Amphiphilic hydrolyzable polydimethylsiloxane-b-poly(ethyleneglycol methacrylate-co-trialkylsilyl methacrylate) block copolymers for marine coatings. II. Antifouling laboratory tests and field trials.

Poly(dimethylsiloxane) (PDMS) elastomer coatings containing an amphiphilic hydrolyzable diblock copolymer additive were prepared and their potential as marine antifouling and antiadhesion materials was tested. The block copolymer additive consisted of a PDMS first block and a random poly(trialkylsilyl methacrylate (TRSiMA, R = butyl, isopropyl)-co-poly(ethyleneglycol) methacrylate (PEGMA) copolymer second block. PDMS-b-TRSiMA block copolymer additives without PEGMA units were also used as additives. The amphiphilic character of the coating surface was assessed in water using the captive air bubble technique for measurements of static and dynamic contact angles. The attachment of macro- and microorganisms on the coatings was evaluated by field tests and by performing adhesion tests to the barnacle Amphibalanus amphitrite and the green alga Ulva rigida. All the additive-based PDMS coatings showed better antiadhesion properties to A. amphitrite larvae than to U. rigida spores. Field tests provided meaningful information on the antifouling and fouling release activity of coatings over an immersion period of 23 months.

Modified 3D-printed device for mercury determination in waters.

3D printing technology is increasingly used in flow analysis, to develop low cost and tailor-made devices. The possibility of grafting specific molecules onto 3D printed parts offers new perspectives for the development of flow systems. In this study, a MPFS system including a dicarboxylate 1,5-diphenyl-3-thiocarbazone grafted 3D-printed device has been developed for mercury determination. For this purpose, the surface of 3D-printed cuboids was first modified with amine functional groups and then grafted with dicarboxylate 1,5-diphenyl-3-thiocarbazone. This new grafted device resulted in selective mercury preconcentration with extraction and elution yields higher than 90% even at high sampling flow rates. The detection can then be carried out in two ways: a direct detection of mercury extracted onto 3D-printed grafted cuboids by atomic absorption spectrophotometry after amalgam on gold or a detection of mercury in solution after elution with l-cysteine by spectrophotometry or cold vapour atomic absorption spectrometry.

Hydrolyzable Additive-Based Silicone Elastomers: A New Approach for Antifouling Coatings.

Fouling Release Coatings are marine antifouling coatings based on silicone elastomers. Contrary to commonly used biocide-based antifouling coatings, they do not release biocides into the marine environment, however, they suffer from poor antifouling efficacy during idle periods. To improve their antifouling performances in static conditions, various amounts of hydrolyzable polymers were incorporated within a silicone matrix. These hydrolyzable polymers were chosen for the well-known hydrolytic degradation mechanism of their main chain, e.g. poly(ε-caprolactone) (PCL), or of their ester pending groups, e.g. poly(bis(trimethylsilyloxy)methylsilyl methacrylate) (PMATM2). The degradation kinetics of such hydrolyzable silicone coatings were assessed by mass loss measurements during immersion in deionized water. Coatings containing PMATM2 exhibited a maximum mass loss after 12 weeks, whereas PCL-based coatings showed no significant mass loss after 24 weeks. Dynamic contact angle measurements revealed the modifications of the coatings surface chemistry with an amphiphilic behavior after water exposure. The attachment of macrofoulers on these coatings were evaluated by field tests in the Mediterranean Sea, demonstrating the short or long-term antifouling effect of these hydrolyzable polymers embedded in the silicone matrix. The settlement of A. amphitrite barnacles on the different coatings indicated inhospitable behaviors towards larval barnacles for coatings with at least 15 wt % of additives.

3D-printed lab-on-valve for fluorescent determination of cadmium and lead in water.

In recent years, the development of 3D printing in flow analysis has allowed the creation of new systems with various applications. Up to now, 3D printing was mainly used for the manufacture of small units such as flow detection cells, preconcentration units or mixing systems. In the present study, a new 3D printed lab-on-valve system was developed to selectively quantify lead and cadmium in water. Different technologies were compared for lab-on-valve 3D printing. Printed test units have shown that stereolithography or digital light processing are satisfactory techniques for creating complex lab-on-valve units. The lab-on-valve system was composed of two columns, eight peripheral ports and a central port, and a coil integrating baffles to increase mixing possibilities. A selective extraction of lead was first carried out by TrisKem Pb™ Resin column. Then, cadmium not retained on the first column was extracted on a second column of Amberlite® IR 120 resin. In a following step, lead and cadmium were eluted with ammonium oxalate and potassium iodide, respectively. Finally, the two metals were sequentially detected by the same Rhod-5N™ fluorescent reagent. This 3D printed lab-on-valve flow system allowed us to quantify lead and cadmium with a linear response from 0.2 to 15 µg L-1 and detection limits of 0.17 and 0.20 µg L-1 for lead and cadmium, respectively, which seems adapted for natural water analysis.

RAFT Polymerization of Tert-Butyldimethylsilyl Methacrylate: Kinetic Study and Determination of Rate Coefficients.

