Appropriate characterisation of manufactured nanomaterials (NMs) is vital for many aspects of their synthesis, product formulation, toxicological testing and regulation. As the range and quantity of ...NMs in production has expanded, the interest in their potential environmental and toxicological consequences has grown. With this growth, there is increased need for clarity and rigour in characterising appropriate physicochemical parameters. Which physicochemical parameters should be characterised and under what conditions remains a topic of debate, along with the most appropriate techniques and methodologies to best describe any one characteristic. This review assesses the characterisation requirements of current and future regulatory frameworks for NMs, with specific focus on the incoming REACH framework of the EU. For regulatory compliance, characterisation requirements will be necessarily prescriptive. The minimum physicochemical parameters required to adequately describe NMs for regulatory purposes are proposed, along with a discussion of the most appropriate mechanisms to obtain those data in terms of the overarching delivery mechanism. Guiding principles for particle characterisation during the hazard testing required to comply with regulations are examined.
► Robust regulation relies on accurate description and hence characterisation of NMs. ► Approaches to differentiating between bulk substances and nanoforms are described. ► Criteria for differentiating related nanoforms of the same substance are presented. ► Strategies for improving access to characterisation facilities are proposed. ► Definition, variability and material dynamics of NMs are explored as common themes.
New amphiphilic block copolymers S nSz m consisting of blocks with varied degrees of polymerization, n and m, of polystyrene, S, and polystyrene carrying an amphiphilic ...polyoxyethylene-polytetrafluoroethylene chain side-group, Sz, were prepared by controlled atom transfer radical polymerization (ATRP). The block copolymers, either alone or in a blend with commercial SEBS (10 wt% SEBS), were spin-coated in thinner films (200-400 nm) on glass and spray-coated in thicker films ( approximately 500 nm) on a SEBS underlayer (150-200 microm). Angle-resolved X-ray photoelectron spectroscopy (XPS) measurements proved that at any photoemission angle, varphi, the atomic ratio F/C was larger than that expected from the known stoichiometry. Consistent with the enrichment of the outer film surface (3-10 nm) in F content, the measured contact angles, theta, with water (theta w > or = 107 degrees ) and n-hexadecane (theta h > or = 64 degrees ) pointed to the simultaneous hydrophobic and lipophobic character of the films. The film surface tension gamma S calculated from the theta values was in the range 13-15 mN/m. However, the XPS measurements on the "wet" films after immersion in water demonstrated that the film surface underwent reconstruction owing to its amphiphilic nature, thereby giving rise to a more chemically heterogeneous structure. The atomic force microscopy (AFM) images (tapping mode/AC mode) revealed well-defined morphological features of the nanostructured films. Depending on the chemical composition of the block copolymers, spherical (ca. 20 nm diameter) and lying cylindrical (24-29 nm periodicity) nanodomains of the S discrete phase were segregated from the Sz continuous matrix (root-mean-square, rms, roughness approximately 1 nm). After immersion in water, the underwater AFM patterns evidenced a transformation to a mixed surface structure, in which the nanoscale heterogeneity and topography (rms = 1-6 nm) were increased. The coatings were subjected to laboratory bioassays to explore their intrinsic ability to resist the settlement and reduce the adhesion strength of two marine algae, viz., the macroalga (seaweed) Ulva linza and the unicellular diatom Navicula perminuta. The amphiphilic nature of the copolymer coatings resulted in distinctly different performances against these two organisms. Ulva adhered less strongly to the coatings richer in the amphiphilic polystyrene component, percentage removal being maximal at intermediate weight contents. In contrast, Navicula cells adhered less strongly to coatings with a lower weight percentage of the amphiphilic side chains. The results are discussed in terms of the changes in surface structure caused by immersion and the effects such changes may have on the adhesion of the test organisms.
