors with which the SIPC shares 29% sequence homology) were used in the adsorption experiments as positive and negative standards, respectively. The mass uptake of the SIPC was comparable to that of fibrinogen, with adsorption observed even on the protein-resistant oligo(ethylene glycol) surface. Notably, on the positively charged SAM the SIPC showed a kinetic overshoot, indicating a metastable configuration causing the amount of adsorbed protein to temporarily exceed its equilibrium value. A2M adsorption was low or negligible on all SAMs tested, except for the positively charged surface, indicating that A2M adsorption is mainly driven by electrostatics. Evaluation of SIPC non-specific adsorption kinetics revealed that it adsorbed irreversibly and non-cooperatively on all surfaces tested.

  • 5.
    Petrone, Luigi
    et al.
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Di Fino, Alessio
    Newcastle University.
    Aldred, Nick
    Newcastle University.
    Sukkaew, Pitsiri
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Ederth, Thomas
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Clare, Anthony S
    Newcastle University.
    Liedberg, Bo
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Effects of surface charge and Gibbs surface energy on the settlement behaviour of barnacle cyprids (Balanus amphitrite)2011In: Biofouling (Print), ISSN 0892-7014, E-ISSN 1029-2454, Vol. 27, no 9, p. 1043-1055Article in journal (Refereed)
    Abstract [en]

    Gibbs surface energy has long been considered to be an important parameter in the design of fouling-resistant surfaces for marine applications. Rigorous testing of the hypothesis that settlement is related to Gibbs surface energy however has never been accomplished, due mainly to practical limitations imposed by the necessary combination of surface engineering and biological evaluation methods. In this article, the effects of surface charge and Gibbs surface energy on the settlement of cyprids of an important fouling barnacle, Balanus amphitrite, were evaluated. Settlement assays were conducted on a range of self-assembled monolayers (SAMs) (CH(3)-, OH-, COOH-, N(CH(3))(3)(+)-, NH(2)-terminated), presented in gold-coated polystyrene well plates, varying in terms of their surface charge and Gibbs surface energy. Contrary to contemporary theory, settlement was not increased by high-energy surfaces, rather the opposite was found to be the case with cyprids settling in greater numbers on a low-energy CH(3)- SAM compared to a high-energy OH- SAM. Settlement was also greater on negatively-charged SAMs, compared to neutral and positively-charged SAMs. These findings are discussed in the context of data drawn from surfaces that varied in multiple characteristics simultaneously, as have been used previously for such experiments. The finding that surface charge, rather than total surface energy, may be responsible for surface selection by cyprids, will have significant implications for the design of future fouling-resistant materials.

  • 6.
    Suriyanarayanan, Subramanian
    et al.
    Linnaeus University, Sweden .
    Petrone, Luigi
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Ederth, Thomas
    Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, Faculty of Science & Engineering.
    Nicholls, Ian A.
    Linnaeus University, Sweden .
    Biotinyl moiety-selective polymer films with highly ordered macropores2013In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 49, no 46, p. 5274-5276Article in journal (Refereed)
    Abstract [en]

    Macroporous polymer films with long-range uniformity and biotinyl-moiety selective recognition sites have been developed. A hierarchical molecular imprinting strategy afforded significant enhancements in quartz crystal microbalance (QCM) sensitivities towards biotinylated compounds.

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