Well-defined poly(tert-butyldimethylsilyl methacrylate)s (TBDMSMA) were prepared by the reversible addition-fragmentation chain transfer (RAFT) process using cyanoisopropyl dithiobenzoate (CPDB) as chain-transfer agents (CTA). The experimentally obtained molecular weight distributions are narrow and shift linearly with monomer conversion. Propagation rate coefficients (kp) and termination rate coefficients (kt) for free radical polymerization of TBDMSMA have been determined for a range of temperature between 50 and 80 °C using the pulsed laser polymerization-size-exclusion chromatography (PLP-SEC) method and the kinetic method via steady-state rate measurement, respectively. The CPDB-mediated RAFT polymerization of TBDMSMA has been subjected to a combined experimental and PREDICI modeling study at 70 °C. The rate coefficient for the addition reaction to RAFT agent (kß1, kß2) and to polymeric RAFT agent (kß) is estimated to be approximately 1.8 × 104 L·mol-1·s-1 and for the fragmentation reaction of intermediate RAFT radicals in the pre-equilibrium (k-ß1, k-ß2) and main equilibrium (k-ß) is close to 2.0 × 10-2 s-1. The transfer rate coefficient (ktr) to cyanoisopropyl dithiobenzoate is found to be close to 9.0 × 10³ L·mol-1·s-1 and the chain-transfer constant (Ctr) for CPDB-mediated RAFT polymerization of TBDMSMA is about 9.3.

3D-printed flow system for determination of lead in natural waters.

The development of 3D printing in recent years opens up a vast array of possibilities in the field of flow analysis. In the present study, a new 3D-printed flow system has been developed for the selective spectrophotometric determination of lead in natural waters. This system was composed of three 3D-printed units (sample treatment, mixing coil and detection) that might have been assembled without any tubing to form a complete flow system. Lead was determined in a two-step procedure. A preconcentration of lead was first carried out on TrisKem Pb Resin located in a 3D-printed column reservoir closed by a tapped screw. This resin showed a high extraction selectivity for lead over many tested potential interfering metals. In a second step, lead was eluted by ammonium oxalate in presence of 4-(2-pyridylazo)-resorcinol (PAR), and spectrophotometrically detected at 520nm. The optimized flow system has exhibited a linear response from 3 to 120µgL-1. Detection limit, coefficient of variation and sampling rate were evaluated at 2.7µgL-1, 5.4% (n=6) and 4 sampleh-1, respectively. This flow system stands out by its fully 3D design, portability and simplicity for low cost analysis of lead in natural waters.

Polysiloxane-based block copolymers with marine bacterial anti-adhesion properties.

Di- and triblock copolymers based on tert-butyldimethylsilyl methacrylate (MASi) and poly(dimethylsiloxane) (PDMS) macro-RAFT agents were synthesized resulting in copolymers with predictable molar masses and low dispersities (D < 1.2). The block copolymers exhibited two glass transition temperatures, corresponding to the PDMS- and poly(tert-butyldimethylsilyl methacrylate) (PMASi)-enriched phases, respectively. Contact angle measurements revealed the influence of the copolymer composition on their surface free energy, with block copolymers exhibiting surface free energies as low as 15.0 mJ m(-2). A laboratory assay using 96-well plates was used to assess the activity of the block copolymers against two marine bacteria (Pseudoalteromonas sp. and Shewanella sp.) isolated from the Mediterranean Sea. Coatings based on PDMS-based block copolymers demonstrated anti-adhesive performances against the two strains better than that of the coating containing only PMASi-based polymers. Coatings based on diblock copolymers demonstrated antifouling performances in the field that were better than those of the corresponding coatings containing triblock copolymers. Results of both lab and field assays showed that the antifouling properties were related to coatings possessing the highest receding water contact angle.

Surface modification of silk fibroin fibers with poly(methyl methacrylate) and poly(tributylsilyl methacrylate) via RAFT polymerization for marine antifouling applications.

In this study, silk fibroin surface containing hydroxyl and aminogroups was firstly modified using a polymerizable coupling agent 3-(trimethoxysilyl) propyl methacrylate (MPS), in order to induce vinyl groups onto the fiber surface. The reversible addition-fragmentation chain transfer (RAFT)-mediated polymerization of methyl methacrylate (MMA) and tributylsilyl methacrylate (TBSiMA) through the immobilized vinyl bond on the silk fibroin surface in the presence of 2-cyanoprop-2-yl dithiobenzoate (CPDB) as chain-transfer agent and 2,2'-azobis(isobutyronitrile) (AIBN) as initiator was conducted in toluene solution at 70°C for 24h. The structure and properties of the modified fiber were characterized by Fourier Transform Infrared Spectroscopy, (13)C, (29)Si Nuclear Magnetic Resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), confirming the presence of the coupling molecule and the methacrylate groups onto the silk fibroin fiber surface. Molecular weight distributions were assessed by triple detection size exclusion chromatography (TD-SEC) in order to verify the livingness of the polymerization.

Assessment and modelling of Ni(II) retention by an ion-imprinted polymer: application in natural samples.

