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.

Protein resistance of self-assembled monolayers (SAMs) of hexa(ethylene glycols) (EG(6)) has previously been shown to be dependent on the alkoxyl end-group termination of the SAM, which determines wettability [S. Herrwerth, W. Eck, S. Reinhardt, and M. Grunze, J. Am. Chem. Soc. 125, 9359 (2003)]. In the present study, the same series of hexa(ethylene glycols) was used to examine the correlation between protein resistance and the settlement and adhesion of eukaryotic algal cells, viz., zoospores of the macroalga Ulva and cells of the diatom Navicula, which adhere to the substratum through the secretion of protein-containing glues. Results showed that the initial settlement of Ulva zoospores was highest on the hydrophilic EG(6)OH but that cells were only weakly adhered. The number of Ulva zoospores and Navicula cells firmly adhered to the SAMs systematically increased with decreasing wettability, as shown for the protein fibrinogen. The data are discussed in terms of hydration forces and surface charges in the SAMs.

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.

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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.

Introduction Increased mortality has been demonstrated in older adults with COVID-19, but the effect of frailty has been unclear. Methods This multi-centre cohort study involved patients aged 18 years and older hospitalised with COVID-19, using routinely collected data. We used Cox regression analysis to assess the impact of age, frailty, and delirium on the risk of inpatient mortality, adjusting for sex, illness severity, inflammation, and co-morbidities. We used ordinal logistic regression analysis to assess the impact of age, Clinical Frailty Scale (CFS), and delirium on risk of increased care requirements on discharge, adjusting for the same variables. Results Data from 5,711 patients from 55 hospitals in 12 countries were included (median age 74, IQR 54–83; 55.2% male). The risk of death increased independently with increasing age (>80 vs 18–49: HR 3.57, CI 2.54–5.02), frailty (CFS 8 vs 1–3: HR 3.03, CI 2.29–4.00) inflammation, renal disease, cardiovascular disease, and cancer, but not delirium. Age, frailty (CFS 7 vs 1–3: OR 7.00, CI 5.27–9.32), delirium, dementia, and mental health diagnoses were all associated with increased risk of higher care needs on discharge. The likelihood of adverse outcomes increased across all grades of CFS from 4 to 9. Conclusions Age and frailty are independently associated with adverse outcomes in COVID-19. Risk of increased care needs was also increased in survivors of COVID-19 with frailty or older age.

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.