The influence of the number of repeating units in self-assembled monolayers (SAMs) of ethylene glycol and of their end-group termination on the settlement and adhesion of two types of algal cells, ...viz., zoospores of the macroalga Ulva and cells of the diatom Navicula , was studied. The findings are related to the resistance of these surfaces against fibrinogen adsorption. Results showed that settlement and adhesion of algal cells to oligo(ethylene glycol) (OEG; 2-6 EG units) and poly(ethylene glycol) (PEG; MW = 2000, 5000) SAMs was low, while resistance was less effective for mono(ethylene glycol) (EG(1)OH)-terminated surfaces. These findings concur with former protein adsorption studies. In situ microscopy showed that PEG surfaces inhibited the settlement of zoospores, i.e., zoospores did not attach to the surfaces and remained motile. In contrast, on EG(2-6)OH surfaces, although zoospores settled, i.e., they secreted adhesive and lost motility, adhesion between secreted adhesive and the surface was extremely weak, and the settled spores were unable to bond to the surfaces. The influence of surface properties such as hydration, conformational degrees of freedom, and interfacial characteristics of the SAMs is discussed to understand the underlying repulsive mechanisms occurring in (ethylene glycol)-based coatings.
We describe the synthesis of a series of mono-, di-, and trisaccharide-functionalized alkanethiols as well as the formation of fouling-resistant self-assembled monolayers (SAMs) from these. The SAMs ...were characterized using ellipsometry, wetting measurements, and infrared reflection-absorption spectroscopy (IRAS). We show that the structure of the carbohydrate moiety affects the packing density and that this also alters the alkane chain organization. Upon increasing the size of the sugar moieties (from mono- to di- and trisaccharides), the structural qualities of the monolayers deteriorated with increasing disorder, and for the trisaccharide, slow reorganization dynamics in response to changes in the environmental polarity were observed. The antifouling properties of these SAMs were investigated through protein adsorption experiments from buffer solutions as well as settlement (attachment) tests using two common marine fouling species, zoospores of the green macroalga Ulva linza and cypris larvae of the barnacle Balanus amphitrite. The SAMs showed overall good resistance to fouling by both the proteins and the tested marine organisms. To improve the packing density of the SAMs with bulky headgroups, we employed mixed SAMs where the saccharide-thiols are diluted with a filler molecule having a small 2-hydroxyethyl headgroup. This method also provides a means by which the steric availability of sugar moieties can be varied, which is of interest for specific interaction studies with surface-bound sugars. The results of the surface dilution study and the low nonspecific adsorption onto the SAMs both indicate the feasibility of this approach.
The interaction of spores of Ulva with bioinspired structured surfaces in the nanometer–micrometer size range is investigated using a series of coatings with systematically varying morphology and ...chemistry, which allows separation of the contributions of morphology and surface chemistry to settlement (attachment) and adhesion strength. Structured surfaces are prepared by layer‐by‐layer spray‐coating deposition of polyelectrolytes. By changing the pH during application of oppositely charged poly(acrylic acid) and polyethylenimine polyelectrolytes, the surface structures are systematically varied, which allows the influence of morphology on the biological response to be determined. In order to discriminate morphological from chemical effects, surfaces are chemically modified with poly(ethylene glycol) and tridecafluoroctyltriethoxysilane. This chemical modification changes the water contact angles while the influence of the morphology is retained. The lowest level of settlement is observed for structures of the order 2 µm. All surfaces are characterized with respect to their wettability, chemical composition, and morphological properties by contact angle measurement, X‐ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy.
The interaction of spores of green algae with bioinspired structured surfaces in the nanometer–micrometer‐size range is investigated using a series of coatings with systematically varied morphology and chemistry. Structured surfaces are prepared by layer‐by‐layer spray coating deposition of polyelectrolytes at varying pH and subsequently chemically functionalized. The influence of morphology on the biological response is determined.
Amphiphilic diblock copolymers, Sz6 and Sz12, consisting of a poly(dimethylsiloxane) block (average degree of polymerisation = 132) and a PEGylated-fluoroalkyl modified polystyrene block (Sz, average ...degree of polymerisation = 6, 12) were prepared by atom transfer radical polymerization (ATRP). Coatings were obtained from blends of either block copolymer (1-10 wt%) with a poly(dimethylsiloxane) (PDMS) matrix. The coating surface presented a simultaneous hydrophobic and lipophobic character, owing to the strong surface segregation of the lowest surface energy fluoroalkyl chains of the block copolymer. Surface chemical composition and wettability of the films were affected by exposure to water. Block copolymer Sz6 was also blended with PDMS and a 0.1 wt% amount of multiwall carbon nanotubes (CNT). The excellent fouling-release (FR) properties of these new coatings against the macroalga Ulva linza essentially resulted from the inclusion of the amphiphilic block copolymer, while the addition of CNT did not appear to improve the FR properties.