Three novel Ni(II)-Ion-Imprinted Polymer (IIP) were synthesized by precipitation polymerization of ethylene glycol dimethacrylate (crosslinker) with a complex of nickel(II) and vinylbenzyl iminodiacetic acid (VbIDA). The three IIPs were prepared with various mixtures of porogen solvents: methanol, methanol/2-methoxyethanol and methanol/acetonitrile (IIP1, IIP2 and IIP3, respectively). Non-Imprinted Polymers (NIP1, NIP2 and NIP3) were prepared as control polymers in similar conditions but with pure VbIDA instead of VbIDA-Ni. These polymers were characterized by FTIR, BET, SEM and tested for their efficiency and selectivity in Ni(II) retention. The most efficient (IIP1, around 12 mg g(-1) of nickel) was then positively checked for Ni(II) retention in presence of some competing species over a wide range of concentration. Finally Ni(II) retention by IIP1 was successfully demonstrated in natural samples. The modelling of the different experiments (Langmuir, Freundlich but also PROSECE and WHAM VII, frequently used in environmental studies) allowed demonstrating the presence of completely different binding sites when considering the ion-imprinted polymer and the non-imprinted one, and therefore led to a better understanding of what the imprinting effect is.

Inverse suspension polymerization as a new tool for the synthesis of ion-imprinted polymers.

Ion-imprinted polymer beads are prepared for the first time by inverse suspension polymerization in mineral oil using nickel(II) as the template ion. As water is not used as the continuous phase, this new route of synthesis avoids the risk that the ion template leaves the suspension for the aqueous phase. The leaching of nickel from the resin beads is very good due to the large porosity of the polymer beads. The ratio between the ligand and the crosslinker has been increased leading to higher adsorption capacities. Comparing these values with those of the non-imprinted polymers and studying the effect of some interfering ions proves that an optimum can be found for the ratio ligand/crosslinker.

New insights into the adsorption of 3-(trimethoxysilyl)propylmethacrylate on hydroxylated ZnO nanopowders.

Functionalization of zinc oxide (ZnO) nano-objects by silane grafting is an attractive method to provide nanostructured materials with a variety of surface properties. Active hydroxyl groups on the oxide surface are one of the causes governing the interfacial bond strength in nanohybrid particles. Here, "as-prepared" and commercially available zinc oxide nanopowders with a wide range of surface hydroxyl density were functionalized by a well-known polymerizable silane coupling agent, i.e., 3-(trimethoxysilyl)propylmethacrylate (MPS). Fourier transform infrared (FTIR) and solid-state (13)C and (29)Si nuclear magnetic resonance (NMR) spectroscopic investigations demonstrated that the silane coupling agent was fully hydrolyzed and linked to the hydroxyl groups already present on the particle surface through covalent and hydrogen bonds. Due to a basic catalyzed condensation of MPS with water, a siloxane layer was shown to be anchored to the nanoparticles through mono- and tridentate structures. Quantitative investigations were performed by thermogravimetric (TGA) and elemental analyses. The amount of silane linked to ZnO particles was shown to be affected by the amount of isolated hydroxyl groups available to react on the particle surface. For as-prepared ZnO nanoparticles, the number of isolated and available hydroxyl groups per square nanometer was up to 3 times higher than the one found on commercially available ZnO nanoparticles, leading to higher amounts of polymerizable silane agent linked to the surface. The MPS molecules were shown to be mainly oriented perpendicular to the oxide surface for all the as-prepared ZnO nanoparticles, whereas a parallel orientation was found for the preheated commercially ZnO nanopowders. In addition, ZnO nanoparticles were shown to be hydrophobized by the MPS treatment with water contact angles higher than 60°.

On-line solid-phase extraction and multisyringe flow injection analysis of Al(III) and Fe(III) in drinking water.

A new analytical method was developed for on-line monitoring of residual coagulants (aluminium and iron salts) in potable water. The determination was based on a sequential procedure coupling an extraction/enrichment step of the analytes onto a modified resin and a spectrophotometric measurement of a surfactant-sensitized binary complex formed between eluted analytes and Chrome Azurol S. The optimization of the solid phase extraction was performed using factorial design and a Doehlert matrix considering six variables: sample percolation rate, sample metal concentration, flow-through sample volume (all three directly linked to the extraction step), elution flow rate, concentration and volume of eluent (all three directly linked to the elution step). A specific reagent was elaborated for sensitive and specific spectrophotometric determination of Al(III) and Fe(III), by optimizing surfactant and ligand concentrations and buffer composition. The whole procedure was automated by a multisyringe flow injection analysis (MSFIA) system. Detection limits of 4.9 and 5.6 microg L(-1) were obtained for Al(III) and Fe(III) determination , respectively, and the linear calibration graph up to 300 microg L(-1) (both for Al(III) and Fe(III)) was well adapted to the monitoring of drinking water quality. The system was successfully applied to the on-site determination of Al(III) and Fe(III) at the outlet of two water treatment units during two periods of the year (winter and summer conditions).