This work describes the fabrication, characterization, and biological evaluation of a thin protein-resistant poly(ethylene glycol) (PEG)-based hydrogel coating for antifouling applications. The ...coating was fabricated by free-radical polymerization on silanized glass and silicon and on polystyrene-covered silicon and gold. The physicochemical properties of the coating were characterized by infrared spectroscopy, ellipsometry, and contact angle measurements. In particular, the chemical stability of the coating in artificial seawater was evaluated over a six-month period. These measurements indicated that the degradation process was slow under the test conditions chosen, with the coating thickness and composition changing only marginally over the period. The settlement behavior of a broad and diverse group of marine and freshwater fouling organisms was evaluated. The tested organisms were barnacle larvae (Balanus amphitrite), algal zoospores (Ulva linza), diatoms (Navicula perminuta), and three bacteria species (Cobetia marina, Marinobacter hydrocarbonoclasticus, and Pseudomonas fluorescens). The biological results showed that the hydrogel coating exhibited excellent antifouling properties with respect to settlement and removal.
Conditioning, ie the adsorption of proteins and other macromolecules, is the first process that occurs in the natural environment once a surface is immersed in seawater, but no information is ...available either regarding the conditioning of surfaces by artificial seawater or whether conditioning affects data obtained from laboratory assays. A range of self-assembled monolayers (SAMs) with different chemical terminations was used to investigate the time-dependent formation of conditioning layers in commercial and self-prepared artificial seawaters. Subsequently, these results were compared with conditioning by solutions in which zoospores of the green alga Ulva linza had been swimming. Spectral ellipsometry and contact angle measurements as well as infrared reflection absorption spectroscopy (IRRAS) were used to reveal the thickness and chemical composition of the conditioning layers. The extent that surface preconditioning affected the settlement of zoospores of U. linza was also investigated. The results showed that in standard spore settlement bioassays (45-60 min), the influence of a molecular conditioning layer is likely to be small, although more substantial effects are possible at longer settlement times.
Amphiphilic copolymers containing different amounts of poly(ethylene glycol)-fluoroalkyl acrylate and polysiloxane methacrylate units were blended with a poly(dimethyl siloxane) (PDMS) matrix in ...different proportions to investigate the effect of both copolymer composition and loading on the biological performance of the coatings. Laboratory bioassays revealed optimal compositions for the release of sporelings of Ulva linza, and the settlement of cypris larvae of Balanus amphitrite. The best-performing coatings were subjected to field immersion tests. Experimental coatings containing copolymer showed significantly reduced levels of hard fouling compared to the control coatings (PDMS without copolymer), their performance being equivalent to a coating based on Intersleek 700™. XPS analysis showed that only small amounts of fluorine at the coating surface were sufficient for good antifouling/fouling-release properties. AFM analyses of coatings under immersion showed that the presence of a regular surface structure with nanosized domains correlated with biological performance.
This article reports on the preparation and partial characterisation of silicone-based coatings filled with low levels of either synthetic multiwall carbon nanotubes (MWCNTs) or natural sepiolite ...(NS). The antifouling and fouling-release properties of these coatings were explored through laboratory assays involving representative soft-fouling (Ulva) and hard-fouling (Balanus) organisms. The bulk mechanical properties of the coatings appeared unchanged by the addition of low amounts of filler, in contrast to the surface properties, which were modified on exposure to water. The release of Ulva sporelings (young plants) was improved by the addition of low amounts of both NS and MWCNTs. The most profound effect recorded was the significant reduction of adhesion strength of adult barnacles growing on a silicone elastomer containing a small amount (0.05%) of MWCNTs. All the data indicate that independent of the bulk properties, the surface properties affect settlement, and more particularly, the fouling-release behaviour, of the filled materials.
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